molecules
Review
Advances in Rosin-Based Chemicals: The Latest
Recipes, Applications and Future Trends
Szymon Kugler 1, * , Paula Ossowicz 1 , Kornelia Malarczyk-Matusiak 1
and Ewa Wierzbicka 2
1
2
*
Faculty of Chemical Engineering, West Pomeranian University of Technology in Szczecin, Pulaskiego 10,
70-322 Szczecin, Poland; paula.ossowicz@zut.edu.pl (P.O.); kornelia.malarczyk@zut.edu.pl (K.M.-M.)
Industrial Chemistry Research Institute, Rydygiera 8, 01-793 Warsaw, Poland; ewa.wierzbicka@ichp.pl
Correspondence: skugler@zut.edu.pl
Received: 22 March 2019; Accepted: 23 April 2019; Published: 26 April 2019
Abstract: A comprehensive review of the publications about rosin-based chemicals has been compiled.
Rosin, or colophony, is a natural, abundant, cheap and non-toxic raw material which can be easily
modified to obtain numerous useful products, which makes it an excellent subject of innovative
research, attracting growing interest in recent years. The last extensive review in this research area
was published in 2008, so the current article contains the most promising, repeatable achievements in
synthesis of rosin-derived chemicals, published in scientific literature from 2008 to 2018. The first
part of the review includes low/medium molecule weight compounds: Especially intermediates,
resins, monomers, curing agents, surfactants, medications and biocides. The second part is about
macromolecules: mainly elastomers, polymers for biomedical applications, coatings, adhesives,
surfactants, sorbents, organosilicons and polysaccharides. In conclusion, a critical evaluation of
the publications in terms of data completeness has been carried out with an indication of the most
promising directions of rosin-based chemicals development.
Keywords: rosin; curing agent; resin; surfactant; biocide; medicine; polymer
1. Introduction
The natural origin, low price, abundance and chemical modification potential of rosin make it a
valuable raw material in numerous applications [1–14]. Besides the mentioned advantages, rosin is
also safe for living organisms [15]. Its derivatives are claimed as non-toxic as well, despite their
allergenicity [16,17]. This unique set of beneficial properties of rosin determines it as an attractive
subject of innovative research characterized by a considerably growing interest in recent decades,
as can be seen in Figure 1.
Unfortunately, the awareness of the possibility of using rosin as a raw material for obtaining
valuable chemicals is generally unsatisfactory. There is a burning need to bring this topic to the
attention of a larger group of scientists. Furthermore, the growing number of publications causes
difficulties in keeping up with the latest research, as well as in selection of more promising discoveries.
Sadly, the last comprehensive review document dedicated exclusively to rosin and its modifications
was published in 2008 [1]. Since then, only fragmentary information on rosin has appeared in review
articles on bio-based polymers and resin systems [2–21], as well as in reviews on rosin derivatives in
catalysis [12], controlled drug-delivery systems [13] and small-molecule compounds [14].
In view of these facts, publication of a wide, comprehensive and critical review of achievements
since 2008 is an important solution to solve the problem of a severe lack of current review literature in
this field. The growing number of publications is not the only obstacle in creating a literature review
on rosin. No less important challenge is to collect information from existing literature. Quite often
Molecules 2019, 24, 1651; doi:10.3390/molecules24091651
www.mdpi.com/journal/molecules
Molecules 2019, 24, 1651
Molecules 2019, 24, x FOR PEER REVIEW
2 of 52
2 of 51
articles do not contain full information about a particular reaction, but refer to earlier articles, which,
not contain
information
particular
reaction,online,
but refer
earlier
in turn,often
mayarticles
refer todoeven
earlierfull
articles,
whichabout
mayanot
be available
ortomay
notarticles,
be in English.
which, in turn, may refer to even earlier articles, which may not be available online, or may not be in
The current article is a direct answer to the aforementioned issues. Its aims are: (I) to provide
English.
a precise review of the scientific literature from 2008 to 2018, (II) select promising studies with clear
The current article is a direct answer to the aforementioned issues. Its aims are: (I) to provide a
practicalprecise
application
and
an overall
assessment
in with
orderclear
to identify
review of
the(III)
scientific
literature
from 2008 of
to the
2018,reviewed
(II) select achievements
promising studies
the most
perspective
development
directions
of rosin-based
chemicals.
The review
is identify
presented in a
practical
application
and (III) an overall
assessment
of the reviewed
achievements
in order to
thepleasant-to-browse
most perspective development
directionswith
of rosin-based
Thereaction
review is schemes.
presented in
a article
modern,
form, illustrated
patientlychemicals.
completed
The
modern,
pleasant-to-browse
form,
illustrated
with
patiently
completed
reaction
schemes.
The
article
provides concise, but exhaustive information on the achievements in preparation of rosin-derived
provides concise, but exhaustive information on the achievements in preparation of rosin-derived
chemicals in the last decade. Its main idea is to inspire and encourage the world of science to actively
chemicals in the last decade. Its main idea is to inspire and encourage the world of science to actively
take interest
in rosin and the possibilities of its modification.
take interest in rosin and the possibilities of its modification.
Figure
1. Number
of scientific
articlesand
andpatent
patent documents
containing
the keyword
“rosin”“rosin”
in the in the
Figure 1.
Number
of scientific
articles
documents
containing
the keyword
years 1990-2017.
years 1990–2017.
Basic Information
about
Rosin
2. Basic2.Information
about
Rosin
or colophony, is a solid and brittle mixture of non-volatile conifer tree resin components.
Rosin, Rosin,
or colophony,
is a solid and brittle mixture of non-volatile conifer tree resin components.
It can display colors ranging from almost colorless, through shades of yellow and brown to black.
It can display colors ranging from almost colorless, through shades of yellow and brown to black.
Depending on the origin, two industrially important types of rosin can be distinguished, i.e. gum
Depending
two
industrially
ofremaining
rosin canafter
be distinguished,
i.e.,
gum rosin
rosinon
andthe
tallorigin,
oil rosin.
Gum
rosin is theimportant
non-volatiletypes
residue
distillation of tree
resin
and tallobtained
oil rosin.byGum
rosin
is thetrees.
non-volatile
residue
remaining
after pulping
distillation
treeprocess.
resin obtained
tapping
of living
Tall oil rosin
is a by-product
of wood
in theofkraft
Gumofrosin
accounts
of world
rosin production,
whereas
tall in
oil the
rosin
is ca.process.
35%. In the
by tapping
living
trees. for
Tallca.oil60%
rosin
is a by-product
of wood
pulping
kraft
Gum rosin
past,
rosin
was
widely
obtained
from
the
solvent
extraction
of
harvested
wood
as
so-called
wood
accounts for ca. 60% of world rosin production, whereas tall oil rosin is ca. 35%. In the past, rosin was
rosin, but nowadays, this technology is of little importance [1,22]. The price of rosin in the first half
widely obtained from the solvent extraction of harvested wood as so-called wood rosin, but nowadays,
of 2018 ranged from 300 to 2750 USD/ton depending on its origin, supplier and color. Annual world
this technology
is of little importance [1,22]. The price of rosin in the first half of 2018 ranged from 300
production of rosin is ca. 1.2 million tons and has remained stable in the last decades [1,2,22].
to 2750 USD/ton
depending
ongeneral
its origin,
supplier
and color.
Annual
production
rosin is ca.
Resin acids,
with the
formula
C19H29COOH,
constitute
up world
to 95 wt.%
of rosin, of
while
1.2 million
tons
and has remained
in the
[1,2,22].
neutral
compounds
are present stable
in amounts
of alast
fewdecades
percent. A
number of resin acids based on a few
diterpene
wereformula
identifiedCso
far29[1].
The most
abundant
acids
are of
built
on while
Resin
acids,carbon
with skeletons
the general
COOH,
constitute
upresin
to 95
wt.%
rosin,
19 H
abietane
and
pimarane
skeletons.
Their
structural
formulas
are
shown
in
Figure
1.
It
should
neutral compounds are present in amounts of a few percent. A number of resin acids basedbeon a few
emphasized, that abietane-structured acids are characterized by conjugated double bond systems,
diterpene carbon skeletons were identified so far [1]. The most abundant resin acids are built on abietane
which makes them particularly susceptible to chemical modifications. It is noteworthy, that abietaneand pimarane
skeletons.
Their structural
aretoshown
in Figure
2. It should
be emphasized,
structured
acids isomerize
at elevated formulas
temperature
afford readily
reactive
levopimaric
acid,
that abietane-structured
areother
characterized
by conjugated
systems,
according to Scheme acids
1. On the
hand, pimarane-type
acids do double
not have bond
conjugated
doublewhich
bond makes
systems, which
limits their
chemical modifications.
processability. The
chemical
of rosin acids
them particularly
susceptible
to chemical
It isdetailed
noteworthy,
thatcomposition
abietane-structured
depends
on
its
type
(gum,
tall
oil
or
wood),
thermal
history,
species
of
tree
and
geographical
isomerize at elevated temperature to afford readily reactive levopimaric acid, accordingorigin
to Scheme 1.
Compositions of gum rosin from various sources are presented in Table 1, where it can be
On the [23,24].
other hand,
pimarane-type acids do not have conjugated double bond systems, which limits
their chemical processability. The detailed chemical composition of rosin depends on its type (gum,
tall oil or wood), thermal history, species of tree and geographical origin [23,24]. Compositions of gum
rosin from various sources are presented in Table 1, where it can be seen that the content of abietanetype acids may vary between 64 and 87 wt.%. Such detailed composition of a rosin can be determined,
e.g., by the capillary electrophoresis method [25].
Molecules 2019, 24, x FOR PEER REVIEW
3 of 51
Molecules
1651
3 of 52
seen2019,
that24,the
content of abietane- type acids may vary between 64 and 87 wt.%. Such detailed
composition of a rosin can be determined, eg. by the capillary electrophoresis method [25].
COOH
COOH
COOH
A) Abietic acid
B) Levopimaric acid
C) Palustric acid
COOH
D) Neoabietic acid
Molecules 2019, 24, x FOR PEER REVIEW
4 of 51
included in the schemes. There are situations where some data simply has not been reported by
original authors, eg. product morphology or yield. Such missing data could not be presented in this
review. What
does the above mean?
The more data provided,
the more advancedCOOH
the research on a
COOH
COOH
COOH
compound, and the more reliable the recipe. The lack of data should indicate that the research on a
E) Dehydroabietic
H) Pimaric acid
F) Sandaracopimaric
G) Isopimaric acid
certain
rosin derivative is probably
at an early, basic stage. It has to be underlined that reaction
acid
acid
schemes do not take into account advanced stereochemistry. Finally, almost all reactions were
Figure
1. Structural
thenitrogen
most common
abietane-structured
(A–E)
and
Figure
2. Structural
of theofmost
common
abietane-structured
(A–E)
and pimarane-structured
conducted
under
an formulas
inertformulas
atmosphere:
or
argon,
so reaction
schemes
do
notpimaraneinclude this
structured
(F–H) resin acids.
information.
(F–H)
resin acids.
Table 1. Composition of resin acids in gum rosin from different sources [23].
Species
Origin
Pinus massoniana
Pinus elliotti
NH2
Pinus merkusii
Pinus sylvestris
DehydroPinus halepensis
abietylamine
China
Brazil
Indonesia
Russia
NH3 Greece
>150°C France
Portugal
Pinus pinaster
Spain
O
Cl
P
USA
Cl
Cl
HOOC
Abietane-type Acids Content (wt.%)
Other Acids
HOOCPalustric/Levopimaric Neoabietic Dehydroabietic
(wt.%)
Abietic
Rosin
39
25
16
7
13
37
15
16
5
27
28
27
5
4
36
35
23
15
10
17
HOOC
45
23
13
5
14
Abietic acid
35 Ni
20 180°C
15
9
21
200°C
3h
34
21
19
9
17
26
22
27
6
19
O
O
14
39
18
4
25 O
HOOC
Levopimaric acid
Dehydroabietic acid
O
O
OH for making films, coatings and
In recent studies
unmodified rosin was used
adhesives [26–42],
65°C/3h
O
biomedical applications [43–55], or in mining, metallurgy and construction [56–58] and for filler
230°C, 3h
O
pTSA
COOH
purposes [59–64]. However, chemical modification
of rosin gives many-fold
greater possibilities of
in CH3COOH
using
of this12h
article.
O=C this raw material, which are described in the next, main section 120°C,
in CHCl3
HOOC
Cl
chloride
3.Dehydroabietyl
Rosin-based Chemicals
(yield 93%)
HOOC
Acrylpimaric acid
yield: 73- 93%
Maleopimaric acid
yield: 92%
3.1. General Comments
on the
Whole Review
Scheme
Synthesis
of essential
essential rosin-based
Scheme
1.1.Synthesis
of
rosin-basedsubstrates/intermediates.
substrates/intermediates.
The review contains short, but exhaustive descriptions of rosin-derived compound syntheses
Table 1. Composition
of resin acids in gum rosin from different sources [23].
3.2.
Small and
Moleculeliterature
Compounds
published
in Medium
the scientific
from the JCR list since 2008. It does not include older
achievements
in the
field ofrosin-derived
rosin, that were
widely described
in
previous
reviewwith
literature
and
Abietane-type
Acids
Content
(wt.%)
This section
describes
small/medium
molecule
compounds
strictly[1,65]
defined
Other
Acids
Species
Origin
commercialized
It includes
preparations
of
completely
new
chemicals,
as
well
as
new
ways
(wt.%)
structures
that do[66–80].
not contain
the
repeated
units
typical
for
macromolecules.
Abietic
Palustric/Levopimaric Neoabietic
Dehydroabietic
to synthesize already
known compounds.
Only
products with
declared or7 obvious practical
Pinus massoniana
China
39
25
16
13
applications
into two 16sections according
to the general
3.2.1.
PinusIntermediates
elliotti have been
Brazilchosen. The
37 review is divided
15
5
27
Pinus merkusii
Indonesia
28 compounds,27
5 is divided according
4
36
molecular
structure
of the prepared
while each section
to practical
are the products
of simple 23
rosin modifications,
which are10necessary for17the
PinusIntermediates
sylvestris
35
15
application
and theRussia
structure similarity
of the compounds. The collected
data are given in the article
Pinus halepensis
45
5 described ways
14
preparation
of manyGreece
new compounds.
They can 23
be synthesized in13very simple, well
text and in schemes.
The following
name, product
France
35 information20are presented in
15the text: product
9
21
with high yields. The
sustainability
of these processes is high: They
usually use
a biobased main
Portugal
21
19 applications.9 On the other hand,
17
morphology,
substrates
name(s), 34
separation techniques
and practical
Pinus pinaster
substrate
(rosin) in solvent-free
processes.
Some drawback
can be 27
the separation processes,
that19
may
Spain
26
22
6
data such as reaction scheme, catalyst use, reaction media, temperature, pressure, time and yield are
14 high viscosity,
39 m.p. and stickiness
18
4
not always be easy, USA
because of the
of products.
In view of25the
above, rosin-based intermediates have very high commercialization potential and some of them are
commercially available in certain regions of the world.
In recent studies unmodified rosin was used for making films, coatings and adhesives [26–42],
Maleopimaric acid is an off-white solid (m.p. 223 °C). It can be prepared from abietic acid and
biomedical applications [43–55], or in mining, metallurgy and construction [56–58] and for filler
maleic anhydride via a Diels-Alder reaction according to Scheme 1 [81], followed by recrystallization
[82]. Maleopimaric acid is one of the crucial products in rosin chemistry. It can be used directly as an
epoxy resin hardener, but its applications are much wider. They include preparation of epoxy resins
[83,84], acrylic resins [85–87], allyl resins [88–90], polyols [91], bio-based curing agents for synthetic
epoxy resins [92–98] or bio-based ones [99], surfactants [100–103], intermediates [104,105],
biologically active compounds [105–108], polyurethanes [109-112], chemicals for NMR techniques
[113] and photolitography [114], sorbents [115], organosilicon compounds [116], printing inks [117]
Molecules 2019, 24, 1651
4 of 52
purposes [59–64]. However, chemical modification of rosin gives many-fold greater possibilities of
using this raw material, which are described in the next, main section of this article.
3. Rosin-based Chemicals
3.1. General Comments on the Whole Review
The review contains short, but exhaustive descriptions of rosin-derived compound syntheses
published in the scientific literature from the JCR list since 2008. It does not include older
achievements in the field of rosin, that were widely described in previous review literature [1,65] and
commercialized [66–80]. It includes preparations of completely new chemicals, as well as new ways to
synthesize already known compounds. Only products with declared or obvious practical applications
have been chosen. The review is divided into two sections according to the general molecular structure
of the prepared compounds, while each section is divided according to practical application and the
structure similarity of the compounds. The collected data are given in the article text and in schemes.
The following information are presented in the text: product name, product morphology, substrates
name(s), separation techniques and practical applications. On the other hand, data such as reaction
scheme, catalyst use, reaction media, temperature, pressure, time and yield are included in the schemes.
There are situations where some data simply has not been reported by original authors, e.g., product
morphology or yield. Such missing data could not be presented in this review. What does the above
mean? The more data provided, the more advanced the research on a compound, and the more reliable
the recipe. The lack of data should indicate that the research on a certain rosin derivative is probably at
an early, basic stage. It has to be underlined that reaction schemes do not take into account advanced
stereochemistry. Finally, almost all reactions were conducted under an inert atmosphere: nitrogen or
argon, so reaction schemes do not include this information.
3.2. Small and Medium Molecule Compounds
This section describes rosin-derived small/medium molecule compounds with strictly defined
structures that do not contain the repeated units typical for macromolecules.
3.2.1. Intermediates
Intermediates are the products of simple rosin modifications, which are necessary for the
preparation of many new compounds. They can be synthesized in very simple, well described ways
with high yields. The sustainability of these processes is high: They usually use a biobased main
substrate (rosin) in solvent-free processes. Some drawback can be the separation processes, that may
not always be easy, because of the high viscosity, m.p. and stickiness of products. In view of the
above, rosin-based intermediates have very high commercialization potential and some of them are
commercially available in certain regions of the world.
Maleopimaric acid is an off-white solid (m.p. 223 ◦ C). It can be prepared from abietic acid and
maleic anhydride via a Diels-Alder reaction according to Scheme 1 [81], followed by recrystallization [82].
Maleopimaric acid is one of the crucial products in rosin chemistry. It can be used directly as an
epoxy resin hardener, but its applications are much wider. They include preparation of epoxy
resins [83,84], acrylic resins [85–87], allyl resins [88–90], polyols [91], bio-based curing agents for
synthetic epoxy resins [92–98] or bio-based ones [99], surfactants [100–103], intermediates [104,105],
biologically active compounds [105–108], polyurethanes [109–112], chemicals for NMR techniques [113]
and photolitography [114], sorbents [115], organosilicon compounds [116], printing inks [117] and
for the hydrophobization of wood surfaces [118–120]. It is noteworthy that the main degradation
products of maleopimaric acid are water, carbon dioxide, formamide and also aliphatic and aromatic
derivatives [121]. It is worth noting that fumaropimaric acid is an isomer of hydrated maleopimaric
acid, which can be synthesized in a similar way [122], but its importance to rosin chemistry is much
smaller: it can be used in synthesis of triglycidyl epoxy resin [122] and water-borne polyurethanes [109].
Molecules 2019, 24, x FOR PEER REVIEW
5 of 51
derivatives [121]. It is worth noting that fumaropimaric acid is an isomer of hydrated maleopimaric
acid, which
be synthesized in a similar way [122], but its importance to rosin chemistry is much
Molecules
2019, can
24, 1651
5 of 52
smaller: it can be used in synthesis of triglycidyl epoxy resin [122] and water-borne polyurethanes
[109].
◦ C). It can be prepared from abietic acid and acrylic
Acrylpimaric
off-white
solid
(m.p.
220220
Acrylpimaricacid
acidisisanan
off-white
solid
(m.p.
°C). It can be prepared from abietic acid and
acid
according
to Scheme
1, followed
by precipitation,
filtration,filtration,
washing washing
and recrystallization
[123,124].
acrylic
acid according
to Scheme
1, followed
by precipitation,
and recrystallization
It
is noteworthy
that neat that
rosinneat
canrosin
be acrylated
as well [125].
an important
material
in rosin
[123,124].
It is noteworthy
can be acrylated
as wellAs
[125].
As an important
material
in
chemistry,
acrylpimaric
acid
can
be
used
for
preparation
of
diallyl
acrylpimarate
[123],
polyesters
of
rosin chemistry, acrylpimaric acid can be used for preparation of diallyl acrylpimarate [123],
acrylated
and polyethylene
glycols
[125], epoxy
resins[125],
[126,127],
acrylpimaryl
dichloride
[128,129],
polyestersrosin
of acrylated
rosin and
polyethylene
glycols
epoxy
resins [126,127],
acrylpimaryl
acrylpimaric
acid amides
[130], cyclic
diamide
ammonium
salts [132–136],
calcium
dichloride [128,129],
acrylpimaric
acid
amides[131],
[130],quaternary
cyclic diamide
[131], quaternary
ammonium
and
zinc
salts
[137]
as
well
as
polyesters
[138].
Moreover,
it
can
be
used
directly
as
an
epoxy
salts [132–136], calcium and zinc salts [137] as well as polyesters [138]. Moreover, it can becuring
used
agent
[139].
directly as an epoxy curing agent [139].
Another
is aa viscous,
viscous,
Another important
important compound
compound in
in this
this subsection
subsection is
is dehydroabietyl
dehydroabietyl chloride.
chloride. ItIt is
yellow,
oily
liquid
[140,141].
It
can
be
prepared
using:
(i)
oxalyl
chloride
according
to
Scheme
1
yellow, oily liquid [140,141]. It can be prepared using: (i) oxalyl chloride according to Scheme 1 prior
prior
to evaporation
of unnecessary
substances
[142],
phosphorustrichloride
trichlorideinin chloroform
chloroform (yield
to evaporation
of unnecessary
substances
[142],
(ii)(ii)
phosphorus
(yield
92.5%)
[140]
or
(iii)
thionyl
chloride
in
presence
of
4-dimethylaminopyridine
[143].
It can
used
92.5%) [140] or (iii) thionyl chloride in presence of 4-dimethylaminopyridine [143]. It can
bebe
used
as
as
a
substrate
for
the
synthesis
of
macroinitiators
for
atom
transfer
radical
polymerization
(ATRP)
a substrate for the synthesis of macroinitiators for atom transfer radical polymerization (ATRP)
reactions
[142], rosin
rosinphosphate
phosphateesters
esters
[140],
N-hydroxyethylacrylamide
ester
of dehydroabietic
reactions [142],
[140],
N-hydroxyethylacrylamide
ester
of dehydroabietic
acid
acid
[144],
dehydroabietic
ethyl
methacrylate
[145,146],
dehydroabietic
propargyl
ester [147]
[144], dehydroabietic ethyl methacrylate [145,146], dehydroabietic propargyl ester
[147]
dehydroabietic
hexylacrylate
acrylate
[148],
as well
as intermediates
other intermediates
in synthesis
various
dehydroabietic hexyl
[148],
as well
as other
in synthesis
of various of
surfactants
surfactants
[143,149]
and
medicines
[141,150,151].
[143,149] and medicines [141,150,151].
◦ C). It is commercially
Dehydroabietylamine,
also known
known as
44.5 °C).
Dehydroabietylamine, also
as leelamine,
leelamine, is
is aa solid
solid (m.p.
(m.p. 44.5
It is commercially
available.
Its
application
in
antitumor
therapies
was
investigated
in
recent
years
[152–155].
Moreover,
available. Its application in antitumor therapies was investigated in recent years [152–155]. Moreover,
it
can
be
a
substrate
for
preparation
of
epoxy
resin
[156],
bio-based
benzoxazines
[157],
quaternary
it can be a substrate for preparation of epoxy resin [156], bio-based benzoxazines [157], quaternary
ammonium
surfactants [158,159],
[158,159], acrylic
acrylicmonomers:
monomers:glycidyl
glycidyl
methacrylate
monomer
[160]
or
ammonium surfactants
methacrylate
monomer
[160]
or NN-dehydroabietic
acrylamide
[161].
dehydroabietic acrylamide [161].
3.2.2. Resins and Monomers
3.2.2. Resins and Monomers
Rosin-based resins and monomers are compounds which contain epoxy, acrylic, allyl, hydroxyl or
Rosin-based resins and monomers are compounds which contain epoxy, acrylic, allyl, hydroxyl
oxazine reactive groups, that enable cross-linking, polymerization or building in the polymer matrix.
or oxazine reactive groups, that enable cross-linking, polymerization or building in the polymer
Their preparations are usually well described and easy to perform. The syntheses are similar to
matrix. Their preparations are usually well described and easy to perform. The syntheses are similar
conventional resins/monomers preparations, however the necessity of using organic solvents in several
to conventional resins/monomers preparations, however the necessity of using organic solvents in
reactions is a disadvantage in the context of Green Chemistry rules. The high modification potential
several reactions is a disadvantage in the context of Green Chemistry rules. The high modification
of rosin derivatives allows one to prepare resins and monomers showing diverse and designable
potential of rosin derivatives allows one to prepare resins and monomers showing diverse and
properties. They can exhibit adjustable glass transition temperatures, low volume shrinkage, as well as
designable properties. They can exhibit adjustable glass transition temperatures, low volume
improve elastic modulus, Young’s modulus, shape-memory, flame retardancy, corrosion protection
shrinkage, as well as improve elastic modulus, Young's modulus, shape-memory, flame retardancy,
features of final casts/polymers in comparison with petroleum-based compounds. Therefore, the best
corrosion protection features of final casts/polymers in comparison with petroleum-based
described recipes show high commercialization potential in the segment of resins, adhesives and
compounds. Therefore, the best described recipes show high commercialization potential in the
paints, but in most cases, additional applied research should be performed to increase their technology
segment of resins, adhesives and paints, but in most cases, additional applied research should be
readiness level (TRL).
performed to increase their technology readiness level (TRL).
Triglycidyl ester of maleopimaric acid is a beige, viscous liquid. It can be prepared from
Triglycidyl ester of maleopimaric acid is a beige, viscous liquid. It can be prepared from
maleopimaric acid, epichlorohydrin and sodium hydroxide according to Scheme 2, followed by
maleopimaric acid, epichlorohydrin and sodium hydroxide according to Scheme 2, followed by
filtration, washing and evaporation [83]. It can be used in liquid epoxy resins [83], non-cytotoxic
filtration, washing and evaporation [83]. It can be used in liquid epoxy resins [83], non-cytotoxic biobio-based epoxypolyurethanes [162] as well as synthesis of rosin-based cyclic carbonates [132]. Similar
based epoxypolyurethanes [162] as well as synthesis of rosin-based cyclic carbonates [132]. Similar
liquid resin can be synthesized from fumaropimaric acid [122].
liquid resin can be synthesized from fumaropimaric acid [122].
O
Maleopimaric
acid
1.
O
O
COOH
Cl
O
O
O
2. NaOH
O
O
TBA Br
in H2O
70-130°C, 10h
O
COO
O
O
Scheme 2. Synthesis of triglycidyl ester of maleopimaric acid.
Maleopimaric acid
triglycidyl ester
yield: 75%
Molecules
2019,
24,
xx FOR
PEER
REVIEW
Molecules
2019,
24,24,
FOR
PEER
REVIEW
Molecules
2019,
x FOR
PEER
REVIEW
Molecules 2019, 24, 1651
66 of
51
6of of5151
6 of 52
Scheme
2.
Synthesis
of
triglycidyl
ester
of
maleopimaric
acid.
Scheme
2. 2.
Synthesis
ofof
triglycidyl
ester
ofof
maleopimaric
acid.
Scheme
Synthesis
triglycidyl
ester
maleopimaric
acid.
yellowish
liquid.
Diglycidyl
can
bebeprepared
prepared
isisa ayellowish
yellowish
liquid.
ItItItcan
can
be
prepared
from
acrylpimaric
acid,
Diglycidylacrylpimarate
acrylpimarateis
yellowishliquid.
liquid.It
canbe
preparedfrom
fromacrylpimaric
acrylpimaricacid,
acid,
and
filtration,
epichlorohydrin
sodium
hydroxide
according
to
Scheme
3,
prior
to
filtration,
washing
epichlorohydrinand
and sodium hydroxide according to Scheme 3, prior tofiltration,
filtration,washing
washingand
and
drying
can
be
used
in
materials
showing
improved
thermal,
mechanical
and
[126].
It
can
be
used
in
epoxy
materials
showing
improved
thermal,
mechanical
and
drying
[126].
It It
can
bebe
used
ininepoxy
epoxy
materials
showing
improved
thermal,
mechanical
and
shapedrying[126].
[126].It
can
used
epoxy
materials
showing
improved
thermal,
mechanical
andshapeshapememory
properties
[126].
shape-memory
properties
memory
properties
[126].
memory
properties
[126].[126].
COOH
COOH
COOH
Acrylpimaric
acid
Acrylpimaric
acid
Acrylpimaric
acid
2.
N
2. 2.
N aOH
aOH
N aOH
TEBAC
TEBAC
TEBAC
115-60°C,
5h
115-60°C,
5h5h
115-60°C,
COOH
COOH
COOH
COO
COO
COO
Cl
Cl O
1.
1. 1. Cl O O
O
OO
Diglycidyl
Diglycidyl acrylpimarate
acrylpimarate
acrylpimarate
yield:
yield:88%
88%
Diglycidyl
O
O O yield: 88%
COO
COO
COO
Scheme
3. 3.
Synthesis
of
diglycidyl
acrylpimarate.
Synthesis
ofof
diglycidyl
Scheme
3.
acrylpimarate.
Scheme
Synthesis
diglycidyl
acrylpimarate.
Another
diglycidyl
derivative
of
acrylpimaric
acid
and
its
siloxane modification
modification can
be
prepared
Another
diglycidyl
derivative
ofof
acrylpimaric
acid
and
itsits
siloxane
can
bebe
prepared
Another
diglycidyl
derivative
acrylpimaric
acid
and
siloxane modification
can
prepared
according
to Scheme 4,
prior to
washing,
filtration
and
vacuum
evaporation
[127]. Prepared
epoxy
washing,
according
toto
washing,
filtration
and
vacuum
evaporation
accordingtotoScheme
Scheme4,4,prior
priorto
washing,filtration
filtrationand
andvacuum
vacuumevaporation
evaporation[127].
[127].Prepared
Preparedepoxy
epoxy
resins
can
improve
the
thermal
stability
and
flame
retardancy
of
products
[127].
the
thermal
stability
and
flame
retardancy
of
products
[127].
resins
can
improve
the
thermal
stability
and
flame
retardancy
of
products
[127].
resins can improve the thermal stability and flame retardancy of products [127].
COOH
COOH
COOH
O
OO
O
OO
O
OO
O
OO
(C
))33N
22H
(C(C
H255H
N
5)3N
110°C
110°C
110°C
COOH
COOH
COOH
O
OO
O
OO
O
OO
O
OO
O
OO
COO
COO
COO
Acrylpimaric
Acrylpimaric
Acrylpimaric
acid
acid
acid
OH
OHOH
OCH
CH3
CH
3
3
OCH
CHCH
3 3
3 3 CH
3 3
OCH
CH
CH
3
CHCH
3 3
H
CO
Si
O
Si
O
Si
O)
(
)
(
)
(
H33H
CO
Si
O
Si
O
Si
(
)
(
)
(
m
k
CO
Si
O
(
3
m)m( Si Ok)k( SiO )On
n)n
Ph
OCH
Ph
3
PhPh
OCH
3 3 PhPh
OCH
TPT
TPT
TPT
120°C
120°C
120°C
ORO
CH
ORO
3
3
CHCH
CHCH
ORO CH
3 3
3 3
ORO
Si
O
Si
O
Si
O ) RO
(
)
(
)
(
ORO
Si
O
Si
( Si( SiO )Om
(
)
(
ORO
k
Si
O
Si
)
(
)
(
mm
k k O )On
n)RO
nRO
ORO
Ph
ORO
PhPh
PhPh
ORO Ph
O
OO
HO
HOHO
COO
COO
COO
Ethylene
glycol
diglycidyl
Ethylene
glycol
diglycidyl
Ethylene
glycol
diglycidyl
ether
modified
acrylpimaric
acid
ether
modified
acrylpimaric
acid
ether modified acrylpimaric
acid
(AP-EDGE)
(AP-EDGE)
(AP-EDGE)
Siloxane
modified
AP-EDGE
Siloxane
modified
AP-EDGE
Siloxane
modified
AP-EDGE
yield:
81-89%
yield:
81-89%
COO
yield:
81-89%
COO
COO
R
R=
=
R=
O
OO
O
OO
O
OO
O
OO
O
OO
O
OO
COO
COO
COO
EEW
(experimental
EEW
(experimental
EEW
(experimental
value)
(g/mol)
=
481,
value)
(g/mol)
==
481,
value)
(g/mol)
481,
645,
714,
952,
645,
714,
952,
1190
645,
714,
952,1190
1190
Scheme
4.
Preparation
of
ethylene
glycol
diglycidyl
ether
modified
acrylpimaric
acid
and
its
siloxane
Scheme
4.4.
Preparation
ofethylene
ethylene
glycol
diglycidyl
ether
modified
acrylpimaric
acid
and
its
4.
Preparation
ofof
ethylene
glycol
diglycidyl
ether
modified
acrylpimaric
acid
and
itsits
siloxane
Scheme
Preparation
glycol
diglycidyl
ether
modified
acrylpimaric
acid
and
siloxane
derivative.
siloxane
derivative.
derivative.
derivative.
Dimaleopimaryl
yellow
solid.
from
levopimaric
acid
Dimaleopimaryl
brownish
prepared
Dimaleopimaryl
ketone
isisaaa abrownish
brownish
yellow
solid.
It Itcan
can
bebeprepared
prepared
from
levopimaric
acid
Dimaleopimarylketone
ketoneis
brownishyellow
yellowsolid.
solid.It
canbe
preparedfrom
fromlevopimaric
levopimaricacid
acid
and
maleic
anhydride
according
to
Scheme
5,
prior
to
washing
and
recrystallization
[163].
It
can
be
washing
and
maleic
anhydride
according
to
Scheme
5,
prior
to
washing
and
recrystallization
[163].
It
can
and maleic anhydride according to Scheme 5, prior to washing and recrystallization [163]. It canbebe
used
directly as
an epoxy resin
hardener, as
well
as
for
the
synthesis
of
bio-based
epoxy
resins,
i.e.,
well
for
bio-based
used
asas
well
asas
for
the
synthesis
ofof
bio-based
epoxy
resins,
i.e.
useddirectly
directlyasasananepoxy
epoxyresin
resinhardener,
hardener,as
wellas
forthe
thesynthesis
synthesisof
bio-basedepoxy
epoxyresins,
resins,i.e.
i.e.
tetraglycidyl
dimaleopimaryl
ketone,
according
to
Scheme
5
[163].
according
to
Scheme
5
[163].
tetraglycidyl
dimaleopimaryl
ketone,
according
to
Scheme
5
[163].
tetraglycidyl dimaleopimaryl ketone, according to Scheme 5 [163].
O
OO
O
OO
O
OO
pTSA
pTSA
pTSA
in
in toluene
toluene
in
toluene
135-230°C
135-230°C
135-230°C
5h
5h 5h
COOH
COOH
COOH
Levopimaric
Levopimaric
Levopimaric
acid
acid
acid
O
OO
O
O
OO OO O
OO
O
OO
zinc
acetate
zinc
acetate
zinc
acetate
in
33COOH
in CH
CHCH
COOH
in
3COOH
?°C,
12h
?°C,
12h12h
O
?°C,
O
O
OO
O
OO
1.
NaOH
1. 1.
NaOH
NaOH
Cl
Cl O
2.
2. 2. Cl O O
O
OO
zinc
acetate
zinc
acetate
zinc
acetate
in
?°C,
6h
in DMF,
DMF,
?°C,
6h 6h
in
DMF,
?°C,
O
Dipimaryl
ketone
Dipimaryl
ketone
Dipimaryl
ketone
yield:
97%
yield:
97%
yield: 97%
O
OO
O
OO
O
OO
O
OO
O
OO
Dimaleopimaryl
ketone
Dimaleopimaryl
ketone
Dimaleopimaryl
ketone
yield:
85%
yield:
85%
yield:
85%
O
OO
O
OO
O
OO
O
OO
O
OO
O
OO
O
O O Tetraglycidyl
Tetraglycidyl
Tetraglycidyl
dimaleopimaryl
ketone
dimaleopimaryl
ketone
dimaleopimaryl
ketone
Scheme
5.
Synthesis
of
tetraglycidyl
dimaleopimaryl
ketone.
Scheme
5. 5.
Synthesis
of
tetraglycidyl
dimaleopimaryl
ketone.
Scheme
Synthesis
tetraglycidyl
dimaleopimaryl
ketone.
Scheme
5.
Synthesis
ofof
tetraglycidyl
dimaleopimaryl
ketone.
Molecules 2019, 24, 1651
7 of 52
Molecules2019,
2019,24,
24,xxFOR
FORPEER
PEERREVIEW
REVIEW
Molecules
of 51
51
77 of
Rosin
It
can
be
prepared
from
epoxidized
rosin, water,
potassium
Rosinpentaglycidyl
pentaglycidylether
etheris
isaaasolid.
solid. It
It can
can be
be prepared
prepared from
from epoxidized
epoxidized rosin,
rosin,
water, potassium
potassium
Rosin
pentaglycidyl
ether
is
solid.
water,
hydroxide
and
epichlorohydrin
according
to
Scheme
6,
and
using
such
separation
methods
as
vacuum
hydroxide
and
epichlorohydrin
according
to
Scheme
6,
and
using
such
separation
methods
as
hydroxide and epichlorohydrin according to Scheme 6, and using such separation methods as
drying,
filtration,
precipitation
and
washing
[164].
It
can
be
used
as
a
component
in
epoxy
resin
vacuum drying,
drying, filtration,
filtration, precipitation
precipitation and
and washing
washing [164].
[164]. ItIt can
can be
be used
used as
as aa component
component in
in epoxy
epoxy
vacuum
systems
showing
high glass
transition
temperature
as wellasaswell
elastic
modulus
[164]. [164].
resin
systems
showing
high
glass
transition
temperature
as
elastic
modulus
resin systems showing high glass transition temperature as well as elastic modulus [164].
3-chloro3-chloroperoxybenzoic
peroxybenzoic
acid
acid
in
CH
Cl2
in CH22Cl
2
0°C,
6-8h
0°C, 6-8h
Rosin
Rosin
O
O
HH22OO
O
O
OH
OH
OH
OH
OHaq
aq
inCC2HH5OH
in
2 5
90°C, 36h
36h
90°C,
COOH
COOH
COOH
COOH
2.
2.
Cl
Cl
O
O
O
O
O
O
O
O
CC
O
O
Rosin
Rosin
pentaglycidyl
pentaglycidyl
ether
ether
Hydroxylated rosin
rosin
Hydroxylated
O
O
O O
O
O
O
O
O O
O
O
Cl
inCH
CH2Cl
in
2 22
80°C, 7h
7h
80°C,
COOH
COOH
Epoxidized rosin
rosin
Epoxidized
O
O
1. KOH
KOH
1.
OH
OH
OH
OH
Scheme
6.
Synthesis of
of
rosin
pentaglycidyl
ether.
Scheme 6.
6. Synthesis
of rosin
rosin pentaglycidyl
pentaglycidyl ether.
ether.
Scheme
Polygral
is
solid
byproduct
of
the
paper
and forestry
forestry
industry,
containing
rosin
acids
and
their
Polygral is
is aaa solid
solid byproduct
byproduct of
of the
the paper
paper and
forestry industry,
industry, containing
containing rosin
rosin acids
acids and
and their
their
Polygral
oligomers
[165].
It
can
be
epoxidized
to
prepare
bio-based
epoxy
resins.
Endocyclic
epoxidized
oligomers [165].
[165]. It can be
be epoxidized
epoxidized to
to prepare
prepare bio-based
bio-based epoxy
epoxy resins.
resins. Endocyclic
Endocyclic epoxidized
epoxidized
oligomers
polygral
is
a
solid,
which
can
be
prepared
using
3-chloroperoxybenzoic
acid,
according
polygral
is
red
brown
solid,
which
can
be
prepared
using
3-chloroperoxybenzoic
acid,
according
to
polygral is a red brown solid, which can be prepared using 3-chloroperoxybenzoic acid, according
to
to
Scheme
7,
prior
to
vacuum
evaporation.
On
the
other
hand,
exocyclic
epoxidized
polygral
is
a
Scheme
7,
prior
to
vacuum
evaporation.
On
the
other
hand,
exocyclic
epoxidized
polygral
is
a
viscous
Scheme 7, prior to vacuum evaporation. On the other hand, exocyclic epoxidized polygral is a viscous
0 -diisopropyl
viscous
red
brown
liquid,
that
can
be
prepared
in
two
ways,
using
oxalyl
chloride
or
N,N
red brown
brown liquid,
liquid, that
that can
can be
be prepared
prepared in
in two
two ways,
ways, using
using oxalyl
oxalyl chloride
chloride or N,N′-diisopropyl
N,N′-diisopropyl
red
carbodiimide
before
addition
of
glycidol,
according
to
Scheme
7
prior
to
washing
and
vacuum
drying.
carbodiimide
before
addition
of
glycidol,
according
to
Scheme
7
prior
to
washing
and vacuum
vacuum
carbodiimide before addition of glycidol, according to Scheme 7 prior to washing
and
They
can
be
used
for
preparing
bisphenol
A-free
epoxy
resins
[165].
drying. They
They can
can be
be used
used for
for preparing
preparing bisphenol
bisphenol A-free
A-free epoxy
epoxy resins
resins [165].
[165].
drying.
COOH
COOH
3-chloro3-chloroperoxybenzoic
O
peroxybenzoic
O
acid
acid
HOOC
HOOC
O
inCH
CH2Cl
Cl
O
in
2 22
-5°C, 10h
10h
-5°C,
O
O
Endocyclic
Endocyclic
epoxidized
epoxidized
polygral
polygral
O
O
1.NN CC NN
1.
HOOC
HOOC
2.
2.
O
OH O
OH
O
O
O CC
O
pTSA/DMAP
pTSA/DMAP
in CH
CH2Cl
Cl
in
2 22
0°C, 72h
72h
0°C,
COOH
COOH
Polygral
Polygral
(C2HH5))3NN
(C
2 5 3
in
toluene
in toluene
20°C, 24h
24h
20°C,
Cl
Cl
O
O
O
O
Cl
Cl
COO
COO
O
O
Cl
Cl
O CC
O
COCl
COCl
O
O
OH
OH
Exocyclic
Exocyclic
epoxidized
epoxidized
polygral
polygral
(C2HH5))3NN
(C
2 5 3
intoluene
toluene
in
0°C, ?h
?h
0°C,
Scheme 7.
7. Preparation
Preparation of
of epoxidized
epoxidized rosin
rosin oligomers.
oligomers.
Scheme
Diglycidyl
is
can be
be
Diglycidyl dehydroabietylamine
dehydroabietylamine is
is aaa yellowish
yellowish sticky
sticky liquid.
liquid. ItIt can
be synthesized
synthesized from
from
Diglycidyl
dehydroabietylamine
yellowish
sticky
liquid.
synthesized
from
dehydroabietylamine,
epichlorohydrin
and
sodium
hydroxide
according
to
Scheme
8,
prior
to
filtration,
dehydroabietylamine,
epichlorohydrin
and
sodium
hydroxide
according
to
Scheme
8,
prior
to
dehydroabietylamine, epichlorohydrin and sodium hydroxide according to Scheme 8, prior to
washing,
drying
and
vacuum
distillation
[156].
It
can
be
applied
in
epoxy
resins
exhibiting
better
filtration,
washing,
drying
and
vacuum
distillation
[156].
It
can
be
applied
in
epoxy
resins
exhibiting
filtration, washing, drying and vacuum distillation [156]. It can be applied in epoxy resins exhibiting
thermal
stabilitystability
and higher
transition
temperatures
than petroleum-based
products [156].
better thermal
thermal
stability
andglass
higher
glass transition
transition
temperatures
than petroleum-based
petroleum-based
products
better
and
higher
glass
temperatures
than
products
Rosin
maleimidodicarboxylic
acid
diglycidyl
ether
is
a
yellowish
solid.
It
can
be
prepared
from
[156].
[156].
epichlorohydrin
and
dicarboxylic
derivative
of
maleimide
(described
in
more
detail
in
Section
3.2.3)
Rosin
maleimidodicarboxylic
acid
diglycidyl
ether
is
a
yellowish
solid.
It
can
be
prepared
from
Rosin maleimidodicarboxylic acid diglycidyl ether is a yellowish solid. It can be prepared from
according
to Scheme
prior to filtration,
washing,
drying and(described
rotary evaporation
It in
shows
higher
epichlorohydrin
and9dicarboxylic
dicarboxylic
derivative
of maleimide
maleimide
(described
in more
more[84].
detail
in subsection
subsection
epichlorohydrin
and
derivative
of
in
detail
glass
transition
temperature,
modulus
and
thermal
stability
than
its
plant
oil
counterparts
[84].
3.2.3)
according
to
Scheme
9
prior
to
filtration,
washing,
drying
and
rotary
evaporation
[84].
It
shows
3.2.3) according to Scheme 9 prior to filtration, washing, drying and rotary evaporation [84]. It shows
higherglass
glasstransition
transitiontemperature,
temperature,modulus
modulusand
andthermal
thermalstability
stabilitythan
thanits
itsplant
plantoil
oilcounterparts
counterparts[84].
[84].
higher
1.
Cl
O
2. NaOH
Dehydroabietylamine
O
H2O ; TBA Br
45°C, 153h
Molecules 2019, 24, 1651
Molecules
Molecules 2019,
2019, 24,
24, xx FOR
FOR PEER
PEER REVIEW
REVIEW
NH2
Cl
Cl
N
Diglycidyl
8 of 52
88 of
dehydroabietylamine
of 51
51
yield: 90%
O
O
O
1.diglycidyl
Scheme 8. Synthesis of1.
dehydroabietylamine.
2.
2. NaOH
NaOH
O
Dehydroabietylamine
O
Dehydroabietylamine
O
H2N
O
NH
NH22
COOH
O
O
O
COOH
H
Br
H22O
O ;; TBA
TBA
Br
45°C,
45°C, 153h
153h
N
N
N
O
Diglycidyl
Diglycidyl
dehydroabietylamine
dehydroabietylamine
COO
N
yield:
yield: 90%
90%
O
O
O
Cl
O
Scheme 8.
8. Synthesis
Scheme
dehydroabietylamine.
Synthesis of
of diglycidyl
diglycidyl dehydroabietylamine.
in DMF
COO
160°C, 4h
COOH
O
O
O
O
O
O
O
MaleopimaricO
acid
NaH
in DMF
150°C, 5h
H
H22N
N
Rosin-maleimidodicarboxylic
O
O diglycidyl ether
acid
yield: 47%
COOH
COOH
COOH
N
N
Rosin-maleimidodicarboxylic
acid
O
O
yield: 87%
COOH
COOH
Cl
Cl
O
O
COO
COO
N
N
O
O
O
O
O
O
Scheme
acidCOO
diglycidylOether.
in DMF9. Preparation of rosin maleimidodicarboxylic
NaH
in DMF
160°C,
160°C, 4h
4h
NaH
in
in DMF
DMF
150°C,
150°C, 5h
5h
trimethylolpropane
O
COO
Rosin-maleimidodicarboxylic
Rosin-maleimidodicarboxylic
COOH
COOH
acid
ether
Triester of maleopimaric acid and
is a dark yellow solid.
can be prepared
acidItdiglycidyl
diglycidyl
ether
COOH
COOH
yield:
yield: 47%
47%of
according
to
Scheme
10,
prior
to
washing
and
vacuum
distillation
[98].
It
can
be
used
in
synthesis
Maleopimaric
Maleopimaric
Rosin-maleimidodicarboxylic
acid
Rosin-maleimidodicarboxylic
acid
rosin-based
epoxy
resin
[98].
acid
acid
yield:
yield: 87%
87%
Epoxy resin having EEW = 199.68 g/eq based on maleopimaric acid and trimethylolpropane ester
9.
of
rosin
maleimidodicarboxylic
diglycidyl
ether.
9. Preparation
acid
diglycidyl
ether.
Scheme
Preparation
of 10,
rosin
maleimidodicarboxylic
ether. [98]. It can be
can be preparedScheme
according
to Scheme
prior
to extraction andacid
vacuum
distillation
used directly as an epoxy compound, or transformed into acrylate resin [98].
Triester
maleopimaric
acid
is
Triester
of
maleopimaric
yellow
It
Triester
ofresin
maleopimaric
acid and
and trimethylolpropane
trimethylolpropane
is aa dark
dark yellow
yellow solid.
solid.
It can
can be
be prepared
prepared
Acrylateof
based on epoxidized
maleopimaric-trimethylolpropane
adduct
according
to
Scheme
10,
prior
to
washing
and
vacuum
distillation
[98].
can
be
used
in
synthesis
of
It
according to Scheme 10,
priorIttocan
washing
distillationby
[98].
It can methacrylated
be used in synthesis
of
10 [98].
be usedand
as avacuum
resin crosslinked
styrene,
eugenol
[98].
rosin-based
epoxy
resin
[98].
rosin-based
epoxy
resin
[98].
or methacrylated guaiacol [98].
Epoxy
Epoxy resin
resin having
having EEW
EEW == 199.68
199.68 g/eq
g/eq based
based on
on maleopimaric
maleopimaric acid
acid and
and trimethylolpropane
trimethylolpropane ester
ester
HO
OH
can
be
prepared
according
to
Scheme
10,
prior
to
extraction
and
vacuum
distillation
[98].
It
can
O
OH
Crosslinked
resinbe
can be prepared according to Scheme 10, prior to extraction and vacuum distillation
[98]. It can
be
O
used
or
transformed
into
acrylate
resin
[98].
styrene
used directly
directly as
as an
an epoxy
epoxy compound,
compound,
or
transformed
into
acrylate
resin
[98].
OH
OH
O
or methacrylated
eugenol
Acrylate
on
maleopimaric-trimethylolpropane
adduct
can
Acrylate resin
resin based
based
on epoxidized
epoxidized
maleopimaric-trimethylolpropane
adductguaiacol
can be
be prepared
prepared
or methacrylated
pTSA
OH O
according
to
Scheme
10
[98].
It
can
be
used
as
a
resin
crosslinked
by
styrene,
methacrylated
xylene It can be used
O as a resin crosslinked by styrene, methacrylated eugenol
according to Scheme 10in [98].
eugenol
O O
O
OH
or
O
or methacrylated
methacrylated guaiacol
guaiacol [98].
[98].
COOH
O
O
O
O
Maleopimaric
acid
O
O
O
O
COOH
COOH
O
O
O
Maleopimaric
Maleopimaric
O
acid
acid
O
O
O
O
O
O
O
O
O
HO
1. K OH/
HO
OH
NaOH
HO
OH
Cl O
2.
OH
OH
OH
OH
OH
OH
pTSA
pTSA in DMSO OH
OH
in
<24°C,18h
in xylene
xylene
1.
K
1. O
K OH/
OH/
NaOH
NaOH
O
Cl
Cl O
O
2.
2.
O
O
O
O
COO
O
O
O
O
O
O
OH
OH
OH
Maleopimaric acid
trimethylolpropane ester
OH
OH 93%
O
yield:
styrene
styrene
HO
or
or methacrylated
methacrylated eugenol
eugenol
O
or
methacrylated
guaiacol
or methacrylated guaiacol
OH
O
COO
COO
OH
OH
O
O
O
O
O
HO
HO
O
O
O
O
O
in
in DMSO
DMSO
<24°C,18h
<24°C,18h
O
O
Crosslinked
resin
Crosslinked
resin
O
OH
O
O
O
O
HO
OH
Maleopimaric
Maleopimaric acid
acid
O
O O
trimethylolpropane
ester
PPh3
O
trimethylolpropane
ester
O
O
Maleopimaric acid
O
O
O
HQ
yield:
93%
O
O
yield: 93%
trimethylolpropane-based
85°C, 3.5h
O
O
Oepoxy resin yield:
O 85%
OH
OH
O
O
O
O
O
O
O
O
O
O
O
O
O
O O
HO
HO
HO
OH
O
O
O
O
O
O
HO
HO
O
O
O
O
O
O
O
O
O
O
O
O
O
Maleopimaric
acid
O
trimethylolpropane-based
O
OH
epoxy acrylate resin
yield: 95%
OH
O
O
O
O
O
O
O
O
O
HO
O
O
Scheme
10.
Preparation
of
maleopimaric
acid-trimethylolpropane
ester-based
epoxy acrylate
acrylate
resin
HO
O Preparation of maleopimaric acid-trimethylolpropane ester-based epoxy
OScheme 10.
resin
O
O
OH
OH
O
O
crosslinked by
by unsaturated
unsaturated monomers.
monomers.
crosslinked
O
O
O
O
O
O
O
PPh
O
33
PPh
Maleopimaric
acid
Maleopimaric
acid
O
Maleopimaric
acid
O
Epoxy
maleopimaric acid and trimethylolpropane
ester
O Maleopimaric acid
O resin having EEW = 199.68 g/eq based onHQ
HQ
trimethylolpropane-based
trimethylolpropane-based
trimethylolpropane-based
3.5h
85°C,
3.5h
can be prepared
according to
Scheme 10, prior to85°C,
extraction
and vacuumtrimethylolpropane-based
distillation [98]. It can be
epoxy
epoxy
epoxy resin
resin yield:
yield: 85%
85%
epoxy acrylate
acrylate resin
resin yield:
yield: 95%
95%
used directly as an epoxy compound, or transformed into acrylate resin [98].
Scheme
Scheme 10.
10. Preparation
Preparation of
of maleopimaric
maleopimaric acid-trimethylolpropane
acid-trimethylolpropane ester-based
ester-based epoxy
epoxy acrylate
acrylate resin
resin
crosslinked
crosslinked by
by unsaturated
unsaturated monomers.
monomers.
Molecules 2019, 24, 1651
9 of 52
Acrylate resin based on epoxidized maleopimaric-trimethylolpropane adduct can be prepared
according to Scheme 10 [98]. It can be used as a resin crosslinked by styrene, methacrylated eugenol or
Molecules
2019, 24, guaiacol
x FOR PEER
REVIEW
9 of 51
methacrylated
[98].
Dehydroabietic ethyl methacrylate is a white powder. It can be prepared from dehydroabietyl
chloride and hydroxyethyl methacrylate according to Scheme 11, prior to neutralization, drying,
O
evaporation and chromatography
[146]. It can be widely used
as 2a)2Omonomer in preparation of graft
HO(CH
O(CH
2)2OH
and block copolymers [146,166–170].
It is worth noting, that a similar
O compound dehydroabietic
ethyl acrylate
hydroxyethyl
and
(CH3)from
pyridine liquid, which can be prepared
3N
O(CH2)2Ois a yellow, viscous
O(CHacrylate
2)2O
COCl
CHfiltration,
in CH
2Cl2
2Cl2
O
O
dehydroabietyl
chloride
priorinto
precipitation
and vacuum
distillation
[171].
for
O
O It can be used
50°C, 4h
Dehydroabietyl
0-25°C, 48h
Dehydroabietic
Dehydroabietic
preparation
of homopolymer with no declared application [171]. Moreover, rosin ethyl
acrylate can be
chloride
ethylinacrylate
ethyl methacrylate
used
preparation
bio-based
Molecules
2019, 24, x FORof
PEER
REVIEWgraft copolymers of chitosan for controlled release applications9[172].
of 51
Scheme 11. Synthesis of dehydroabietic ethyl acrylates.
Cl
HO(CH2)2O
O
O
O
HO(CH2)6OH
O(CH2)2OH
pyridine
O(CH
2)2O
Molecules
2019,
24, xDMAP
FOR PEER REVIEW
O
O
in THF
Dehydroabietic
50°C, 12h
COCl
ethyl
acrylate
Dehydroabietyl
chloride
in CH2Cl2
50°C, 4h
(CH3)3N
(CH3)3N
HQ in CH2Cl2
in THF
0-25°C, 48h
25°C, 10h
HO
COCl
O
O(CH2)2O 9 of 51
OO
Dehydroabietyl
Dehydroabietic
O
O
chloride
ethyl
methacrylate
O Dehydroabietic
O O Hydroxyhexyl
HO(CH2)2O
dehydroabietate
yield:
72%
hexyl
acrylate yield: 41%
O(CH
)
OH
Scheme
11.
Synthesis
of
dehydroabietic
ethyl
acrylates.
2 2
O
Scheme 11. Synthesis of dehydroabietic ethyl acrylates.
O
(CH3)3acrylate.
N
pyridine
Scheme
12. Synthesis of dehydroabietic hexyl
O(CH ) O
O(CH ) O
2 2
2 2
Cl
Dehydroabietic
hexyl acrylate
It can be synthesized
chloride,
in CH2Cl2is a solid. COCl
in CH2Cl2from dehydroabietyl
O
O
O
O
50°C, 4h
Dehydroabietyl
0-25°C,
48h separationDehydroabietic
hexanediol
and
acryloyl
chloride
according
to
Scheme
12,
and
using
methods
such as
Dehydroabietic
Dehydroabietic ethyl methacrylate is a white
powder. It Ocan be prepared from dehydroabietyl
chloride
HO(CH2)6OH
ethyl acrylate
ethyl
methacrylate
filtration,
precipitation,
washing
and
vacuum
drying
[148].
Its
application
is
a
soft
acrylic
monomer
(CH3)3N11, prior to neutralization, drying,
chloride and hydroxyethyl methacrylate according
to Scheme
◦ C), whichHO
DMAP
(glass
transition
temperature
of
−23
can
impart
a
flexibility
to the integrated
polymer
[148].
HQ
Scheme 11.
Synthesis
dehydroabietic
ethyl
evaporation and chromatography
[146].
It canofbe
widely used
as aacrylates.
monomer
in preparation
of
O graft
in THF
in THF
O
and block
[146,166–170]. ItOis worth noting, that25°C,
a similar
50°C, 12h
10h compound dehydroabietic ethyl
COCl copolymers
O
Cl
acrylate
is
a
yellow,
viscous
liquid,
which
can
be
prepared
from
hydroxyethyl
acrylate
and
Dehydroabietyl
O Hydroxyhexyl
O Dehydroabietic
O
chloride
dehydroabietyl
chloride
prior
to
filtration,
precipitation
and
vacuum
distillation
[171]. It can
be41%
used
dehydroabietate
yield:
72%
hexyl
acrylate
yield:
HO(CH2)6OH
(CH3)3N[171]. Moreover, rosin ethyl acrylate
for preparation of homopolymer with no declared
application
HO
DMAP Scheme 12. Synthesis of dehydroabietic
HQhexyl acrylate.
O
can be used in preparation
of bio-based graft copolymers
in THF
in THF of chitosan for controlled release
O
50°C,
12h
25°C, 10h
O
COCl [172].
applications
Dehydroabietic
ethyl methacrylate
is a white powder. It can be preparedO from dehydroabietyl
Dehydroabietyl
OisHydroxyhexyl
O Dehydroabieticchloride,
Dehydroabietic
hexyl acrylate
a solid.
It can to
be Scheme
synthesized
from to
dehydroabietyl
chloride
and hydroxyethyl
methacrylate
according
11, prior
neutralization, drying,
chloride
dehydroabietate
yield:
72%
hexyl
acrylate
yield: 41%
hexanediol
and
acryloyl
chloride
according
to
Scheme
12,
and
using
separation
methods
such
as
evaporation and chromatography [146]. It can be widely used as a monomer in preparation
of graft
filtration,
precipitation,
washing
and
vacuum
drying
[148].
Its
application
is
a
soft
acrylic
monomer
Scheme
12.
Synthesis
of
dehydroabietic
hexyl
acrylate.
and block copolymers [146,166–170].
It is worth
that a similar
compound dehydroabietic ethyl
Scheme 12. Synthesis
of noting,
dehydroabietic
hexyl acrylate.
(glass
transition
temperature
of −23
°C), which
a flexibility
to the
integrated polymer
acrylate
is a yellow,
viscous
liquid,
which can
canimpart
be prepared
from
hydroxyethyl
acrylate[148].
and
Dehydroabietic
ethyl
methacrylate
is
a
white
powder.
It
can
be
prepared
from
dehydroabietyl
N-hydroxyethylacrylamide ester
ester of
of dehydroabietic
dehydroabietic acid is a viscous,
yellow liquid.
be
N-hydroxyethylacrylamide
viscous,
liquid.
It
can
dehydroabietyl chloride prior to filtration, precipitation and vacuum distillation [171]. It can be used
chloridefrom
and hydroxyethyl
methacrylate
according
to Scheme 11, prior toaccording
neutralization,
drying,13,
prepared
dehydroabietyl
chloride and
N-hydroxyethylacrylamide
according
to Scheme
Scheme
13,
N-hydroxyethylacrylamide
to
for preparation of homopolymer with no declared application [171]. Moreover, rosin ethyl acrylate
evaporation
andwashing,
chromatography
[146].
It canchromatography
be
widely used as[144].
a[144].
monomer
inbe
preparation
of graft in
prior
to
drying
and
column
It It
can
be
used
as as
a monomer
to filtration,
filtration,
washing,
drying
and
column
chromatography
can
a monomer
can be
used in preparation
of bio-based
graft
copolymers of
chitosan
forused
controlled
release
and
block
copolymers
[146,166–170].
It
is
worth
noting,
that
a
similar
compound
dehydroabietic
thermoset
system
with
soybean
oil-based
resin
forfor
coating
andand
adhesive
applications
[144].
in
thermoset
system
with
soybean
oil-based
resin
coating
adhesive
applications
[144].ethyl
applications
[172].
acrylate is a yellow, viscous liquid, which can be prepared from hydroxyethyl acrylate and
Dehydroabietic
hexylprior
acrylate
is a Osolid.
It can beand
synthesized
from dehydroabietyl
chloride,
dehydroabietyl
chloride
to filtration,
precipitation
vacuum distillation
[171]. It can be
used
hexanediol
and acryloyl
chloride with
according
to Scheme
12, and
using
separation
methods
such as
forDehydroabietyl
preparation
of homopolymer
no declared
application
[171].
Moreover,
rosin
ethyl
acrylate
Dehydroabietic acid
NH
filtration,
washingofand
vacuum
drying
[148]. Its application
a soft
acrylic ester
monomer
chloride
can be precipitation,
used
in preparation
bio-based
graft
copolymers
of chitosanisfor
controlled
release
N-hydroxyethylacrylamide
(glass
transition
temperature
of
−23
°C),
which
can
impart
a
flexibility
to
the
integrated
polymer
[148].
purity: 90%, yield: 80%
applications [172].
OH
N-hydroxyethylacrylamide
esteris of
dehydroabietic
acid is a viscous,
yellow liquid.chloride,
It can be
Dehydroabietic hexyl acrylate
a solid.
It can be synthesized
from dehydroabietyl
N
O
H and using separation
Etaccording
3N
prepared
from
dehydroabietyl
chloride
and toN-hydroxyethylacrylamide
according
to
Scheme
hexanediol
and
acryloyl chloride
Scheme
12,
methods
such
as13,
C O
COCl
in CH2Cl2 ; 45°C/4h O
filtration,
precipitation,
washing
and
vacuum
drying
[148].
Its
application
is
a
soft
acrylic
monomer
prior to filtration, washing, drying and column chromatography [144]. It can be used as a monomer
transition
temperature
of −23
°C), which
can for
impart
a flexibility
to the integrated
polymer
in (glass
thermoset
system
with
soybean
resin
coating
and of
adhesive
applications
[144].[148].
Scheme
13. Synthesis
ofoil-based
N-hydroxyethylacrylamide
ester
dehydroabietic
acid.
Synthesis
N-hydroxyethylacrylamide ester of dehydroabietic acid is a viscous, yellow liquid. It can be
prepared
from high
dehydroabietyl
chlorideO and N-hydroxyethylacrylamide
according
13,
Rosin-based
high
adhesion polyurethane
polyurethane
acrylate is
is aa faint-yellow
It can
cantobe
synthesized
Rosin-based
adhesion
acrylate
faint-yellow solid.
solid.
It
beScheme
synthesized
Dehydroabietyl
Dehydroabietic
acid
prior
to
filtration,
washing,
drying
and
column
chromatography
[144].
It
can
be
used
as
a
monomer
from hydrogenated
rosin,
and
2-hydroxyethyl
acrylate
according
to Scheme
14,
from
hydrogenated
rosin,isophorone
isophoronediisocyanate
diisocyanate
and
2-hydroxyethyl
acrylate
according
to Scheme
NH
chloride
in thermoset
system with soybean oil-based resin for coating andN-hydroxyethylacrylamide
adhesive applications [144].ester
14, prior to precipitation, vacuum drying and column chromatography
[173].
Its80%
application is an
purity: 90%,
yield:
adhesive having a high polymerizationOHrate,
low
volume
shrinkage
and
high
adhesion
[173].
O
Dehydroabietyl
chlorideCOCl
Et3N
NH
in CH2Cl2 ; 45°C/4h
O
C
O
N
H
O
Dehydroabietic acid
N-hydroxyethylacrylamide ester
purity: 90%, yield: 80%
Molecules 2019, 24, x FOR PEER REVIEW
Molecules 2019, 24, 1651
NCO
10 of 51
10 of 52
O
Rosin-based
high
adhesion
O
O
NCOand column chromatography [173]. Its application
prior to precipitation, vacuum
drying
is an adhesive
polyurethane
O
dibutyltin dilaurate
having a highNCO
polymerization
rate, low volume shrinkage and high adhesion [173].
acrylate
Molecules
2019, 24, x FORp-methoxyphenol
PEER REVIEW
10 of 51
O
HN
Isophorone
NH
40°C
diisocyanate
O
NCO
O
O
NCO
O
Rosin-based
O
COOH
O
O
HO
HO
high
adhesion
O
O
NCO
O
O
NCO
MgCl2 in butyl acetate
N
N
polyurethane
O
O
O
H
NCO dibutyltin dilaurate
dibutyltin dilaurate
NCO
O
O
O
acrylate
p-methoxyphenol
O
p-methoxyphenol
O
HN
O
Isophorone
HN
O
75-100°C
NH
NH
40°C
O
N
diisocyanate
H
O
O
O
HO
COOH
COOH
O
O
O
O
Scheme 14. Synthesis of rosin-based
high
adhesion
MgCl
in butyl
acetatepolyurethane acrylate.
2
2
O
O
N
N
N
N
H
H
dibutyltin dilaurate
p-methoxyphenol
O
O
monomers
are viscous
75-100°C
O
O
O
O
O
O
Rosin-based glycidyl methacrylate
liquids: brown rosin acid-glycidyl
O
O
O
O
Nprepared
methacrylate and colorless dehydroabietylamine-glycidyl methacrylate. They can be N
from
H
H
glycidyl methacrylate and rosin or dehydroabietylamine according to Scheme 15, prior to the use of
Scheme 14.
polyurethane
acrylate.
14. Synthesis
of rosin-based
highand
adhesion
polyurethane
acrylate.
such separation Scheme
techniques
as washing,
extraction
evaporation
[160,174].
They significantly
improve
thermal
and
mechanical
properties
of
soybean
oil-based
thermosets
[160].
Moreover,
they
Rosin-based
glycidyl
methacrylate
monomers
are
viscous
liquids:
brown
rosin
acid-glycidyl
Rosin-based
glycidyl
methacrylate
monomers
are
viscous
liquids:
brown
rosin
acid-glycidyl
can be used in copolymerization with other acrylate monomers [175], or as an advanced tackifier in
methacrylate
and
dehydroabietylamine-glycidyl
methacrylate. They can be prepared from
methacrylate
and colorless
colorless
dehydroabietylamine-glycidyl
the
UV-crosslinking
pressure
sensitive adhesives [174,176].methacrylate. They can be prepared from
glycidyl
methacrylate
and
rosin
or
dehydroabietylamine
accordingtotoScheme
Scheme
prior
glycidyl methacrylate and rosin or dehydroabietylamine according
15,15,
prior
to to
thethe
useuse
of
of
such
separation
techniques
as
washing,
extraction
and
evaporation
[160,174].
They
significantly
such separation techniques as washing,
extraction and evaporation [160,174]. They significantly
O
improve
thermal
mechanical
properties
ofof
soybean
oil-based
thermosets
[160].
Moreover,
theythey
can
O
improveCOOH
thermaland
and
mechanical
properties
soybean
oil-based
thermosets
[160].
Moreover,
O
O
HO
O
be
in copolymerization
withwith
other
acrylate
monomers
[175],
or asoran
tackifier
in the
canused
be used
in copolymerization
other
acrylate
monomers
[175],
asadvanced
an advanced
tackifier
in
O
O
UV-crosslinking
pressure
sensitive
adhesives
[174,176].
the UV-crosslinking pressure sensitive adhesives
[174,176].
NH2
N
OH
TBA Br
in MEK
COOH
COOH <80°C, 24h
O
O
O
Rosin acid
O
O
Rosin
acid-glycidyl
OH
OH
methacrylate monomer
TBA Br
yield: 95%
in MEK
O
O
O
O
O
O
in MEK
<80°C, 24h
Rosin acid
O
O
O
NH
NH22
Dehydroabietylamine
HO
O
O
O
O
O
HO
HO
in ethanol
40-80°C, 60h
O
N
N
O
Dehydroabietylamine-glycidyl
O
HO
HO
methacrylate
monomer
O
O
O
O
O yield: 89%
O
O
O
in ethanol
Rosin
acid-glycidyl
Scheme
15. Synthesis
of rosin-based glycidyl methacrylate
monomers.
40-80°C,
60h
O
O
methacrylate monomer
Dehydroyield:
95%
Ethylene glycol maleic rosinate
(meth)acrylate
can
be preparedDehydroabietylamine-glycidyl
from maleated rosin, ethylene
abietylamine
methacrylate monomer
glycol and (meth)acrylic acid according to Scheme 16 [85]. It can be applied in styrene-acrylate
yield: 89%
copolymers increasing their thermal stability [86], as well as in preparation of moleculary imprinted
Scheme
15. Synthesis
rosin-based
methacrylate
monomers.[85,87].
polymers for stationary
phases
used inof
chromatography
Scheme
15.
Synthesis
ofhigh-performance
rosin-based glycidyl
glycidylliquid
methacrylate
monomers.
Diallyl acrylpimarate is a yellow liquid [123]. It can be prepared from acrylpimaric acid and an
Ethylene
glycol
maleic
rosinate
(meth)acrylate
can
be
prepared
from
maleated
rosin, ethylene
ethylene
maleic
rosinate
(meth)acrylate
can be
from
maleated
rosin,
allyl Ethylene
halide byglycol
different
methods,
according
to Scheme
17,prepared
and using
separation
methods
such as
glycol
and
(meth)acrylic
acid
according
to
Scheme
16
[85].
It
can
be
applied
in
styrene-acrylate
glycol andwashing,
(meth)acrylic
acid according
to Scheme
16 [85]. It
filtration,
extraction
and evaporation
[88,123,177].
It can
can be
be applied
applied in
asstyrene-acrylate
a monomer in
copolymers
increasingresins
their thermal
thermal
stabilityresources
[86], as
as well
well
as or
in in
preparation
ofaminated
moleculary
imprinted
copolymers
increasing
their
stability
[86],
as
in
preparation
of
moleculary
imprinted
polyester
unsaturated
from
renewable
[123],
synthesis of
curing
agent
polymers
for
stationary
phases
used
in
high-performance
liquid
chromatography
[85,87].
polymers
stationary phases used in high-performance liquid chromatography [85,87].
for
epoxy for
[178].
Diallyl acrylpimarate is a yellow liquid [123]. It can be prepared from acrylpimaric acid and an
allyl halide by different
to Scheme 17, and using
separation
methods such as
O methods, according
O
O
HO
R
filtration, washing, extraction and
evaporation [88,123,177]. It can be applied
O R as a monomer in
O
O
O
polyester unsaturated resins
from renewable resources [123], or in synthesis of aminated
curing
agent
Ethylene
glycol
O
O
maleic rosinate
for epoxy [178].
O
O
(meth)acrylate
ZnO
O
O
R O
HOOC
200-220°C,
3h
O
Maleic rosin
O
O
O
HO
O
HO
O
R
R
O
O
O
O
O
O
O
R
O
O R
R
O
O
O
O
O acrylate.
O
Scheme 16. Preparation
Preparation
of ethylene
ethylene glycol
glycol maleic rosinate
of
O
O
O
O
HOOC
HOOC
Maleic rosin
ZnO
200-220°C, 3h
O
O
O
O
O
O
R
R
O
O
O
O
O
O
R
R
Scheme 16. Preparation of ethylene glycol maleic rosinate acrylate.
R = H- or CH3-
Ethylene glycol
maleic rosinate
(meth)acrylate
R
R=
= HH- or
or CH
CH33--
Molecules 2019, 24, 1651
11 of 52
Molecules 2019, 24, x FOR PEER REVIEW
11 of 51
Diallyl acrylpimarate is a yellow liquid [123]. It can be prepared from acrylpimaric acid and
an allyl
halide by
different
methods, according
to Schemesolid.
17, and
using
methods
such
Aminated
diallyl
acrylpimarate
is a yellow-brown
It can
be separation
synthesized
from diallyl
as
filtration, washing,
extraction
and evaporation
[88,123,177].
It can
applied
as a monomer
in
acrylpimarate
and cysteamine
hydrochloride
according
to Scheme
17,be
prior
to washing,
extraction
Molecules 2019, 24, x FOR PEER REVIEW
11 of 51
polyester
unsaturated
resins
from
renewable
resources
[123],
or
in
synthesis
of
aminated
curing
agent
and evaporation [178]. It can be applied as a resin or a curing agent for epoxy resins, giving them
for
epoxy [178].
improved
thermal
and acrylpimarate
shape-memoryisproperties
[178]. solid. It can be synthesized from diallyl
Aminated
diallyl
a yellow-brown
acrylpimarate and cysteamine hydrochloride according to Scheme 17, prior to washing, extraction
COOH
COO
and evaporation [178]. It can be applied asCla resin or a curing agent for epoxy
resins, giving them
NH2
COO
HS
HDMA
Cl
improved thermal and shape-memory
properties
[178].
COONa
COOH
in DMF
<60°C, <2h
microwaves 700W
Cl
NaOH
in ethanol
25°C, 1h
DMAP
in dioxane+ethanol
UV 36W, 4h
COO
HS
HDMA Cl
in DMF Br
<60°C,
<2h
K2CO
3
microwaves
700W
in acetone
COONa
70°C, 12h
COONa
COOH
NaOH
COO
NH2
COO S
S
COO
DMAP
in dioxane+ethanol
Aminated di-allyl
UV 36W, 4h acrylpimarate
Acrylpimaricin ethanol
Sodium
Di-allyl
H2N
acid
25°C, 1h
yield: 58% NH2
S
acrylpimarate
acrylpimarate
COO
S
COOH
Br
yield: 100%
yield: 85-92%
COO
Aminated di-allyl
K2CO3
Acrylpimaric
acrylpimarate
Scheme 17.
17. Synthesis of
diallyl acrylpimarate
acrylpimarate
and its
its aminated
aminated derivative.
derivative.
Sodium
Di-allyland
H2N
Scheme
diallyl
in acetone
acid
COONa
yield: 58% NH2
70°C,
12h
acrylpimarate
acrylpimarate
100%acrylpimarate
yield:
85-92%
Aminated
diallyl
a yellow-brown
solid.from
It can
be synthesized
diallyl
Sodiumyield:
maleopimarate
is a solid,iswhich
can
be prepared
maleopimaric
acid from
according
to
acrylpimarate
and
cysteamine
hydrochloride
according
to
Scheme
17,
prior
to
washing,
extraction
and
Scheme 18 prior
to
drying
at
40
°C
[89].
Its
applications
include
the
synthesis
of
triallyl
Scheme 17. Synthesis of diallyl acrylpimarate and its aminated derivative.
evaporation
[178]. It can be applied as a resin or a curing agent for epoxy resins, giving them improved
maleopimarate.
thermal
and shape-memory
Sodium
maleopimarateproperties
is a solid, [178].
which can be prepared from maleopimaric acid according to
O
O
O
Sodium
maleopimarate
a solid,
which
prepared
from
maleopimaric
acid according
to
Scheme 18 prior to dryingis at
40 °C
[89].can
Itsbeapplications
include
the synthesis
of triallyl
Cl
O
O Na
◦
Scheme
18 prior to drying at 40 C [89]. Its applications include the synthesis of triallyl maleopimarate.
maleopimarate.
O
O
O
NaOH
25°C, 1h
O
COOH
Maleopimaric acid
O
O
O
in H2O
NaOH
in H2O
25°C, 1h
O Na
O Na
Sodium
maleopimarate
O Na
yield 100%
O
COO Na
HDMA Cl
in DMF, microwaves
<60°C, <3.5h
or: Cl
Br
HDMA Cl
Kin
DMF,
microwaves
2CO
3 p-benzoquinone
<60°C,
<3.5h
in acetone
or: 70°C, 12h
O
O
C=O
O
O
O
Tri-allyl
O
maleopimarate
yield:
91-93%
O
Br
COO Na
Sodiumof triallyl maleopimarate.
Scheme
18. Synthesis
K CO p-benzoquinone
C=O
Tri-allyl
O
2
3
maleopimarate
Maleopimaric acid
maleopimarate
in acetone
yield 100%
yield:agents
91-93%for
70°C, 12h for use as nucleating
In a similar way dehydroabietic acid salts can be synthesized
isotactic polypropylene in aScheme
non-isothermal
crystallization
process, improving the crystallization
18. Synthesis
Scheme 18.
Synthesis of
of triallyl
triallyl maleopimarate.
maleopimarate.
temperature and accelerating the nucleation rate [179,180]. Triallyl maleopimarate is a white viscous
liquid,
canway
be prepared
from sodium
maleopimarate
and allylfor
halide
according
to Scheme
18,
In which
a similar
dehydroabietic
acid salts
can be synthesized
use as
nucleating
agents for
prior to extraction,
washing,
filtration
and vacuum
distillation
[88,89].improving
It can be used
as a monomer
non-isothermal
crystallization
crystallization
isotactic
polypropylene
in a non-isothermal
crystallization
process,
the crystallization
in
UV-cured
polymer
films
and
coatings,
giving
them
improved
adhesion
and
mechanical
properties
temperature and accelerating the nucleation rate [179,180]. Triallyl maleopimarate is a white
viscous
[89], aswhich
well as
in be
thermally
cured
bio-based
resin systems
exhibiting
can
prepared
maleopimarate
and allyl
halide satisfactory
according tothermal
Schemeand
18,
liquid,
fromfully
sodium
mechanical
properties
[88].
prior
to
extraction,
washing,
filtration
and
vacuum
distillation
[88,89].
It
can
be
used
as
a
monomer
to extraction, washing, filtration and vacuum distillation [88,89]. It can be used as a monomer in
Mono-allyl
rosin
derivatives
have
been
also
synthesized
inadhesion
recent
Allyl rosinate
can
be
in UV-cured
polymer
films
coatings,
giving
them
improved
and
mechanical
properties
UV-cured
polymer
films
andand
coatings,
giving
them
improved
adhesion
andyears.
mechanical
properties
[89],
prepared
[181]
orcured
ethanol
[182]
medium
from
rosin, exhibiting
sodium
hydroxide
and thermal
allyl
chloride
[89],
as well
asthermally
in thermally
fully
bio-based
resin
systems
exhibiting
satisfactory
thermal
as
well
asininaqueous
cured
fully
bio-based
resin
systems
satisfactory
and
according
to
Scheme
19,
prior
to
filtration
and
distillation
[181].
It
can
be
potentially
applied
as
an
mechanical properties [88].
unsaturated
monomer
in
copolymerization
reactions
[181]
as
well
as
in
UV-cured
resins
[182].
On
the
recent years.
years. Allyl rosinate can be
Mono-allyl rosin derivatives have been also synthesized in recent
other hand,
allyl maleopimarate
can be
prepared
in THF
acid, oxalyl
chloride
and
prepared
in aqueous
[181] or ethanol
[182]
medium
fromfrom
rosin,maleopimaric
sodium hydroxide
and allyl
chloride
allyl
alcohol
according
to
Scheme
19,
and
using
such
separation
methods
as
vacuum
distillation
distillation [181]. It can be potentially applied asand
according to Scheme 19, prior to filtration and distillation
an
column chromatography
[90]. It can be usedreactions
in unsaturated
and
resins
as a [182].
cross-linking
copolymerization
reactions
[181] as
asresins
well as
UV-cured
resins
[182].
unsaturated
monomer in copolymerization
[181]
well
in epoxy
UV-cured
resins
On the
agenthand,
[90]. allyl maleopimarate can be prepared in THF from maleopimaric acid, oxalyl chloride and
other
COOH
allyl alcohol according to Scheme 19, and using such separation methods as vacuum distillation and
chromatography [90].
[90]. It can be used in unsaturated resins and epoxy resins as a cross-linking
column chromatography
agent [90].
Molecules 2019, 24, x FOR PEER REVIEW
12 of 51
O
O
O
O
O Na
OH
Rosin
O
O
Molecules 2019, 24, x FOR PEER REVIEW
Cl
Molecules 2019,
24, x FOR PEER REVIEW
NaOH
O HDMA Cl
O
in H2O
O in H2O
O
25°C, 1h
O Na
microwaves
<700W
OH
0.5h
Cl
O<65°C,
Na
OH
Sodium
NaOH
rosinate Cl
yield 92% HDMA Cl
1.
O
Molecules 2019, 24, 1651
O
Cl
Cl
O
O
O
O
O
O
O
Allyl rosinate
yield 95%
OH
O(C H Cl
2 5)3
1.
O
Cl
p-benzoquinone
Cl in THF
O
1.
O
O OH
O
OO
Maleopimaric
acid
2.
12 of 52
12 of 51
12 of 51
2.
O
O
O
O
O
50-25°C,
16h
Cl
O
OH
O
O OO
OO
Allyl maleopimarate
2. (C H )
2 5 3 OH
in H2O
yield 62%
HDMA
Cl
p-benzoquinone
OH
O
(C
2H5)3
microwaves
2
in H2O<700W
in THF
p-benzoquinone
<65°C, 0.5h
OH
Scheme
19.
Synthesis
of
mono-allyl
rosin
derivatives.
O
25°C, 1h
O
50-25°C, 16h
Allyl rosinate
microwaves <700W
O
in THF
Sodium rosinate
<65°C, 0.5h yield 95%
MaleopimaricO
50-25°C,
16hmaleopimarate
Allyl rosinate
Allyl
O
inNaOH
H2O
25°C,
in H O1h
Rosin
yield
92%
Sodium
Rosin
Benzoxazines
arerosinate
compounds yield
consisting
acid group with an oxazine
yieldmoiety.
62%
95% of a bicyclic
Maleopimaric
Allyl maleopimarate
yield
92%
Maleopimaric acid imidophenol is a white, crystal solid. It can
be
synthesized
from
maleopimaric
acid
yield
62%
Scheme 19.Synthesis
Synthesis of mono-allyl
rosin derivatives.
mono-allyl
acid and 4-aminobenzoicScheme
phenol19.
according toofScheme
20, rosin
priorderivatives.
to precipitation and drying [96]. It
19. Synthesis
of mono-allyl
can be used in synthesis ofScheme
benzoxazine
monomers
[96]. rosin derivatives.
Benzoxazines
are
compounds
consisting
of a bicyclic
group
with anmoiety.
oxazine
moiety.
Benzoxazines
are
compounds
consisting
of
a
bicyclic
with
an oxazine
Maleopimaric
Rosin-based benzoxazine monomers are orangegroup
solids.
They
can be synthesized
from
Maleopimaric
acid
imidophenol
is
a
white,
crystal
solid.
It
can
be
synthesized
from
maleopimaric
Benzoxazinesis are
compounds
of abebicyclic
groupfrom
withmaleopimaric
an oxazine moiety.
acid
imidophenol
a white,
crystal consisting
solid.
It can
synthesized
acid20,
and
maleopimaric
acid, paraformaldehyde
and aniline
or 4-aminobenzoic
acid, according
to Scheme
acid
and
4-aminobenzoic
phenol
according
to
Scheme
20,
prior
to
precipitation
and
drying
[96].
It
Maleopimaric
acid
imidophenol
is
a
white,
crystal
solid.
It
can
be
synthesized
from
maleopimaric
4-aminobenzoic
phenol
according
to Scheme
20, prior
to precipitation
and drying [96].
can be used
prior to filtration,
washing
and rotary
evaporation
[96].
They can be polymerized
into It
products
of
can be
used
in synthesis ofphenol
benzoxazine
monomers
[96]. 20, prior to precipitation and drying [96]. It
acid
and
4-aminobenzoic
according
to Scheme
in significant
synthesis
of
benzoxazine
monomers
[96].
thermal benzoxazine
stability [96]. monomers are orange solids. They can be synthesized from
can beRosin-based
used in synthesis
of benzoxazine monomers [96].
maleopimaric
acid,
paraformaldehyde
and aniline
or 4-aminobenzoic
acid,
according
to Schemefrom
20,
Rosin-based
benzoxazine monomers
are orange
solids. They
can
be synthesized
OH
O
O
O
prior
to
filtration,
washing
and
rotary
evaporation
[96].
They
can
be
polymerized
into
products
maleopimaric acid, paraformaldehyde and aniline or 4-aminobenzoic acid, according to Scheme of
20,
1. H2N
significant
thermal
stability and
[96].rotary evaporation
O
O of
prior
to filtration,
washing
[96]. TheyRcan be polymerized into
products
N
2. (CH2O)n
significant thermal
[96].
H2N stabilityOH
N
O
O
O
O
O
O
COOH
H
O2N
Maleopimaric H2N
acid
COOH
in DMF
160°C, 4h
O
in DMF
120°C, 5h
OH
OH
in DMF
160°C, 4h
in DMF
160°C, 4h
OH
O
OH
O
1. H2N
N
O
N
O
2. (CH2O)n
1. H2N
OO
R
COOH
R
Maleopimaric
acid
in DMF
2. (CHimidophenol
2O)n
COOH
120°C, 5h
yield: 88%
in DMF
120°C, 5h
R=H O
or COOH
N
R
N
O
Rosin-based
NO
benzoxazine
or COOH
N
O yield: 76-81%
O N
COOH
COOH
R=H
R
R = H or COOH
Rosin-based
Maleopimaric acid
R
COOH
Scheme
acid
imidophenoland
anditsitsbenzoxazines.
benzoxazines.
Scheme20.
20.Synthesis
Synthesisof
ofmaleopimaric
maleopimaric
acid
imidophenol
benzoxazine
COOH
imidophenol
Maleopimaric
Rosin-based
Maleopimaric
acid
yield:
76-81%
yield: 88%
acid
benzoxazine
COOHsolids.
imidophenol
Maleopimaric
Rosin-based
benzoxazine monomers
are orange
They
be synthesized
from
maleopimaric
Dehydroabietylamine-guaiacol
(brown
powder,
m.p.
104can
°C)
and dehydroabietylamine-4yield: 76-81%
yield:
88%
acid
acid,
paraformaldehyde
and
aniline
ormaleopimaric
4-aminobenzoic
acid,
according
Scheme
20, prior
to filtration,
methylumbelliferone
spherical
crystal solid,
131
°C)and
areitsto
fully
bio-based
benzoxazines
Scheme(yellow
20. Synthesis
of
acid m.p.
imidophenol
benzoxazines.
[157]. They
can be evaporation
synthesized from
via Mannich
condensation,
according
to
washing
and rotary
[96]. dehydroabietylamine
They can be polymerized
into products
of significant
thermal
Scheme
20. Synthesis
of maleopimaric
acid
imidophenol
and and
itsand
benzoxazines.
Scheme
21. They
can compound
resins
with strong
corrosion
protection
thermal stability [157].
Dehydroabietylamine-guaiacol
(brown
powder,
m.p. 104
°C)
dehydroabietylamine-4stability
[96].
◦ C)
methylumbelliferone
(yellow spherical
crystalpowder,
solid, m.p.
131 °C)
fully
benzoxazines
Dehydroabietylamine-guaiacol
(brown
m.p.
104are
andbio-based
dehydroabietylamine-4Dehydroabietylamine-guaiacol (brown powder, m.p.◦ 104 °C)O andOHdehydroabietylamine-4[157].
They
can
be
synthesized
from
dehydroabietylamine
via
Mannich
condensation,
according to
methylumbelliferone (yellow spherical crystal solid, m.p. 131 C) are fully bio-based
benzoxazines
[157].
O
methylumbelliferone
(yellow spherical
crystal
solid,
m.p. 131
°C) are fully
bio-based
benzoxazines
Scheme
21.
They
can
compound
resins
with
strong
corrosion
protection
and
thermal
stability
[157]. 21.
NHcondensation,
2
They
can
be
synthesized
from
dehydroabietylamine
via
Mannich
according
to
Scheme
[157]. They can be synthesized from dehydroabietylamine via Mannich condensation, according to
HOstrong corrosion
O
O
They
can compound
resins
with
protection
thermal
stability O[157].
O
OH thermal stability [157].
Scheme
21. They can
compound
resins with strong
corrosionand
protection
and
N
N
O
O
O
Dehydroabietylamine
N
-4-methylumbelliferone
benzoxazine
yield:
70%
O
O
O
N
paraformaldehyde
in dioxane
<90°C, 20h
HO
O
NH2
paraformaldehyde
in dioxane O
O 85°C, OH
20h
OO
Dehydroabietylamine
NH2 paraformaldehyde
Dehydroabietylamine
N
-guaiacol benzoxazine
in dioxane
O
O
yield: 64%
85°C, 20h
O
paraformaldehyde
O
in dioxane
N
<90°C, 20h
paraformaldehyde
paraformaldehyde
Dehydroabietylamine
in
dioxane
Dehydroabietylamine
Scheme 21.
Synthesis of
fully bio-based benzoxazines.
in dioxane
85°C, 20h-guaiacol benzoxazine
<90°C, 20h
HO
Dehydroabietylamine
O
O
O-4-methylumbelliferone
yield: 64%
benzoxazine yield: 70%
Dehydroabietylamine
Dehydroabietylamine
Dehydroabietylamine
3.2.3. Hardeners
-guaiacol benzoxazine
-4-methylumbelliferone
Scheme 21. Synthesis of fully bio-based benzoxazines.
yield: 64%or
benzoxazine
yield:
70%
Rosin-based
hardeners,
i.e. curing agents, are compounds containing anhydride, carboxyl
hydroxyl
groups, which allows
one
apply them
in epoxy
or urethane resin systems. In comparison
3.2.3. Hardeners
Scheme
21.to
Synthesis
of fully
fully
bio-based
Scheme
21.
Synthesis
of
bio-basedbenzoxazines.
benzoxazines.
with petroleum-based hardeners they bring improved endurance and thermal properties to resin
Rosin-based hardeners, i.e. curing agents, are compounds containing anhydride, carboxyl or
3.2.3.
Hardeners
3.2.3.
Hardeners
hydroxyl groups, which allows one to apply them in epoxy or urethane resin systems. In comparison
Rosin-based
hardeners,
i.e. curing
curing
agents,
are compounds
containing
anhydride,
carboxyl
with
petroleum-based
hardeners
they bring
improved
endurance
and thermal
properties
to resinor or
Rosin-based
hardeners,
i.e.,
agents,
compounds
containing
anhydride,
carboxyl
hydroxyl
groups,
which
allowsone
onetotoapply
applythem
them in
in epoxy or
comparison
hydroxyl
groups,
which
allows
or urethane
urethaneresin
resinsystems.
systems.InIn
comparison
with
petroleum-basedhardeners
hardenersthey
they bring
bring improved
improved endurance
to to
resin
with
petroleum-based
enduranceand
andthermal
thermalproperties
properties
resin
Molecules 2019, 24, x FOR PEER REVIEW
13 of 51
systems. Moreover, rosin-based anhydrides are non-toxic, as opposed to conventional anhydride
curing agents. Their preparation is simple and well described, and usually does not require the use
of solvents. These strengths cause the great interest in use of rosin based chemicals as hardeners of
conventional
and bio-based resins resulting in several commercializations of eg., maleated rosins. 13 of 52
Molecules
2019, 24, 1651
Methyl maleopimarate is a white solid. It can be prepared from abietic acid, iodomethane and
maleic2019,
anhydride,
to Scheme 22, prior to recrystallization [82]. It can be used as bio-based
Molecules
24, x FOR according
PEER REVIEW
13 of 51
curing
agent
for
epoxies
[82,183],
as
well
as
in
synthesis
of
binaphthyl-appended
crown
ethers
systems. Moreover, rosin-based anhydrides are non-toxic, as opposed to conventional anhydride
systems.
Moreover,
rosin-based
are
non-toxic,
as opposed
to conventional
anhydride
derived
from
rosin
[184].
curing
agents.
Their
preparation
isanhydrides
simple and
well
described,
and usually
does not require
the use
curing agents. Their preparation is simple and well described, and usually does not require the use
of solvents.
These strengths cause the great interest in use of rosin basedOchemicals
as hardeners of
O
O
O
OThese
O
of solvents.
cause the great interest in use of rosin based chemicals
asOhardeners
of
O
O strengths
O
conventional and bio-based
resins resulting in several
commercializations
of
e.g.,
maleated
rosins.
CH3I
O
O bio-based resins resulting in several commercializations of eg., maleated rosins.
conventional and
Methyl maleopimarate is a white
prepared
acid, iodomethane and
180°C solid. It can
K2CObe
180°Cfrom abieticpTSA
3
Methyl maleopimarate
is a white
3h solid. It can be prepared3hfrom abietic acid, iodomethane and
pTSA
in DMF
maleic anhydride,in according
to Scheme 22, prior
to recrystallization [82]. inItCH
can
be used as bio-based
3COOH
CHaccording
3COOH
maleic anhydride,
to Scheme 22, prior
to 24h
recrystallization [82]. It can
be12h
used as bio-based
25°C,
120°C,
120°C, 12h
curing
agent
for
epoxies
[82,183],
as
well
as
in
synthesis
of
binaphthyl-appended
crown
ethersethers
derived
curing agent for epoxies [82,183],
as
well
as
in
synthesis
of
binaphthyl-appended
crown
COO
COOH
COO
COOH
COOH
from
rosin from
[184].
COO
derived
rosin [184].
Methyl abietate
Abietic
Levopimaric
Maleopimaric
Methyl
maleopimarate
O
O
O
O
O
yield: 81%
acid
acid
O
O
O
O
O
acid yield: 92%
yield 90%
CH I
3
O
O
180°C of maleopimaric
Scheme 22. Synthesis
K2CO3 acid and methyl
180°C maleopimarate.
pTSA
3h
pTSA
in CH3COOH
Rosin-maleimidopolycarboxylic
120°C, 12h
3h
in DMF
in CH3COOH
24h
12h They can be
acids are25°C,
white/yellowy
or gray/brown 120°C,
powders.
COO
COOH
COOH
prepared from maleopimaricCOO
acid with aspartic or 4-aminobenzoic
acid, or rosin with 1,1′COOH
COO
(methylenedi-4,1-phenylene)bismaleimide, according to Scheme 23, before separation via such
Methyl
abietate
Levopimaric [94,185]. They have a
methods as precipitation, filtration,
washing,
dryingAbietic
and recrystallization
Maleopimaric
Methyl maleopimarate
yield: 81%
acid agents [94,185].
acid
potential to replace petroleum-based
epoxy curing
Furthermore,
rosinacid
yield:
92%
yield 90%
maleimidodicarboxylic acid can be used for synthesis of rosin-based chain extender for
Scheme
22.Synthesis
Synthesis
of maleopimaric
maleopimaric acid
polyurethanesScheme
[186],
or22.
epoxy
resins of
[84].
acidand
andmethyl
methylmaleopimarate.
maleopimarate.
Rosin-polycaprolactone flexible dianhydride are solids with a melting point depending on the
Rosin-maleimidopolycarboxylic
acids
are
white/yellowy
ororrosin,
gray/brown
powders.
They
can
be be
length
of oligoester diol chain. They
can are
be synthesized
from
oligocaprolactone
diols
and
Rosin-maleimidopolycarboxylic
acids
white/yellowy
gray/brown
powders.
They
can
prepared
from
maleopimaric
acid
with
aspartic
or
4-aminobenzoic
acid,
or
rosin
with
1,1′0
maleic
anhydride
according
to
Scheme
24
and
using
vacuum
evaporation
as
a
separation
method
prepared from maleopimaric acid with aspartic or 4-aminobenzoic acid, or rosin with 1,1 -(methylenedi(methylenedi-4,1-phenylene)bismaleimide,
according
to resins
Scheme
23, before separation
via such as
[97]. Their application is bio-based
curingtoagent
for epoxy
[97].
4,1-phenylene)bismaleimide,
according
Scheme
23,
before
separation
via such methods
methods
as
precipitation,
filtration,
washing,
drying
and
recrystallization
[94,185].
They
Tall-oil based polyol can be prepared from diethanolamine and tall oil containing up to 20 have
wt.% a
precipitation, filtration, washing, drying and recrystallization [94,185]. They have a potential to
of rosin acids,
according
to Scheme 25, prior
to vacuum
evaporation
water [187].
It can be used
as
potential
to replace
petroleum-based
epoxy
curing
agents of
[94,185].
Furthermore,
rosinreplace petroleum-based epoxy curing agents [94,185]. Furthermore, rosin-maleimidodicarboxylic acid
chain extenders in ureaurethane
their thermal
resistance and
storage
modulsfor
maleimidodicarboxylic
acid canelastomers,
be used improving
for synthesis
of rosin-based
chain
extender
can be
used for synthesis of rosin-based chain extender for polyurethanes [186], or epoxy resins [84].
[187].
polyurethanes
[186], or epoxy resins [84].
Rosin-polycaprolactone flexible dianhydride are solids with a melting point depending on the
length of
diol chain. They canCOOH
be synthesized fromLevopimaric
rosin, oligocaprolactone diols and
H2Noligoester COOH
acid
O
maleic anhydride according to NScheme 24 and using vacuum evaporation as a separation method
HOOC
in DMF
O
[97]. Their application
agent for epoxyO resins [97]. O
160°C, 4h is bio-based curing
pTSA; in CH3COOH
O
Tall-oil
based polyol can be prepared from diethanolamine and tall oil containing
up to 20 wt.%
O
120°C, 12h
N
N
of rosin acids, according to Scheme 25, prior to vacuum evaporation of water [187]. It can be used as
O
O
O
chain extenders in ureaurethane elastomers, improving their
thermal resistance
and storage moduls
COOH
[187].
O
H2N
COOH
Rosin-maleimidodicarboxylic
acid yield: 87%
COOH
COOH
O
Maleopimaric
in DMFNH2
acid
160°C, 4h
O
COOH
HOOC
N
COOH
O
COOH
Rosin-maleimidotricarboxylic
acid COOH
yield: 54%
O
O
HOOC
O
N
N
O
O
N
Levopimaric
acid
O
O
HOOC COOH
O
in DMF
O
165-180°C
6.5h
N
N
O
pTSA; in CH3COOH
COOH
COOH
120°C, 12h
O
Dirosin-maleimidodicarboxylic
acid yield: 87%
O
N
Rosin-maleimidodicarboxylic
Scheme 23. Synthesis of rosin-maleimidodicarboxylic acids.
acid yield: 87%
N
O
O
O
Rosin-polycaprolactone flexible dianhydride are solids with a melting point depending on the
O
Maleopimaric NH2
length
be synthesized from rosin, oligocaprolactone diols and
acidof oligoester diol chain. They canHOOC
maleic anhydride
according
to
Scheme
24
and
using vacuum evaporation as a separation method [97].
HOOC COOH
N
COOH
COOH
COOH
Their application
is bio-based curing agent for epoxy resins [97].
in DMF
O
COOH
165-180°C
Tall-oil based
polyol
can be prepared from diethanolamine and tall
oil containing up to 20 wt.% of
Rosin-maleimidotricarboxylic
Dirosin-maleimidodicarboxylic
6.5h
rosin acids, according to Scheme
25,
prior
to
vacuum
evaporation
of
water
[187].
can be
used as chain
acid yield: 54%
acid Ityield:
87%
extenders in ureaurethane elastomers, improving their thermal resistance and storage moduls [187].
Molecules 2019,
2019, 24,
24, xx FOR
FOR PEER
PEER REVIEW
REVIEW
Molecules
Molecules 2019,
24, x FOR
PEER REVIEW
Molecules 2019, 24, 1651
14 of
of 51
14
14 of
51 51
14 of 52
Scheme
23.
Synthesis
of
rosin-maleimidodicarboxylic
acids.
Scheme
acids.
Scheme23.
23.Synthesis
Synthesis of
of rosin-maleimidodicarboxylic
rosin-maleimidodicarboxylic acids.
OO
O
COOH
COOH
COOH
HOHO
HO
RR
HOHO R
HO
O
OO
OO
O
RR
R
OO O
OO
O
O
O O
O
OO
O
OO
O
O
O
O
O O O
O O
O
OO
pTSA
pTSA
pTSA
nano-ZnO)
(or(or
nano-ZnO)
(or
nano-ZnO)
230-240°C,
230-240°C,
5h5h
230-240°C,
5h
Abietic
Abietic
Abietic
acidacid
acid
O
OO
HH33PO
PO4 4
H3PO
4
180-190°C
180-190°C
180-190°C
4h
4h
R R
R
O O
OO
O
O
4h
OO
O O
O
O
O
O
HOHO R =
HO
O(CH2)2O(CH2)2O [ C
R == H H O(CH
[ O(CH
2)5 CC ]mO(CH
O(CH2))2O
O[C
C
HOR
[
]
2))5 C
2))2O(CH
m
H
O(CH
O(CH
HO
[
]m
2 5
2 2
2 2 [
HO
(CH2)5O ]n H
(CH2))5O
O ]n H
H
(CH
2 5 ]n
M = 530, 1000, 1250
O O
O
O
Rosin-polycaprolactone
anhydride
Rosin-polycaprolactone
anhydride
Rosin-polycaprolactone
anhydride
curing
agent
yield:
76%
curing agent yield:
76%
curing agent yield: 76%
n 530, 1000, 1250
Mn ==
M
n 530, 1000, 1250
Scheme 24.Synthesis
Synthesisof
ofrosin-polycaprolactone
rosin-polycaprolactone anhydride curing
agent.
Scheme
Scheme 24.
24. Synthesis
Synthesis of
of rosin-polycaprolactone
rosin-polycaprolactone anhydride
anhydride curing
curing agent.
agent.
Scheme
24.
anhydride
curing
agent.
O
HO
O
O
O
R
R
R
OH
N
H
HO
HO
OH
N
N
H
140°C,
5h
H
OH
TallOH
oil
R
OH
OH
O
R
R
140°C, 5h
5h
140°C,
Tall oil
oil
Tall
OH
O
O
R
R= CH3 (CH2)7 CH
OH
OH
N
O
O
O
and
OH
OH
O
O
and
and
OH
R
R
O
NH
O
Tall oil-based
polyol
NH
O
NH
CH
(CH2)7
CH3 (CH
(CH2))7 CH
CH CH
CH
R= CH
R=
3
2 7
OH
N
N
(CH2))7
(CH
2 7
or R=
OH
OH
or R=
R=
or
Tall oil-based polyol
Tall
Scheme
25.oil-based
Synthesispolyol
of tall oil-based polyol.
Scheme 25.
25. Synthesis
Synthesis of
of tall
tall oil-based
oil-based polyol.
polyol.
Scheme
3.2.4. Surfactants
3.2.4.
Surfactants
3.2.4. Surfactants
3.2.4.
Small/medium molecule rosin-based surfactants are ionic or non-ionic compounds that lower
surface
tension between
different
substances.
In comparison
with
counterparts,
Small/medium
molecule
rosin-based
surfactants
are ionic
or
non-ionic
that
lower
Small/medium
molecule
rosin-based
ionic
orpetrochemical
non-ionic compounds
compounds
thatthey
lower
Small/medium
molecule
rosin-based
surfactants are ionic
or
non-ionic
compounds
that
lower
are
characterized
by
designable
surface
activity,
affinity
to
many
chemicals
(especially
cycloaliphatic
surface
tension
between
different
substances.
In
comparison
with
petrochemical
counterparts,
they
surface
tension
between
different
substances.
In
comparison
with
petrochemical
counterparts,
they
surface tension between different substances. In comparison with petrochemical counterparts, they
and
aromatic),
non-toxicity,
mild
biocidal
properties
and
enhanced
thermal
stability.
Unfortunately,
are
characterized
by
designable
surface
activity,
affinity
to
many
chemicals
(especially
cycloaliphatic
are characterized
characterized by
by designable surface activity,
activity, affinity
affinity to
to many
many chemicals
chemicals (especially
(especially cycloaliphatic
cycloaliphatic
are
their
syntheses
are designable
less wellmild
described
than
rosin-based
resins
and hardeners,
eg. reaction yields are
and
aromatic),
non-toxicity,
biocidal
properties
and
enhanced
thermal stability.
and
aromatic),
non-toxicity,
mild
biocidal
properties
Unfortunately,
andoften
aromatic),
non-toxicity,
mildthe
biocidal
properties
and enhanced
thermal
Unfortunately,
unavailable.
Moreover,
use of
unsustainable
chemicals
in the stability.
mentioned
reactions
their
reaction
yields are
their syntheses
syntheses are
areless
lesswell
welldescribed
describedthan
thanrosin-based
rosin-basedresins
resinsand
andhardeners,
hardeners,e.g.,
eg. reaction
are
their
syntheses
are
less
well
described
than
rosin-based
resins
and
hardeners,
eg.
yields
noticeably decreases the “green” aspect of these rosin derivatives. Therefore, it is an urgent need
toare
often
unavailable.
Moreover,
the
use
of
unsustainable
chemicals
in
the
mentioned
reactions
noticeably
often unavailable.
unavailable. Moreover, the
the use of
of unsustainable
unsustainable chemicals
chemicals in
in the
the mentioned
mentioned reactions
reactions
often
undertake appliedMoreover,
studies on theseuse
compounds,
as well as to find more
sustainable preparation
decreases
the
“green”the
aspect
of these
rosin
derivatives.
Therefore, it
is an urgent
need
to undertake
noticeably
decreases
“green”
aspect
of
these
rosin
derivatives.
Therefore,
it
is
an
urgent
need to
noticeably
the
“green”
aspect
ofgroup
these of
rosin
processesdecreases
in order to
increase
TRL
of this
rosinderivatives.
derivatives.Therefore, it is an urgent need to
applied
studies
on these
compounds,
ascompounds,
well as to find
more
sustainable
preparation
processes
in order
undertake
applied
studies
on
these
as
well
as
to
find
more
sustainable
preparation
undertake
applied studies
on these
compounds,
as well
as toliquid.
find more
sustainable
preparation
Dehydroabietyl
phosphate
diester
is a yellow
viscous
It can
be prepared
from
to
increase
TRL
of
this
group
of
rosin
derivatives.
processes
in
order
to
increase
TRL
of
this
group
of
rosin
derivatives.
dehydroabietyl
decanediol,
and
polyphosphorus
acid according to Scheme 26, prior to
processes
in order chloride,
to increase
TRL of this
group
of rosin derivatives.
Dehydroabietyl
phosphate
diester
is
yellow
viscous
can be
prepared
from
Dehydroabietyl
phosphate and
diester
is a[140].
yellow
viscous
liquid.
ItIt can
can
from
washing,
vacuum evaporation
drying
It can
be usedliquid.
as highly-active
surfactant
[140],
Dehydroabietyl
phosphate
diester
is
aa yellow
viscous
liquid.
It
be
prepared
from
dehydroabietyl
chloride,
decanediol,
and
polyphosphorus
acid
according
to
Scheme
26,
prior
dehydroabietyl
chloride,
26, prior
prior to
to
phosphorus source
and crystal
growthand
control
agent in synthesis
hydroxyapatite
[188]. 26,
dehydroabietyl
chloride,
decanediol,
polyphosphorus
acidofaccording
to Scheme
to
washing,
vacuum
evaporation
and
drying
[140].
It can be used as highly-active surfactant [140],
washing,
vacuum
evaporation
and
drying
[140].
It
washing, vacuum evaporation and drying [140]. It can be used as highly-active surfactant [140],
phosphorus
control
phosphorus source
source and
andcrystal
crystalgrowth
growth
controlagent
agentin
insynthesis
synthesisof
ofhydroxyapatite
hydroxyapatite[188].
[188].
O
phosphorus
source
and
crystal
growth
control
agent
in
synthesis
of
hydroxyapatite
[188].
HO(CH2)10OH
in CHCl3
<80°C;reflux
HO(CH2))105h
OH
HO(CH
2 10OH
COCl
in CHCl3
in CHCl3
<80°C;reflux
<80°C;reflux
5h
Dehydroabietyl
5h
COCl
chloride
COCl
Dehydroabietyl
Dehydroabietyl
chloride
chloride
HO P
O H
NaOH
OH
O
n
O
in P
CHCl
HO
O
H
HO P O 3 H
reflux;6h
OH
COO
OH
in CHCl
CHCl3
in
(CH2)103
reflux;6h
reflux;6h
HO
COO
COO
yield 90.2%
(CH2))10
(CH
2 10
nn
NaOH
NaOH
COO(CH2)10O O(CH2 )10OOC
O
P
OH
Dehydroabietyl
COO(CH2))10O
O O(CH
O(CH2))10OOC
OOC
COO(CH
phosphate
(DDPD)
2 diester
10
2 10
O 82.8%
OH
yield
P OH
O
P
COO(CH2)10O O(CH2 )10OOC
O
P
ONa
DDPD sodium salt
COO(CH2))10O
O O(CH
O(CH2))10OOC
OOC
COO(CH
2 10
2 10
O
O
P
P
ONa
ONa
Dehydroabietyl
DDPD sodium
sodium salt
salt
Dehydroabietyl
Scheme 26. HO
Synthesis of phosphate
dehydroabietyl
phosphate
diester sodiumDDPD
salt.
diester
(DDPD)
HO
phosphate diester
(DDPD)
yield 82.8%
82.8%
yield 90.2%
90.2%
yield
yield
Rosin-based chloride can be prepared from maleated rosin and phosphorus trichloride
Scheme
26. Synthesis
Synthesis
of dehydroabietyl
dehydroabietyl
phosphate
diester
sodium
salt.
according to Scheme
27, 26.
prior
to evaporation
[101]. It can
be used as
a substrate
for
synthesis of rosinScheme
phosphate
diester
sodium
salt.
Scheme
26.
of
based ester amines [101].
Rosin-based
be prepared
from from
maleated
rosin and
phosphorus
trichloridetrichloride
according
Rosin-basedchloride
chloridecan
can
be prepared
prepared
from maleated
maleated
rosin
and phosphorus
phosphorus
trichloride
Rosin-based
chloride
can
be
rosin
and
to
Scheme
27,
prior
to
evaporation
[101].
It
can
be
used
as
a
substrate
for
synthesis
of
rosin-based
ester
according to
to Scheme
Scheme 27,
27, prior
prior to
to evaporation
evaporation [101].
[101]. It
It can
can be
be used
used as
as aa substrate
substrate for
for synthesis
synthesis of
of rosinrosinaccording
amines
[101].
based ester
ester
amines [101].
[101].
based
amines
Rosin-based ester tertiary amine can be prepared from rosin chloride and N,N-dimethyl
Molecules 2019, 24, x FOR PEER REVIEW
15 of 51
ethanolamine according to Scheme 27, prior to washing, drying, extraction, evaporation and
recrystallization
[101].
Potential
include drug carriers and surfactants. Its surface activity
Molecules
2019, 24, x FOR
PEER
REVIEWapplications
15 of 51
Rosin-based
ester
tertiary
amine can be prepared from rosin chloride and N,N-dimethyl
significantly increases in presence of rosin phosphate ester (Scheme 26) [101].
ethanolamine according to Scheme 27, prior to washing, drying, extraction, evaporation and
Rosin-based
esterPotential
tertiary applications
amine can include
be prepared
from rosin chloride and N,N-dimethyl
Molecules
2019, 24, 1651[101].
15 of 52
recrystallization
activity
O
O drug carriers and surfactants. Its surface
O
ethanolamine
according
to
Scheme
27,
prior
to
washing,
drying,
extraction,
evaporation
and
significantly increases in presence
of rosin phosphate ester (Scheme
N 26) [101].
PCl3
OH Potential
N
recrystallization [101].
applications includeCldrugHO
carriers and surfactants. Its surface activity
N
significantly increases
of rosin phosphate
(Scheme
26) [101].
2H5)3N
OOH ininpresence
O Cl ester (C
O
CHCl3
O OH
O
OH
OH
O
OH
COOH
Maleic rosin
COOH
55°C,
PCl33h
in CHCl
COCl
PCl3 3
55°C, 3h Rosin-based
in CHCl3
55°C, 3h
O Cl
O
Cl
Cl
chloride
O
Cl
in benzene
N
HO25°C, 3h
(C2H5)3NN
HOin benzene
(C25°C,
H ) 3h
N
N
COO
N
N
N
Rosin-based ester
O tertiary
N
amine purity
81.18%
N
2 5 3
in benzene
COO
O
25°C,
3h
Scheme 27. Synthesis of rosin-based ester
tertiary
amine.
O
O
O
COCl
O
Rosin-based ester tertiary
N
amine purity 81.18%
COOH
COCl
COO
Rosin-based
ester tertiary
Solid
N-dodecyl-maleimidepimaric
acid
(C12-MPA) can be prepared
from maleopimaric
acid
Maleic
rosin
Rosin-based
chloride
Scheme27.
27. Synthesis
Synthesis of rosin-based ester
amine. amine purity 81.18%
Scheme
ester tertiary
tertiary
and dodecylamine according
to Scheme
28, prior to washing,
drying,amine.
filtration, rotary evaporation
and purification via Scheme
column chromatography
[100]. Sodium
N-dodecylmaleimidepimaric
Synthesis
of
rosin-based
tertiary
amine.
Rosin-based
ester tertiary 27.
amine
can
be
preparedester
from
chloride
and N,N-dimethyl
Solid N-dodecyl-maleimidepimaric
acid
(C12-MPA)
can
be rosin
prepared
from maleopimaric
acid
carboxylate is a product of C12-MPA neutralization using NaOH, prior to evaporation,
ethanolamine
according
to Scheme
27, 28,
prior
to towashing,
extraction,
evaporation
and
and dodecylamine
according
to Scheme
prior
washing, drying,
drying, filtration,
rotary
evaporation
recrystallization
and vacuum drying. It
forms
micellescan
ofbevarious
shapes, maleopimaric
depending onacid
its
N-dodecyl-maleimidepimaric
acid
(C12-MPA)
prepared
recrystallization
[101].
include
drugSodium
carriers
andfrom
surfactants. Its surface
and Solid
purification
via Potential
column applications
chromatography
[100].
N-dodecylmaleimidepimaric
concentration
[102]. It can be used
in oil extraction,
and
industrial
washing
[100].
and
dodecylamine
to presence
Scheme
28,
prior
tocosmetics
washing,
drying,
filtration,
rotary
evaporation
carboxylate
is a according
product
C12-MPA
neutralization
using
NaOH,
prior
to evaporation,
activity
significantly
increases of
in
of rosin
phosphate
ester
(Scheme
26)
[101].
Acrylpimaryl
dichloride
is
an
orange,
sticky
paste.
It
can
be
prepared
from
acrylpimaric
acid
and
purification
via
column
chromatography
[100].
Sodium
N-dodecylmaleimidepimaric
recrystallization
and vacuum drying.acid
It forms
micelles
of prepared
various shapes,
depending acid
on and
its
Solid N-dodecyl-maleimidepimaric
(C12-MPA)
can be
from maleopimaric
according
to Scheme
29, priorofto solvent
evaporation
[128]. Itusing
can beNaOH,
used in synthesis
ofevaporation,
surfactants
carboxylate
a product
C12-MPA
neutralization
prior to[100].
concentrationisaccording
[102].
It cantobe
used
in28,
oilprior
extraction,
cosmetics
and industrial
dodecylamine
Scheme
to washing,
drying,
filtration,washing
rotary evaporation and
[128],
herbicides [129],
fungicidesdrying.
[189] and
[190]of various shapes, depending on its
recrystallization
and
vacuum
It insecticides
forms
micelles
Acrylpimaryl
dichloride
is an orange,
sticky
paste.
It can be prepared from acrylpimaric
acid
purification
via column
chromatography
[100].
Sodium
N-dodecylmaleimidepimaric
carboxylate
is a
Acrylic
rosin
ester
diethylamine
tertiary
amine
surfactant
is industrial
a sticky paste.
It can
be prepared
concentration
[102].
It
can
be
used
in
oil
extraction,
cosmetics
and
washing
[100].
according
to Schemeneutralization
29, prior to solvent
[128].
It can be used
in synthesis of and
surfactants
product
of C12-MPA
usingevaporation
NaOH, prior
to evaporation,
recrystallization
vacuum
fromAcrylpimaryl
acrylpimaryl chloride,
N,N-diethylethanolamine
andIthydrochloric
acid according
to Scheme
29
dichloride
is an[189]
orange,
sticky
paste.
can be prepared
from acrylpimaric
acid
[128], herbicides
[129],
fungicides
anddepending
insecticides
[190]
drying.
It
forms
micelles
of
various
shapes,
on
its
concentration
[102].
It
can
be
used
in
[128]. Thistoproduct,
in
mixture
with soapnut
saponin
noteworthy
surfaceofactivity
andoil
according
Scheme
29,adiethylamine
prior
to solvent
evaporation
[128].exhibits
It canisbe
used inpaste.
synthesis
surfactants
Acrylic
rosin
ester
tertiary
amine surfactant
a sticky
It can be
prepared
extraction,
cosmetics
and
industrial
washing
[100].
emulsification
ability
tofungicides
apply in pharmacy,
cosmetics and
commodity chemicals [128].
[128],
herbicides
[129],
[189] and insecticides
[190]
from acrylpimaryl
chloride,
N,N-diethylethanolamine
and
hydrochloric acid according to Scheme 29
rosin ester
tertiary
amine
surfactant
is anoteworthy
sticky paste.surface
It can be
prepared
[128].Acrylic
This
product,
in2 diethylamine
a mixture
soapnut
saponin
exhibits
activity
and
C12Hwith
O
C12H25NH
O
25
O acrylpimaryl
O
from
chloride,
N,N-diethylethanolamine
and
hydrochloric
acid
according
to
Scheme
29
emulsification ability to apply inNpharmacy, cosmetics and commodity chemicals [128].
in DMF
[128]. This product,
in a mixture
with
O
O soapnut saponin exhibits noteworthy surface activity and
N
NaOH
<165°C, 8h
O
emulsification
ability
to2 apply inCpharmacy,
cosmetics and commodityO chemicals [128].
C12H25NH
12H25
Maleic rosin
Rosin-based chloride
in C2H5OH
O
O
O
DMF
Cin
12H25NH2
O <165°C,
COOH 8h
O
in DMF
<165°C, 8h
O
O
N
C12H25 O
70°C, 12h
O
ON
NaOH
COO Na
Sodium
N-dodecyl-maleimidepimaric
ON
MaleopimaricCOOH N-dodecylcarboxylate
in C2H5OH
acid
Sodium
70°C,
12h 29% COO Na
yield
O 76%
maleimidepimaric acid
yield
COOH
N-dodecyl-maleimidepimaric
COOH
COO Na
Maleopimaric
carboxylate
Scheme28.
28. Synthesis
Synthesis of sodium N-dodecyl-maleimidepimaric
carboxylate.
Sodium
Scheme
N-dodecyl-maleimidepimaric
carboxylate.
N-dodecylCOOH
acid
yield
76%
N-dodecyl-maleimidepimaric
maleimidepimaric acid yield 29%
Maleopimaric dichloride
COOH
COCl
carboxylate
Acrylpimaryl
is
an orange, sticky paste. It can be
prepared from acrylpimaric acid
N-dodecylH
PCl3 28. Synthesis of sodium N-dodecyl-maleimidepimaric
Nyield 76%
OH
acid Scheme
carboxylate.
N
maleimidepimaric
acid
yield
29%
N
according to Scheme 29, prior to solvent evaporation [128]. It can be used in synthesis ofClsurfactants
[128],
Cl
in CHCl3
herbicides
[129],
fungicides
[189]
and
insecticides
[190]
COOH
COCl of sodium N-dodecyl-maleimidepimaric carboxylate.
55°C, 3h 28. Synthesis
Scheme
COOH
PCl3
in CHCl3
PCl3h
3
55°C,
COOH
Acrylic rosin
N
in CHCl3
COOH
55°C, 3h
COCl
O
in C2H5OH
COOH
70NaOH
°C, 12h
COCl
(C2H5)3NOH
N
in benzene
25°C, 3h
OH
N
(C2H5)3N
COCl
Acrylic rosin
in benzene
chloride
Acrylic
(C25°C,
H ) 3h
N
COO
COO
N
HCl
N
N
COO
Cl
HCl
ClCOO
N
COO
H
N
H
N
H
N Cl
H Cl
N
COO
HCl
COO
COO
rosin
H
2 5 3
N
yield 96%COCl
N
N,N-diethyl
in benzene
Acrylic rosin
Acrylic rosin
ethanolamine
diester
Acrylic
rosin
ester
COO
25°C, 3h
COO
chloride
Acrylic
rosin
yield
87%
diethylamine tertiary amine
Acrylic rosin
Acrylic
rosin
yield 96%
N,N-diethyl
surfactant yield: 100%
COO
COO
chloride
Acrylic
rosin diester
ethanolamine
Acrylic rosin ester
yield
Scheme 29. Preparation
of 96%
acrylic rosin ester
tertiarydiethylamine
amine surfactant.
N,N-diethyl
yielddiethylamine
87%
tertiary amine
ethanolamine diester
Acrylicyield:
rosin 100%
ester
surfactant
yield 87%
diethylamine tertiary amine
Scheme 29. Preparation of acrylic rosin ester diethylamine tertiary amine
surfactant.yield: 100%
surfactant
COOH
Scheme29.
29.Preparation
Preparation of
of acrylic
acrylic rosin
Scheme
rosin ester
ester diethylamine
diethylaminetertiary
tertiaryamine
aminesurfactant.
surfactant.
Acrylic rosin ester diethylamine tertiary amine surfactant is a sticky paste. It can be prepared from
acrylpimaryl chloride, N,N-diethylethanolamine and hydrochloric acid according to Scheme 29 [128].
Molecules 2019, 24, 1651
16 of 52
This product, in a mixture with soapnut saponin exhibits noteworthy surface activity and emulsification
Molecules 2019, 24, x FOR PEER REVIEW
16 of 51
Molecules
2019, 24,in
x FOR
PEER REVIEW
16 of 51
ability
to apply
pharmacy,
cosmetics and commodity chemicals [128].
Quaternary
Theycan
canbe
beprepared
preparedfrom
from
Quaternaryammonium
ammonium salts
salts of
of rosin
rosin esters
esters are
are yellow
yellow solids.
solids. They
Quaternary
ammonium
salts in
ofSection
rosin esters
are
yellow
solids. They can be prepared
from
maleopimaryl
chloride
(described
3.2.5)
and
N,N-diethylethanolamine
with
hexadecyl
maleopimaryl chloride (described in subsection 3.2.5) and N,N-diethylethanolamine with hexadecyl
maleopimaryl chloride (described
in subsection 3.2.5) and N,N-diethylethanolamine
with
hexadecyl
bromide,
to Scheme
Scheme 30,
30,and
andusing
usingsuch
suchseparation
separation
bromide,ororepichlorohydrin
epichlorohydrinwith
withtriethylamine,
triethylamine, according
according to
bromide, or epichlorohydrin with triethylamine, according to Scheme 30, and using such separation
methods
drying,extraction
extractionand
andrecrystallization
recrystallization[104,191].
[104,191].
methodsasasvacuum
vacuumdistillation,
distillation,filtration,
filtration, washing, drying,
methods as vacuum distillation, filtration, washing, drying, extraction and recrystallization [104,191].
Maleopimaric
Maleopimaric
acid
acid
O
O
O
O
O
O
COOH
COOH
O
O
Cl
Cl
O
O
Maleopimaryl
Maleopimaryl
chloride
chloride
N
N
(CH2)15CH3
(CH2)15CH3
HO
HO
O
O
(C2H5)3N
(Ctoluene
2H5)3N
in
in toluene
98°C,
6h
98°C, 6h
N
N
CH3(CH2)15Br
CH3(CH2)15Br
C
O C
O O
O
Cl O
Cl O
(C2H5)3N
(C2H5)3N
50°C
50°C
4h
4h
OH
OH
O
O
O
O
O
O
O
O
90°C, 5h
90°C, 5h
N
N
COO
COO
Diethylaminoethyl rosin ester
Diethylaminoethyl
rosin ester
quaternary ammonium
salt
quaternary
ammonium
salt
yield: 85%
yield: 85%
Rosin
Rosin
2-hydroxypropyl
2-hydroxypropyl
chloride
ester
O
chloride ester
O
O
O
O
O
O
O
COCl
COCl
O
O
O
O
Cl
Cl
O
O
in toluene
in toluene
95°C,
4h
95°C, 4h
O
O
COO
COO Br
Br
Cl
Cl
C
O C
O O
O
O
O
Rosin diethylaminoethyl
Rosin diethylaminoethyl
ester
yield: 80%
ester
yield: 80%
O
O
N
N
Cl
Cl
OH
OH
Rosin 2-hydroxypropyl-triethyl
Rosin 2-hydroxypropyl-triethyl
ammonium
chloride yield: 72%
ammonium chloride yield: 72%
Scheme30.
30. Synthesis of
of quaternary ammonium
salts
Scheme
saltsof
ofrosin
rosinesters.
esters.
Scheme 30.Synthesis
Synthesis ofquaternary
quaternary ammonium
ammonium salts
of
rosin
esters.
Their
[104,191,192]dispersants
dispersantsfor
formagnetite
magnetite
Theirpotential
potentialapplications
applicationsinclude
include corrosion
corrosion inhibitiors [104,191,192]
Their potential applications include corrosion inhibitiors [104,191,192] dispersants for magnetite
(Fe
3O
nanoparticles[191,192]
[191,192] and
and inhibitors in protein
(Fe
protein aggregation
aggregationprocesses
processes[193–195].
[193–195].InInaddition,
addition,
3O
4 )4)nanoparticles
(Fe3O4) nanoparticles [191,192] and inhibitors in protein aggregation processes [193–195]. In addition,
similarrosinyl
rosinyltriquaternary
triquaternaryammonium
ammoniumsalt
salt having
having antifungal
antifungal activity
a asimilar
activity was
was also
alsoreported
reported[196].
[196].
a similar rosinyl triquaternary ammonium salt having antifungal activity was also reported [196].
Anotherapproach
approach to
to introduce
introduce quaternary
quaternary ammonium
ammonium moieties
Another
moieties into
into rosin
rosinisispresented
presentedinin
Another approach to introduce quaternary ammonium moieties into rosin is presented in
Scheme3131[197].
[197].As
Asititcan
canbe
beseen,
seen, rosin
rosin bisquaternary
bisquaternary ammonium
Scheme
ammonium chloride
chloridecan
canbe
beprepared
preparedfrom
from
Scheme 31 [197]. As it can be seen, rosin bisquaternary ammonium chloride can be prepared from
rosin,
ethanol,
fumaric
acid
and
epoxy
quaternary
ammonium
salt,
and
using
such
separation
rosin,
ethanol,
fumaric
acidacid
and and
epoxy
quaternary
ammonium
salt, and
separation
methods
rosin,
ethanol,
fumaric
epoxy
quaternary
ammonium
salt,using
andsuch
using
such separation
asand
washing
and
drying.
Thusgemini
obtained
gemini surfactant
has good
surfaceand
activity
and
asmethods
washing
drying.
Thus
obtained
surfactant
has
good
surface
activity
antifungal
methods as washing and drying. Thus obtained gemini surfactant has good surface activity and
antifungal
activity
fungi responsible
for wood
[197].
activity
against
fungiagainst
responsible
for wood decay
[197].decay
antifungal
activity
against
fungi responsible
for wood
decay [197].
HOOC
HOOC
OH
OH
ZnO
ZnO3.5h
180°C,
180°C, 3.5h
COOH
COOH
Levopimaric
Levopimaric
acid
acid
COOH
COOH
O
O
p-hydroquinone
p-hydroquinone
230°C, 3h
230°C, 3h
OH
OH
O
O
OH
OH
O
O
Cl
Cl
N
N
82°C, 8.5h
82°C, 8.5h
Cl
Cl N
N OH
OH
O
O
O
O
O
O
O
O
Cl
Cl
N
N
OH
OH
COO
Ethyl COO
Ethyl
levopimarate
levopimarate
Ethyl
Ethyl
fumaropimarate
fumaropimarate
COO
COO
Rosin
Rosin
bisquaternary
bisquaternary
ammonium
salt ammonium
yield: 93%
salt yield: 93%
COO
COO
Scheme 31. Preparation of rosin bisquaternary ammonium salt.
Scheme31.
31.Preparation
Preparationof
of rosin
rosin bisquaternary
bisquaternary ammonium
Scheme
ammonium salt.
salt.
Dehydroabietyltrimethyl ammonium bromide is a yellow solid. It can be prepared from
Dehydroabietyltrimethyl
can be
be prepared
prepared from
from
Dehydroabietyltrimethyl ammonium
ammonium bromide
bromide is
is aa yellow
yellow solid.
solid. ItIt can
dehydroabietylamine, formic acid and methyl bromide according to Scheme 32, and using such
dehydroabietylamine,formic
formic acid
acid and
and methyl
methyl bromide
bromide according
according to
dehydroabietylamine,
to Scheme
Scheme 32,
32, and
and using
usingsuch
such
separation techniques as washing, extraction and evaporation, drying, vacuum distillation and
separationtechniques
techniquesasaswashing,
washing, extraction
extraction and
and evaporation,
evaporation, drying,
separation
drying, vacuum
vacuum distillation
distillationand
and
recrystallization [158]. Such surfactant can be used for preparation of ordered porous titania [159],
recrystallization[158].
[158].Such
Suchsurfactant
surfactant can
can be used for preparation
recrystallization
preparation of
of ordered
orderedporous
poroustitania
titania[159],
[159],
zirconia [198] or silica [158] with potential applications in catalysis and separation.
zirconia
[198]ororsilica
silica[158]
[158]with
withpotential
potentialapplications
applications in
in catalysis
catalysis and separation.
separation.
zirconia
[198]
Molecules 2019, 24, 1651
17 of 52
Molecules 2019,
2019, 24,
24, xx FOR
FOR PEER
PEER REVIEW
REVIEW
Molecules
17 of
of 51
51
17
HCOOH
CH33Br
in acetone
25°C, 4h
4h
25°C,
HCHO
HCHO
O
in ethanol/H
ethanol/H22O
in
<80°C, 9h
9h
<80°C,
NH222
NH
N
N
N,N-dimethyl
N,N-dimethyl
dehydroabietylamine
dehydroabietylamine
Dehydroabietylamine
Dehydroabietylamine
Br
Br
N
N
Dehydroabietyltrimethyl
Dehydroabietyltrimethyl
ammonium bromide
bromide
ammonium
Scheme 32.
32. Synthesis
of dehydroabietyltrimethyl
dehydroabietyltrimethyl ammonium
ammonium bromide.
Synthesis of
bromide.
bromide.
Scheme
Another
can
be
prepared
from
dehydroabietyl
chloride,
Anotherrosin-based
rosin-basedgemini
gemini surfactants
surfactants [143,199]
[143,199] can
can be
be prepared
prepared from
from dehydroabietyl
dehydroabietyl chloride,
chloride,
Another
rosin-based
gemini
surfactants
[143,199]
3-(dimethylamino)-1-propylamine
and
α,ω-dibromoalkanes
to
Scheme
33.
The
product
3-(dimethylamino)-1-propylamine and
α,ω-dibromoalkanes
according
Scheme
33.
The
product
and
to
to
separation
separation methods
methods include
include column
column chromatography,
chromatography, vacuum
vacuum drying
drying and
and recrystallization
recrystallization from
from
separation
methods
include
column
chromatography,
vacuum
drying
and
recrystallization
from
ethanol/ethyl
They can
can be used
used
preparation
of
three-dimensional
mesoporous
ethanol/ethyl acetate
acetate [143].
[143]. They
preparation
of
three-dimensional
mesoporous
used in
in
in
materials
materialsfor
forseparations,
separations,catalysis
catalysisand
anddrug
drugdelivery
delivery[143].
[143].
materials
for
separations,
catalysis
and
drug
delivery
[143].
H222N
N
H
Br
(( ))n-2
n-2 Br
Br
Br
n={3,6,8,10}
n={3,6,8,10}
in C
C22H
H55OH
OH
in
80°C,
°C, 36h
36h
80
N
N
0°C, 2h
COCl
COCl
O
O
Dehydroabietyl
Dehydroabietyl
chloride
chloride
C
C
N
N
H
H
Br
Br
O
O
N
N
C
C
3-(N,N-dimethyl)-propyl
3-(N,N-dimethyl)-propyl
dehydroabietamide
N
N
H
H
N
N
Br
Br
( )n-2
n-2 N
N
N
N
H
H
C
C
O
O
Rosin-based Gemini
Gemini surfactant
surfactant
Rosin-based
Scheme 33.
33. Synthesis
Synthesis of
of rosin-based
rosin-based gemini
gemini surfactant.
surfactant.
Scheme
Rosin-based
cyclic tricarbonate
tricarbonate is
brownsolid.
solid.It
It can
be prepared
maleopimaric
Rosin-based cyclic
tricarbonate
isisaaabrown
brown
solid.
It can
can
be prepared
prepared
fromfrom
maleopimaric
acid
Rosin-based
be
from
maleopimaric
acid
acid
triglycidyl
and carbon
dioxide
according
to Scheme
34, to
prior
to washing
and vacuum
triglycidyl
ester ester
and carbon
carbon
dioxide
according
to Scheme
Scheme
34, prior
prior
to
washing
and vacuum
vacuum
drying
triglycidyl
ester
and
dioxide
according
to
34,
washing
and
drying
drying
[132].
Its applications
synthesis
of quaternary
ammonium
salt derivatives
and
[132]. Its
applications
includeinclude
synthesis
of quaternary
ammonium
salt derivatives
[132] [132]
and nonnon-isocyanate
polyurethanes
[200].
Rosin-based
carbamate
group-containing
quaternary
ammonium
isocyanate polyurethanes
polyurethanes [200].
[200]. Rosin-based
Rosin-based carbamate
carbamate group-containing
group-containing quaternary
quaternary ammonium
ammonium
isocyanate
salt
derivatives are
are brown
brownsolids.
solids.They
They
be prepared
rosin-based
tricarbonate,
salt derivatives
are
brown
solids.
They
cancan
be prepared
prepared
fromfrom
rosin-based
cycliccyclic
tricarbonate,
N,Nsalt
can
be
from
rosin-based
cyclic
tricarbonate,
N,NN,N-dimethylaminopropylamine
and alkyl
bromides
according
to Scheme
and vacuum
using vacuum
dimethylaminopropylamine and alkyl
bromides
according
to Scheme
34, and34,
using
drying
drying
and recrystallization
[132].exhibit
They exhibit
strong
antimicrobial
properties
and recrystallization
recrystallization
[132]. They
They
exhibit
strong antimicrobial
antimicrobial
properties
[132]. [132].
and
[132].
strong
properties
[132].
CO22
O
O
Maleopimaric acid
acid
Maleopimaric
triglycidyl ester
ester
triglycidyl
O
O
O
O
O
O
O
O
O
O
COO
COO
O
O
O
O
O
R N
N
R
H
H
O
O
N
N
R=
R=
Rosin-base
carbamate
yield: 92%
92%
yield:
R N
N
R
H
H
COO
COO
or:
R=
R=
N
N
O
O
OH
OH
O
O
O
O
Rosin-based
Rosin-based
cyclic carbonate
carbonate
cyclic
O
O
yield: 89%
89%
yield:
O
O
2, or
or 5,
5, or
or 11
11
nn == 2,
O
O
O
O
OH
OH
O
O
Br(CH222))nnnCH
CH333
Br(CH
O
O
O
O
O
O
in ethanol; 70°C, 15h
O
O
H
H
R N
N
R
in ethanol
ethanol
in
75°C, 2h
2h
75°C,
H222N
N
H
N
N
O
O
O
O
O
O
O
O
O
O
N
N
H
H
R N
N
R
O
O
O
O
LiBr/ethane-1,2-diol
O
O
in NMP
NMP
in
110°C, 2MPa
2MPa
110°C,
7h
7h
O
O
O
COO
COO
O
O
COO
COO
R N
N
R
H
H
Br
Br
N
N
(CH222))nnnCH
CH333
(CH
N
N
(CH222))nnnCH
CH333
(CH
Br
Br
Rosin-basedcarbamate
group-containing quaternary
quaternary
group-containing
ammonium salt
salt derivative
derivative
ammonium
yield: 78%,
78%, or
or 85%,
85%, or
or 80%
80%
yield:
R N
N
R
H
H
Br
Br
N
N
(CH222))nnnCH
CH333
(CH
Scheme34.
34.Synthesis
Synthesis
of rosin-based
rosin-based
carbamate
and carbamate
carbamate
group-containing
quaternary
Scheme
34.
Synthesis
of
carbamate
and
group-containing
quaternary
Scheme
of rosin-based
carbamate
and carbamate
group-containing
quaternary ammonium
ammonium
salt derivatives.
derivatives.
ammonium
salt
salt
derivatives.
Molecules 2019, 24, 1651
18 of 52
Molecules
Molecules 2019,
2019, 24,
24, xx FOR
FOR PEER
PEER REVIEW
REVIEW
Molecules 2019, 24, x FOR PEER REVIEW
18
18 of
of 51
51
18 of 51
Maleopimaric
acid diethanolamide
diethanolamideis
solid.It
It can
be
synthesized
from
maleopimaric
Maleopimaric
be
from
maleopimaric
acid
and
Maleopimaric acid
acid
diethanolamide
isisaaasolid.
solid.
It can
can
be synthesized
synthesized
from
maleopimaric
acidacid
and
Maleopimaric acid
diethanolamide
is a35solid.
It It
can
bebe
synthesized
from
maleopimaric
acid and
and
diethanolamine
according
to
Scheme
[103].
can
applied
as
a
dispersant
and
a
viscosity
diethanolamine
diethanolamine according
according to
to Scheme
Scheme 35
35 [103].
[103]. It
It can
can be
be applied
applied as
as aa dispersant
dispersant and
and aa viscosity
viscosity
diethanolamine
according to Scheme
35 [103]. It can be applied as a dispersant and a viscosity
depressant
depressant
in
coal-water
slurry
[103].
depressant in
in coal-water
coal-water slurry
slurry [103].
[103].
depressant in coal-water slurry [103].
OH
OH
OH
O
O
O
N
N
N
O
O
O
Maleopimaric
Maleopimaric
Maleopimaric
acid
acid
acid
OH
OH
OH
KOH
KOH
KOH 4h
160°C,
160°C,
4h
160°C, 4h
O
O
O
COOH
COOH
COOH
O
O
O
O
O
O
N
N
N
OH
OH
O
OH O
O
OH
OH
OH
N
N
N
OH
OH
OH
OH
OH
OH
N
N
N
OH
OH
OH
Maleopimaric
Maleopimaric acid
acid
Maleopimaric
acid
diethanolamide
diethanolamide
diethanolamide
OH
OH
OH
Scheme
Scheme 35.
35. Synthesis
Synthesis of
of maleopimaric
maleopimaric acid
acid diethanolamide.
diethanolamide.
Scheme 35. Synthesis of maleopimaric acid diethanolamide.
Acrylpiamric
Acrylpiamric acid
acid salts
salts of
of calcium
calcium and
and zinc
zinc are
are solids.
solids. They
They can
can be
be prepared
prepared from
from acrylpimaric
acrylpimaric
Acrylpiamric acid salts of calcium and zinc are solids. They can be prepared from acrylpimaric
acid,
acid, sodium
sodium hydroxide
hydroxide and
and calcium
calcium chloride
chloride or
or zinc
zinc sulfate
sulfate according
according to
to Scheme
Scheme 36
36 and
and using
using such
such
acid, sodium hydroxide and calcium chloride or zinc sulfate according to Scheme 36 and using such
separation
methods
as
washing,
filtration
and
drying
[137].
They
can
be
used
stabilizer
They
can
be
used
as
a
separation methods as washing, filtration and drying [137]. They can be used as a stabilizer of
of
separation methods as washing, filtration and drying [137]. They can be used as a stabilizer of
poly(vinyl
showing
better
thermal
stability
than
commercial
Ca/Zn
stearate
[137].
poly(vinyl chloride)
chloride) showing
showing better
betterthermal
thermalstability
stabilitythan
thancommercial
commercialCa/Zn
Ca/Znstearate
stearate[137].
[137].
poly(vinyl chloride) showing better thermal stability than commercial Ca/Zn stearate [137].
COO
COO
COO
ZnSO
ZnSO44** 7H
7H22O
O
ZnSO4* 7H2O
22
COO
COO
COO
Zn
Zn2
Zn
Zinc
Zinc acrylpimarate
acrylpimarate
Zinc acrylpimarate
COOH
COOH
COOH
NaOH
NaOH
NaOH
NaOH
NaOH
NaOH
in
in
in acetone/water
acetone/water
in acetone/water
acetone/water
in water/ethanol
acetone/water
in water/ethanol
acetone/water
water/ethanol
water/ethanol
water/ethanol
water/ethanol
-15-50°C
-15-50°C
COOH
-15-50°C
-15-50°C
COOH
-15-50°C
-15-50°C
COOH
27h
27h
27h
27h
Acrylpimaric
acid
Acrylpimaric
acid
27h
27h
Acrylpimaric acid
COO
COO
COO
CaCl
CaCl22
CaCl2
22
COO
COO
Ca
Ca2
Ca
Calcium
acrylpimarate
Calcium COO
acrylpimarate
Calcium acrylpimarate
Scheme
36.
acid
divalent
metal
salts.
Scheme 36.
36. Synthesis
Synthesis of
of acrylpimaric
acrylpimaric acid
acid divalent
divalent metal
metal salts.
salts.
Scheme
Synthesis
of
acrylpimaric
Synthesis
of
acrylpimaric
Rosin-derived
binapthyl-appended
22-crown-6
ether
can
from
Rosin-derivedbinapthyl-appended
binapthyl-appended
22-crown-6
ether
can be
be synthesized
synthesized
from methyl
methyl
Rosin-derived
22-crown-6
ether can
be synthesized
from methyl maleopimarate,
Rosin-derived
binapthyl-appended
22-crown-6
ether
can be synthesized
from methyl
maleopimarate,
sodium
borate
and
sodium
hydride
according
to
Scheme
37
It
can
maleopimarate,
sodium
borate
and
sodiumto
hydride
according
to
Scheme
37in[184].
[184].
Itenantioselective
can be
be used
used in
in
sodium
borate
and
sodium
hydride
according
Scheme
37
[184].
It
can
be
used
highly
maleopimarate, sodium borate and sodium hydride according to Scheme 37 [184]. It can be used in
highly
enantioselective
reactions
because
of
its
amines
enantiomeric
recognition
ability
[184].
Very
highly
enantioselective
reactions
because
of
its
amines
enantiomeric
recognition
ability
[184].
Very
reactions
because of its amines
enantiomeric
ability [184]. Very
similar compounds
be
highly
enantioselective
reactions
because of recognition
its amines enantiomeric
recognition
ability [184].can
Very
similar
compounds
can
also
synthesized
directly
from
or
similar
compounds
can be
be
also
synthesizedor
directly
from maleopimaric
maleopimaric
or fumaropimaric
fumaropimaric acid
acid [201].
[201].
also
synthesized
directly
from
maleopimaric
fumaropimaric
acid
[201].
similar compounds can be also synthesized directly from maleopimaric or fumaropimaric acid [201].
O
O
O
O
O
O
COO
COO
COO
O
O
O
Methyl
Methyl maleopimarate
maleopimarate
Methyl maleopimarate
OH
OH
OH
OH
OH
OH
NaBH
NaBH44
NaBH4
dioxane
dioxane
dioxane
0.5h
0.5h
0.5h
COO
COO
COO
O
O
O
O
O
O
NaH
NaH
NaH
in
in THF
THF
in THF
50h
50h
50h
Rosin-based
Rosin-based diol
diol (yield:
(yield: 53%)
53%)
Rosin-based diol (yield: 53%)
O
O
O
O
O
O
O
O
O
O
O
O
COO
COO
COO
Rosin-derived
Rosin-derived
Rosin-derived
binaphthyl-appended
binaphthyl-appended 22-crown-6
22-crown-6 ether
ether
binaphthyl-appended 22-crown-6 ether
Scheme
Scheme 37.
37. Synthesis
Synthesis of
of rosin-derived
rosin-derived binapthyl-appended
binapthyl-appended 22-crown-6
22-crown-6 ether.
ether.
Scheme
Scheme 37.
37. Synthesis
Synthesis of
of rosin-derived
rosin-derived binapthyl-appended
binapthyl-appended 22-crown-6
22-crown-6 ether.
ether.
3.2.5.
3.2.5. Biologically
Biologically Active
Active Compounds
Compounds
3.2.5.
Biologically
Active
Compounds
Biologically
Active
Compounds
Pure
abietic
acid
isolated
from
rosin
and
its
derivatives
exhibit
many
potential
activities
of
Pure abietic
abietic acid
acid isolated
isolated from
from rosin
rosin and
and its
its derivatives
derivatives exhibit
exhibit many
many potential
potential activities
activities of
of
Pure
interest
to
the
pharmaceutical
industry,
for
example,
antitumor,
anti-inflammatory,
antimycotic
and
interest to
the
pharmaceutical
industry,
for example,
antitumor,
anti-inflammatory,
antimycotic
and
interest
tothe
thepharmaceutical
pharmaceuticalindustry,
industry,
example,
antitumor,
anti-inflammatory,
antimycotic
to
forfor
example,
antitumor,
anti-inflammatory,
antimycotic
and
anti-arteriosclerotic
properties
and
uses
in
treating
digestive
canal,
acute
and
chronic
gastritis,
and
anti-arteriosclerotic
properties
and
uses
in
treating
digestive
canal,
acute
and
chronic
gastritis,
and
and anti-arteriosclerotic
properties
and uses
in treating
digestive
and chronic
gastritis,
anti-arteriosclerotic
properties
and uses
in treating
digestive
canal,canal,
acuteacute
and chronic
gastritis,
and
erosive
gastritis,
allergy,
asthma,
arthritis
and
psoriasis
[202].
In
this
subsection
rosin-based
chemicals
erosive
gastritis,
allergy,
asthma,
arthritis
and
psoriasis
[202].
In
this
subsection
rosin-based
chemicals
and erosive
gastritis,
allergy,
asthma,
arthritis
and psoriasis
In this subsection
rosin-based
erosive
gastritis,
allergy,
asthma,
arthritis
and psoriasis
[202]. In[202].
this subsection
rosin-based
chemicals
with
main
applications
as
biologically
active
compounds
can
be
found.
They
include
both
with
main
applications
as
biologically
active
compounds
can
be
found.
They
include
both
chemicals
main applications
as biologically
compounds
found.They
Theyinclude
include both
with
mainwith
applications
as biologically
active active
compounds
can can
be be
found.
medications
and
biocides.
Their
synthetic
routes
are
usually
characterized
in
detail
and,
from
the
medications
and
biocides.
Their
synthetic
routes
are
usually
characterized
in
detail
and,
from
the
medications and
and biocides.
biocides. Their
Their synthetic
synthetic routes
routes are
are usually
usually characterized
characterized in
in detail
detail and,
and, from the
medications
chemical
point
of
view,
their
TRLs
are
rather
high.
It
is
worth
noting,
that
although
the
sustainability
chemical
point
of
view,
their
TRLs
are
rather
high.
It
is
worth
noting,
that
although
the
sustainability
chemical point of view, their TRLs are rather high. It is
is worth
worth noting,
noting, that
that although
although the
the sustainability
sustainability
of
of their
their syntheses
syntheses is
is usually
usually worse
worse than
than for
for other
other rosin
rosin derivatives
derivatives (due
(due to
to the
the necessity
necessity of
of using
using more
more
of their syntheses is usually worse than for other rosin derivatives (due to the necessity of using more
dangerous
dangerous chemicals),
chemicals), it
it is
is still
still better
better than
than their
their petrochemical
petrochemical counterparts
counterparts (thanks
(thanks to
to the
the use
use of
of biobiodangerous chemicals), it is still better than their petrochemical counterparts (thanks to the use of biobased
rosin
as
a
main
substrate).
based rosin as a main substrate).
based rosin as a main substrate).
Methyl dehydroabietate is a white solid. It can be prepared from dehydroabietyl chloride and
methanol according to Scheme 38, prior to vacuum evaporation and recrystallization [141]. It can be
used as a substrate in the synthesis of antimicrobial agents and medicines [141,150].
Methyl 7-oxodehydroabietate is a yellow oil. It can be prepared from methyl dehydroabietate
and
chromium
trioxide according to Scheme 38, followed by extraction, drying and column
Molecules
2019, 24, 1651
19 of 52
chromatography [141]. It can be used as a substrate in synthesis of antimicrobial agents and medicines
Molecules 2019, 24, x FOR PEER REVIEW
19 of 51
[141,150].
dangerous
chemicals),acid
it isderivative
still better QC4
than can
theirbe
petrochemicalfrom
counterparts
(thanks to the use of
Dehydroabietic
methyl
7-oxodehydroabietate,
Methyl
dehydroabietate
is a white solid.
It can prepared
be prepared from
dehydroabietyl
chloride and
bio-based
rosin
as
a
main
substrate).
phenylhydrazine
hydrochloride,
1,2-dibromoethane
and
N-methyl
piperazine,
according
methanol according to Scheme 38, prior to vacuum evaporation and recrystallization [141].toItScheme
can be
Methyl dehydroabietate
is a white
solid. It
canand,
be prepared
from
dehydroabietyl
chloride
and
38 [141,150].
It shows
antimicrobial
properties
[150]
moreover,
induces
gastric cancer
cell death
used
as a substrate
in the
synthesis of
antimicrobial
agents
and medicines
[141,150].
methanol
according
to
Scheme
38,
prior
to
vacuum
evaporation
and
recrystallization
[141].
It
can
via oncosis
apoptosis [151]. Another
dehydroabietic
derivativefrom
QC2methyl
is reported
to be ablebe
to
Methyland
7-oxodehydroabietate
is a yellow
oil. It canacid
be prepared
dehydroabietate
used
as
a
substrate
in
the
synthesis
of
antimicrobial
agents
and
medicines
[141,150].
inhibit
skin
cancer
cell
lines
[203].
and chromium trioxide according to Scheme 38, followed by extraction, drying and column
chromatography [141]. It can be used as a substrate in synthesis of antimicrobial agents and medicines
CrO3
COO
Dehydroabietyl
HN NH2
[141,150].
N
chloride
3COO)2O QC4 can be prepared from methyl 7-oxodehydroabietate,
Dehydroabietic acid (CH
derivative
CH3OH
CH3COOH
O
phenylhydrazine hydrochloride, 1,2-dibromoethane
and N-methyl
according to Scheme
N
Br(CH2piperazine,
)2Br
25°C/12h
H
N
38 [141,150].2hIt shows antimicrobial properties [150] and, moreover, induces gastric cancer cell death
HCl
K
CO
2
3
TBAB
via oncosis and apoptosis [151]. Another dehydroabietic
acid derivative
QC2
to
in EtOH
KI is reported to be able
NaOH
N
4h
COO [203].
COO
in CH3CN
25°C
inhibit skin cancer cell lines
Methyl
Methyl 7-oxoyield:
yield:
N
yield:
COCl dehydroabietateCrO dehydroabietate
61%
QC4
3
56%
COO
18-67%
Dehydroabietyl yield: 92%
HN NH2
yield: 64%
N
chloride
(CH COO) O
3
2
Scheme
38. Synthesis
Synthesis of
of dehydroabietic
dehydroabietic
derivative QC4.
QC4.
Scheme
38.
derivative
CH3COOH
O
CH3OH
Br(CH2)2Br
25°C/12h
2h
N
H
N
Methyl
7-oxodehydroabietate is a yellow
oil. It can
be their
prepared
from
methyl
dehydroabietate
N-(2-methyl-naphthyl)maleopimaric
acid diimides
and
methyl
esters
are white
solids (m.p.
HCl
K
2CO3
TBAB
in
EtOH
KI
NaOH
and
chromium
trioxide
to Scheme
38, followed acid,
by
extraction,
drying and column
215-290°C).
They
can beaccording
synthesized
from maleopimaric
2-methyl-1-naphtylamine
N and
4h
COO
COO
in CH3CN
25°C
chromatography
[141].
It
can
be
used
as
a
substrate
in
synthesis
of
antimicrobial
agents
and
dimethyl sulfate according
to
Scheme
39,
and
using
separation
methods
such
as
extraction,
washing,
Methyl
Methyl 7-oxoyield:
yield:
N
yield:
medicines
[141,150].
drying, evaporation
and
recrystallization
[106,107].
They
show
significant
antitumor
cytotoxicity
dehydroabietate 61%
COCl dehydroabietate
QC4
56%
18-67%
yield:acid
92%
yield:
64%
Dehydroabietic
derivative
QC4
can beNCI
prepared
methyl
7-oxodehydroabietate,
against
several human
cancer
cell lines,
especially
cells andfrom
MGC-803
cells
[106].
phenylhydrazine
hydrochloride,
1,2-dibromoethane
and N-methyl
piperazine,
accordingthey
to
Anticancer effects
of various rosin
derivatives, especially
thioureas, were
also investigated;
Scheme 38. Synthesis of dehydroabietic derivative QC4.
Scheme
[141,150]. Itcytotoxicity
shows antimicrobial
properties
[150]
and, moreover,
induces
showed38
significantly
toward diverse
human
carcinoma
cell lines
[108].gastric cancer cell
deathN-(2-methyl-naphthyl)maleopimaric
via oncosis and apoptosis [151]. Another
dehydroabietic
acid
derivative
is reported
to be
acid diimides and their methyl esters QC2
are white
solids (m.p.
R
R
O
NH
2
able
to
inhibit
skin
cancer
cell
lines
[203].
215-290°C).O They can be synthesized from maleopimaric acid, 2-methyl-1-naphtylamine and
N
N
N-(2-methyl-naphthyl)maleopimaric
acid
diimides
and their
methyl
are white
solids
O using
O esters
O
O
(CH
dimethyl
sulfateO according to Scheme
39, and
separation
methods
such
as extraction,
washing,
3)2SO4
◦
R=
or
(m.p.
215–290
C).
They
can
be
synthesized
from
maleopimaric
acid,
2-methyl-1-naphtylamine
and
drying, evaporation and recrystallization [106,107]. They show significant antitumor cytotoxicity
K2CO3
dimethyl
sulfate
according
to
Scheme
39,
and
using
separation
methods
such
as
extraction,
washing,
(C2H
5)3N
against several human
cancer
cell lines, especially in
NCI
cells and MGC-803 cells [106].
acetone
hexamethyl
disilazane
drying,
evaporation
and
recrystallization
[106,107].
They
significant
cytotoxicity
reflux,
6h show
Anticancer effects
of various rosin derivatives, especially
thioureas,
wereantitumor
also investigated;
they
in DMF
against
several
human
cancer
cell
lines,
especially
NCI
cells
and
MGC-803
cells
[106].
COOH
COO
reflux,
4h
showed significantly
cytotoxicity
toward diverse
human carcinoma cell lines [108].
COOH
O
Maleopimaric
O
acid
NH2
O
R
(2-methyl-naphthy)
N
maleopimaric
acid
diimides
O
O
(CH3)2SO4
yield: 30-41%
R
(2-methyl-naphthy) methyl
N
maleopimaric
Oacid diimides
O
yield: 46-53% R =
or
K2CO3
(C2H39.
5)3NSynthesis of N-(2-methyl-naphthyl)maleopimaric
Scheme
acid diimides.
in acetone
hexamethyl disilazane
reflux, 6h
in DMF
Thiadiazole
amides of dehydroabietic
or acrylpimaric COO
acids can
COOH
reflux, 4h
COOH group-containing
be prepared
from adequate rosin acid, thiosemicarbazide and an acyl chloride according to Scheme 40, and using
such
separation methods as filtration,
vacuum drying, recrystallization
and column
chromatography
Maleopimaric
(2-methyl-naphthy)
(2-methyl-naphthy)
methyl
[130].
applied as insecticides
[130,190].
acid They can be potentiallymaleopimaric
acid diimides
maleopimaric acid diimides
yield: 30-41%
yield: 46-53%
Scheme 39.
39. Synthesis
N-(2-methyl-naphthyl)maleopimaric acid
acid diimides.
diimides.
Scheme
Synthesis of
of N-(2-methyl-naphthyl)maleopimaric
Thiadiazoleeffects
group-containing
amides
of dehydroabietic
acrylpimaric
acidsinvestigated;
can be prepared
Anticancer
of various rosin
derivatives,
especially or
thioureas,
were also
they
from adequate
rosin acid,
thiosemicarbazide
and human
an acyl carcinoma
chloride according
Scheme 40, and using
showed
significantly
cytotoxicity
toward diverse
cell linesto
[108].
suchThiadiazole
separation methods
as filtration,
vacuum
drying, recrystallization
andacids
column
chromatography
group-containing
amides
of dehydroabietic
or acrylpimaric
can be
prepared from
[130]. They
can acid,
be potentially
applied asand
insecticides
[130,190].
adequate
rosin
thiosemicarbazide
an acyl chloride
according to Scheme 40, and using such
separation methods as filtration, vacuum drying, recrystallization and column chromatography [130].
They can be potentially applied as insecticides [130,190].
in POCl3
reflux, 4h
(C2H5)3N
in CH2Cl2
0°C, 12h
COOH
O
NH
H2N
S
Dehydroabietic acid
amide with thiadiazole
group yield:78-86%
Molecules 2019, 24, x FOR PEER REVIEW
S
NH2 Scheme 40.
O
N
R
Cl
H
R
in P OCl3
reflux, 4h
N
N
Dehydroabietic
acid 2019, 24, 1651
Molecules
N
H
COOH
Acrylpimaric
acid
O
O
R
(C2H5)3N
in CH2Cl2
0°C, 12h
NH
S
N
N
20 of 52
Acrylpimaric acid amide with
20 of 51
thiadiazole groups yield:58-85%
Synthesis of rosinRacid
amides
with thiadiazole groups.
= {-CH
3, -C6H11, -C6H5, -C6H5R' }
R
R
Cl
N
COOH
N
NH
S
H2N
O
Acrylpimaric
acid-based aromatic
diacylthioureas can SbeNHprepared
from acrylpimaryl
2
O
O
in POCl3
(C
H
)
N
2 5 3
NH
R
dichloride, potassium thiocyanate
and aromatic
amines according
to
Scheme
41,
prior to vacuum
N
O
H2N
R
Cl
reflux, 4h
H
in CH2Cl2
S They may be applied as botanical herbicides showingRhigher
evaporation and recrystallization
[129].
in
P
OCl
0°C,
12h
(C2H5)3N
3
COOH
N
NH
reflux,
4h
activity than similar dicarboxamide, dihydrazone
and diimide
compounds
[129].
Moreover,
some
in CH2Cl
N
2
S
0°C,Staphylococcus
12h
Dehydroabietic
Dehydroabietic
acidactivities against
acrylpimaryl
diimides possess
antibacterial
Gram-positive
aureus and
COOH
N
acid
amide
with
thiadiazole
Gram-negative Escherichia coli [204]. Furthermore, some acrylpimaryl dicarboxamidesN show
Acrylpimaric
Acrylpimaric acid amide with
group yield:78-86%
antibacterial properties against E. coli, whereas their
Gram-positive
bacteria was
acid activity against
thiadiazole
groups yield:58-85%
significantly lower [205].
Scheme
40.
of
amides
thiadiazole
Solid acrylpimaryl
quaternary
ammonium
salts
canwith
be synthesized
from acrylpimaryl acid,
Scheme
40. Synthesis
Synthesis
of rosin
rosin acid
acid
amides
with
thiadiazole groups.
groups.
oxalyl chloride, epichlorohydrin and volatile tertiary amines according to Scheme 41 and using such
Acrylpimaric
acid-basedaromatic
aromatic
diacylthioureas
be prepared
from acrylpimaryl
Acrylpimaric
acid-based
diacylthioureas
can and
becan
prepared
from acrylpimaryl
dichloride,
separation
methods
as vacuum distillation,
extraction
recrystallization
[189]. They
show
dichloride,
potassium thiocyanate
and
aromatic
aminestoaccording
to prior
Scheme
41, priorevaporation
to vacuum
potassium
thiocyanate
and
aromatic
amines
according
Scheme
41,
to
vacuum
fungicidal activity and can be applied in wood preservation [189]. Very similar acrylpimaryl
evaporation
and recrystallization
[129].
mayasbe
applied herbicides
as botanical
herbicides
showing
higher
and recrystallization
[129]. They
may
beThey
applied
botanical
showing
higher
activity
than
materials
that can be applied
as surfactants
were also
prepared [133]. Another
fungicidal
rosin-based
activity
than
similar
dicarboxamide,
dihydrazone
and
diimide
compounds
[129].
Moreover,
some
similar dicarboxamide,
dihydrazone
and
diimide
[129]. Moreover,
acrylpimaryl
materials
can be prepared
in similar
way
fromcompounds
rosin, epichlorohydrin
and some
amines
[134–136].
acrylpimaryl
diimides
possessactivities
antibacterial
activities
against Gram-positive
Staphylococcus
aureus and
diimides
possess
antibacterial
against
Gram-positive
Staphylococcus
aureus
and
Gram-negative
Maleopimaryl chloride is a yellowish solid. It can be prepared from maleopimaric acid and oxalyl (or
Gram-negative
Escherichia
coli [204].
some acrylpimaryl
dicarboxamides show
Escherichia
coli [204].
Furthermore,
some30Furthermore,
acrylpimaryl
dicarboxamides
show antibacterial
thionyl)
chloride,
according
to Scheme
or 42, prior to
vacuum distillation
and washingproperties
[104,105].
antibacterial
properties
against
E.
coli,
whereas
their
activity
against
Gram-positive
bacteria
against
E.
coli,
whereas
their
activity
against
Gram-positive
bacteria
was
significantly
lower
[205].was
It can be used as an intermediate in preparation of surfactants [104] or fungicides [105].
significantly lower [205].
Solid acrylpimaryl
quaternary ammonium
salts can be synthesized
from acrylpimaryl
acid,
Acrylpimaryl
diacarboxamide
Acrylpimaryl
diacylthiourea
R = {-H, -CH3, -(CH3)2, -OCH3,
,
-F,
-Cl,
-Br,
-OH,
-NO
}
-CF
oxalyl
chloride,
epichlorohydrin
and
volatile
tertiary
amines
according
to
Scheme
41
and
using
such
compound yield:58-85%
compound yield:60-77%
3
2
O
O
S
separation methods as vacuum distillation, extraction and recrystallization [189]. They show
NH2
1. KSCN [189]. Very similar Cacrylpimaryl
C
fungicidal
activity and can be applied
in wood preservation
N
R
HN
NH
H
materials that can be applied as surfactants were also prepared [133]. Another fungicidal rosin-based
R
2. H2N
materials can be prepared in similar way from rosin, epichlorohydrin and amines R[134–136].
COCl
Maleopimaryl chloride is a yellowish
from maleopimaric acid and oxalyl (or
(C2H5)3Nsolid. It can be prepared
in acetonitrile
R
H
Cand
NH washing
25°C,
4h
in
CH
Cl
;
<5°C,
12h
thionyl) chloride,
according to 2Scheme
30 or 42, prior to vacuum distillation
[104,105].
N C
2
N
H
O
R
R
O
It can be used as an intermediate in preparation of surfactants 1.[104]
or
fungicides
[105].
S
NH3*H2O
O
N
C
Acrylpimaryl diacarboxamide
N
H
compound yield:58-85%
O
HN
C
R
R = {-H, -CH3, -(CH3)2, -OCH3,
COCl
-NO2 }
-CF3, -F, -Cl, -Br, -OH,
R
NH2
C
1. in THF
2. in EtOH
0-25°C, 17hR
R
N
H
1. N2H4
2. CHO
N
O
Acrylpimaryl dihydrazone
(C2H5)3N
R
in CH2Cl2; <5°C, 12h
compound
yield:45-60%
N C
R
H
Acrylpimaryl
chloride
COCl
2. LiAlH4
3. CHO
R
Acrylpimaryl diacylthiourea
N
compound
yield:60-77%
O
1. KSCN
R
1. in THF
2. in THF
2. H23.N in EtOH
0-25°C, 17h
O
in acetonitrile
25°C, 4h
R
C
S
N
H
NH
R
R
N
Acrylpimaryl diimide
H
C NH
compound
Nyield: 22-59%
O
S
R
1. diacylthioureas,
NH3*H2O
Scheme
41.O Synthesis
acid-based
dicarboxamides,
Scheme 41.
Synthesis ofof acrylpimaric
acrylpimaric
acid-based aromatic
aromatic
diacylthioureas,
dicarboxamides,
1. N2H4
2. LiAlH
4
2.
N
dihydrazones
and
diimides.
CHO
3.
CHO
dihydrazones
C and diimides.
N
H
COCl
N
R
R
Solid acrylpimaryl quaternary ammonium
salts can be synthesized
from acrylpimaryl acid,
Acrylpimaryl
R
oxalyl chloride, epichlorohydrin and volatilechloride
tertiary amines according to Scheme 41 and using such
R
1. in THF
1. in THF
R
separation methods
as vacuum distillation,
extraction and recrystallization
[189]. They show fungicidal
2. in EtOH
2. in THF
R
C N
N
0-25°C, preservation
17h
in EtOHacrylpimaryl materials that can
activity Hand can be applied in wood
[189]. Very 3.similar
N
0-25°C, 17h
O
be applied as surfactants were also prepared [133]. Another fungicidal rosin-based materials can be
Acrylpimaryl dihydrazone
Acrylpimaryl diimide
prepared
in similar
way from rosin, epichlorohydrin and amines [134–136]. Maleopimaryl
chloride
is a
compound
yield:45-60%
compound yield:
22-59%
yellowish solid. It can be prepared from maleopimaric acid and oxalyl (or thionyl) chloride, according
Scheme30 41.
Synthesis
acrylpimaric
aromatic
diacylthioureas,
to Scheme
or Scheme
42,ofprior
to vacuumacid-based
distillation
and washing
[104,105]. dicarboxamides,
It can be used as an
dihydrazones and diimides.
intermediate in preparation of surfactants [104] or fungicides [105].
Molecules 2019, 24, 1651
21 of 52
Molecules 2019,
2019, 24,
24, xx FOR
FOR PEER
PEER REVIEW
REVIEW
Molecules
21 of
of 51
51
21
COCl
COCl
COCl
R ==
= CH
CH33 or
or CH
CH CH
CH
R
R
CH
3 or CH222CH333
COO
COO
COO
OH
OH
OH
1.NaOH
NaOH
1.
1.
NaOH
2.
2.
2.
O
O
O
Cl
Cl
Cl
in CH
CH222Cl
Cl222
in
50°C, 4h
4h
50°C,
COCl
COCl
COCl
Cl
Cl
Cl
OH
OH
OH
COO
COO
COO
Acrylpimaryl dichloride
dichloride
Acrylpimaryl
R
R
R
R
R
R
N
N
N
COO
COO
COO
OH
OH
OH
R
R
R
OH
OH
OH
(C222H
H555))333N
N
(C
in alcohol
alcohol
in
85°C, 3.5h
3.5h
85°C,
Cl
Cl
Cl
R
R
R
N
N
N
COO
COO
COO
Cl
Cl
Cl
R
R
R
N R
R N
R
R
N
R
R
R
R
R
Cl
Cl
Cl
R
R
R
Acrylpimaryl quaternary
quaternary
Acrylpimaryl
ammonium salt
salt yield:
yield: 71-82%
71-82%
ammonium
Scheme 42.
42. Synthesis
Synthesis
of acrylpimaryl
acrylpimaryl quaternary
quaternary ammonium
ammonium salts.
salts.
Scheme
Synthesis of
of
acrylpimaryl
quaternary
◦
Maleated rosin-based
dithioureacompounds
compoundsare
areyellow
yellowsolids
solids(m.p.
(m.p.162–216
162–216
They
rosin-based dithiourea
dithiourea
compounds
are
yellow
solids
(m.p.
162–216
°C).C).
They
cancan
be
Maleated
°C).
They
can
be
be
prepared
from
maleated
rosin
acyl
chloride,
hydrazine
and
substituted
benzoyl
isothiocyanates,
prepared from
from maleated
maleated rosin
rosin acyl
acyl chloride,
chloride, hydrazine
hydrazine and
and substituted
substituted benzoyl
benzoyl isothiocyanates,
prepared
according to
to Scheme
Scheme 43,
43, and
and
using
separation
methods
such
as
rotary
recrystallization
and using
using separation
separation methods
methods such
such as
as rotary
rotary evaporation,
evaporation, recrystallization
recrystallization
according
evaporation,
and
column
chromatography
[105].
They
can
be
potentially
used
as
fungicides
[105].
column
chromatography
[105].
potentially
used
as
fungicides
[105].
and column chromatography [105]. They can be potentially used as fungicides [105].
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
N22H
H ** H
HO
O
N
N
2H444* H222O
in benzene
benzene
in
<80°C, 5h
5h
<80°C,
in CH
CH222Cl
Cl222
in
0-25°C, 4h
4h
0-25°C,
Maleated rosin
rosin
Maleated
R ==
= {{{ H;
H; -CH
-CH33;;; -OCH
-OCH ;; -Cl
-Cl }}
R
R
H;
-CH
3 -OCH333; -Cl }
O
O
O
O
O
O
NCS
NCS
NCS
N
N
N
R
R
R
NH22
NH
NH
2
COCl
COCl
COCl
C
C
C
NH
NH
NH
O
O
O
in acetonitrile
acetonitrile
in
reflux, 44hh
reflux,
C
C
C
O
O
O
O
O
O
Maleated rosin
rosin
Maleated
acyl chloride
chloride
acyl
yield: 85%
85%
yield:
R
R
R
N
N
N
O
O
O
O
O
O
Cl S
S Cl
Cl
Cl
Cl
S
Cl
COOH
COOH
COOH
NH22
NH
NH
2
Maleated rosin
rosin
Maleated
hydrazide yield:
yield: 75%
75%
hydrazide
H
H
H
N
N
N N
N
N
H
H
H
O
O
O
H
H
H
N
N
N
NH
NH
NH
S
S
S
H
H
H
N
N
N
S
S
S
O
O
O
R
R
R
Maleated rosin-based
rosin-based
Maleated
dithiourea
dithiourea
Scheme 43. Synthesis
Synthesis of maleated
maleated rosin-based dithiourea
dithiourea compounds.
Scheme
Scheme 43.
43. Synthesis of
of maleated rosin-based
rosin-based dithiourea compounds.
compounds.
be prepared
prepared from
from dehydroabietic
dehydroabietic acid
acid and
and glucose
glucose according
according to
to
Glucose
Glucose dehydroabietate
dehydroabietate can
can be
Scheme 44
44 prior
prior to
to vacuum
vacuum distillation,
distillation, filtration
filtration and
and washing
washing [206].
[206]. Its
Its potential
potential application
is as
as aa
Scheme
application is
surfactant in
in food
food industry
industry [206].
[206].
surfactant
OH
OH
OH
HO
HO
HO
OH
OH
OH
KOH
KOH
in propanediol
propanediol
in
190°C, 6h
6h
190°C,
COOH
COOH
COOH
HO
HO
HO
OH
OH
OH
HO
HO
HO
Dehydroabietic
Dehydroabietic
acid
acid
Glucose dehydroabietate
dehydroabietate
Glucose
yield: 51%
51%
yield:
OH
OH
OH
COO
COO
COO
OH
OH
OH
OH
OH
OH
Scheme 44.
44. Preparation
Preparation
of glucose
glucose dehydroabietate.
dehydroabietate.
Scheme
Scheme
44.
Preparation of
of
glucose
dehydroabietate.
Acrylic rosin
rosin cyclic
cyclic diamide
diamide is
is aa solid.
solid. It
It can
can be
be prepared
prepared from
from acrylpimaric
acrylpimaric acid
acid and
and diethylene
diethylene
Acrylic
triamine
according
to
Scheme
45
prior
to
washing
and
drying
[131].
It
can
be
used
as
a
fungicide
for
Scheme 45 prior
prior to
to washing
washing and
and drying
drying [131].
[131]. It can be used as a fungicide for
triamine according to Scheme
wood preservation
preservation [131].
[131].
wood
preservation
[131].
COOH
COOH
COOH
Acrylpimaric
Acrylpimaric
acid
acid
C O
O
C
C
O
NH
NH
NH
H22N(CH
N(CH )) NH(CH
NH(CH )) NH
NH
H
H
2N(CH222)222NH(CH222)222NH222
xylene
xylene
<180°C, 8h
8h
<180°C,
COOH
COOH
COOH
C NH
C
NH
C
NH
O
O
O
NH
NH
NH
Scheme 45.
Preparation of
of acrylic
acrylic rosin
rosin cyclic
cyclic diamide.
diamide.
Scheme
45. Preparation
3.2.6. Other
Other Small/Medium
Small/Medium Molecule
Molecule Products
Products
3.2.6.
Acrylic rosin
rosin
Acrylic
cyclic diamide
diamide
cyclic
Molecules 2019, 24, x FOR PEER REVIEW
22 of 51
Molecules 2019, 24, 1651
22 of 52
Hydroabietic acid can be prepared from rosin and hydrogen using palladium/SBA-15
mesoporous silica catalyst, according to Scheme 46 [207]. This catalyst is more efficient than others
[208,209]
Its Small/Medium
applications
oxidation-resistant
solvent-borne tackifiers and coatings, a substrate
Molecules
2019,
24,
x FOR PEERinclude
REVIEW
22 of 51
3.2.6.
Other
Molecule
Products
for esterification with glycerol [210], additives for polyvinylidene difluoride binders for lithium
Hydroabietic
acid
beIt prepared
from
hydrogen
using epoxy
palladium/SBA-15
mesoporous
Hydroabietic
acidcan
can
be be
prepared
fromand
rosin
and liquid
hydrogen
using
titanium
oxide anodes
[76].
can
used
inrosin
high-performance
resinspalladium/SBA-15
[83], for
synthesis
silica
catalyst,
according
to
Scheme
46
[207].
This
catalyst
is
more
efficient
than
others
[208,209]
mesoporous
silicapolyurethane
catalyst, according
to[173].
Scheme
[207]. This catalyst
is more efficient
than
others
of high adhesion
acrylate
It is46noteworthy,
that non-catalytic
decarboxylation
of
Its
applications
include
oxidation-resistant
solvent-borne
tackifiers
and
coatings,
a
substrate
for
[208,209]
Its
applications
include
oxidation-resistant
solvent-borne
tackifiers
and
coatings,
a
substrate
rosin can take place at temperatures above 200 °C, and the main product of such decomposition is
esterification
withwith
glycerol
[210],[210],
additives
for polyvinylidene
difluoride
binders binders
for lithium
for
esterification
glycerol
additives
for polyvinylidene
difluoride
fortitanium
lithium
norabieta-8,11,13-triene
[211].
oxide
anodes
[76].
It
can
be
used
in
high-performance
liquid
epoxy
resins
[83],
for
synthesis
of
titanium oxide anodes [76]. It can be used in high-performance liquid epoxy resins [83], for synthesis
high
adhesion
polyurethane
acrylate
of
of
high
adhesion
polyurethane
acrylate[173].
[173].ItItisisnoteworthy,
noteworthy,that
thatnon-catalytic
non-catalytic decarboxylation
decarboxylation of
H2
◦ C, and the main product of such decomposition is
rosin
can
take
place
at
temperatures
above
200
rosin can take place at temperatures above 200 °C, and the main product of such decomposition is
> 200°C
Pd/SiO
2
norabieta-8,11,13-triene
[211].
norabieta-8,11,13-triene
[211].
in ethanol
Norabieta160°C,8MPa,4h
Hydroabietic acid
-8,11,13-triene
COOH Rosin
COOH yield: >97%
H2
> 200°C
Scheme
46. Hydrogenation of rosin to hydroabietic
acid.
Pd/SiO
2
in ethanol
160°C,8MPa,4h
Hydroabietic acid
Norabieta-8,11,13-triene
Rosin-based standard-quality biodiesel can be prepared in a catalyst-free process
from darkCOOH Rosin
COOH yield: >97%
grade rosin, heavy turpentine and supercritical methanol in supercritical CO2 as a green medium.
Yields >93% were obtained
after 46.
3 hHydrogenation
at 340 °C, under
a pressure
of 11 MPa
[212]. Yield of >85% can be
Scheme
of
to
acid.
Scheme
46.
Hydrogenation
of rosin
rosin
to hydroabietic
hydroabietic
acid.
achieved using Pt/mesoporous aluminosilicate catalyst after 4 h at 300–350 °C, 5 MPa [213]. A yield
standard-quality
biodiesel
can
be
prepared
a after
catalyst-free
process
standard-quality
biodiesel
can
be
prepared
in aincatalyst-free
from
dark-grade
>99%Rosin-based
can be achieved
using Ni/layered
double
hydroxide
catalyst
<2 hprocess
at 190
°C, 5 from
MPa dark[214].
grade
rosin,
heavyofturpentine
and
supercritical
methanol
supercritical
CO
2medium.
as a green
medium.
rosin,
heavy
turpentine
and is
supercritical
methanol
inout
supercritical
CO2 as a green
Yields
>93%
Catalytic
cracking
rosin
also
possible
to carry
usinginacid-activated
montmorillonite
[215].
◦ C,
Yields
>93% were
obtained
after
at 340a °C,
underlevopimaric
a pressure
of
11 MPa
Yieldcan
ofaccording
>85%
can be
were
obtained
after
3 h at 340
under
pressure
of
11 MPa [212].
Yield[212].
of >85%
be achieved
Acrylpimaryl
nitrile
can
be3 h
prepared
from
acid
and
acrylonitrile
to
◦
achieved
using
Pt/mesoporous
aluminosilicate
catalyst
4 h atC,
300–350
MPa
A yield
using
Pt/mesoporous
aluminosilicate
catalyst
4 h atafter
300–350
5ItMPa
[213].
A yield
>99%
can
Scheme
47,
prior
to extraction,
filtration
and after
precipitation
[216,217].
can°C,
be 5used
in[213].
synthesis
of
>99%
can be using
achieved
using
Ni/layered
double
hydroxide
catalyst
h at
190 °C,
5 MPa
[214].
be
achieved
Ni/layered
double hydroxide
catalyst
<2 h after
at 190<2◦ C,
5 MPa
[214].
Catalytic
diacrylpimaryl
ketone
and acrylpimaryl
amidoxime
[217].after
Catalytic
cracking
of
rosin
is
also
possible
to
carry
out
using
acid-activated
montmorillonite
[215].
cracking
of
rosin
is
also
possible
to
carry
out
using
acid-activated
montmorillonite
[215].
Acrylpimaryl nitrile amidoximes can be prepared from adequate acrylpimaryl nitriles and
Acrylpimaryl
nitrile
be prepared
to
Acrylpimaryl
nitrile can
from
levopimaric acid
and acrylonitrile
hydroxylamine
according
to Scheme
47, prior
to precipitation,
washing,
filtration andaccording
drying [217]
Scheme
47, can
priorbetoused
It
be
of
extraction,
filtration
andthin
precipitation
It can
cannanoparticles
be used in synthesis
[218]. They
to prepare
bioactive
films filled[216,217].
by magnetite
for oil spill
diacrylpimaryl
and acrylpimaryl
amidoxime
[217].
collecting [217] ketone
and thorium
ions removal
[218].
Acrylpimaryl nitrile amidoximes can be prepared from adequate acrylpimaryl nitriles and
O and drying [217]
O
hydroxylamine according to Scheme
47, priorOto precipitation, washing, filtration
(
)
3
N
N
[218]. They
can be used
2. Triethylene4. NHto
2OHprepare bioactive thin films filled by magnetite nanoparticles for oil spill
H
H
collecting tetramine
[217] and thorium
ions removal [218].
70°C, 2h
in toluene
10°C, 24h
O
1. Oxalyl
chloride
in toluene
50°C, 4h
3.
CNN
in DMF
185°C, 12h
CN
185°C, 12h
N
HOOC
C
N
OH
H2N
C
H2N
NH2OH
70°C
4h
HOOC
H2N
N
OH
HO
Diacrylpimaryl nitrile
amidoxime ketone
HO
H2N
N
OH
O
N sulfonic acid; in toluene
p-toluene
Diacrylpimaryl
235°C,
NH2 4h
Diacrylamidoxime
triethylenetetralevopimaramide
nitrile
amidoxime ketone
C
C
N
NH2
NH2OH 70°C, 4h
HO
N
NH2
NH2OH 70°C, 4h
O
p-toluene sulfonic acid; in toluene
N
OH
235°C, 4h COOH
Levopimaric
Acrylpimaryl nitrileH2N
acid
185°C, 12h
yield: 78%NH2OH
CNHOOC
O
O
1. Oxalyl
3.
N(
N )3
NH2OH
2. Triethylene4.CN
H
H
HO
OH
chloridetetramine
N
N
in DMF
70°C, 2h
NH
H
N
in toluene
185°C,
12h
2
in toluene
Diacrylamidoxime 2
50°C, 4h
10°C, 24h
triethylenetetralevopimaramide
Acrylpimaryl
amidoxime
CN
CN
Diacrylpimaryl nitrile
ketone yield: 80%
70°C of Nacrylpimaryl
Scheme 47.
47. Synthesis
nitrile and
and
acrylpimaryl
amidoximes.
OH
COOH
Scheme
Synthesis
of acrylpimaryl
nitrile
acrylpimaryl
CNamidoximes.
4h
CN
HOOC
Levopimaric
Acrylpimaryl
Diacrylpimaryl nitrile
Acrylpimaryl
nitrilecan be
acidAcrylpimaryl
amidoxime
Rosin-oil dimernitrile
acids amidoximes
mixture
from rosin
industrial
fatty oils according
to
canprepared
be prepared
from and
adequate
acrylpimaryl
nitriles and
ketone yield: 80%
yield: 78%
Scheme 48, prior
to washing
and rotary
evaporation
[219]. It washing,
can be used
for preparation
a liquid
hydroxylamine
according
to Scheme
47, prior
to precipitation,
filtration
and dryingof[217,218].
Scheme 47. Synthesis of acrylpimaryl nitrile and acrylpimaryl amidoximes.
Rosin-oil dimer acids mixture can be prepared from rosin and industrial fatty oils according to
Scheme 48, prior to washing and rotary evaporation [219]. It can be used for preparation of a liquid
Molecules 2019, 24, 1651
23 of 52
They can be used to prepare bioactive thin films filled by magnetite nanoparticles for oil spill
23 of 51
removal [218].
23 of
of 51
51
23
Rosin-oil
dimer
acids
mixture
can
be
prepared
from
rosin
and
industrial
fatty
oils
according
to
thermal stabilizer [219]. It is noteworthy, that dimerized rosin is usually produced separately and can
Scheme
48,
prior
to
washing
and[220,221]
rotary evaporation
[219].
It
can
be used
for preparation
of stability
aand
liquid
thermal
stabilizer
[219].
It is
is noteworthy,
noteworthy,
that
dimerized
rosin
is usually
usually
produced
separately
can
thermal
stabilizer
[219].
It
that
dimerized
rosin
is
produced
and
can
be
applied
in
acrylic
adhesives
to improve
their
wetting,
adhesion
andseparately
thermal
thermal
stabilizer
[219].
It
is
noteworthy,
that
dimerized
rosin
is
usually
produced
separately
and
can
be applied
applied in
in acrylic
acrylic adhesives
adhesives [220,221]
[220,221] to
to improve
improve their
their wetting,
wetting, adhesion
adhesion and
and thermal
thermal stability
stability
be
[220].
be
applied in acrylic adhesives [220,221] to improve their wetting, adhesion and thermal stability [220].
[220].
[220].
Molecules 2019, 24, x FOR PEER REVIEW
collecting
[217]
ions
Molecules 2019,
2019,
24, xxand
FORthorium
PEER REVIEW
REVIEW
Molecules
24,
FOR
PEER
HOOC
CH3(CH2)5
(CH2)7COOH
(CH22))55
CH33(CH
CH
fatty acids
HOOC
HOOC
(CH22))77COOH
COOH
(CH
(CH2)7CH3
fatty acids
acids
fatty
catalyst
(CH22))77CH
CH33
(CH
240°C,0.5MPa,5h
catalyst
catalyst
240°C,0.5MPa,5h
240°C,0.5MPa,5h
COOH
COOH
COOH
(CH22))77COOH
COOH
(CH
COOH
COOH
COOH
Rosin
Rosin
Rosin
COOH
(CH2)7COOH
COOH
COOH
COOH
Mixture of rosin-oil dimer acids
Mixture of
of rosin-oil
rosin-oil dimer
dimer acids
acids
Mixture
COOH
COOH
Scheme 48. Preparation of rosin-oil dimer acids mixture.
Scheme 48.
48. Preparation
Preparation of
of rosin-oil
rosin-oil dimer
dimer acids
acids mixture.
mixture.
Scheme
Scheme
Solid rosin-based chain extender for polyurethanes can be synthesized from rosinSolid
rosin-basedacid,
chain
extender
for
polyurethanes
can
be
synthesized
from
Solid rosin-based
rosin-based
chain
extender
forand
polyurethanes
can
be synthesized
synthesized
from
rosinSolid
chain
extender
for
polyurethanes
can
be
from
maleimidodicarboxylic
thionyl
chloride
ethylene
glycol,
according
to Scheme
49,
and rosinusing
rosin-maleimidodicarboxylic
acid, thionyl
chloride
and ethylene
glycol, according
49,
maleimidodicarboxylic
acid,
thionyl
chloride
and ethylene
ethylene
glycol,
according
to
Scheme
49,Scheme
and using
using
maleimidodicarboxylic
acid,
chloride
and
glycol,
according
to
Scheme
49,
and
such
separation methods
as thionyl
vacuum
distillation,
washing
and evaporation
[186].
Its to
application
in
and
using
such
separation
methods
as
vacuum
distillation,
washing
and
evaporation
[186].
Its
application
such
separation
methods
as
vacuum
distillation,
washing
and
evaporation
[186].
Its
application
in
such
methods as vacuum
distillation,
washing
and evaporation
[186].
application in
shapeseparation
memory polyurethanes
improves
shape recovery
at >1000%
strain up to
96%Its
[186].
in
shape
memory
polyurethanes
improves
shape
recovery
at
>1000%
strain
up
to
96%
[186].
shape memory
memory polyurethanes
polyurethanes improves
improves shape
shape recovery
recovery at
at >1000%
>1000% strain
strain up
up to
to 96%
96% [186].
[186].
shape
O
O
O
Cl
COOH Cl
Cl
DMF
COOH 85°C, 5h
COOH
N
NN
O
O
O
COOH
COOH
COOH
O
O Cl HO
O
S
HO
HO
Cl
SS Cl
O
OH
pyridine OH
inpyridine
toluene
pyridine
110°C,
5h
in
toluene
in
toluene
110°C, 5h
5h
110°C,
DMF
DMF
85°C, 5h
5h
Rosin-maleimido-85°C,
dicarboxylic
acid
Rosin-maleimidoRosin-maleimidodicarboxylic acid
acid
dicarboxylic
O
O
O
OH
COOH
N
O
O
C
NN
O
C
C
O
O
O
COOH
COOH
O
O
HO
HO
HO
Rosin-based
chain
Rosin-based
Rosin-based
extender
chain
chain
extender
extender
Scheme 49. Synthesis of rosin-based chain extender for polyurethanes.
Scheme 49.
49. Synthesis
Synthesis
of
rosin-based chain
chain extender
extender for
for polyurethanes.
polyurethanes.
Scheme
Scheme
49.
Synthesis of
of rosin-based
rosin-based
chain
extender
for
polyurethanes.
Chiral thioureas and thiouronium salts containing dehydroabietyl groups are well characterized
thiouronium
containing
dehydroabietyl
well characterized
characterized
Chiral
thioureas
and thiouronium
thiouronium
salts containing
dehydroabietyl
groups
are
and
salts
dehydroabietyl
well
whiteChiral
or thioureas
yellow solids
[222]. They
can
be prepared
from groups
chiralare
amines
(including
or
yellow
solids
[222].
They
can
be
prepared
from
chiral
amines
(including
dehydroabietylamine),
white
or
yellow
solids
[222].
They
can
be
prepared
from
chiral
amines
(including
white
or
yellow
solids
[222].
They
can
be
prepared
from
chiral
amines
(including
dehydroabietylamine), carbon disulfide and butyl halides according to Scheme 50 and using
such
carbon
disulfide
and
butyl
halides
according
to
Scheme
50
and
using
such
separation
methods
as
dehydroabietylamine),
carbon
disulfide
and
butyl
halides
according
to
Scheme
50
and
using
such
dehydroabietylamine),
carbon disulfide
butyldrying,
halidesevaporation
according to
Scheme
50chromatography
and using such
separation methods as filtration,
washing,and
vacuum
and
column
filtration,
washing,
drying,
evaporation
anddrying,
column
chromatography
[222].
can be useful
separation
methods
as filtration,
filtration,
washing,
vacuum
drying,
evaporation
and column
column
chromatography
separation
methods
as
washing,
vacuum
evaporation
and
chromatography
[222].
They
can bevacuum
useful
for
the
physical
separation
of racemic
mixtures
[222]. They
Moreover,
rosinfor
the
physical
separation
of
racemic
mixtures
[222].
Moreover,
rosin-derived
thioureas
can
be
used
as
[222].
They
can
be
useful
for
the
physical
separation
of
racemic
mixtures
[222].
Moreover,
[222].
They
can
be
useful
for
the
physical
separation
of
racemic
mixtures
[222].
Moreover,
rosinderived thioureas can be used as enantioselective catalysts for many reactions [12]. In recent rosinyears
enantioselective
catalysts
for
many
reactions
[12].
In
recent
years
these
were:
Michael
addition
[223,224],
derived
thioureas
can
be
used
as
enantioselective
catalysts
for
many
reactions
[12].
In
recent
years
derived
thioureas
canaddition
be used as
enantioselective
for many reactions
In recent
years
these were:
Michael
[223,224],
tandem catalysts
Michael/cyclization
sequence[12].
[225],
asymmetric
tandem
Michael/cyclization
sequence
[225],
asymmetric
Michael/hemiketalization
[226],
these were:
were:
Michael addition
addition
[223,224],
tandem
Michael/cyclization
sequence [225],
[225],
asymmetric
these
Michael
[223,224],
tandem
Michael/cyclization
sequence
asymmetric
Michael/hemiketalization
[226],
asymmetric
aza-Henry
reaction
[227], asymmetric
tandem
reaction
aza-Henry
reaction
[227], asymmetric
tandem aza-Henry
reaction
[228],
Mannich
reaction
[229,230],
Friedel–Crafts
Michael/hemiketalization
[226], asymmetric
asymmetric
aza-Henry
reaction
[227],
asymmetric
tandem
reaction
Michael/hemiketalization
[226],
reaction
[227],
asymmetric
tandem
reaction
[228],
Mannich
reaction
[229,230],
Friedel–Crafts
alkylation
[231],
enantioand diastereoselective
alkylation
[231],
enantioandasdiastereoselective
addition
[232],
as
well
as synthesis
of
[228], Mannich
Mannich
reaction
[229,230],
Friedel–Crafts
alkylation
[231], enantioenantioand
diastereoselective
[228],
reaction
[229,230],
alkylation
[231],
diastereoselective
asymmetric
addition
[232],
wellFriedel–Crafts
as synthesisasymmetric
of
chiral amines
[233]
or and
N-protected
β-amino
chiral
amines
[233]
or
N-protected
β-amino
malonates
[234].
In
recent
studies
rosin-derived
thioureas
asymmetric
addition
[232],
as
well
as
synthesis
of
chiral
amines
[233]
or
N-protected
β-amino
asymmetric
addition
[232],
as
well
as
synthesis
of
chiral
amines
[233]
or
N-protected
β-amino
malonates [234]. In recent studies rosin-derived thioureas are dominant majority of all investigated
are
dominant
majority
ofThey
all
investigated
rosin-derived
catalysts.
Theyarticle
are
not
explored
further
in
malonates
[234].
In recent
recent
studies
rosin-derived
thioureas
are
dominant
majority
of all
all they
investigated
malonates
[234].
In
studies
thioureas
are
majority
of
investigated
rosin-derived
catalysts.
are rosin-derived
not
explored
further
in
thedominant
current
because
are the
the
current
article
because
they
arenot
theexplored
subject [12].
offurther
a comprehensive
review
publication
[12].
For
rosin-derived
catalysts.
They
are
not
explored
further
in the
the
current
article
because
theycatalysts
arenow,
the
rosin-derived
catalysts.
They
are
in
current
article
because
they
are
the
subject
of a comprehensive
review
publication
For now,
reports
on another
rosin-based
subject
of
a
comprehensive
review
publication
[12].
For
now,
reports
on
another
rosin-based
catalysts
reports
on
another
rosin-based
catalysts
are
rare
[235–237].
subject
of
a
comprehensive
review
publication
[12].
For
now,
reports
on
another
rosin-based
catalysts
are rare [235–237].
are rare
rare [235–237].
[235–237].
are
R'
CS2
R'
R'
NH2
CS22
CS
DCC
in (CDCC
2H5)2O
DCC
NH22
NH
<20°C,
) OO
in
(C HH )12h
in
(C
22 55 22
<20°C,12h
12h
<20°C,
R'
R"
S
NH2
R'
R" NH
NH22
R'
R"
N C S in CH2Cl2
<20°C,
12h
inCH
CH22Cl
Cl
NN CC SS in
22
<20°C,12h
12h
<20°C,
SS
C4H9
X
CC44HH99 XX
in C2H5OH
N
N
R' H
R" 65-90°C, 24 h
H R"
R'
inCC22HH55OH
OH
in
NN
NN
HH
HH
Chiral
65-90°C,24
24hh
65-90°C,
R'
R"
thiourea
Chiral
Chiral
yield:
76-91%
thiourea
thiourea
yield: 76-91%
76-91%
yield:
S
R'
N
R' H
R'
NN
HH
SS
C4H9
CC44HH99
R" X
N
R" XX
H R"
NN
HH
Chiral thiouronium salt
yield:
83-99.5% salt
Chiral
thiouronium
salt
Chiral
thiouronium
yield: 83-99.5%
83-99.5%
yield:
X = Cl or Br or I
X = Cl
Cl or
or Br
Br or I
X
R'=and/or
R" = or I
R' and/or R" =
R'
or and/or R" =
or
or
Scheme 50. Synthesis
Synthesis of
of chiral
chiral thioureas
thioureas and their thiouronium salts.
Scheme 50.
50. Synthesis
Synthesis of
of chiral
chiral thioureas
thioureas and
and their
their thiouronium
thiouronium salts.
salts.
Scheme
Optically pure rosin-based chiral alcohols and their phosphorus derivatizing agents are white
Optically
pure
rosin-based chiral
chiralmaleopimaric
alcohols and
and their
theirin
phosphorus
derivatizing
agents
are white
white
Optically
pure
rosin-based
alcohols
phosphorus
derivatizing
agents
are
solids.
They can
be synthesized
from
acid
two main ways
according
to Scheme
51
solids.
They
canseparation
be synthesized
synthesized
from
maleopimaric
acid in
in
two main
main
ways according
according
to Scheme
Scheme 51
51
solids.
They
can
be
from
acid
two
ways
to
and
using
such
methods
asmaleopimaric
washing, filtration,
drying,
evaporation,
and recrystallization
and using
using such
such separation
separation methods
methods as
as washing,
washing, filtration,
filtration, drying,
drying, evaporation,
evaporation, and
and recrystallization
recrystallization
and
Molecules 2019, 24, 1651
24 of 52
Optically pure rosin-based chiral alcohols and their phosphorus derivatizing agents are white
MoleculesThey
2019, 24,
FOR
PEER REVIEW
51
solids.
canx be
synthesized
from maleopimaric acid in two main ways according to Scheme 24
51 of
and
Molecules 2019, 24, x FOR PEER REVIEW
24 of 51
using such separation methods as washing, filtration, drying, evaporation, and recrystallization [113].
[113]. They can be 31
used in 31P-NMR-based determination of enantiomeric excess in solutions
They
can
be can
usedbe
in used
P-NMR-based
determination
of enantiomeric excess in solutions containing
[113].
They
in 31amines
P-NMR-based
containing chiral alcohols and
[113]. determination of enantiomeric excess in solutions
chiral
alcohols
and
amines
[113].
containing chiral alcohols and amines [113].
O
O
O
O
1. PCl3
O
2. PCl
CH3OH
1.
O 3. LiAlH
2. CH3OH
4
4. LiAlH
PhCH(OCH
3.
3)2
4
4. PhCH(OCH3)2
CH2OH
COOH
COOH
Maleopimaric
Maleopimaric
acid
acid
1. PCl3
2. PCl
CDCl
1.
3 3 / pyridine
3. CDCl
Chiral3 diol
or acid
/ pyridine
2.
4. Chiral
S8
3.
diol or acid
4. S8
O
O
O
O
Y = O or N
Y = O or N
CH2OH chiral alcohols
Rosin-based
Rosin-based
alcohols
yield: chiral
53-65%
yield: 53-65%
CH2
CH2
phosphorus
Rosin-based
chiral agens
phosphorus
derivatizing
derivatizing agens
1. PCl3
2. PCl
CDCl
1.
3 3 / pyridine
3. CDCl
Chiral3 single
alcohol
/ pyridine
2.
or monoamine
3. Chiral
single alcohol
4. or
S8monoamine
4. S8
OH
OH
OH
OH
1. SOCl2 / DMF
2. SOCl
Piperidine
1.
2 / DMF
3. Piperidine
LiAlH4 / THF
2.
3. LiAlH4 / THF
S
SP Y
Y
CH2O P Y
CH2O
Y
Rosin-based chiral
O
O
O
O
O
O P
O P
O
CH2
CH2
N
N
Y
Y
R
R
N
N
Scheme 51. Synthetic routes of rosin-based chiral alcohols and phosphorus derivatizing agents.
Scheme
Scheme 51.
51. Synthetic
Synthetic routes
routes of
of rosin-based
rosin-based chiral
chiral alcohols
alcohols and
and phosphorus derivatizing agents.
Rosin-based molecular glass photoresists can be prepared from maleopimaric acid,
molecular
glass
photoresists
can be prepared
maleopimaric
acid, hydroxylamine,
Rosin-based
molecular
glass
photoresists
canchloride
be from
prepared
from maleopimaric
acid,
hydroxylamine, 2-diazo-1-naphthoquinone-4-sulfonyl
and unsaturated
compounds: vinyl
2-diazo-1-naphthoquinone-4-sulfonyl
chloride and unsaturated
compounds:
vinyl
ethyl ether, or
hydroxylamine,
2-diazo-1-naphthoquinone-4-sulfonyl
chloride
and
unsaturated
compounds:
ethyl ether, or dihydropyran,
or cyclohexyl vinyl ether,
according
to Scheme 52
and using vinyl
such
dihydropyran,
or
cyclohexyl vinyl
ether,
according
toether,
Scheme
52 and using
such separation
methods
as
ethyl
ether,
or
dihydropyran,
or
cyclohexyl
vinyl
according
to
Scheme
52
and
such
separation methods as filtration, washing and vacuum drying [114]. These materials canusing
be applied
filtration,
washing
and
vacuum
drying
[114].
These
materials
can
be
applied
in
photolithography
[114].
separation
methods as
filtration, washing and vacuum drying [114]. These materials can be applied
in photolithography
[114].
in photolithography [114].
Maleopimaric
Maleopimaric
acid
acid
O
O
O
O
O
O
O
O
HO
HO
COOH
COOH
in ethyl acetate
NH2
25-45°C,3h
in
ethyl acetate
NH2
25-45°C,3hO
O
N2
N2
O
O
N OH
N OH
O
O
COOH
COOH
N-hydroxymaleopimarimide
N-hydroxymaleopimarimide
(NHMPI) yield: 70%
(NHMPI) yield: 70%
SO2Cl
SO2Cl
(C2H5)3N
(C2acetone
H5)3N
in
4h
in25°C,
acetone
25°C, 4h
O
O
N2
N2
R=
R=
SO2
O SO
2
N O
O
N
O
COOH
COOH
O
O
or:
or:
O
or:
or:
O
O
O
O
O
O
O
Unsaturated
compound
Unsaturated
compound
in ethyl acetate
3-4h
in50-60°C,
ethyl acetate
50-60°C, 3-4h
NHMPI 2-diazoNHMPI 2-diazo1-naphthoquinone1-naphthoquinone4-sulfonate
yield: 94%
4-sulfonate yield: 94%
N2
N2
SO2
O SO
2
N O
O
N
O
COOR
COOR
Rosin-based molecular
Rosin-based
molecular
glass compound
glass compound
yield: 90%
yield: 90%
Scheme 52.
52. Synthesis
molecular glass
glass compound.
compound.
Scheme
Synthesis of
of rosin-based
rosin-based molecular
Scheme 52. Synthesis of rosin-based molecular glass compound.
3.3. Macromolecular Compounds
3.3. Macromolecular Compounds
repeated
units
typical
of
This section
section describes
describesrosin-derived
rosin-derivedmacromolecular
macromolecularcompounds
compoundswith
with
repeated
units
typical
This section describes
rosin-derived
macromolecular
compounds with
typical of
macromolecules.
It contains
polymers,
oligomers,
and
polymer
functionalized
of
macromolecules.
It contains
polymers,
oligomers,macroinitiators
macroinitiators
and repeated
polymer units
functionalized
macromolecules.
It contains
oligomers,
macroinitiators
and polymer
functionalized
some polymers,
small/medium
molecule
compounds,
are not presented
materials. Additionally,
Additionally,
molecule
compounds, which
which
in the
materials.
Additionally,
some
small/medium
molecule
compounds,
which
are
not
presented
the
previous section,
section,but
butnecessary
necessary
to obtain
appropriate
macromolecules,
are described
here. inNonprevious
to obtain
appropriate
macromolecules,
are described
here. Non-toxicity,
previous
section,
but
necessary
to
obtain
appropriate
macromolecules,
are
described
here.
Nontoxicity,origin,
natural
origin,
rigidhydrophobicity,
structure, hydrophobicity,
excellent
thermal
properties,
natural
low
price, low
rigidprice,
structure,
excellent thermal
properties,
anticorrosive
toxicity,
natural
origin,
low
price,
rigid
structure,
hydrophobicity,
excellent
thermal
properties,
anticorrosive performance,
biocidaland
properties
andare
stickiness
areattractive
the mostreasons
attractive
to
performance,
mild biocidalmild
properties
stickiness
the most
to reasons
use rosin
anticorrosive
biocidalof
properties
and
stickiness
are
the most
attractive
reasons to
use rosin derivatives
in themild
preparation
polymerA
materials.
A disadvantage
of
these
in
derivatives
inperformance,
the preparation
of polymer
materials.
disadvantage
of these
processes
in processes
comparison
use
rosin
derivatives
in
the
preparation
of
polymer
materials.
A
disadvantage
of
these
processes
in
comparison with petrochemical counterparts is the relatively lower reactivity of rosin derivatives
comparison
with
counterparts
is the relatively
lower
of rosin
derivatives
resulting from
thepetrochemical
steric hinderance
of the diterpene
skeleton and
thereactivity
usually lower
purity
of rosinresulting
from
the
steric
hinderance
of
the
diterpene
skeleton
and
the
usually
lower
purity
of rosinbased intermediates, as discussed in subsection 3.2.1. As a result, rosin-based polymer materials
are
based
intermediates,
as
discussed
in
subsection
3.2.1.
As
a
result,
rosin-based
polymer
materials
are
usually characterized by distinct polydispersity and molecular weights rather far from their
usually characterized by distinct polydispersity and molecular weights rather far from their
Molecules 2019, 24, 1651
25 of 52
Molecules 2019, 24, x FOR PEER REVIEW
25 of 51
with petrochemical counterparts is the relatively lower reactivity of rosin derivatives resulting from the
theoretical
values.
Therefore,
their
TRL and
is lower
than for
small/medium
molecule intermediates,
compounds of
steric
hinderance
of the
diterpene
skeleton
the usually
lower
purity of rosin-based
rosin.
It
is
noteworthy,
that
compared
to
non-renewable
counterparts,
the
use
of
rosin
significantly
as discussed in Section 3.2.1. As a result, rosin-based polymer materials are usually characterized
increases
the
sustainability
of
preparation
processes
according
to
Green
Chemistry
rules,
so25there
is
by distinct
and molecular weights rather far from their theoretical values. Therefore,
Molecules
2019,polydispersity
24, x FOR PEER REVIEW
of 51
stillTRL
highisdemand
forfor
basic
and appliedmolecule
researchcompounds
in this field.of rosin. It is noteworthy, that compared
their
lower than
small/medium
theoretical
values.counterparts,
Therefore, their
TRL
lower
than for increases
small/medium
molecule compounds
of
to non-renewable
the use
of is
rosin
significantly
the sustainability
of preparation
3.3.1.ItPolymers
for Biomedical
Applications
rosin.
is according
noteworthy,
compared
to non-renewable
counterparts,
the usefor
of rosin
processes
to that
Green
Chemistry
rules, so there is
still high demand
basic significantly
and applied
increases
the
sustainability
preparation
Green
Chemistry
rules,polyethylene
so there is
research
in
this
field.glycol) of
Poly(ethylene
rosin
esters areprocesses
oligomers,according
which cantobe
prepared
from rosin,
still
highand
demand
basic and according
applied research
in this
glycol
maleicfor
anhydride,
to Scheme
53 field.
prior to drying at 40–70 °C [81,238]. Proposed
3.3.1. Polymers for Biomedical Applications
applications include shells for controlled drug delivery [238,239] and dental films for periodontitis
3.3.1.
Polymers
forMoreover,
Biomedical
Applications
treatment
[240].
maleopimaric
acid PEG which
esters can
carbon from
steel rosin,
corrosion
protection
Poly(ethylene
glycol) rosin
esters are oligomers,
can show
be prepared
polyethylene
◦
properties
[241].
glycol
and maleic anhydride,
according
Scheme 53which
priorcan
to drying
at 40–70
[81,238].
Proposed
Poly(ethylene
glycol) rosin
esters aretooligomers,
be prepared
fromCrosin,
polyethylene
Block
copolymer
of dehydroabietyl
methacrylate
ethylene
glycol
group
applications
include
shells
foraccording
controlled
drug
delivery
[238,239]
andatdental
films
fordisulfide
periodontitis
glycol
and maleic
anhydride,
toethyl
Scheme
53 prior
toand
drying
40–70
°Cwith
[81,238].
Proposed
can
be
prepared
via
ATRP
according
to
Scheme
54,
prior
to
neutralization,
evaporation
and
treatment
[240].
Moreover,
maleopimaric
acid
PEG
esters
can
show
carbon
steel
corrosion
protection
applications include shells for controlled drug delivery [238,239] and dental films for periodontitis
precipitation
Potential
applications
drug-delivery
nanocarriers
for cancer
therapy
properties
[241].[168].
treatment
[240].
Moreover,
maleopimaric
acidinclude
PEG esters
can show carbon
steel corrosion
protection
[168].
properties [241].
O
O
O
O
Block copolymer of dehydroabietyl
ethyl methacrylate and ethylene glycol with disulfide group
O
can be prepared via ATRP according
to Scheme 54, prior to neutralization, evaporation and
O
O
O
precipitation [168]. Potential applications include drug-delivery nanocarriers for cancer therapy
160°C, 2h
[168].
O
O
O
COO [ (CH2)2O]9 H
O[(CH2)2O]nH
O
Levopimaric
acid PEG 400 ester
O
COOH
O[(CH2)2O]nH
O
Maleopimaric acid
yield: 42%
2+
pTSA
200°C, ?h
O[(CH2)2O]nH
O
O
COO[(CH2)2O]9 H
O
Maleopimaric acid
O
PEG 400 ester
160°C, 2h
HO(CH2CH2)9H Zn
(PEG 400)
220°C, 5h
O COO [ (CH2)2O]9 H
CH3O[CH2CH2O]nH
O[(CH2)2O]
nH 750)
(PEG
O
O
O
O
COO[(CH2)2O]9 H
O
Levopimaric
acid
PEG 400 ester
O
COOH
180-220°C
Maleopimaric acid 4h
yield: 42%
COO [ (CH2)2O]n+1H
CH3O[CH2CH2O]nH
Maleopimaric
(PEG 750)acid
2+
O
HO(CH2CH2)9H Zn
(PEG 400)
220°C, 5h
COOH
O
pTSA
200°C, ?h
PEG 750 ester
CH3O[CH2CH2O]nH
(PEG 750)
Maleopimaric acid
PEG 400 ester
pTSA
200°C, ?h
COO [ (CH2)2O]n+1H
Levopimaric acid
PEG 750 ester
Levopimaric acid
CH O[CH CH O] H
O
3
2
2 n
180-220°C
(PEG 750)
Scheme53.
53.Synthesis
Synthesis
poly(ethyleneglycol)
glycol)
rosinesters.
esters.
4h
Scheme
ofofpoly(ethylene
rosin
pTSA
200°C, ?h
COO [ (CH2)2O]n+1H
COO [ (CH2)2O]n+1H
Maleopimaric
acid of dehydroabietyl ethyl methacrylate
Levopimaric
acid
Block copolymer
and ethylene glycol
with disulfide
COOH
PEG
ester
PEG
750 esterand
Levopimaric
acid
O
group
can750
be
prepared
via
ATRP
according
to
Scheme
54,
prior
to
neutralization,
evaporation
Poly(ethylene glycol) with
O
precipitation
[168]. Potential
applications
drug-delivery nanocarriers for cancer therapy [168].
(bromoisobutyryl)ethyl
disulfide
group include
Scheme
53. Synthesis
Oof poly(ethylene glycol) rosin esters.
O
(
O
O
)113
O
S
S
O
Poly(ethylene glycol) with
(bromoisobutyryl)ethyl disulfide group
(
O
)113
O
O
O
O
O
CuBr/PMDETA in anisole; 47°C, <2h
O
O
O
O
Br
S
O(
O
Br
O
)113
O
O
O
O
O
S
OO
S
O
(O
)n Br
O
O
S
O
Poly(dehydroabietic
ethyl methacrylate-b-ethylene
glycol) with disulfide group
O
O
O
(PEG113-ss-PMrosin
CuBr/PMDETA
in anisole; 47°C,
27) <2h
O
O
O
S
O
Scheme 54. Preparation of block copolymer of dehydroabietyl
)113 ethyl
( glycol
)n Br
O(
O methacrylate
O
S and ethylene
O
with disulfide group.
Poly(dehydroabietic ethyl methacrylate-b-ethylene glycol) with disulfide group
(PEG113-ss-PMrosin27)methacrylate) can be prepared
The rosin derivative quaternized poly-(N,N-dimethylaminoethyl
via Scheme
“living”
reversibleof
chain-transfer
polymerization
(RAFT)
54. Preparation
Preparation
ofaddition-fragmentation
block copolymer
copolymer of
of dehydroabietyl
dehydroabietyl
ethyl methacrylate
methacrylate
and ethylene
ethylene
glycol from
54.
block
ethyl
and
glycol
dehydroabietic
acid, 3-chloropropanol, N,N-dimethylaminoethyl methacrylate and cumyl
with disulfide group.
dithiobenzoate as a RAFT transfer agent, according to Scheme 55, and using gel chromatography,
precipitation
and vacuum
drying as
separation techniques [242]. methacrylate)
It can be usedcan
asbe
amphipathic
The rosin derivative
quaternized
poly-(N,N-dimethylaminoethyl
prepared
antibacterial
in a wide
variety of biomedical and
general use polymerization
applications [242].(RAFT) from
via
“living” agent
reversible
addition-fragmentation
chain-transfer
dehydroabietic acid, 3-chloropropanol, N,N-dimethylaminoethyl methacrylate and cumyl
dithiobenzoate as a RAFT transfer agent, according to Scheme 55, and using gel chromatography,
precipitation and vacuum drying as separation techniques [242]. It can be used as amphipathic
Molecules 2019, 24, 1651
26 of 52
The rosin derivative quaternized poly-(N,N-dimethylaminoethyl methacrylate) can be prepared via
“living” reversible addition-fragmentation chain-transfer polymerization (RAFT) from dehydroabietic
acid, 3-chloropropanol, N,N-dimethylaminoethyl methacrylate and cumyl dithiobenzoate as a RAFT
transfer agent, according to Scheme 55, and using gel chromatography, precipitation and vacuum
drying as separation techniques [242]. It can be used as amphipathic antibacterial agent in a wide
variety
of biomedical and general use applications [242].
Molecules 2019, 24, x FOR PEER REVIEW
26 of 51
Molecules 2019, 24, x FOR PEER REVIEW
Cl
Cl
COOH
COOH
Dehydroabieticacid
acid
Dehydroabietic
N
N
26 of 51
OH
OH
oxalylchloride
chloride
oxalyl
triethylamine
triethylamine
in THF; 0°C, 15h
in THF; 0°C, 15h
COO
COO
Cl
Cl
Cl
Cl
3-chloropropyl
3-chloropropyl
dehydroabietate
yield: 65%
dehydroabietate yield:
65%
S
S
O
O
O
O
N,N-dimethylaminoethyl
N,N-dimethylaminoethyl
methacrylate (DMAEMA)
methacrylate (DMAEMA)
N
N
COO
COO
Rosin derivative
Rosin derivative
quaternized
quaternized
poly-DMAEMA
poly-DMAEMA
Mn=8300, 14400, 17600,
Mn=8300, 14400, 17600,
19300,
19600, 59800
19300, 19600, 59800
S
S
)n
SS
O
O
O
O
N
N
)n SS
O
O
O
O
AIBN
AIBN 5h
60°C,
60°C, 5h
n-m
O
O
O
O
in
in
acetonitrile
acetonitrile
80°C, 72h
80°C, 72h
S
S
(
(
S
)n-m
) S
))m ((
m
((
Poly-DMAEMA
Poly-DMAEMA
Mn=5490, 7500, 1400 or 41000
Mn=5490, 7500, 1400 or 41000
N
N
Scheme 55. Preparation of the rosin derivative quaternized poly(dimethylaminoethyl methacrylate).
Scheme 55. Preparation of the rosin derivative quaternized
quaternized poly(dimethylaminoethyl
poly(dimethylaminoethyl methacrylate).
methacrylate).
3.3.2. Elastomers
3.3.2.
3.3.2. Elastomers
Elastomers
Poly(dehydroabietic ethyl
methacrylate-β-n-butyl
acrylate-β-dehydroabietic
ethyl methPoly(dehydroabietic
methacrylate-β-n-butyl
acrylate-β-dehydroabietic
ethyl meth-acrylate)
Poly(dehydroabieticethyl
ethyl
methacrylate-β-n-butyl
acrylate-β-dehydroabietic
ethyl methacrylate)
triblock
copolymer
can
be
prepared
in
ATRP
polymerization
from
butyl
acrylate,
triblock
copolymer
can be prepared
in prepared
ATRP polymerization
from butyl acrylate,
dehydroabietic
acrylate)
triblock
copolymer
can
be
in
ATRP
polymerization
from
butyl
acrylate,
dehydroabietic
hydroxyethyl
acrylate
and
diethyl
meso-2,5-dibromoadipate
according
to
Scheme
56,
hydroxyethyl
acrylate
and diethyl
meso-2,5-dibromoadipate
according to Scheme
56, prior
to diluting,
dehydroabietic
hydroxyethyl
acrylate
and
diethyl
meso-2,5-dibromoadipate
according
to
Scheme
56,
prior to diluting,
neutralization,
evaporation,
precipitation
and vacuum
drying
[146]. Its
application
neutralization,
evaporation,
precipitation
and
vacuum
drying
[146].
Its
application
is
sustainable
prior
to diluting,
neutralization,
evaporation,
is sustainable
thermoplastic
elastomers
[146]. precipitation and vacuum drying [146]. Its application
thermoplastic
elastomers
[146].
is sustainable thermoplastic
elastomers [146].
C4H9
C4H9
O
O
O
O
Butyl
Butyl
acrylate
acrylate
O
Br
Br O
OO
Br
OO
O
NiBrBr2(PPh3)2O
C4H9
C4O
H9
O O
O
Br (
Br (
O
O O
O
)n
)n
Poly(n-butyl acrylate)
Poly(n-butyl
acrylate)
macroinitiatior
macroinitiatior
yield: 58%
yield: 58%
NiBr
85°C,
P, 17h
2(PPh
3)2
85°C, P, 17h
(
(
O
O O
O
Br
O
)nBr
)n O
O
O
O O
O
O
CO
4H9
O
Cl (
C4H9
C4H9
O
O
Cl
(
CO
4H9
O
O
O
)m(
)m(
O
Poly(dehydroabietic
Poly(dehydroabietic
ethyl
methacrylate-bethyl
methacrylate-b-n-butyl
acrylate-b-n-butyl acrylate-b-dehydroabietic
ethyl
-dehydroabietic
methacrylate)
yield: ethyl
36%
methacrylate) yield: 36%
O O
)n
)n
O
(
(
O
O O
O
O
O
OO
O
O
O
CuCl/PMDETA
in DMF; 90°C, 8h
O
CuCl/PMDETA in DMF; 90°C, 8h
O
O
Cl
)m Cl
)m
O
O
O
O
O9
C4H
O
O
)n (
)nO (
C4H9O
O
Mn=76kg/mol
Mn=76kg/mol
Scheme 56. Synthesis of rosin-based triblock copolymer.
Scheme 56. Synthesis of rosin-based triblock copolymer.
copolymer.
Cellulose/rosin ATRP macroinitiators can be prepared from dehydroabietic acid, cellulose and
Cellulose/rosin
ATRP
can
from
dehydroabietic
acid,
2-bromoisobutyryl
according to Scheme
57, prior to
drying
at 40 °C [142].
It iscellulose
used for and
the
Cellulose/rosin bromide,
ATRP macroinitiators
macroinitiators
can be
be prepared
prepared
from
dehydroabietic
acid,
cellulose
and
◦ C [142]. It is used for the
2-bromoisobutyryl
bromide,
according
to
Scheme
57,
prior
to
drying
at
40
preparation of graftbromide,
copolymers
[142]. to Scheme 57, prior to drying at 40 °C [142]. It is used for the
2-bromoisobutyryl
according
preparation
of
Rosin-acid-modified
ethyl [142].
cellulose/butyl
acrylate graft copolymer can be prepared in ATRP
preparation
of graft
graft copolymers
copolymers
[142].
reaction
from dehydroabietic
acid, cellulose,acrylate
2-bromoisobutyryl
bromide
butyl in
acrylate
Rosin-acid-modified
ethyl cellulose/butyl
graft copolymer
can beand
prepared
ATRP
accordingfrom
to Scheme
57, prior to
sorption
of CuBr
x and precipitationbromide
in methanol.
reaction
dehydroabietic
acid,
cellulose,
2-bromoisobutyryl
and [142].
butylPotential
acrylate
applications
include thermoplastic
elastomers
and coatings
with UV absorption
property
[142].
according
to Scheme
57, prior to sorption
of CuBr
x and precipitation
in methanol.
[142].
Potential
applications include thermoplastic elastomers and coatings with UV absorption property [142].
Molecules 2019, 24, 1651
27 of 52
Molecules 2019, 24, x FOR PEER REVIEW
OR
Mn=7750-17100 g/mol
R = H or Et
RO
HO
Bu
RO
O
Molecules 2019, 24, x FOR PEER REVIEW
O
Br
O
OH
Br OR
OR
2-bromoisobutyryl
and Ethyl
R = H or Et
RO
bromide
cellulose (EC)
RO
DMAP inOTHF;
25°C, 24h
HO
O
Br
RO
O
O
O
RO
O
2-bromoisobutyryl
and Ethylchloride
Cl
Dehydroabietyl
bromide
cellulose (EC)
O
C
EC-g-(DA)-Br
OR
RO
O
ATRP macroinitiator
O
O
27 of 51
O
O
OR
O
Bu
O
O
O
RO
O
O
RO
O
Mn=7750-17100 g/mol
O
CuBr/PMDETA
in THF/DMF
Bu
70°C, 6h
Br
OR
O
O
OR
O
OH
Br
C
OR
C
OR
O
O
C
OR
( )n
O
27 of 51
O
RO
O
O
O
Br
EC-g-(DA)-g-poly(butyl
acrylate)
O
RO
OR
CuBr/PMDETA
Oyield 76%
in THF/DMF
O
RO
Bu
OR
O
( )n
70°C, 6h
O butyl acrylate.
DMAP in57.
THF;
25°C, 24hof graft copolymer of rosin-modified ethyl
Scheme
Synthesis
and
Scheme
57. Synthesis
of graft copolymer of rosin-modified ethylcellulose
cellulose
and butyl acrylate.
O
)n(
)m
Cellulose grafted byethyl
copolymer
ofBrrosin acid
ethyl methacrylate
and alkyl
Br
Rosin-acid-modified
cellulose/butyl
acrylate
graft copolymer
can(meth)acrylate
be preparedcan
in be
ATRP
EC-g-(DA)-Br
acrylate)
prepared via ATRP, according to Scheme
58, prior to sorption andEC-g-(DA)-g-poly(butyl
precipitation in methanol
[166].
reaction
from
O dehydroabietic acid, cellulose, 2-bromoisobutyryl bromide and butyl acrylate according
Cl
ATRP
macroinitiator
Dehydroabietyl
chloride“green”
yield 76%hydrophobic,
Potential
applications
include
thermoplastic
elastomers having significant
to Scheme 57, prior to sorption of CuBrx and precipitation in methanol. [142]. Potential applications
thermal and
mechanical
features
[166].
Scheme
57. Synthesis
of graft
rosin-modified
ethyl cellulose
and[142].
butyl acrylate.
include thermoplastic
elastomers
andcopolymer
coatingsofwith
UV absorption
property
Cellulose grafted by copolymer
of rosin acid ethyl methacrylate and alkyl (meth)acrylate can
OR
ROrosin OH
Cellulose grafted by copolymer of
acid ethyl methacrylate and alkyl (meth)acrylate can be
be prepared via ATRP, according to Scheme 58,
prior to sorption and precipitation in methanol [166].
prepared via ATRP, according
to
Scheme
58,
prior to sorption and
methanol [166].
O
O precipitation in
O
O
Potential
applications
include
“green”
thermoplastic
elastomersOhaving
havingsignificant
significant
hydrophobic,
Potential applications include “green” thermoplastic elastomers
hydrophobic,
OH
O(CH2)2O
RO
thermal
and
mechanical
features
[166].
OR
l
thermal and mechanical features [166].
O
O
O
O
)m
RO
Cellulose
R =inHtoluene;
or
CuBr/PMDETA
80-90°C, 24h
macroinitiator
O
(Cell) and
instead of BA
butyl acrylate (BA)
Cell-g-P(BA-co-DAEMA)
lauryl methacrylate
O
yield: 80%O
C4H9
O also works
C12H25
O
Mn = 27000, 28000, 31700, 49300, 40700, 54800,
RO
O
83300, 101100, 129900,
142800, 200100, 242600
CuBr/PMDETA in toluene; 80-90°C, 24h
RO
O
OH
O
l
O
O
RO
O
OH
O(CH2)2O
O
O OH
O
O(CH2)2O
O
OH
O C4H9
l
O
O
O
)n
(
O(CH2)2O
O
O
)m(
Dehydroabietic
ethyl methacrylate
(DAEMA)
O
O
(
O(CH2)2O
Br
O
O
)n(
OR C12Hl25
O
(
Br
(
O
Cellulose
R = H or
macroinitiator
OR
RO
OH
(Cell) and
instead of BA
butyl acrylate (BA) O
O
lauryl methacrylate
O
C4H9
O also works
OH
RO
O
O
)m(
O
Cell-g-P(BA-co-DAEMA)
Scheme 58. Synthesis
of graft copolymer
of cellulose, rosin acid and butyl acrylate (or lauryl
O C4H9
Dehydroabietic
yield: 80%
methacrylate).
)n
ethyl methacrylate
Mn = 27000, 28000, 31700, 49300, 40700, 54800,
(DAEMA)
83300, solids,
101100, 129900,
242600in several
O(CH
2)2O according to Scheme
Rosin alcohols are colorless
which142800,
can be200100,
prepared
ways
O
O drying [243,244]
59, and using such separation methods like evaporation, extraction, washing and
[245].
They
be used in graft
preparation
of ofcross-linked
structures
with
acrylamide
and
N,N′Scheme
58. can
Synthesis
copolymer
cellulose,
rosin
acidand
and
butyl
acrylate
lauryl
Scheme
58.
Synthesisofofgraft
copolymer of
cellulose, rosin
acid
butyl
acrylate
(or (or
lauryl
methylenebisacrylamide
[243,244],
as
well
as
norbornene-based
monomers
[245].
methacrylate).
methacrylate).
Rosin-norbornene monomers, i.e. dehydroabietanyl norborn-5-ene-2-carboxylate and 4((norborn-5-ene-2-carbonyl)oxy)butyl
dehydroabietate,
are
oily in
liquids
[245].ways
They
can
be
Rosin
alcoholsare
are colorless
which
can becan
prepared
in several
ways
according
to Scheme
Rosin
alcohols
colorlesssolids,
solids,
which
be viscous
prepared
several
according
synthesized
from
dehydroabietic
acid
derivatives
and
norbornenecarboxylic
acid
according
toand
59, and using
suchusing
separation
like methods
evaporation,
washing
and drying
[243,244]
to Scheme
59, and
such methods
separation
likeextraction,
evaporation,
extraction,
washing
Scheme
59, prior
to
washing, drying
and column
chromatography
[245]. Its application
[245].
They
can
beevaporation,
usedcan
in be
preparation
of cross-linked
structures
with acrylamide
and N,N′-and
drying
[243,244]
[245].
They
used in preparation
of cross-linked
structures
with acrylamide
is
polymerization, or block
copolymerization
with
norbornene, via
“living” [245].
ring-opening metathesis
methylenebisacrylamide
[243,244],
as
well
as
norbornene-based
monomers
0
N,N -methylenebisacrylamide [243,244], as well as norbornene-based monomers [245].
polymerization
(ROMP) process
[245,246].
Rosin-norbornene
monomers,
i.e. dehydroabietanyl norborn-5-ene-2-carboxylate and 4Rosin-norbornene monomers, i.e., dehydroabietanyl norborn-5-ene-2-carboxylate and
Homopolymers of rosin-modifieddehydroabietate,
norbornene can be
synthesized
vialiquids
ROMP[245].
process
according
((norborn-5-ene-2-carbonyl)oxy)butyl
are
viscous oily
They
can be
4-((norborn-5-ene-2-carbonyl)oxy)butyl
dehydroabietate,
are viscous
oily liquids
[245]. can
They can
to
Scheme
59
[246].
Moreover,
triblock
and
pentablock
copolymers
with
norbornene
segments
synthesized from dehydroabietic acid derivatives and norbornenecarboxylic acid according be
to
be synthesized from dehydroabietic acid derivatives and norbornenecarboxylic acid according to
Scheme 59, prior to evaporation, washing, drying and column chromatography [245]. Its application
Scheme
59, prior to evaporation,
washing, drying
column chromatography
[245]. Its
application
is polymerization,
or block copolymerization
withand
norbornene,
via “living” ring-opening
metathesis
polymerization (ROMP) process [245,246].
Homopolymers of rosin-modified norbornene can be synthesized via ROMP process according
to Scheme 59 [246]. Moreover, triblock and pentablock copolymers with norbornene segments can be
Molecules 2019, 24, 1651
28 of 52
Molecules 2019, 24, x FOR PEER REVIEW
28 of 51
is polymerization,
or block copolymerization with norbornene, via “living” ring-opening metathesis
prepared [246]. They can be applied as bio-based thermoplastic elastomers showing well-designed
polymerization
(ROMP)
process
[245,246].
architecture and high elastic
recovery
[245,246].
Dehydroabietic acid
Molecules 2019, 24, x FOR PEER REVIEW
OH
HO(CH2)4OH
SOCl2
28 of 51
O
prepared [246]. They can be applied as
bio-based
thermoplastic
elastomers
showing well-designed
O
OH
O
(CH2)4
in DMF
(C2H5)3N
architecture
and
high
elastic
recovery
[245,246].
trimethylacetic
0°C, 3h
in CH2Cl2
(CH )
O
0-40°C, 18h
OH
Dehydroabietic acid
O
4'-hydroxybutyl
OH
dehydroabietate
(CH
yield: 73% 2)4
O
HO(CH2)4OH
SOCl2
(C2H5)3N
in CH2Cl2
0-40°C, 18h
in DMF
LiAlH4 in THF
0°C, 3h
0°C, 13h
OH
O
O
O
4'-hydroxybutyl
O
OH
LiAlH4 in THF
0°C, 13h
Dehydroabietane-18-ol yield: 84%
O
OH
OH
O
in THF
60°C, 24h
OH
anhydride
DMAP
in THF
60°C
24h
O
Grubbs' cat.
in CH2Cl2
0.75h
O
O
in CH2Cl2
0.75h
Dehydroabietanyl
O
norborn-5-ene-2-carboxylate
O
Grubbs'85%
cat.
(Monomer 1) yield:
(CH2)4
O
O
O
O
OH 4-((norborn-5-ene-2O
trimethylacetic -carbonyl)oxy)butyl
(CH2)4
dehydroabietate
anhydride
Grubbs' cat.
O 82%
DMAP (Monomer 2) yield:
in CH2Cl2
dehydroabietate
O
trimethylacetic yield: 73% Grubbs' cat.
O
2 4
anhydride
DMAP
in THF
60°C, 24h
O
0.75h
n
Polymer
O (CH22)4
O
O
O
4-((norborn-5-ene-2-carbonyl)oxy)butyl
dehydroabietate
O
(Monomer
2) yield: 82%
O
m
n
O
n
O
Polymer 2
1h
m
Copolymer
1
n
n
trimethylacetic
O
Polymer 1
Mn=114-187 kg/mol
anhydride
in CH2Cl2
O
O
DMAP
0.75h
O
in THF
DehydroabietaneScheme
Synthesisofofrosin-norbornene
rosin-norbornene monomers
monomers
and
Scheme
59.59.
Synthesis
and polymerization
polymerizationofofthem.
them.
Dehydroabietanyl
60°C
-18-ol yield: 84%
24h
norborn-5-ene1h
Rosin-based waterborne
polyurethanes
can can
be prepared
from maleopimaric
acid, according
diethylene
Homopolymers
of rosin-modified
norbornene
be synthesized
via ROMPCopolymer
process
to
-2-carboxylate
1
n
glycol,59polyether
glycol, toluene
diisocyanate,
propionic
acid andMtrimethylamine
Polymer
1with norbornene
(Monomer
1) pentablock
yield: 85%dimethylol
Scheme
[246]. Moreover,
triblock
and
copolymers
segments
can
be
=114-187
kg/mol
n
according
to They
Scheme
and using
such separation
methods
as vacuum
dryingwell-designed
and rotary
prepared
[246].
can60,
be applied
as bio-based
thermoplastic
elastomers
showing
evaporation
[111].
Such
polymers
can
be
also
synthesized
using
fumaropimaric
rosin
instead of
Scheme
59.
Synthesis
of
rosin-norbornene
monomers
and
polymerization
of
them.
architecture and high elastic recovery [245,246].
maleopimaric
acid
[109].
These
materials
exhibit
excellent
mechanical
properties,
thermal
stability,
Rosin-based waterborne polyurethanes can be prepared from maleopimaric acid, diethylene
waterRosin-based
resistance, antimicrobial
properties against
Gram-negative
Escherichia
coli andacid,
Gram-positive
waterborne polyurethanes
can be
prepared from
maleopimaric
diethylene
glycol, polyether glycol, toluene diisocyanate, dimethylol propionic acid and trimethylamine according
Staphylococcus
aureus
[109,111]
and an
affinity for cellulose
nanocrystals
allows to apply
glycol,
polyether
glycol,
toluene
diisocyanate,
dimethylol
propionic[112],
acidwhich
and trimethylamine
to Scheme 60, and using such separation methods as vacuum drying and rotary evaporation [111].
them in various
biomass-based
and composite
according
to Scheme
60, and polymer
using such
separationmaterials.
methods as vacuum drying and rotary
Such polymers can be also synthesized using fumaropimaric rosin instead of maleopimaric acid [109].
evaporation [111]. Such polymers can be also synthesized using fumaropimaric rosin instead of
These materials
exhibit excellent mechanical
thermal
stability,
resistance,
antimicrobial
O
OHproperties,
HO DEG
TDI PEG
TDI water
DEG MPA
DEG TDI
H
maleopimaric
stability,
HO [109]. These
OH materials exhibit excellent mechanical properties, thermal TEA
O acid
O
properties against Gram-negative
Escherichia
coli and Gram-positive Staphylococcus aureus [109,111]
DEG
DMPA
water resistance,
antimicrobial
properties
against
Gram-negative
Escherichia
coli
and
Gram-positive
O
(DEG) nanocrystals [112], which allows to apply them in various biomass-based
COO
andStaphylococcus
an affinity for
cellulose
HO and
DEG an
MPA
aureus
[109,111]
affinity forHO
cellulose
nanocrystals
[112],MPA
which
DEG TDI
PEG TDI DEG
DEGallows
TDI to apply
120-240°C
polymer
and
composite
8hmaterials.
them in
various
biomass-based
and composite materials.
Rosin-based waterborne polyurethane
HO polymer
OH
(PEG)
O
HO
O
COOH
OCN
O
O
(DEG)
Maleopimaric acid120-240°C
8h
(MPA)
TDI
OCN
PEG
COOH
TDI
DEG
OH
HO
DEG
110-80°C
3hOH
NCO DEG
MPA
HO
DEG
HO
NCONCO
OCN
PEG
TDI
N
DEG
MPA DEG
30°C TDI
(TEA)
OCN
DEG
TDI
NCO
DEG
TDI DEG
N
60°C
3h
PEG
PEG
TDI
TDI
30°CTDI
MPA DEG
(TEA)
DEG
DEG
(DMPA)
60°C
3h
0.5h
HO
HO
DEG
TDI
PEG
TDI
DMPA
DEG
DEG
MPA DEG
TDI
DEG
Scheme
polyurethane.
Scheme60.
60.Preparation
Preparationof
ofrosin-based
rosin-based waterborne
waterborne polyurethane.
3.3.3. Coatings and Adhesives
TEA H
DMPA
COO
DEG HO
TDI
PEG
DEG TDI PEG TDI DEG MPA DEG TDI
OH
TDI waterborne
DEG MPA DEG
TDI
Rosin-based
polyurethane
COOH
DMPA COOH
Maleopimaric acid
Scheme 60. Preparation ofHO
rosin-basedOHwaterborneTDI
polyurethane.
DEG MPA
(MPA)
(TDI)
COOH
TDI PEG TDI DEG MPA
3.3.3. Coatings
and Adhesives
0.5h
HO
HO
OH
(TDI)
(PEG)
MPA DEG TDI 110-80°C(DMPA)
3h
TDI
HO
TDI
COOH
Molecules 2019, 24, x FOR PEER REVIEW
Molecules 2019, 24, 1651
29 of 51
29 of 52
Rosin-modified poly(acrylic acid) is a solid. It can be prepared from poly(acrylic acid) and abietic
acid according to Scheme 61, prior to washing and vacuum drying [247]. It can be applied as an
3.3.3.
Coatings
and
Adhesives
Molecules
2019, 24,
24,
FOR
PEER REVIEW
REVIEW
29 of
of 51
51
Molecules
2019,
xx FOR
PEER
29
excellent
binder
for
silicon-graphite
negative electrodes in lithium-ion batteries [247].
Rosin-modified poly(acrylic acid) is a solid. It can be prepared from poly(acrylic acid) and abietic
Rosin-modified
poly(acrylic acid)
acid) is
is aa solid.
solid. It
It can
can be
be prepared
prepared from
from poly(acrylic
poly(acrylic acid)
acid) and
and abietic
abietic
Rosin-modified
n=? poly(acrylic
HO vacuum
acid according
to M
Scheme
61, prior to washing
and
drying [247].
It
O can be applied as an
acid according
according
to Scheme
Scheme 61,
61, prior
prior to
to washing
washing
and vacuum
vacuum drying
drying [247]. It
It can
can be
be applied as an
O
OH to
H
acid
and
excellent
binder for
silicon-graphite
negative
in lithium-ion[247].
batteries
[247].applied as an
O
OH electrodes
H 3O
excellent
binder
for
silicon-graphite
negative
electrodes
in
lithium-ion
batteries
[247].
O
O
excellent binder for silicon-graphite negative electrodes in lithium-ion batteries [247].
O
(
)n
(acid-catalyzed
(
)
activation)
n
(nucleophilic
addition
Mn=?
=?
Poly(acrylic acid)
HO
M
n
HO
25°C, 3h
(
)OnO
& elimination)
Activated PAA
PAA-Rosin
O
OH
(PAA)
H
O
OH
H
100°C, 12h
O
OH
H3O
O
O
O
OH
O
H
3
O
O
O
O
Scheme
61.
Preparation
of
rosin-modified
poly(acrylic
acid).
((
))nn
(acid-catalyzed
(acid-catalyzed
activation)
(nucleophilic addition
addition
((
))nn
Poly(acrylic acid)
acid)
activation)
(nucleophilic
Poly(acrylic
25°C, 3h
3h
& elimination)
elimination)
Activated
PAA
PAA-Rosin
25°C,
((
))dehydroabietylamine
&
(PAA)
Activated
PAA
nn
PAA-Rosin
N-dehydroabietic
acrylamide
is a white
solid. It can
be 12h
synthesized from
(PAA)
100°C,
100°C,
12h
and acryloyl chloride according to Scheme 62, prior to washing and vacuum distillation. It can be
Scheme61.
61.Preparation
Preparationof
of rosin-modified
rosin-modified poly(acrylic
poly(acrylic
acid).
Scheme
poly(acrylic
acid). of rigid petroleumScheme
61.
Preparation
of
rosin-modified
used as a bio-based acrylic
monomer
in compolymerization
processes acid).
instead
based monomers [161].
N-dehydroabieticacrylamide
acrylamideisis
isaaawhite
whitesolid.
solid. It
It can
can be
be synthesized
from
dehydroabietylamine
N-dehydroabietic
It
synthesizedfrom
fromdehydroabietylamine
dehydroabietylamine
N-dehydroabietic
acrylamide
white
solid.
Rosin
and soybean
oil-based acrylic
copolymers
cansynthesized
be prepared from
N-dehydroabietic
and
acryloyl
chloride
according
to
Scheme
62,
prior
to
washing
and
vacuum
distillation.
It can
can
be
and
acryloyl
chloride
according
to
Scheme
62,
prior
to
washing
and
vacuum
distillation.
can
beare
used
and
acryloyl
chloride
according
to
Scheme
62,
prior
to
washing
and
vacuum
distillation.
It
be
acrylamide and acrylated epoxidized soybean oil according to Scheme 62 [161].It They
as aa bio-based
bio-based
acrylic monomer
monomer
in compolymerization
compolymerization
processes
instead
of rigid
rigid
petroleumas characterized
aused
bio-based
acrylic
monomer
inhydrophobicity
compolymerization
processes
instead
ofalso
rigid
petroleum-based
used
as
acrylic
in
processes
instead
of
petroleumby considerable
and heat
resistivity
and
other
properties
based
monomers
[161].
based monomers
[161]. petroleum-based materials [161].
monomers
[161].
comparable
with similar
Rosin and
and soybean
soybean oil-based
oil-based acrylic
acrylic copolymers
copolymers can
can be
be prepared
prepared from
from N-dehydroabietic
N-dehydroabietic
Rosin
acrylamide
and
acrylated
epoxidized
soybean
oil
according
to
Scheme
62
[161]. They
They are
are
O
acrylamide and O
acrylated epoxidized
soybean oil according
to Scheme 62 [161].
O
HN hydrophobicity and heat resistivity and also other properties
characterized
by
considerable
characterized by
considerable hydrophobicity and heat resistivity and also other properties
Cl
Triglyceride
comparable with
with similar
similar petroleum-based
petroleum-based materials
materials
[161]. O
1-3
comparable
[161].
in CH2Cl2
Acrylated epoxidized
DHAAM
-5-23°C, 0.5h
soybean oil (AESO)
O
O
O
O
O
NH2
( AESO )m( DHAAM )n
HN
tert-butyl benzoilO peroxide
HN
Cl
<170°C,
9h
Cl
Rosin
and soybean oil-based
N-dehydroabietic
Triglyceride
O
Triglyceride
O
1-3
1-3
in CH
CH2Cl
Cl2 acrylamide (DHAAM)
acrylic
copolymer
Dehydroabietylamine
in
Acrylated
epoxidized
2 2
Acrylated epoxidized
DHAAM
DHAAM
-5-23°C, 0.5h
0.5h
-5-23°C,
soybean
oil
(AESO)
oil (AESO)
Scheme62.
62.Preparation
Preparationof
of rosin
rosin and
andsoybean
plant oil-based
acrylic
AESO )m( DHAAM
NH2 Scheme
plant
oil-based
acryliccopolymers.
copolymers.
NH
tert-butyl
benzoil peroxide
peroxide
(( AESO
)m( DHAAM ))nn
2
tert-butyl
benzoil
<170°C,
9h
Rosin
and
soybean
oil-based
N-dehydroabietic
<170°C, 9h
Rosin and soybean oil-based
N-dehydroabietic
Rosin
and
POSS-based
non-isocyanate
polyurethanes
can be prepared
from rosin-based
cyclic
acrylic
copolymer
Dehydroabietylamine
Rosin
and
soybean
oil-based
acrylic
copolymers
can
be
prepared
from
N-dehydroabietic
acrylamide
acrylamide
(DHAAM)
acrylic copolymer
Dehydroabietylamine acrylamide (DHAAM)
carbonate,
polyamine
and
cyclic
carbonate-functionalized
POSS
according
to
Scheme
63
[200].
Theirby
and acrylated epoxidized soybean oil according to Scheme 62 [161]. They are characterized
Scheme 62.
62. Preparation
Preparation of
of rosin
rosin and
and plant
plant oil-based
oil-based acrylic
acrylic copolymers.
copolymers.
Scheme
applications
include
coatings
showing
improved
water
tolerance,
hardness
and
thermal
stability
considerable hydrophobicity and heat resistivity and also other properties comparable with similar
[200].
petroleum-based
[161].
Rosin and
and materials
POSS-based
non-isocyanate polyurethanes
polyurethanes can
can be
be prepared
prepared from
from rosin-based
rosin-based cyclic
cyclic
Rosin
POSS-based
non-isocyanate
Rosin
and
POSS-based
non-isocyanate
polyurethanes
can
be
prepared
from
rosin-based
cyclic
carbonate,
polyamine
and
cyclic
carbonate-functionalized
POSS
according
to
Scheme
63
[200].
Their
O carbonate-functionalized
carbonate, polyamine and cyclic
1. H2N R' NH2 POSS according to
(H) SchemeO63 [200]. Their
O
R'
NH
O
R
N
carbonate,
polyamine
and
cyclic
carbonate-functionalized
POSS
according
to
Scheme
63
[200].
Their
O
O
applications
include
coatings
showing
improved
water
tolerance,
hardness
and
thermal
stability
O
Rosin-based
applications
include coatings showing improved water tolerance, hardness and thermal stability
O
R'
NH
R
N
O
O
applications
include
coatings
showing
improved
water
tolerance,
hardness
and
thermal
stability
[200].
cyclic
carbonate
[200].
O
(H)
[200].
O
Rosin-based
Rosin-based
cyclic carbonate
carbonate
cyclic
O
O
C=O
O
O
O
O
O
OH
C=O
C=O
O
O
R' =
R=
R=
OH
OH
Scheme
O
O
O
O
O
R=
O
O
OO
O
O
OH
or: O
O
O
O
O
O
O
or:
O
O
O
O
O
O
or:
or:
O
(CH2)2 or:
OH
OH
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
2.
H2N
N R'
R' NH
NH2
1. H
1.
2
in2 DMF
O
O
100°C, 12h
O
O
2.
2.
O
O
in DMF
DMF
in
100°C, 12h
12h
100°C,
or:
(
N )2
H
O
O
O
O
O
O
O
(H)
O
(H)
R' NH
NH
O
R N
N R'
= cyclic carbonate
O
R
functionalized POSS
R'
NH
R
N
O
R N
O
(H) R' NH
(H)
O
O
O
OO
O
O
COO
R N R' NH
O
(H)
cyclic carbonate
carbonate
== cyclic
functionalized
POSS
functionalized POSS
Rosin & POSS-based
O
O
non-isocyanate polyurethane
COO
COO
R' NH
NH
N R'
R N
R
(H)
(H)
O
O
63. Preparation of rosin & POSS-based non-isocyanate polyurethane.
Rosin &
& POSS-based
POSS-based
N ))2
(CH2))2 or:
or:
or: ((
Rosin
N
(CH
or:
or:
2 2 or:
H 2
H
non-isocyanate
polyurethane
Rosin can be introduced as a chain extender into polyurethanes
to obtain rosin-based
urethanenon-isocyanate
polyurethane
amide hard segments, according to Scheme 64 [248]. A potential application of the prepared materials
Scheme 63.
63. Preparation
Preparation of
of rosin
rosin &
& POSS-based
POSS-based non-isocyanate
non-isocyanate polyurethane.
Scheme
is as sealants Scheme
for
non-invasive
disc regeneration
surgery [248].
Physicalpolyurethane.
mixtures of rosin and 1,463. Preparation
of rosin
& POSS-based
non-isocyanate
polyurethane.
butanediol were also investigated for this use [249].
Rosincan
canbe
be introduced
introduced
asas
chain
extender
into polyurethanes
polyurethanes
to obtain
obtain rosin-based
rosin-based
urethaneRosin
can
be
aa chain
extender
into
to
urethaneRosin
introducedas
a chain
extender
into polyurethanes
to obtain rosin-based
amide
hard
segments,
according
to
Scheme
64
[248].
A
potential
application
of
the
prepared
materials
amide hard segments,
according
to Scheme
[248]. A64potential
of the prepared
materials
urethane-amide
hard segments,
according
to64
Scheme
[248]. Aapplication
potential application
of the
prepared
is as
as sealants
sealants for
for non-invasive
non-invasive disc
disc regeneration
regeneration surgery
surgery [248].
[248]. Physical
Physical mixtures
mixtures of
of rosin
rosin and
and 1,41,4is
butanediol were
were also
also investigated
investigated for
for this
this use
use [249].
[249].
butanediol
R' ==
R'
Molecules 2019, 24, 1651
30 of 52
materials is as sealants for non-invasive disc regeneration surgery [248]. Physical mixtures of rosin and
1,4-butanediol
were also investigated for this use [249].
Molecules 2019, 24, x FOR PEER REVIEW
30 of 51
Molecules 2019, 24, x FOR PEER REVIEW
30 of 51
O
Molecules
2019,Ur
24, xUr
FORNCO
PEER REVIEW
OCN
O
OCN
80°C,Ur0.1hUr NCO HN
HN O
Ur
80°C, 0.1h
OCN
Ur
Ur
NCO
OCN
Ur
Ur
NCO
Ur
HN
Ur
OCN
OCN
Ur
Ur
NCO
80°C, 0.1h
COOH
Rosin
Ur
Ur
O
O
H
N
HN
OCN Ur Ur N
Ur Ur NCO
NO
O
OCN Ur Ur H
Ur Ur NCO
N
ON
Urethane-amide
hard segment
NCO
Ur UrNCO
COOH
COOH
Rosin
Rosin
30 of 51
Ur
NCO
NCO
OCN
Ur Ur
Ur Ur NCO
Urethane-amide
hard
segment
O
Scheme
64. Preparation
urethane-amide
hard segments.
segments.hard segment
Urethane-amide
Scheme 64.
Preparation of
of rosin-modified
rosin-modified urethane-amide
hard
Scheme 64. Preparation of rosin-modified urethane-amide hard segments.
Scheme 64. Preparation of rosin-modified urethane-amide hard segments.
Maleopimaric acid-modified polyester polyol aqueous dispersion can be prepared from
Maleopimaric acid-modified polyester polyol aqueous dispersion can be prepared from
maleopimaric
acid, adipic
acid, isophtalic
5-sulfoisophtalic
acid, neopentyl
glycol
and
Maleopimaric
polyester acid,
polyol
aqueous dispersion
be prepared
from
maleopimaric
acid, acid-modified
adipic acid, isophtalic
acid, 5-sulfoisophtalic
acid,canneopentyl
glycol
and
trimethylolpropane,
according
totoScheme
65,
prior
dissolving/dispersing
in water and
diethylene
maleopimaric acid,
adipic acid,
isophtalic
acid,to
acid, neopentyl
glycol
and
trimethylolpropane,
according
Scheme
65, prior
to5-sulfoisophtalic
dissolving/dispersing
in water and
diethylene
glycol
monoethyl
ether
acetate
as
a
cosolvent
[91].
It
can
be
applied
in
two-component
waterborne
cosolvent
[91].
be
applied
in
two-component
waterborne
trimethylolpropane,
according
65, prior
in water and diethylene
glycol
monoethyl ether
acetate to
as Scheme
a cosolvent
[91].to
It dissolving/dispersing
can be applied in two-component
waterborne
polyurethane
materials
and
coatings
showing
improved
stability,
hardnesshardness
and
resistances
polyurethane
materials
and
coatings
[110]
showing
improved
thermal
stability,
hardness
and
glycol monoethyl
ether
acetate
as [110]
a cosolvent
[91].
It canimproved
be thermal
appliedthermal
in two-component
waterborne
polyurethane
materials
and
coatings
[110]
showing
stability,
and
polyurethane
materials
and
coatings
[110] showing improved thermal stability, hardness and
to
ethanol
and
water
[91,110].
resistances
to to
ethanol
and
[91,110].
resistances
ethanol
andwater
water
[91,110].
resistances to ethanol and water [91,110].
HOOC
HOOC
HOOC
COOH
COOH
HOHO
COOH
OH
OH
HO
OH
HO
HO ((
HO
butyl
stannoicacid
acid
butyl
stannoic
butyl
stannoic acid
150-205°C
SOSO
150-205°C
3Na3Na
SO3Na
5-sulfoisophtalic
acid 150-205°C
(
O
O
O
O
O
O
O
O
OO ))nn
O )n
O
Hydrophilic
polyester
polyester
OH Hydrophilic
OH
polyester
OH Hydrophilic
intermediate
(HPI)
intermediate
(HPI)
intermediate (HPI)
SO
SO33Na
Na
SO3Na
5-sulfoisophtalic acid
5-sulfoisophtalic acid
O
O
O
OH
OH
OH
HO
OH
HO
OH
OH
OH HO
HOHO
OH
Neopentyl
HO
OHNeopentyl
Neopentyl
glycol
HOOC
COOH Trimethylolglycol
glycol
HOOC
COOH
TrimethylolHOOC
COOH
(NPG)
Trimethylolpropane (TMP) (NPG)
(NPG)
propane
(TMP)
propane
(TMP)
COOH
COOH
COOH
COOH
HOOC
COOH
COOH
HOOC
HOOC
Isophtalic acid
Adipic acid
Maleopimaric
Isophtalic
Adipic
acid
Maleopimaric
Isophtalic
acidacid
Adipic
acid
Maleopimaric
(IPA)
(AA)
acid
(AA)
acid
(IPA)(IPA)
(AA)
acid
(MPA)
(MPA)
(MPA)
butyl stannoic acid
butylstannoic
stannoic
acid
O butyl
acid
OO in
in xylene
xylene
in150-230°C,
xylene
3.5h
150-230°C, 3.5h
O 150-230°C, 3.5h
OO
Mn = 2422
n = 2422
Mn =M2422
Maleopimaric
Maleopimaric
Maleopimaric
acid-modified
acid-modified
NPG MPA HPI IPA acid-modified
polyester polyol
MPAHPIHPI IPAIPApolyester
NPG
NPG MPA
polyol
polyester
polyol
NPG ( IPA HPI MPA TMP AA HPI ) IPA NPG
NPG
AA AA
HPI HPI
IPA IPA
NPG NPG
MPATMP
)m m
NPG( ( IPA
IPA HPI
HPI MPA
TMP
)m
Scheme
Preparation
hydrophilic
maleopimaricacid-modified
acid-modified
poliester
polyol.
Scheme
65.65.
Preparation
ofof
hydrophilic
acid-modified
poliester
polyol.
Scheme
Preparationof
ofhydrophilic
hydrophilic maleopimaric
maleopimaric
poliester
polyol.
Scheme
65.65.
Preparation
maleopimaric
acid-modified
poliester
polyol.
3.3.4.
Surfactants
3.3.4.
3.3.4.Surfactants
Surfactants
3.3.4. Surfactants
Rosin-based
comb-like polymeric
surfactants
can
bebe
prepared
from
rosin
glycidyl
methacrylate
and
Rosin-based
surfactants
can
prepared
from
rosin
glycidyl
methacrylate
Rosin-basedcomb-like
comb-like polymeric
polymeric surfactants
can
be prepared
from
rosin
glycidyl
methacrylate
Rosin-based
comb-like
polymeric
surfactants
can
be
prepared
from
rosin
glycidyl
methacrylate
methacrylate
polyethylene
glycol
ester
according
to
Scheme
66,
prior
to
vacuum
drying,
precipitation,
and
ester according
according to
to Scheme
Scheme 66,
66,prior
priortotovacuum
vacuumdrying,
drying,
and methacrylate
methacrylate polyethylene
polyethylene glycol
glycol ester
andprecipitation,
methacrylate
polyethylene
glycol
ester
according
to
Scheme
66,
prior
to
vacuum
drying,
dialysis
and
freezing
[175].
Their
application
include
preparation
of
pymetrozine
water
suspension
dialysis
and
freezing
[175].
Their
application
include
preparation
of
pymetrozine
water
precipitation, dialysis and freezing
Their application include preparation of pymetrozine water
precipitation,
dialysis
and
freezing
[175].
Their
application
include
preparation
of
pymetrozine
water
concentrates
[175].
suspension
concentrates
[175].
suspension concentrates [175].
suspension concentrates [175].
O
O
O
O
OO
O
CH22O)
O)nnCH
CH33
O(CH22CH
O(CH
OHMethacrylate polyethylene
OH
AIBN (MAPEG)
glycol ester
in ethanol
ethanol
OH
AIBN 13h
<80°C,
13h
in ethanol
<80°C, 13h
((
(
OO
O
)x)x( (
)y)y
) (
OO x
O
( ))n )n
n
methacrylate
(RGMA)
O
Methacrylate polyethylene
Methacrylate
polyethylene
O(CH CH2O)nCH3
glycol ester 2(MAPEG)
(MAPEG)
O)O
y
O
((
Rosinglycidyl
glycidyl
Rosin
methacrylate
methacrylate
Rosin glycidyl
(RGMA)
(RGMA)
O
O
O
OO
O
HO
HO
HO
OO
O
OO
MM
6336,
7271,
7940,
7969
n==
6336,
7271,
7940,
7969
O n
Mn = 6336, 7271, 7940, 7969
Poly-(RGMA-co-MAPEG)
Poly-(RGMA-co-MAPEG)
Scheme66.
66.Preparation
Preparation
Scheme
of
comb-like
surfactants. Poly-(RGMA-co-MAPEG)
Scheme
66.
Preparation of
ofcomb-like
comb-likesurfactants.
surfactants.
Scheme
66.
Preparation
ofglycols
comb-like
Polyesters
ofacrylated
acrylated
rosin
and
polyethylene
can
be
according
Polyesters
of acrylated
rosin
andand
polyethylene
glycols
can
besurfactants.
prepared
according
toto
Scheme
6767[125].
Polyesters
of
rosin
polyethylene
glycols
can
beprepared
prepared
according
toScheme
Scheme
67
[125].
They
can
be
used
as
surfactants
in
preparation
of
stable
emulsions
[125].
They
canThey
be used
in preparation
of stable
[125]. [125].
[125].
can as
be surfactants
used as surfactants
in preparation
of emulsions
stable emulsions
Polyesters of acrylated rosin and polyethylene glycols can be prepared according to Scheme 67
[125]. They can be used as surfactants in preparation of stable emulsions [125].
Molecules 2019, 24, 1651
31 of 52
Molecules 2019, 24, x FOR PEER REVIEW
Molecules 2019, 24, x FOR PEER REVIEW
Molecules 2019, 24, x FOR PEER REVIEW
COOH
COOH
COOH
COOH
COOH
COOH
31 of 51
31 of 51
31 of 51
O
O
CO
CO
C O
O
HO-[(CH2)2O]x-H
HO-[(CH
O]x-H
ZnO22))22O]
HO-[(CH
x-H
270°C,
6-8h
ZnO
ZnO 6-8h
270°C,
270°C, 6-8h
(
((
)
))
O
O x O
O
x O
x O
HO
HO
HO
COOH
COOH
Mn = 864-3082
Mn = 864-3082
polyethylene
glycol
n Mn = 864-3082
O
O
Polyester
O
Acrylated rosin
COOH
Acrylated rosin
Acrylated rosin
n
of acrylated rosin and
n
Polyester of acrylated rosin and polyethylene
glycol
Polyester
of acrylated
rosin
and polyethylene glycol
Scheme 67. Preparation of acrylated rosin/polyethylene
glycol
polyester.
Scheme 67. Preparation of acrylated rosin/polyethylene glycol polyester.
Scheme 67. Preparation of acrylated rosin/polyethylene glycol polyester.
Scheme 67. Preparation of acrylated rosin/polyethylene glycol polyester.
Rosinimide
imidepolyethers
polyethersare
arelight
light brown
brown solids.
solids. They
rosin,
poly(ethylene
Rosin
Theycan
canbe
beprepared
preparedfrom
from
rosin,
poly(ethylene
Rosin
imide
polyethers
are light
brown solids.
They
cansuch
be prepared
from
rosin, poly(ethylene
glycol)
and
polyamines
according
to
Scheme
68,
and
using
separation
methods
as as
washing,
imide polyethers
are light
brown solids.
They
can be
prepared
from methods
rosin, poly(ethylene
glycol) Rosin
and polyamines
according
to Scheme
68, and
using
such
separation
washing,
glycol) precipitation
and polyamines
according
to SchemeThey
68, and
using
such separation
methods
as
washing,
drying,
and
filtration
[250,251].
can
be
applied
as
petroleum
crude
oil
sludge
glycol)
and
polyamines
according
to
Scheme
68,
and
using
such
separation
methods
as
washing,
drying,
precipitation
and
be applied
applied as
as petroleum
petroleumcrude
crudeoiloilsludge
sludge
drying,
precipitation
andfiltration
filtration[250,251].
[250,251]. They
They can
can be
dispersants
[250].
drying, precipitation
and filtration [250,251]. They can be applied as petroleum crude oil sludge
dispersants
[250].
dispersants [250].
dispersants [250].
COOH
COOH
Levopimaric
Levopimaric
acid
Levopimaric
acid
acid
135°C
in DMF
DMF
2h
COO in135°C
135°C
2h
COO
2h
COO
PEG
PEG
maleopimarate
PEG
maleopimarate
R = -(CHmaleopimarate
2)4- or -[(CH2)2]NH]2(CH2)2-
COO
COO
COO
Rosin imide
Rosin imide
yield:
Rosin85-95%
imide
yield: 85-95%
yield: 85-95%
R
R
NR
N
N
in
DMF5h
170°C,
170°C, 5h
H
N
O )m H
H (
N
H
O )m
H (
N
O )m
H O(
H
O
H
O
HO
O
O
)n)n )n
)n)n )n
O O O
140°C,
O O 1h
O
240°C
Zn
140°C, 1h
Zn
140°C, 1h
240°C
COOH
240°C
R NH2
R NH
N R NH22
O
H
N
O
HO
H
O
N
(
H
O
O )m H O
HO HO
O
HO (
O )mH
O in( DMF O )m
O 170°C,
5h
in DMF
(( (
O O O
O
H
O
NH2 O
H
O
HO R NH
NH2 2 O
O R NH2 O
NH2
O inRDMF
NH2
)n)n )n
HO
HO
Zn
HO
O
O
O
(( (
(( (
)n)n )n
O
O
O
(( (
H
H
HO
O
O
COO
COO
COO
Mn = 2310-3610 g/mol
M = 2310-3610 g/mol
Mnn= 2310-3610
Rosing/mol
imide
ether
Rosin
imide
ether
yield:imide
80-93%
Rosin
ether
yield: 80-93%
Scheme 68. Preparation of non-ionic rosin imide polyethers. yield: 80-93%
R = -(CH2)4- or -[(CH2)2]NH]2(CH2)2R = -(CH2)4- or -[(CH2)2]NH]2(CH2)2-
Scheme 68.Preparation
Preparation ofnon-ionic
non-ionic rosin
rosin imide
imide polyethers.
Scheme
polyethers.
Scheme68.
68. Preparationof
of non-ionic rosin
imide polyethers.
3.3.5. Sorbents
3.3.5.
Sorbents
3.3.5.
Sorbents
3.3.5.Rosin-poly(acrylamide)
Sorbents
star copolymers can be prepared according to Scheme 69, prior to
Rosin-poly(acrylamide)
star
copolymers
can be prepared
prepared
according
to
Scheme
69,
prior
toto
Rosin-poly(acrylamide)
star
copolymers
can
according
to
Scheme69,
69,prior
priorto
Soxhlet
extraction using acetone
and
drying [243,244,252].
They canaccording
be used forto
wastewater
treatment
Rosin-poly(acrylamide)
star
copolymers
can be
be prepared
Scheme
Soxhlet
extraction
using
acetone
and
drying
[243,244,252].
They
can
be
used
for
wastewater
treatment
Soxhlet
extraction
using
acetone
and
drying
[243,244,252].
They
can for
bewastewater
used for wastewater
[243,244,252]
and as
a matrix
for Fe
3Odrying
4 nanoparticles
[253].They can
Soxhlet
extraction
using
acetone
and
[243,244,252].
be used
treatment
[243,244,252]
and as aand
matrix
for
Fe3O4for
nanoparticles
[253].
treatment
[243,244,252]
as
a
matrix
Fe
O
nanoparticles
[253].
3 4
[243,244,252] and as a matrix for Fe3O4 nanoparticles
[253].
NaBH4
NaBH4
NaBH
in diethyl 4
inether
diethyl
in diethyl
25°C,
24h
ether
ether24h
25°C,
OH 25°C, 24h
OH
C OH
C
OC
O
acid
O
Rosin
Rosin acid
Rosin acid
O
O
O NH
2
NHO
2
NH2
O
N O
N
N
HN
HN
H in HHO
K2S2O
H8
H2
O
O
ON
OH
OH
OH
Rosin alcohol
Rosin alcohol
Rosin alcohol
O
[
O
O [
[
O [
O [
O [
K2S65°C,
2hH2O
2O8 in
K2S2O8 in H2O
65°C, 2h
65°C, 2h
Mn=??
M =??
Mnn=??
NH2
NH2
NHO
2
O
]n O
]n
]]nn
]
]nnO
O
NH2 O
NH2
NH2
H
H
NH
N
ON
O
O
H
H
NH
N
ON
O
O
O
O
NO
N
HN
H
H
O
O
NO
N
HN
H
H
H2N
H2N
OH
2N
O
O[
[
[[
[
O [
O
H2N
O
H2N
H2N
O
]n O
]n O
]n]nO
]
]nn OO
Rosin-poly(acrylamide)
Rosin-poly(acrylamide)
Rosin-poly(acrylamide)
Scheme 69. Synthesis of rosin alcohol and rosin-poly(acrylamide) star copolymer.
Scheme 69. Synthesis of rosin alcohol and rosin-poly(acrylamide) star copolymer.
Scheme
Synthesisofofrosin
rosinalcohol
alcohol and
and rosin-poly(acrylamide)
rosin-poly(acrylamide) star
Scheme
69.69.Synthesis
starcopolymer.
copolymer.
Linear rosin-modified cationic poly(acrylamide) can be prepared from dehydroabietyl chloride,
Linear rosin-modified
cationic poly(acrylamide)
can be prepared
from
dehydroabietyl
chloride,
bromopropan-1-ol,
methyldiallylamine,
acrylamide and
dimethyl
ammonium
chloride
in a
Linear
rosin-modified
cationicpoly(acrylamide)
poly(acrylamide)
be
from
dehydroabietyl
chloride,
Linear
rosin-modified
cationic
candiallyl
be prepared
prepared
from
dehydroabietyl
chloride,
bromopropan-1-ol,
methyldiallylamine,
acrylamide
and
diallyl
dimethyl
ammonium
chloride
in a
few-step
process, according
to Scheme 70,acrylamide
followed byand
operations
such as filtration,
washing,
drying
bromopropan-1-ol,
methyldiallylamine,
acrylamide
diallyl
ammonium
chloride
in in
a a
bromopropan-1-ol,
methyldiallylamine,
and
diallyl dimethyl
dimethyl
ammonium
chloride
few-step
process,
according
to
Scheme
70,
followed
by
operations
such
as
filtration,
washing,
drying
and
recrystallization
[149].
Its
utilization
may
be
in
flocculation
processes
[149].
few-step
process,
according
to
Scheme
70,
followed
by
operations
such
as
filtration,
washing,
drying
few-step process, according to Scheme 70, followed by operations such as filtration, washing, drying
and recrystallization [149]. Its utilization may be in flocculation processes [149].
recrystallization
[149].ItsItsutilization
utilizationmay
maybe
be in
in flocculation
flocculation processes
andand
recrystallization
[149].
processes[149].
[149].
Molecules 2019, 24, x FOR PEER REVIEW
32 of 51
Dehydroabietic acid
bromopropyl ester
Molecules
2019, 24, x FOR PEERNREVIEW
yield: 67%
Molecules
2019, 24, x FOR PEER REVIEW
O
Molecules 2019, 24, 1651
m
CH2
NH2
Cl
NO
O
n
Br in THF
65°C, 48h
65°C, 48h
55°C, 8h
C
O C O
O
O
O
O
O
NBr
Br
Diallylmethlyl
N
Cl
32 of 51
NH2
n
m
CH2
O
C
N
NBr
Br
AIBA10h
50°C,
50°C, 10h
O
O
Diallylmethlyl
dehydroabietic
acid propyl
Br
Br
p
N
Br
Dehydroabietic acid
Dehydroabietic
acid in C2H5OH
C
bromopropyl ester
m AIBA NH2
O
N
bromopropyl ester 65°C,N48h O
m 50°C, 10h
NH2
Br
yield: 67%
N
yield: 67%
Cl
C
Diallylmethlyl
O
Br
ClN
O
n
dehydroabietic acid propyl
n
N
(C2H5)3N in C2H5OH
C
ester ammonium
bromide
AIBA
in C2H5OH
N
C O
HO
32 of 52
O 32 of 51
CH2
Hydrophobically
O
modifiedcationic
O
n NH2
m
N polyacrylamide
n NH2
m
N
O
p
p
Cl
Cl
Mn=??
Hydrophobically
Hydrophobically
modifiedcationic
modifiedcationic
polyacrylamide
polyacrylamide
O
C O
C
dehydroabietic acid propyl
(C2H5)3N
ester ammonium bromide
H5)3N
HO
Br (C
ester ammonium bromide
Dehydroabietyl
in2THF
HO
Br in THF
55°C, 8h
O C Cl
chloride
55°C, 8h
Mn=??
Mn=??
Scheme 70. Preparation of linear rosin-poly(acrylamide) copolymer.
Dehydroabietyl
Dehydroabietyl
C Cl tetraethylenepentamine
O Rosin
chloride
amide is a solid. It can be prepared from maleopimaric acid and
O C Cl
chloride
tetraethylenepentamine
according
to
Scheme
71, prior
to precipitation, washing and lyophilization
Scheme
70.Preparation
Preparationof
oflinear
linear rosin-poly(acrylamide)
rosin-poly(acrylamide) copolymer.
Scheme
70.
copolymer.
Scheme
70.
Preparation
of
linear
rosin-poly(acrylamide)
copolymer.
[115]. It creates nano-micelles in aqueous solutions and can act as a sorbent
and sinking agent in metal
ions
removal
[115].
Rosin
tetraethylenepentamine amideisisaasolid.
solid. It
It can be prepared
from
maleopimaric
acid
and
Rosin
tetraethylenepentamine
preparedfrom
frommaleopimaric
maleopimaric
acid
and
Rosin
tetraethylenepentamineamide
amide is a solid. It
can be prepared
acid
and
tetraethylenepentamine
according
to Scheme
71,
prior
to precipitation,
washing
and
lyophilization
tetraethylenepentamine
according
to
Scheme
71,
prior
to
precipitation,
washing
and
lyophilization
[115].
O
tetraethylenepentamine
according to Scheme 71, prior to precipitation,
washing and lyophilization
COOH H2N
Maleopimaric
NH
[115]. Itnano-micelles
creates nano-micelles
in aqueous
solutions
and
can
act
as a sorbent
and
sinking
agent
in metal
It creates
in
aqueous
solutions
and
can
act
as
a
sorbent
and
sinking
agent
in metal
ions
Rosin
acid
[115]. It creates nano-micelles in aqueous solutions and can act as a sorbent and
sinking
agent
in metal
O
ions
removal
[115].
O
tetraethylenepentamine
removal
[115].
H
ions removal [115].
amide
( N
)3 NH2
H2N
HN
NH
H2N
O
N
O
COOH
Maleopimaric
60°C, 12h
H2N
NH
O
COOH H
Maleopimaric
COOH
Rosin
NH
acid COOH
Rosin
O
acid
O
tetraethylenepentamine
O
H
O
tetraethylenepentamine
N
amide
Scheme
Preparation
amide.
(H
)3 NH2of rosin-tetraethylenepentamine
H2N 71.
HN
NH
N
amide
(
)
NH
3
2
N
O H2N
HN
NH
COOH
3.3.6. Organosilicons
COOH
O
60°C, 12h
60°C, 12h
NH
H
COOH
COOH
Scheme
of rosin-tetraethylenepentamine
amide.
Rosin glycidyl ester
is 71.
a Preparation
brown, viscous
liquid. It can be synthesized
from rosin and
Scheme
amide.
Scheme71.
71.Preparation
Preparation of
of rosin-tetraethylenepentamine
rosin-tetraethylenepentamine amide.
epichlorohydrin according to Scheme 72 without further purification [254]. It can be used for
3.3.6.
Organosilicons
preparation
of cross-linking agent for silicone rubber [254].
3.3.6.
Organosilicons
3.3.6.
Organosilicons
Rosin-modified
room-temperature-vulcanized
silicone
be prepared
from
Rosin
glycidyl
ester
is a brown,
viscousIt liquid.
It rubber
can be can
synthesized
from
rosinrosin
and
Rosin
glycidyl
esterester
is a brown,
viscous viscous
liquid.
can be synthesized
from rosin and
epichlorohydrin
Rosin
glycidyl
is a brown,
liquid.
It can be synthesized
from
rosin and
glycidyl
ester,
aminopropyltrietoxysilane,
tetraetoxysilane
and
hydroxyl-terminated
epichlorohydrin
according
to
Scheme
72
without
further
purification
[254].
It
can
be
used
for
according
to Schemeaccording
72 without
purification
[254].
It can
be used for[254].
preparation
epichlorohydrin
tofurther
72
further
purification
can of
becross-linking
used
for
polydimetoxysilane
according
toScheme
Scheme
72 without
[254].
Rosin-modified
silicones showsItsignificantly
better
preparation of cross-linking
agent
for silicone
rubber
[254].
agent
for silicone
rubber [254].
preparation
cross-linking
agent for
rubber
[254].
thermal
and of
mechanical
properties
in silicone
comparison
with
unmodified
silicone
[254–256].
Rosin-modified
room-temperature-vulcanized
silicone
rubber
can be
prepared from rosin
Rosin-modified room-temperature-vulcanized silicone rubber can be prepared from rosin
glycidyl
ester,
aminopropyltrietoxysilane,
tetraetoxysilane
and
hydroxyl-terminated
glycidyl
ester, O aminopropyltrietoxysilane, Otetraetoxysilane
and
hydroxyl-terminated
(
)
H
N
polydimetoxysilane
according to2Scheme 72 [254]. Rosin-modified silicones shows significantly better
Cl
polydimetoxysilane
according to Scheme O72 [254]. Rosin-modified
silicones
Si O
HO ( Si shows
O ) H significantly better
n
thermal and NaOH
mechanical propertiesOinSicomparison
with unmodified silicone
[254–256].
O
thermal and TEBAC
mechanical properties in comparison
with
unmodified
silicone
[254–256].
O
117-60°C
5h O
Cl
O
Cl
COOH NaOH
Rosin
80°C, 1h
O H2N
H2N
O Si O
C
O Si O
O
O
O
NaOH
TEBAC
TEBAC
117-60°C
117-60°C
O
5h
O
5h Rosin glycidyl
O
COOH
COOH
NH
O
O
OH
Si O
Si O C
O
OO
O
( )
( (X)
)
O
(Y)
Rosin-modified
80°C, 1h
NH
80°C, 1haminopropyltrietoxysilane
ester
OH
NH
OH
C
yield: 92%
yield:
100%
C O
C
(Y)
O C
O
O
(Y)
O Si O
HO ( Si O ) H
O O nH
HO ( Si
)
n
dibutyltin
O
O
dilaurate
O
Si
O
25°C,
O Si 0.25h
O (X)
O
O
(X)
Y
X
X
Y
Y
Y
X
X
X
Y
Y X Y X
Y Xmodified
Y X
Rosin
X Y X
silicone
X Yrubber
X
yield:Y 100%
X Y
Y X Y
dibutyltin
O
Rosin Scheme 72. Preparation
dibutyltin
room-temperature-vulcanized
silicone
rubber.
O of rosin-modifiedRosin-modified
Rosin
modified
dilaurate
72. Preparation
of rosin-modified
room-temperature-vulcanized
silicone
rubber.
RosinScheme
O
Rosin-modified
Rosin
modified
dilaurate
25°C, 0.25h
RosinOglycidyl ester
aminopropyltrietoxysilane 25°C,
silicone
rubber
0.25h
Rosinyield:
glycidyl
ester
aminopropyltrietoxysilane
silicone
rubber
92%
100%
yield:rosin
100%
Maleated rosin-modified
vinyl fluorosiliconeyield:
resin
canrubber
be prepared
from
maleopimaric
acid
and
Rosin-modified
room-temperature-vulcanized
silicone
can
be
prepared
from
yield: 92%
yield: 100%
yield: 100%glycidyl
siloxanes
according
to
Scheme
73
prior
to
vacuum
evaporation
[116].
It
can
be
used
in
preparation
of
ester, aminopropyltrietoxysilane,
and hydroxyl-terminated
polydimetoxysilane
Scheme 72. Preparation of tetraetoxysilane
rosin-modified room-temperature-vulcanized
silicone
rubber.
Scheme
72. Preparation
of rosin-modified
room-temperature-vulcanized
silicone
rubber.
fluorosilicone
rubber,
having
improved
mechanical
and
thermal
properties
in
comparison
with
according to Scheme 72 [254]. Rosin-modified silicones shows significantly better thermal and
unmodified
sample
[116].
Maleated
rosin-modified
vinyl fluorosilicone
resin can be prepared
from maleopimaric acid and
mechanical
properties
in comparison
with unmodified
[254–256].
Maleated
rosin-modified
vinyl fluorosilicone
resin silicone
can be prepared
from maleopimaric acid and
siloxanes
according
to
Scheme
73
prior
to
vacuum
evaporation
[116].
It
can
be used
in preparation
of
Maleated
rosin-modified
vinyl
fluorosilicone
can be prepared
from
maleopimaric
acidof
and
siloxanes
according
to Scheme
73 prior
to vacuumresin
evaporation
[116]. It can
be used
in preparation
fluorosilicone
rubber,
having
improved
mechanical
and
thermal
properties
in
comparison
with
siloxanes
according
to
Scheme
73
prior
to
vacuum
evaporation
[116].
It
can
be
used
in
preparation
fluorosilicone rubber, having improved mechanical and thermal properties in comparison with
unmodified sample
[116].
of unmodified
fluorosilicone
rubber,
having improved mechanical and thermal properties in comparison with
sample
[116].
unmodified sample [116].
Molecules 2019, 24, 1651
33 of 52
Molecules2019,
2019,24,
24,xxFOR
FORPEER
PEERREVIEW
REVIEW
Molecules
Molecules 2019, 24, x FOR PEER REVIEW
H2N
H2N
3333of of
5151
33 of 51
F3C
Si O
F3C
Si O
HN
Si
++HO (2 Si O ) H++ F3C OOSi OSi
nH
HO
Si
O
+
+
F3C
Si O
(
)
n
Siloxane 1 Siloxane
OSi OSi
( Si O )n22H F3C
Siloxane 1 HO
Siloxane
Si O3
Siloxane
Siloxane 1 Siloxane 2 F3CSiloxane
3
Siloxane 3
KOH
Si O Si
Si O Si
Si O Si
KOH
100°C, 12h
KOH 12h
100°C,
CF100°C, 12h
H2N
H2N
H2N
CF3+
CF3+
CF +
3
O Si
O Si
O
Si
Si O Si O
Si
O
Si
Si
O Si O O
O Si O Si
Si O 4
Siloxane
Siloxane 4
Siloxane 4
HOOC
HOOC
HOOC
3
CF3
CF3
Si O ( Si O)a ( Si O )b ( Si O )c Si
Si O ( Si O)a ( Si O )b ( Si O )c Si
Si OVinyl
O )c Si
( Si Ofluorosilicone
)a ( Si O )b ( Si resin
150°C, 4h
150°C, 4h
150°C, 4h
COOH
COOH
COOH
O
O
O O
O
OO
O
O
O
O
O
N
N
N
CF3
O
CF3
O
CF3
O
Si O ( Si O )a ( Si O )b ( Si O )c Si
Si O ( Si O )a ( Si O )b ( Si O )c Si
Si O ( Si O )a ( Si O )b ( Si O )c Si
Maleated rosin-modified
Maleated
rosin-modified
vinyl
fluorosilicone
resin
Maleated
rosin-modified
vinyl
fluorosilicone
resin
Vinyl fluorosilicone resin
vinyl fluorosilicone
resin
Vinyl fluorosilicone
resin
Scheme
Preparationof
ofmaleated
maleated rosin-modified
resin.
Scheme
73.73.
Preparation
rosin-modifiedvinyl
vinylfluorosilicone
fluorosilicone
resin.
Scheme 73. Preparation of maleated rosin-modified vinyl fluorosilicone resin.
Scheme 73. Preparation of maleated rosin-modified vinyl fluorosilicone resin.
3.3.7.
Polysaccharides
3.3.7.
Polysaccharides
3.3.7. Polysaccharides
Superhydrophobicwood
woodcan
can be
be prepared
prepared using
using maleated
chloride
and and
3.3.7.
Polysaccharides
Superhydrophobic
maleatedrosin,
rosin,aluminum
aluminum
chloride
Superhydrophobic
woodto can
be prepared
using
maleated
rosin,
aluminum
chloride and
tetrabutyltitanate
according
Scheme
74
[119].
Such
a
hydrophobic
material
is
appreciated
in in
tetrabutyltitanate
according
to Scheme
74 [119]. using
Such a
hydrophobic
material
is chloride
appreciated
Superhydrophobic
wood
be prepared
rosin,material
aluminum
and
tetrabutyltitanate
according
to can
Scheme
74 have
[119].been
Such
amaleated
hydrophobic
is appreciated
in
construction. Related
starch-rosin
materials
also
prepared
[120].
construction.
Relatedaccording
starch-rosin
materials
also
prepared [120].
tetrabutyltitanate
to Scheme
74have
[119].been
Such
a prepared
hydrophobic
material is appreciated in
construction.
Related starch-rosin
materials
have
been
also
[120].
construction.
Related
materials
have been also prepared [120].
OHstarch-rosin
OH OH
OH
OH
OH
OH
OH
OH
OH OH
OH OH
Wood
Wood
Wood
COOH
OH
OH
Maleated rosin
AlCl
Maleated3rosin
Ti(OC4H9)4
Maleated
AlCl3rosin
in H2O/NH
AlCl
3/C
329H
Ti(OC
)45OH
4H
25-180°C,
41h
Ti(OC
H
4
9
in H O/NH /C H)4OH
2
COOH
COOH
COOH
3
COOH
COOH
COOH
COOH
COOH O
HO
O
HO
O
O O HO
O
O
2 5
in H25-180°C,
H5OH
2O/NH3/C241h
25-180°C, 41h
O
O
O
O
O
O
HO Ti
O O
O O
O
O
OO Ti O
HO
O
HO Ti
O
O
Superhydrophobic-surface
wood O
O
O O
O
O
O
O
O
O
AlO O
OO O
Al
Al O
O
Superhydrophobic-surface
wood
Scheme 74. Preparation of rosin-impregnated superhydrophobic
wood.
Superhydrophobic-surface wood
Scheme74.
74.Preparation
Preparation of
of rosin-impregnated
rosin-impregnated superhydrophobic
wood.
Scheme
superhydrophobic
wood.
Rosin-esterified
starch
can
be prepared according
to Schemewood.
75,
prior to filtration,
Scheme
74. biopolymer
Preparation of
rosin-impregnated
superhydrophobic
precipitation,
washing
and
drying
[257,258].
Rosin
decreases
solubility
and
swelling
of starch,
which
Rosin-esterifiedstarch
starchbiopolymer
biopolymer can
can be
be prepared
prepared according
to to
filtration,
Rosin-esterified
accordingtotoScheme
Scheme75,
75,prior
prior
filtration,
potentially
allows tostarch
use this
polymer incan
foodbeand
biomedical
materials
[257]. 75, prior to filtration,
Rosin-esterified
biopolymer
prepared
according
to Scheme
precipitation,
washing
anddrying
drying[257,258].
[257,258]. Rosin
Rosin decreases
starch,
which
precipitation,
washing
and
decreasessolubility
solubilityand
andswelling
swellingofof
starch,
which
precipitation,
washing
and
drying
[257,258].
Rosin
decreases solubility
and
swelling of starch, which
potentially
allows
to
use
this
polymer
in
food
and
biomedical
materials
[257].
potentially
allows to use this polymer in food and biomedical materials [257].
potentially allows to use this polymer in food and biomedical materials [257].
OH
OH
OHOH
OH
OH
OH
HO
O
OH
Starch O
OH O
OH
Starch
Starch
n+m
n+m
n+m
O
lipase
HO1-4h O
in DMSO 40°C,
HO
O
O
O
OH OH
OH
O
OH OH
lipase
Degree1-4h
of substitution:
m
OH
lipase
in DMSO
40°C,
O
0.031-0.092
in DMSO 40°C, 1-4h
Rosin acid starch
O
OH
Degree of substitution:
m
OH
Degree of substitution:
0.031-0.092
m
Scheme 75. Preparation
of rosin-esterified
starch.
Rosin
acid
starch
0.031-0.092
OH
OH
OH
O
O
O
O
O
OH
O
OH O
OH
n
n
n
Rosin acid starch
Scheme
75. Preparation
of rosin-esterified
starch.
Cellulose nanofibers and
nanocrystals
surface-modified
by rosin
can be prepared according to
Scheme75.
75. Preparation of rosin-esterified
Scheme
rosin-esterifiedstarch.
starch.
Scheme 76, prior to washing
in ethanolPreparation
[259,260]. They
can be used as
antibacterial reinforcements in
Cellulose
nanofibers
and nanocrystals
surface-modified
can be
according
bio-based
package
films [260].
In similar way
hemp fibers canby
berosin
modified
byprepared
tall oil rosin
acids into
Cellulose
nanofibers
and
nanocrystals
surface-modified
by
can
according
to to
Cellulose
nanofibers
and
nanocrystals
surface-modified
byrosin
rosin
canbebeprepared
prepared
according
Scheme
76,
prior
to
washing
in
ethanol
[259,260].
They
can
be
used
as
antibacterial
reinforcements
in
order to improve the reinforcement adhesion to an epoxy matrix [261].
Scheme
76,
prior
to
washing
in
ethanol
[259,260].
can
be
used
as
antibacterial
reinforcements
in in
Scheme
76,
prior
to
washing
in
ethanol
[259,260].
They
can
be
used
as
antibacterial
reinforcements
bio-based package films [260]. In similar way hemp fibers can be modified by tall oil rosin acids in
bio-based
package
films
[260].
In
similar
way
hemp
fibers
can
be
modified
by
tall
oil
rosin
acids
in
bio-based
films
[260]. In similar
waytohemp
fibers
can be
modified by tall oil rosin acids in
order to package
improve the
reinforcement
adhesion
an epoxy
matrix
[261].
order
improve
the
reinforcementadhesion
adhesionto
toan
anepoxy
epoxy matrix
matrix [261].
order
to to
improve
the
reinforcement
[261].
Molecules 2019, 24, 1651
34 of 52
Molecules 2019, 24, x FOR PEER REVIEW
Molecules 2019, 24, x FOR PEER REVIEW
Molecules 2019, 24, x FOR PEER REVIEW
Molecules 2019, 24, x FOR PEER REVIEW
O
OH
OH
OH
OH
HO
HO
HO
O HO
O
O
O
OH
OH
OH
OH
O
O
OH
O
HO
OH
HO
OH
HO
Cellulose
OH
HO
OH
OH
OH
nanofibers
OH
Cellulose nanofibers
n
n
n
n
34 of 51
OH
Rosin
Rosin
Rosin
O/HCl
in H2Rosin
in H2O/HCl
in H2O/HCl
130°C,
24h
in
H2O/HCl
130°C,
24h
130°C,
24h
130°C, 24h
O
O
O
OHO
HO
HO
HO
HO
HO
HO
OHO
O
O
O
OH
OH
OH
OH
34 of 51
34 of 51
34 of 51
R = abietate
R or
= abietate
pimarate
R = abietate
or
pimarate
R
abietate
or =pimarate
Degreeorofpimarate
substitution:
Degree
substitution:
0.05 of
Degree
of substitution:
0.05
Degree
0.05 of substitution:
0.05
OH
OH
OH
OH
O
OH
OH
OH
n
RO
n
R O
n
O
R
modified cellulose
nanofibers
n
R
modified cellulose
nanofibers
Rosin
Cellulose nanofibers
Rosin
Cellulose nanofibers
Rosin modified cellulose nanofibers
Rosin modified
cellulose
nanofibers
Scheme 76.
76. Preparation
Preparationof
ofrosin-modified
rosin-modified
cellulose
nanofibers.
Scheme
cellulose
nanofibers.
Scheme
Scheme 76.
76. Preparation
Preparation of
of rosin-modified
rosin-modified cellulose
cellulose nanofibers.
nanofibers.
Scheme 76. Preparation of rosin-modified cellulose nanofibers.
Chitosan grafted
grafted by
by rosin
rosin acrylate
acrylate is
is aa solid.
solid. ItIt can
can be
be prepared
prepared from
from chitosan
chitosan and
and rosin
rosin acid
acid
Chitosan
Chitosan
grafted
by
rosin
acrylate
is
aa solid.
It
can
be
prepared
from
chitosan
and
rosin
acid
Chitosan
grafted
by
rosin
acrylate
is
solid.
It
can
be
prepared
from
chitosan
and
rosin
acid
hydroxyethyl
acrylate
according
Scheme
prior
toItprecipitation,
filtration,
washing
and drying
[172].
Chitosan
grafted
by rosintoacrylate
is77a77
solid.
can
be prepared
from chitosan
and
rosin
acid
hydroxyethyl
acrylate
according
toto
Scheme
prior
to
precipitation,
filtration,
washing
and drying
hydroxyethyl
acrylate
according
77
prior
filtration,
hydroxyethyl
acrylate
according
to Scheme
Scheme
77applications
prior to
to precipitation,
precipitation,
filtration, washing
washing and
and drying
drying
It
can
be
potentially
used
in
controlled
release
[172].
hydroxyethyl
acrylate
according
to
Scheme
77
prior
to
precipitation,
filtration,
washing
and
drying
[172].
It can
be potentially
used inincontrolled
release applications
[172].
[172].
[172]. It
It can
can be
be potentially
potentially used
used in controlled
controlled release
release applications
applications [172].
[172].
[172]. It can be potentially used in controlled release applications [172].
RR
OO R
O R
O
OO
O
K S OO
OHOH
OH
OH
O O
O
OO
K2KS22SO
288
O
O
2 2O
8
O
K2S2COOH
OCOOH
2
NHNH
8
inin
H2H
O/CH
HOHO
2
NH2
2O/CH
3 33COOH
in
H
O/CH
HO
2O/CH COOH
NH2
n
in
H
HO Chitosan
3
n n60°C,
60°C,2h;
2h; microwaves
Chitosan
60°C,22h;microwaves
microwaves
Chitosan
n 60°C,
2h; microwaves
Chitosan
OO
O
O
HO
HO
HO
HO
[[[
[O
OO
O
OH
OH
OH
NH
NH
NH
m
]]m
m
]m
O
O
O
O
RR
==
R=
R=
O
O
O
O
nnChitosan graft
Chitosangraft
graft
n Chitosan
n Chitosan
graft
RR
R
R
rosin
rosinacrylate
acrylate
rosin
acrylate
rosin
acrylate
copolymer
copolymer
copolymer
copolymer
O
O O O
O
O
O
O
Grafting
percentage:
Grafting
percentage:
Grafting
percentage:
72.3%
Grafting
percentage:
72.3%
72.3%
72.3%
Scheme
77.
Preparation
of
chitosan
graft
Scheme
77.
Preparation
of
chitosan
graftrosin
rosinacrylate
acrylatecopolymer.
copolymer.
Scheme
77.
rosin
acrylate
copolymer.
Scheme
77.Preparation
Preparationof
ofchitosan
chitosan graft
graft
acrylate
copolymer.
Scheme 77. Preparation of chitosan graft rosin acrylate copolymer.
3.3.8.
Other
Materials
3.3.8.
Other
Materials
3.3.8.
Other
Materials
3.3.8.
Other
Materials
3.3.8.
Other
Materials
Dehydroabietic
acid-glycerol
carbonate
product
canbe
beprepared
preparedfrom
fromdehydroabietic
dehydroabietic
acid
and
Dehydroabietic
acid-glycerol
carbonate
product
can
acid
and
Dehydroabietic
acid-glycerolcarbonate
carbonateproduct
product can
can
be
prepared
from
dehydroabietic
acid
and
Dehydroabietic
acid-glycerol
be
preparedfrom
fromdehydroabietic
dehydroabieticacid
acid
and
Dehydroabietic
acid-glycerol
carbonate
product
canbe
beapplied
prepared
and
glycerin
carbonates
according
to
Scheme
78
[262].
It
can
be
applied
in
xerographic
tonners
[262].
glycerin
carbonates
according
to
Scheme
78
[262].
It
can
in
xerographic
tonners
[262].
glycerin
carbonates
according to Scheme78
78 [262]. ItIt can
can be applied
applied in
xerographic
tonners
[262].
glycerin
carbonates
according
inxerographic
xerographictonners
tonners[262].
[262].
glycerin
carbonates
accordingtotoScheme
Scheme 78[262].
[262]. It can be
be applied in
O
(1) O
(2) O
(3) O
(4) O
O
(1) O
(2) O
(3) O
(4) O
O O (1)(1)
O O DA
(2)(2)O O DA (3)
(4)
DA
DA
(3)OO
(4) O
O
DA
DA
DA
DA
O
O
DA
O
O
DA
DA O
DA
O DADA O DA
O DA
O
R O O O
O
O
O
O
R
O
O
O
O
O
O
O
O
R R
(C2H5)4N I
OH
OH
(C2H5)4N I R
R
OH
OH
12hI
(C
(C2150°C,
H
5)4IN
52)H
4N
OH O
OH
150°C,
12hR R OH
OHOH
O OH
O
OH
OH
O
O
O
150°C,
12h
150°C,
12h
COOH
OH
OH
O
O O
OH
OH
OO OO
COOH
Dehydroabietic
O
Dehydroabietic OO
COOH
O DA
COOH
O
Dehydroabietic O
DA
acid-glycerin
Dehydroabietic
Dehydroabietic
acid-glycerin
O
Dehydroabietic acid
acid
DA
DA
++
++
++
++
++
++
(5)
(5)
(5)
(5)
O
O
O
O
++ HO
HO
+ HO
O
O
O
O
O
O
O
O
O
O
O
O
acid-glycerin
carbonate
Dehydroabietic
acid acid-glycerin
Dehydroabietic
acid
carbonate product
product yield:
yield: 99%
99%
carbonateproduct
product yield:
yield:99%
99%
carbonate
DA
DA
DA
DA
(6)
(6)
(6)
(6)
O
O
OO
DA
DA
DA
DA
R = H, or CH2OH
R = H, or CH2OH
CH
2OH
RR= =H,H,
oror
CH
2OH
O
O
OO
DA =
DA =
DA= =
DA
O
O
OO DA
DA
O O
DA
DA
O O
DA O
DA O OO OO
DA
DA OO DA
DA
DA
DA
++
++
Scheme
78.
Preparation
of
xerographic
toner.
Scheme78.
78.Preparation
Preparation of
of rosin-glycerin
rosin-glycerin carbonate
carbonate
xerographic
Scheme
rosin-glycerin
carbonatexerographic
xerographictoner.
toner.
Scheme
Preparationof
ofrosin-glycerin
rosin-glycerin carbonate
carbonate
Scheme
78.78.Preparation
xerographictoner.
toner.
Rosin-polyphthalate
resin
glossy
light
maleopimaric
Rosin-polyphthalateresin
resinisis
isaaaglossy
glossy light
light yellow
yellow solid.
solid.
ItItcan
can
be
prepared
from
maleopimaric
Rosin-polyphthalate
yellow
solid.It
canbe
beprepared
preparedfrom
from
maleopimaric
Rosin-polyphthalate
resin is a glossy
lightaccording
yellow solid.
It can be
prepared
from maleopimaric
acid,
and
phthalic
anhydride-glycerol
polyester
to
Scheme
79
prior
to
vacuum
[117].
Rosin-polyphthalate
resin is a glossy
light according
yellow solid.
It can 79
be
prepared
from drying
maleopimaric
acid,
and
phthalic
anhydride-glycerol
polyester
to
Scheme
prior
toto
vacuum
drying
[117].
acid,
and
phthalic
anhydride-glycerol
polyester
to
Scheme
79
prior
vacuum
drying
[117].
acid,
and phthalic
anhydride-glycerol
polyester
according to
Scheme
79[117].
prior to vacuum drying
[117].
Its
application
is
an
environmentally-friendly
phenol-free
printing
ink
acid,
and
phthalic
anhydride-glycerol
polyester
according
to
Scheme
79
prior
to
vacuum
drying
[117].
Its
application
is
an
environmentally-friendly
phenol-free
printing
ink
[117].
Its Its
application
is is
ananenvironmentally-friendly
printing ink
ink[117].
[117].
application
environmentally-friendlyphenol-free
phenol-free printing
Its application is an environmentally-friendly phenol-free printing ink [117].
O
COOH
COOH
COOH
O
O
O
O
O
O
OO
O
O
O
Maleopimaric
acid
Maleopimaric
acid
COOH
Maleopimaric
acid
Maleopimaric acid
R OH
R OH
R OH
OH
R
OH
R R OH
R
OH
R OH
OH
R R OH
R OH
260°C,
2h
260°C, 2h
R OH2h
260°C,
260°C, 2h
O
O R
O R
R
O O
O
R
O
OO
O
O
O R
O R
O RO
OH OH
COO
OH OH
COO
O R
OH
OH
COO R R R
R R R
OH R
OH
R
R
COO
R
R
R
HO
HO
R R
R R
HO
R=
R
R
HO
OH OH
R=
OH
R OH
R
R=
O
OH OH
O
R=
OH
O
OHOH
OH
O O
OH OH
O O
O
OH R
OH
O O
R
R R
O O
Rosin-based
ROHROH
Rosin-based
R
Rosin-based
R phenol-free
phenol-free
Rosin-based
phenol-free
resin
resin
resin
phenol-free
Scheme
Scheme 79.
79. Preparation
Preparation of
of rosin-based
rosin-based phenol-free
phenol-free resin.
resin.resin
Scheme
rosin-basedphenol-free
phenol-freeresin.
resin.
Scheme79.
79.Preparation
Preparation of rosin-based
Scheme
Preparation
of rosin-based
phenol-free
resin.
Rosin
propargyl
ester
is
aa79.
white,
transparent
liquid.
It
can
be
synthesized
from
rosin
chloride
Rosin
propargyl
ester
iswhite,
white,
transparent
liquid.
It
can
be
synthesized
from
rosin
chloride
Rosin
propargyl
ester
is
a
transparent
liquid.
It
can
be
synthesized
from
rosin
chloride
and
Rosin
propargyl
ester
is
a
white,
transparent
liquid.
It
can
be
synthesized
from
rosin
chloride
and
propargyl
alcohol
according
to
Scheme
80,
prior
to
washing
and
column
chromatography
and propargyl alcohol according to Scheme 80, prior to washing and column chromatography [147].
[147].
propargyl
alcohol
according
80, prior
washing
chromatography
[147].
It can
and
propargyl
alcohol
according
to Scheme
80, to
prior
to washing
and
column
chromatography
[147].
Rosin
propargyl
ester
istoa Scheme
white,
transparent
liquid.
Itand
cancolumn
be synthesized
from rosin
chloride
It
It can
can be
be used
used to
to prepare
prepare caprolactone
caprolactone graft
graft copolymers
copolymers [147].
[147].
be
used
to
prepare
caprolactone
graft
copolymers
[147].
It
can
be
used
to
prepare
caprolactone
graft
copolymers
[147].
and propargyl
alcohol according
to Scheme 80, prior to washing
and column chromatography
[147].
Rosin
Rosin ester
ester containing
containing poly(α-azide-ε-caprolactone)
poly(α-azide-ε-caprolactone) can
can be
be prepared
prepared from
from rosin
rosin propargyl
propargyl ester,
ester,
Rosin
ester
containing
poly(α-azide-ε-caprolactone)
can
be
from
rosin
propargyl
ester,
Rosin
ester
containing
poly(α-azide-ε-caprolactone)
can
beprepared
prepared
from
rosin
propargyl
ester,
It can
be
used
to
prepare
caprolactone
graft
copolymers
[147].
α-chloro-ε-caprolactone
and
sodium
azide
according
to
Scheme
80,
and
using
such
separation
α-chloro-ε-caprolactone and sodium azide according to Scheme 80, and using such separation
α-chloro-ε-caprolactone
and
sodium
azide
according
to
Scheme
80,using
and
using
such
separation
α-chloro-ε-caprolactone
and
sodium
azide
according
to Scheme
and
such
separation
methods
Rosin ester
containing
poly(α-azide-ε-caprolactone)
can
be80,
prepared
from
rosin
propargyl
ester,
methods
as
and
copolymer
shows
properties
methods
as centrifugation
centrifugation
and vacuum
vacuum drying
drying [147].
[147]. This
This biodegradable
biodegradable
copolymer
shows
properties
methods
as
centrifugation
and
vacuum
drying
[147].
This
biodegradable
copolymer
shows
properties
α-chloro-ε-caprolactone and sodium azide according to Scheme 80, and using such separation
methods as centrifugation and vacuum drying [147]. This biodegradable copolymer shows properties
Molecules 2019, 24, x FOR PEER REVIEW
35 of 51
similar to poly(methyl acrylate) [263]. Similar polymers with quaternary ammonium groups showing
antimicrobial properties can be also prepared [264].
Molecules 2019,
24, 1651
Acrylic
rosin methacryl diester can be prepared from acrylic rosin and 2-hydroxyethyl35 of 52
methacrylate according to Scheme 81, prior to rotary evaporation and vacuum drying [124]. It can be
used
as acrylic
monomer
orREVIEW
resin [124].
Molecules
2019, 24,
x FOR PEER
35 of 51
as centrifugation
and vacuum drying
[147].
biodegradable
copolymer
shows properties
similar
Poly(styrene-co-acrylic
rosin ester)
canThis
be prepared
via suspension
polymerization
of acrylic
to poly(methyl
acrylate)
[263].
Similar
polymers
with
quaternary
ammonium
groups
showing
similar
to poly(methyl
acrylate)
Similarto
polymers
quaternary
ammonium
groups
showing
rosin
methacryl
ester and
styrene[263].
according
Schemewith
81, prior
to washing,
filtration
and
vacuum
antimicrobial
can
be
also
prepared
[264].
antimicrobial
properties
can be
prepared
[264].
drying
[124].
Its properties
application
isalso
microspheres
[124].
)n
Acrylic rosin methacryl diester can be prepared from acrylic rosin and 2-hydroxyethyl
methacrylate according to Scheme 81, prior to rotary evaporation and vacuum drying [124]. It can be
Molecules 2019, 24,chloride
x FOR PEER REVIEW
35 of 51
Dehydroabietyl
Dehydroabietic propargyl ester
O
used as acrylic monomer or resin [124].
OH ester) can be prepared via suspension polymerization of acrylic
Poly(styrene-co-acrylic
rosin
similar to poly(methyl acrylate) [263]. Similar polymers with quaternary ammonium groups showing
rosin methacryl
ester and
styrene
according to Scheme 81, prior to washing, filtration and vacuum
(Ccan
2H5)be
3N also prepared [264].
antimicrobial
properties
CuI
COCl [124]. Its application
in CH2is
Clmicrospheres
drying
[124].
2diester
DBU acrylic rosinO andO 2-hydroxyethyl
O
Acrylic rosin methacryl
can be
prepared from
O
22°C, 24h
)n
in THF
methacrylate according to Scheme 81, prior to rotary evaporation
and vacuum drying [124]. ItNcan be
35°C, 12h
N
O
Dehydroabietyl
chloride or resinDehydroabietic
N
propargyl
ester
N3
used
as acrylic monomer
[124].
(
α-chloro-ε-caprolactone
O
of acrylic
Cl Poly(styrene-co-acrylic rosin
Rosin ester containing
( O can be prepared
)n via suspension polymerization
OH ester)
poly(α-azide-ε-caprolactone)
rosin methacryl ester and styrene according
to Scheme
filtration and vacuum
O 81, prior to washing,
Poly(α-azide(C2H5)3N
CuI
O COCl
drying
[124]. Its application
is2microspheres
[124].
O
-ε-caprolactone)
in CH
Cl2
M = 10400, 11000, 12200
O
N3
OH
( (O
))n
n
O
nO
N
N
N
( )n
DBU
O
O
in THF
in DMF
NaN3 25°C, 12h
35°C, 12h
Cl
Dehydroabietic propargyl
ester
22°C, 24h
2-hydroxyethyl2-bromoisobutyrate
Dehydroabietyl
chloride
α-chloro-ε-caprolactone
Sn(II) 2-ethylhexanoate
Cl
in toluene
120°C, 12h
O
O
Poly(α-chloro-ε-caprolactone)
Rosin ester containing
poly(α-azide-ε-caprolactone)
O
(
Poly(α-azide- O
(C2H5)3N
CuI
O
O
-ε-caprolactone) DBU
COCl
in CH2Cl2
M = 10400, 11000, 12200
O rosin
O n O
Scheme
80. 80.
Preparation
of
ester
containing
poly(α-azide-ε-caprolactone).
Scheme
Preparation
of
rosin
ester
containing
poly(α-azide-ε-caprolactone).
O
in DMF
in THF
2-hydroxyethyl- 22°C, 24h
N
NaN3 25°C, 12h
35°C, 12h
N
2-bromoisobutyrate
Cl
O
N
N3
PDI=1.17-1.36
2-ethylhexanoate
α-chloro-ε-caprolactone
Acrylic
rosinSn(II)
methacryl
diester
can
be
prepared
from
acrylic
rosin
and
2-hydroxyethyl
methacrylate
COO
COO
COOH
(O
)n Poly(α-chloro-ε-caprolactone)
in toluene
O
Cl
Rosin ester containing
(O
)n
according to Scheme120°C,
81, prior
to rotary evaporation
and
12h
O vacuum drying [124]. It can be used as acrylic
poly(α-azide-ε-caprolactone)
O
Poly(α-azideO
O
O
O
-ε-caprolactone)
Scheme 80. Preparation of rosin ester containing poly(α-azide-ε-caprolactone).
Mn = 10400,
11000, 12200
monomer orO resin
[124].
HO
O
O
AIBN
ZnO, HQ
in DMF
2-hydroxyethylO
(
)n(
)m
O
gelatin
NaN3 25°C,
200-230°C
12h Cl
2-bromoisobutyrate
PDI=1.17-1.36
in
H
O
COOH
COO
COO
2
COO
COO
3.5h
Sn(II)COOH
2-ethylhexanoate
O
O
<90°C,
5h
(O O
)n Poly(α-chloro-ε-caprolactone)
Acrylic rosin in toluene
(
)n(
)m
120°C, 12hAcrylic
O
O
O
O rosin ethyl methacryl
HO
Poly(styrene-co-O
O
diester yield:
92%
AIBN
Scheme
80.
Preparation of rosin ester containing
poly(α-azide-ε-caprolactone).
ZnO,
HQ
-acrylic rosin ester)
O
(
O
200-230°C
COOH
Acrylic rosin
)n(
gelatin
in H2O rosin ester
COO
COO copolymer.
3.5h 81. Preparation
Scheme
of Ostyrene and acrylic
O
<90°C, 5h
)m
PDI=1.17-1.36
( COO)n(
)m
Acrylic
rosin
ethyl
methacryl
Rosin-tung oil Diels-Alder adduct is a yellowish
solid.
It
can
be
prepared
from
levopimaric
acid
Poly(styrene-coO
O
diester yield: 92%
O
HO to Scheme 82, prior toO precipitation and
O
and tung oil according
drying
[265,266].
Its application is a
-acrylic
rosin
ester)
AIBN
ZnO, HQ promoter in polyurethane [265]
filler, tackifier and adhesion
and UV-curable
O adhesives
(
)n([266].
)m
Scheme
81. Preparation of styrene
and acrylic
ester copolymer.
O
gelatin rosin
200-230°C
Scheme
81.
Preparation
of
styrene
and
acrylic
ester copolymer.
in H2O rosinCOO
COOH
COO
3.5h
COOH
COO
O
O
O
<90°C, 5h
O
Acrylic
rosin
( from
)n(levopimaric
)m HOOCacid
Rosin-tung
oil Diels-Alder adduct is a yellowish solid.
It can be prepared
Acrylic
rosin
ethyl
methacryl
Poly(styrene-co-acrylic
rosin
ester)
can
be
prepared
via
suspension
polymerization
O oil (CH
and tung
according
to Scheme 82, prior to precipitation and drying [265,266]. Its application isofa acrylic
2)7
Poly(styrene-codiester yield: 92%
rosin methacryl
ester
and
styrene
according
to Scheme[265]
81, and
prior
to washing,
filtration
filler, tackifier
and
adhesion
promoter
in polyurethane
UV-curable
adhesives
[266]. and vacuum
-acrylic
O rosin ester)
O
(CH )
O
2 7
drying [124].
Its application
is 81.
microspheres
[124]. and acrylic rosin ester copolymer.
Scheme
Preparation of styrene
O
O
HOOC
O
(CH2)7
O
(CH2)7
Rosin-tung
oil Diels-Alder adduct is a yellowish solid. It can be prepared from levopimaric acid
O
(CH2)7
oilto
Diels-Alder
adduct
is ato
yellowish
solid.
It can
prepared
from levopimaric
acid
O
Obe
(CH2)7 [265,266].
and tung oilRosin-tung
according
Scheme 82,
prior
precipitation
and
drying
Its application
is a
O
and
to Scheme 82, prior to precipitation and
drying
[265,266]. Its application is a
O
(CH2)7
O tung oil
O according
filler, tackifier
and
adhesion
promoter
in
polyurethane
[265]
and
UV-curable
adhesives
[266].
O
Tung oil
(CH )
O
7
filler, tackifier
and adhesion promoter in polyurethane2[265]
andO UV-curable
adhesives [266].
HOOC
(CH
2)7
O
(CH2)7
O
Tung oil
O
O
(CH2)7
O
(CH2)7
O
(CH2)7
O
HOOC
Levopimaric acid
HQ; 170-260°C; 4-7h
O
O
(CH2)7
HOOC
(CH2)7
O
O
HOOC
HOOC
Rosin-tung oil adduct
conversion: 72%
O Diels-Alder
Scheme 82.
Preparation Levopimaric
of idealized
adduct.
(CH2)7
acid rosin-tung oil
HOOC
HQ; 170-260°C; 4-7h
Tung oil
O
O
O
O
(CH2)7
HOOC
Rosin-tung oil adduct
conversion: 72%
O
Scheme 82. Preparation of idealized (CH
rosin-tung
oil Diels-Alder
2)7
HOOC adduct.
HOOC
HOOC
Levopimaric acid
HQ; 170-260°C; 4-7h
Rosin-tung oil adduct
conversion: 72%
Scheme 82. Preparation of idealized rosin-tung oil Diels-Alder adduct.
Scheme 82. Preparation of idealized rosin-tung oil Diels-Alder adduct.
Molecules 2019, 24, 1651
Molecules
2019,
x FOR
PEER
REVIEW
Molecules
2019,
24,24,
x FOR
PEER
REVIEW
36 of 52
36 36
of of
51 51
Acrylic-vinyl
copolymer
with
rosin
moieties
is aisslightly
yellow
solid.
It can
be
prepared
from from
rosin
Acrylic-vinyl
copolymer
with
rosin
moieties
is
a slightly
yellow
solid.
can
prepared
from
Acrylic-vinyl
copolymer
with
rosin
moieties
a slightly
yellow
solid.
It It
can
bebe
prepared
ethyl
methacrylate,
styrene
and
divinylbenzene
according
to
Scheme
83,
prior
to
washing,
filtration
rosin
ethyl
methacrylate,
styrene
and
divinylbenzene
according
to
Scheme
83,
prior
to
washing,
rosin ethyl methacrylate, styrene and divinylbenzene according to Scheme 83, prior to washing,
and
drying
[267].
Its application
isapplication
polymerismicrospheres
for adsorption
and
separation
[267].
filtration
and
drying
[267].
is
polymer
microspheres
adsorption
and
separation
filtration
and
drying
[267].
ItsIts
application
polymer
microspheres
forfor
adsorption
and
separation
[267].
[267].
PDI=1.30-3.25
PDI=1.30-3.25
O O
C C
O O
O O
O O
C C
O
O O O
( (
O O
gelatin,
toluene,
AIBN
gelatin,
toluene,
AIBN
in2O
H 2O
in H
80-90°C,
80-90°C,
5h 5h
O O
Rosin
ethyl
methacryalte
Rosin
ethyl
methacryalte
( (
)m()m( )n )n
)m()m( )n )n
Acrylic-vinylO O
Acrylic-vinyl
microspheres O O
microspheres
with
rosin
moieties
with
rosin
moieties
O O
C C
O O
Scheme
Preparation
acrylic-vinyl
copolymer
with
rosin
moieties.
Scheme
83.83.
Preparation
ofof
acrylic-vinyl
copolymer
with
rosin
moieties.
Preparation
of
acrylic-vinyl
copolymer
Rosin/lignin
grafted
copolymers
can can
becan
prepared
from lignin
and
dehydroabietic
acid derivatives
Rosin/lignin
grafted
copolymers
prepared
from
lignin
anddehydroabietic
dehydroabietic
acid
Rosin/lignin
grafted
copolymers
bebeprepared
from
lignin
and
acid
in
two
ways:
simple
grafting
or
ATRP
polymerization,
according
to
Scheme
84
and
using
such
derivatives
two
ways:
simple
grafting
ATRP
polymerization,
according
Scheme
and
using
derivatives
in in
two
ways:
simple
grafting
oror
ATRP
polymerization,
according
to to
Scheme
8484
and
using
separation
methods
as
precipitation,
filtration,
washing
and
vacuum
drying
[169].
These
materials
are
such
separation
methods
as
precipitation,
filtration,
washing
and
vacuum
drying
[169].
These
such separation methods as precipitation, filtration, washing and vacuum drying [169]. These
characterized
by
strongly
increased
hydrophobicity
compared
to
raw
lignin
[169].
materials
characterized
strongly
increased
hydrophobicity
compared
raw
lignin
[169].
materials
areare
characterized
byby
strongly
increased
hydrophobicity
compared
to to
raw
lignin
[169].
X =X2=or2 4or 4
O O
= Hor CH
Y =YHor CH
3- 3
O O
O O O O
LIG
LIG
O O O O
COCl
COCl
5)3N
(C2(C
H52)H3N
in
THF
in THF
50°C,
50°C,
12h12h
O O
O O
2)XO
(CH(CH
2)XO
O O
Br Br
(
( )L )L
Y Y
OHOH
LIGLIGOHOHBr Br
OHOH
Lignin
Lignin
O O
O O
O OLIGLIG O O
Br Br
5)3N O O
(C2(C
H52)H3N
O O
Br Br
in THF
in THF
O
Br
O
0°C,
24h
Br
0°C, 24h
Br Br
Lignin
ATRP
Lignin
ATRP
macroinitiator
macroinitiator
HOHO
LIG(
OH)
=
LIG(
OH)
3 =3
OHOHOHOH
O O
O O
O O
HOHO
O O
O O
O O
O
O O
O O
)
(CH(CH
2)x 2 x
CuBr
CuBr
in THF
in THF
65°C,
65°C,
24h24h
O O
O O Y Y
(
O O
O OLIGLIG
O
O O
O O
O O
Y Y
O O
)Br Br
( ( )L
L
O
)
(CH
O (CH
2)X 2 X
O O
O O O
O
O
O
(
O (CH
)
O (CH
2)X 2 X
O
)
O
)L L Br
Br
Y Y
Rosin
Rosin
polymer
grafted
from
lignin
polymer
grafted
from
lignin
g/mol
MnM
=5470-56
400400
g/mol
n=5470-56
OHOHOHOH
Scheme
Preparation
lignin
materials
hydrophobized
rosin.
Scheme
84.84.
Preparation
of
lignin
materials
hydrophobized
byby
rosin.
Preparation
ofof
lignin
materials
Rosin-caprolactone
diblock
copolymers
canbebeprepared
prepared
fromdehydroabietic
dehydroabietic
ethyl
diblock
copolymers
can be
prepared
from
dehydroabietic
ethyl methacrylate,
Rosin-caprolactone
diblock
copolymers
can
from
ethyl
methacrylate,
ε-caprolactone
and
2-hydroxyethyl
2-bromoisobutyrate
according
prior
ε-caprolactone
and
2-hydroxyethyl
2-bromoisobutyrate
according to Scheme
85 prior
toScheme
precipitation
methacrylate,
ε-caprolactone
and
2-hydroxyethyl
2-bromoisobutyrate
according
to to
Scheme
8585
prior
to
precipitation
and
washing
[170].
They
can
be
applied
in
areas
designed
for
simultaneously
bioand
washing [170].
They can
be They
applied
designed
simultaneously
bio-based bioand
to
precipitation
and washing
[170].
caninbeareas
applied
in areasfor
designed
for simultaneously
based
and
biodegradable
materials
[170].
biodegradable
materials [170].
based
and
biodegradable
materials
[170].
Acrylpimaric
acid
hydroxyethyl
polyesters
light
yellow
solids.
They
can
prepared
Acrylpimaric
acid
hydroxyethyl
polyesters
yellow
solids.
They
can
bebe
Acrylpimaric
acid
hydroxyethyl
polyesters
areare
light
They
can
be
prepared
viavia
polycondensation
of
corresponding
acrylpimaric
diols
according
to
Scheme
86
prior
to
grinding,
polycondensation of
of corresponding
corresponding acrylpimaric
acrylpimaric diols
diols according
according to
to Scheme
Scheme 86
86 prior
prior to
to grinding,
grinding,
polycondensation
washing
and
drying
[138].
Such
polymers
can
potentially
applied
modern
electrical
and
washing
and
drying
[138].
Such
polymers
can
bebe
potentially
applied
in in
thethe
modern
electrical
and
electronic
industries,
especially
for
the
environmentally
friendly
green
products
[138].
electronic industries, especially for the environmentally friendly green products [138].
Molecules 2019, 24, 1651
37 of 52
Molecules 2019, 24, x FOR PEER REVIEW
37 of 51
Molecules 2019,
x FOR [138].
PEER REVIEW
37 ofand
51
washing
and 24,
drying
Such polymers can be potentially applied in the modern electrical
electronic
industries,
especially
for
the
environmentally
friendly
green
products
[138].
Furthermore, rosin can be pyrolized in order to prepare a matrix for silver nanoparticles to apply
Furthermore,rosin
rosincan
canbe
bepyrolized
pyrolizedin
in order
order to
to prepare aa matrix
for
silver
totoapply
Furthermore,
for[268],
silvernanoparticles
apply
as antibacterial
filler for
wooden
furniture
or air prepare
filter for matrix
indoors
ananoparticles
catalyst carrier
with
as antibacterial filler for wooden furniture or air filter for indoors [268], a catalyst carrier with
as
antibacterial
filler
for
wooden
furniture
or
air
filter
for
indoors
[268],
a
catalyst
carrier
with
potential
potential application as counter electrode for dye-sensitized solar cells [269], a coating for bentonite
potential application as counter electrode for dye-sensitized solar cells [269], a coating for bentonite
application
as counter electrode
for dye-sensitizedfor
solar
cells [269],
a coating
for bentonite
particles
and
particles
chromium
ions
adsorption
[270],and
and
activated
particlesand
andsupport
support for
for Fe
Fe22O
O33 nanoparticles
nanoparticles for chromium
ions
adsorption
[270],
activated
support
for Fe2 O3 nanoparticles for chromium ions adsorption [270], and activated carbons [271,272].
carbons
carbons[271,272].
[271,272].
Br
Br
O
O
OO
OO
O
O
HO
HO
O
O
O
O
Br (
Br
(
O
O
O
O
)m
)m
OO
CuBr
CuBr // tris(2-(dimethyltris(2-(dimethylamino)ethyl)amine
amino)ethyl)amine
in
in toluene
toluene
O
O
120°C, 16h
16h
OO
OO
OO
Sn(II)2-ethyl2-ethylSn(II)
hexanoate
hexanoate
OO
OO
OO
Rosin-caprolactone
Rosin-caprolactone
diblock copolymer
copolymer
diblock
(
(
M
Mnn=4700-22
=4700-22 800 g/mol
OO
)n
)n
Dehydroabietic
Dehydroabietic
ethyl
ethylmethacrylate
methacrylate
(DAEMA)
(DAEMA)
HH
Scheme85.
85.Preparation
Preparation of
rosin-caprolactone diblock
Scheme
85.
of rosin-caprolactone
rosin-caprolactone
diblockcopolymer.
copolymer.
Scheme
Preparation
diblock
copolymer.
OO
OO
Acrylpimaric acid
acid
Acrylpimaric
hydroxyethyl ester
ester
hydroxyethyl
yield:86%
86%
yield:
OO
COO
OH
OH
(C2H5)3N
COOH (C2H5)3N
COOH
165°C,1.5h
1.5h
165°C,
COOH
COOH
OO
OO
OO
HO
HO CC
(C2H
H)N
(C
2 55)33N
O
O
165°C,
1.5h
165°C, 1.5h
Acrylpimaric
Acrylpimaric
acid
acid
OH
OH OH
COO
COO
cat.
cat.
vacuum HO
vacuum HO
<245°C
<245°C
10h
10h
OH
Acrylpimaric COO
Acrylpimaric COO
acid dihydroxyethyl ester yield: 82%
acid dihydroxyethyl ester yield: 82%
O C
O C
(experimental)
= 418
MM
nn
(experimental)
= 418
nn
OO
COO
COO
COOH
COOH
Acrylpimaric
Acrylpimaricacid
acid
hydroxyethyl
hydroxyethyl
polyester
polyester
yield:
HH
yield:91%
91%
COO
COO
cat.
cat.
vacuum
vacuum
<245°C
<245°C
8h
8h
O
O
O
O
Acrylpimaric
Acrylpimaricacid
acid
dihydroxyethyl
dihydroxyethyl
polyester
H
polyester
H
yield: 70%
yield: 70%
n (experimental) = 462
n MM
n n (experimental) = 462
Scheme86.
86. Preparation
Preparation of acrylpimaric acid
Scheme
acid hydroxyethyl
hydroxyethylpolyester.
polyester.
Scheme 86. Preparation of acrylpimaric acid hydroxyethyl polyester.
4.4.Conclusions
Conclusions
4. Conclusions
Rosin
for both
both low
lowmolecular
molecularweight
weightproducts
productsand
andpolymers.
polymers.
Rosinisisaahighly
highlymodifiable
modifiableraw
raw material
material for
Rosin origin
is a highly
modifiable raw
material
forand
bothalow
molecular
weightnature,
products
andispolymers.
ItsItsnatural
is
accompanied
with
low
price
diterpene
chemical
which
readytoto
natural origin is accompanied with low price and a diterpene chemical nature, which is ready
Its
natural
origin
is
accompanied
with
low
price
and
a
diterpene
chemical
nature,
which
is
to
introduce
reactive
chemical
groups,
and and
it exhibits
a stiffaconstitution
improving
many ready
thermal,
introduceuseful
useful
reactive
chemical
groups,
it exhibits
stiff constitution
improving
many
introduce
useful
reactive
chemical
groups,
and
it
exhibits
a
stiff
constitution
improving
many
physical,
and functional
properties
of the final
materials.
In recent
yearsyears
rosin-based
thermal,mechanical
physical, mechanical
and functional
properties
of the
final materials.
In recent
rosinthermal,
physical,
mechanical
and
functional
properties
of
the
final
materials.
In
recent
years
rosinchemicals
have
attracted
growing
interest.
They
offer
great
opportunities
to
produce
useful
products:
based chemicals have attracted growing interest. They offer great opportunities to produce
useful
based
chemicals
have
attracted
growing
interest.
They
offer
great
opportunities
to
produce
useful
resins,
curing
agents,
surfactants,
medicines, medicines,
biocides, materials
biomedical
application,
elastomers,
products:
resins,
curing
agents, surfactants,
biocides,for
materials
for biomedical
application,
products:
resins,
curing
agents,
surfactants,
medicines,
coatings,
adhesives,
sorbents
and
catalysts.and
elastomers,
coatings,
adhesives,
sorbents
catalysts.biocides, materials for biomedical application,
elastomers,
adhesives, the
sorbents
and properties
catalysts.
Taking
into
the declared
declared
propertiesofofthethe
prepared
chemicals
Takingcoatings,
intoconsideration
consideration
prepared
chemicals
theythey
seemseem
to beto
Taking
into
consideration
the
declared
properties
of
the
prepared
chemicals
they
seem
be
becompetitive
competitive
alternatives
existing
products
market.
review
presents
well to
over
alternatives
to to
existing
products
on on
the the
market.
This This
review
presents
well over
100
competitive
alternatives
to existing
products
on thedo
market.
This complete
review
presents
wellmakes
over
100
reproducible
recipes.
Sadly,
some
of of
thethe
publications
not
contain
data,
itit
100
reproducible
recipes.
Sadly,
some
publications
do
not
contain
complete
data,which
which
makes
reproducible
recipes.
Sadly,
some
of
the
publications
do
not
contain
complete
data,
which
makes
it
difficult
to
repeat
the
syntheses.
According
to
our
subjective
opinion,
the
following
information
difficult to repeat the syntheses. According to our subjective opinion, the following information should
difficult
to
repeat
the
syntheses.
According
to
our
subjective
opinion,
the
following
information
be provided
(or for
obvious)
be considered
asproduct
complete:
product
name,
product
beshould
provided
(or obvious)
a recipefor
toaberecipe
considered
as complete:
name,
product
morphology,
should
be provided
(or obvious)
forcatalyst,
a recipe
to becatalyst,
considered
aspressure,
complete:
product
name,
product
morphology,
substrate(s)
names,
reaction
scheme,
media,
temperature,
pressure,
time,
yield
substrate(s)
names,
reaction
scheme,
media,
temperature,
time,
yield and
separation
morphology,
substrate(s)
names,
reaction
scheme,
catalyst,
media,
temperature,
pressure,
time,
yield
and
separation
techniques.
Figure
2
shows
the
number
of
complete
and
incomplete
recipes
in
theof
techniques. Figure 3 shows the number of complete and incomplete recipes in the individual parts
and
separation
techniques.
Figure
2
shows
the
number
of
complete
and
incomplete
recipes
in
individual
parts of this review.
Interestingly,
highest number
complete
recipes
absolute
this
review. Interestingly,
the highest
number the
of complete
recipes of
(both
absolute
and (both
relative)
canthe
be
and relative)
can
among
hardeners,
andnumber
monomers,
and also
biologically
active
individual
parts
of be
thisfound
review.
Interestingly,
theresins
highest
of complete
recipes
(bothThe
absolute
found
among
hardeners,
resins
and monomers,
and
also
biologically
active
compounds.
most
compounds.
The
common
missing
is yield.
large number
ofalso
incomplete
recipes
in
and
relative)
can most
be
found
among
hardeners,
and
monomers,
and
active
common
missing
parameter
is yield.
Aparameter
large resins
number
ofA
incomplete
recipes
inbiologically
macromolecular
macromolecular
compounds
section
may
result
from
the
fact
that
polymerizations
are
often
carried
compounds. The most common missing parameter is yield. A large number of incomplete recipes in
out in order to achieve
appropriate
properties,
specific
yields. The summary
presented
macromolecular
compounds
sectionmaterial
may result
from thenot
fact
that polymerizations
are often
carried
out in order to achieve appropriate material properties, not specific yields. The summary presented
Molecules 2019, 24, 1651
38 of 52
Molecules 2019, 24, x FOR PEER REVIEW
38 of 51
compounds section may result from the fact that polymerizations are often carried out in order to
achieve
appropriate
material
properties,
notproperties,
specific yields.
The summary
presented
Figure 3
out in order
to achieve
appropriate
material
not specific
yields. The
summaryinpresented
shows
that
resins, that
monomers,
hardeners and
biologically
active compounds
are the mostare
completely
in Figure
2 shows
resins, monomers,
hardeners
and biologically
active compounds
the most
described
rosin-based
chemicals
in
the
recent
decade,
which
makes
them
the
most
promising
subjects
completely described rosin-based chemicals in the recent decade, which makes them the
most
for
scaling-up
and
commercialization.
However,
this
does
not
change
the
fact
that
rosin
chemistry
is
promising subjects for scaling-up and commercialization. However, this does not change the fact that
able
deliver a serious
of new
environmentally-friendly
solutions in many fields
of science,
rosintochemistry
is able amount
to deliver
a serious
amount of new environmentally-friendly
solutions
in
medicine
and
engineering.
The
current
review
confirms
this,
and
encourages
further
intensive
research
many fields of science, medicine and engineering. The current review confirms this, and encourages
on
rosinintensive
in the near
future.on rosin in the near future.
further
research
Figure 2.
3. Number
Number of
of complete
complete and
and incomplete
incomplete recipes
recipes presented in this review.
review.
Funding:
This work was financially supported by National Centre for Research and Development (project no.
Abbreviations:
LIDER/7/0045/L-8/16/NCBR/2017).
AA, adipic acid;
Conflicts
of Interest: The authors declare no dihydrochloride;
conflict of interest.
AIBA, 2,2′-azobis(2-methylpropionamidine)
AIBN, 2,2′-azobisisobutyronitrile;
Abbreviations
ATRP, atom transfer radical polymerization;
BA, butyl acrylate;
Bu, butyl
AA
adipic
acid; group; cat., catalyst;
0
DA,
dehydroabietic
acid;
DBU, 1,8-diazabicyclo[5.4.0]undec-7-ene;
AIBA
2,2 -azobis(2-methylpropionamidine)
dihydrochloride;
0
DCC,
N,N′-dicyclohexylcarbodiimide;
AIBN
2,2 -azobisisobutyronitrile;
DDPD, dehydroabietyl
phosphate
diester;
DMAP, 4-dimethylaminopyridine;
ATRP
atom transfer
radical
polymerization;
DMF, dimethylformamide;
BA
butyl acrylate;
Bu
group;
DMSO, dimethylbutyl
sulfoxide;
Cat.
catalyst;
EC, ethyl cellulose;
DA
dehydroabietic
EEW, epoxy equivalent
weight; acid;
DBU
Et, ethyl group; 1,8-diazabicyclo[5.4.0]undec-7-ene;
DCC
N,N0 -dicyclohexylcarbodiimide;
HDMA Cl, hexadecyltrimethylammonium
chloride;
DDPD
dehydroabietyl
phosphate diester;
HDTMAB, hexadecyl
trimethyl ammonium
bromide;
DMAP
4-dimethylaminopyridine;
HPI, hydrophilic polyester intermediate;
DMF
dimethylformamide;
HPLC, high-performance
liquid chromatography;
DMSO
dimethyl sulfoxide;
HQ, hydroquinone;
EC
ethyl cellulose;
IPA, isophtalic acid;
EEW
epoxy equivalent weight;
JCR, Journal Citation Reports;
Et
ethyl group;
m.p., melting point; Me, methyl group;
HDMA Cl
hexadecyltrimethylammonium chloride;
MEK, methyl ethyl ketone; MPA, maleopimaric acid;
HDTMAB
hexadecyl trimethyl ammonium bromide;
NMP, N-methyl pyrrolidone;
HPI
hydrophilic polyester intermediate;
NMR, nuclear magnetic
resonance;liquid chromatography;
HPLC
high-performance
NPG,
neopentyl
glycol;
HQ
hydroquinone;
PAA, poly(acrylic acid);
PEG, poly(ethylene glycol);
Ph, phenyl group;
PMDETA, pentamethyldiethylenetriamine;
Molecules 2019, 24, 1651
IPA
JCR
m.p.
Me
MEK
MPA
NMP
NMR
NPG
PAA
PEG
Ph
PMDETA
PPh3
PSA
pTSA
RAFT
ROMP
UV
TBA Br
TEBAC
THF
TMP
TPT
TRL
39 of 52
isophtalic acid;
Journal Citation Reports;
melting point;
methyl group;
methyl ethyl ketone;
maleopimaric acid;
N-methyl pyrrolidone;
nuclear magnetic resonance;
neopentyl glycol;
poly(acrylic acid);
poly(ethylene glycol);
phenyl group;
pentamethyldiethylenetriamine;
triphenylphosphine;
pressure sensitive adhesives;
p-toluene sulfonic acid;
reversible addition-fragmentation chain-transfer polymerization;
ring-opening metathesis polymerization;
ultraviolet;
tetrabutylammonium bromide;
benzyltriethylammonium chloride;
tetrahydrofuran;
trimethylolpropane;
tetraisopropyl titanate;
technology readiness level;
References
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
Silvestre, A.J.D.; Gandini, A. Chapter 4-Rosin: Major sources, properties and applications. In Monomers,
Polymers and Composites from Renewable Resources; Elsevier: Amsterdam, The Netherlands, 2008; pp. 67–88,
ISBN 978-0-08-045316-3.
Ma, S.; Li, T.; Liu, X.; Zhu, J. Research progress on bio-based thermosetting resins. Polym. Int. 2016, 65,
164–173. [CrossRef]
Ding, C.; Matharu, A.S. Recent developments on biobased curing agents: A review of their preparation and
use. ACS Sustain. Chem. Eng. 2014, 2, 2217–2236. [CrossRef]
Wilbon, P.A.; Chu, F.; Tang, C. Progress in renewable polymers from natural terpenes, terpenoids, and rosin.
Macromol. Rapid Commun. 2013, 34, 8–37. [CrossRef]
Kumar, S.; Samal, S.K.; Mohanty, S.; Nayak, S.K. Recent development of biobased epoxy resins: A review.
Polym. Plast. Technol. 2018, 57, 133–155. [CrossRef]
Kumar, S.; Krishnan, S.; Mohanty, S.; Nayak, S.K. Synthesis and characterization of petroleum and biobased
epoxy resins: A review. Polym. Int. 2018, 67, 815–839. [CrossRef]
Wang, Z.; Yuan, L.; Tang, C. Sustainable elastomers from renewable biomass. Acc. Chem. Res. 2017, 50,
1762–1773. [CrossRef]
Baroncini, E.A.; Yadav, S.K.; Palmese, G.R.; Stanzione, J.F. Recent advances in bio-based epoxy resins and
bio-based epoxy curing agents. J. Appl. Polym. Sci. 2016, 133, 44103. [CrossRef]
Zia, K.M.; Noreen, A.; Zuber, M.; Tabasum, S.; Mujahid, M. Recent developments and future prospects on
bio-based polyesters derived from renewable resources: A review. Int. J. Biol. Macromol. 2016, 82, 1028–1040.
[CrossRef] [PubMed]
Gandini, A.; Lacerda, T.M. From monomers to polymers from renewable resources: Recent advances.
Prog. Polym. Sci. 2015, 48, 1–39. [CrossRef]
Parthiban, A. Monomers and polymers derived from renewable or partially renewable resources. In Synthesis
and Applications of Copolymers; Wiley-Blackwell: Hoboken, NJ, USA, 2014; pp. 101–124, ISBN 978-1-118-86016-8.
Narayanaperumal, S.; Rivera, D.G.; Silva, R.C.; Paixão, M.W. Terpene-derived bifunctional thioureas in
asymmetric organocatalysis. ChemCatChem 2013, 5, 2756–2773. [CrossRef]
Molecules 2019, 24, 1651
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
40 of 52
Yadav, B.K.; Gidwani, B.; Vyas, A. Rosin: Recent advances and potential applications in novel drug delivery
system. J. Bioact. Compat. Polym. 2016, 31, 111–126. [CrossRef]
Lu, Y.J.; Xu, R.S.; Zhao, Z.D.; Zhang, P.H.; Wang, M.X. Recent progress on derivation and chemical
modification of rosin acids. Adv. Mater. Res. 2013, 785–786, 1111–1116. [CrossRef]
Robinson, V.; Bergfeld, W.F.; Belsito, D.V.; Klaassen, C.D.; Marks, J.G., Jr.; Shank, R.C.; Slaga, T.J.;
Snyder, P.W.; Alan Andersen, F. Amended safety assessment of tall oil acid, sodium tallate, potassium tallate,
and ammonium tallate. Int. J. Toxicol. 2009, 28, 252S–258S. [CrossRef]
Illing, H.P.A.; Malmfors, T.; Rodenburg, L. Skin sensitization and possible groupings for ‘read across’ for
rosin based substances. Regul. Toxicol. Pharm. 2009, 54, 234–241. [CrossRef]
Botham, P.A.; Lees, D.; Illing, H.P.A.; Malmfors, T. On the skin sensitisation potential of rosin and oxidised
rosin. Regul. Toxicol. Pharm. 2008, 52, 257–263. [CrossRef]
Błażek, K.; Datta, J. Renewable natural resources as green alternative substrates to obtain bio-based
non-isocyanate polyurethanes-review. Crit. Rev. Environ. Sci. Technol. 2019, 1–39. [CrossRef]
Auvergne, R.; Caillol, S.; David, G.; Boutevin, B.; Pascault, J.-P. Biobased thermosetting epoxy: Present and
future. Chem. Rev. 2014, 114, 1082–1115. [CrossRef]
Yadav, S.K.; Schmalbach, K.M.; Kinaci, E.; Stanzione, J.F.; Palmese, G.R. Recent advances in plant-based vinyl
ester resins and reactive diluents. Eur. Polym. J. 2018, 98, 199–215. [CrossRef]
Liu, X.; Zhu, J. Chapter 19: Bio-based epoxies and composites as environmentally friendly alterinative
materials. In Thermosets, 2nd ed.; Elsevier: Amsterdam, Holland, 2018; ISBN 978-0-08-101021-1.
Global Rosin Market-World Rosin Market Size, Trends, Analysis and Segment Forecasts to 2022-Rosin
Industry Research, Outlook, Application, Product, Share, Growth, Key Opportunities, Dynamics, Analysis,
Rosin Report-Grand View Research, Inc. Available online: https://www.grandviewresearch.com/industryanalysis/rosin-market (accessed on 29 May 2018).
La Colophane et Son Avenir Dans le Domaine du Sudoe. Available online: https://docplayer.net/21677781Chemical-division-what-is-rosin-rosin-rosin-is-a-solid-form-of-natural-solid-form-of-natural-resinobtained-from-conifers-and-mainly-pine-trees.html (accessed on 7 January 2019).
Chen, G.F. Developments in the field of rosin chemistry and its implications in coatings. Prog. Org. Coat.
1992, 20, 139–167. [CrossRef]
Mckeon, L.; Regan, F.; Burns, B.; Leonard, R. Determination of resin acid composition in rosin samples using
cyclodextrin-modified capillary electrophoresis. J. Sep. Sci. 2014, 37, 2791–2796. [CrossRef]
Nguyen, T.T.H.; Li, S.; Li, J.; Liang, T. Micro-distribution and fixation of a rosin-based micronized-copper
preservative in poplar wood. Int. Biodeter. Biodegr. 2013, 83, 63–70. [CrossRef]
Nguyen, T.T.H.; Li, S.; Li, J. The combined effects of copper sulfate and rosin sizing agent treatment on some
physical and mechanical properties of poplar wood. Constr. Build. Mater. 2013, 40, 33–39. [CrossRef]
Hien, N.T.T.; Li, J.; Li, S. Effects of water-borne rosin on the fixation and decay resistance of copper-based
preservative treated wood. Bioresources 2012, 7, 3573–3584.
Cavallaro, G.; Lazzara, G.; Milioto, S.; Parisi, F.; Ruisi, F. Nanocomposites based on esterified colophony
and halloysite clay nanotubes as consolidants for waterlogged archaeological woods. Cellulose 2017, 24,
3367–3376. [CrossRef]
Han, Z.; Fina, A.; Malucelli, G. Thermal shielding performances of nano-structured intumescent coatings
containing organo-modified layered double hydroxides. Prog. Org. Coat. 2015, 78, 504–510. [CrossRef]
Gaillard, Y.; Girard, M.; Monge, G.; Burr, A.; Ceretti, E.D.; Felder, E. Superplastic behavior of rosin/beeswax
blends at room temperature. J. Appl. Polym. Sci. 2013, 128, 2713–2719. [CrossRef]
Bellotti, N.; del Amo, B.; Romagnoli, R. Quaternary ammonium “tannate” for antifouling coatings. Ind. Eng.
Chem. Res. 2012, 51, 16626–16632. [CrossRef]
Pinori, E.; Berglin, M.; Brive, L.M.; Hulander, M.; Dahlström, M.; Elwing, H. Multi-seasonal barnacle
(Balanus improvisus) protection achieved by trace amounts of a macrocyclic lactone (ivermectin) included in
rosin-based coatings. Biofouling 2011, 27, 941–953. [CrossRef]
Gutierrez, J.; Tercjak, A. Natural gum rosin thin films nanopatterned by poly(styrene)-blockpoly(4-vinylpiridine) block copolymer. RSC Adv. 2014, 4, 32024–32030. [CrossRef]
Narayanan, M.; Loganathan, S.; Valapa, R.B.; Thomas, S.; Varghese, T.O. UV protective poly(lactic acid)/rosin
films for sustainable packaging. Int. J. Biol. Macromol. 2017, 99, 37–45. [CrossRef]
Molecules 2019, 24, 1651
36.
37.
38.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
51.
52.
53.
54.
55.
56.
41 of 52
Yousaf, B.; Liu, G.; Abbas, Q.; Wang, R.; Ullah, H.; Mian, M.M.; Amina; Rashid, A. Enhanced
removal of hexavalent chromium from aqueous media using a highly stable and magnetically separable
rosin-biochar-coated TiO2@C nanocomposite. RSC Adv. 2018, 8, 25983–25996. [CrossRef]
Ma, C.; Zhang, W.; Zhang, G.; Qian, P.Y. Environmentally friendly antifouling coatings based on biodegradable
polymer and natural antifoulant. ACS Sustain. Chem. Eng. 2017, 5, 6304–6309. [CrossRef]
Dong, Y.; Yan, Y.; Wang, K.; Li, J.; Zhang, S.; Xia, C.; Shi, S.Q.; Cai, L. Improvement of water resistance,
dimensional stability, and mechanical properties of poplar wood by rosin impregnation. Eur. J. Wood Prod.
2016, 74, 177–184. [CrossRef]
Kim, S.-J.; Lee, B.-R.; Oh, E.-S. Application of a bio-derivative, rosin, as a binder additive for lithium titanium
oxide electrodes in lithium-ion batteries. J. Power Sources 2015, 273, 608–612. [CrossRef]
Makhutov, N.A.; Ushakov, B.N.; Vasil’ev, I.E. Strength assessment and defect detection in welded pipeline
seams by means of brittle tensosensitive coatings. Russ. Eng. Res. 2011, 31, 123–127. [CrossRef]
Zhang, Z.; Du, J.; Zhang, D.; Sun, H.; Yin, L.; Ma, L.; Chen, J.; Ma, D.; Cheng, H.-M.; Ren, W. Rosin-enabled
ultraclean and damage-free transfer of graphene for large-area flexible organic light-emitting diodes.
Nat. Commun. 2017, 8, 14560. [CrossRef] [PubMed]
Yu, X.; Bian, P.; Xue, Y.; Qian, X.; Yu, H.; Chen, W.; Hu, X.; Wang, P.; Wu, D.; Duan, Q.; et al. Combination of
microsized mineral particles and rosin as a basis for converting cellulosic fibers into “sticky” superhydrophobic
paper. Carbohydr. Polym. 2017, 174, 95–102. [CrossRef]
Singh, V.; Joshi, S.; Malviya, T. Carboxymethyl cellulose-rosin gum hybrid nanoparticles: An efficient drug
carrier. Int. J. Biol. Macromol. 2018, 112, 390–398. [CrossRef]
Varshosaz, J.; Javanmard, S.H.; Soghrati, S.; Behdadfar, B. Magnetic chondroitin targeted nanoparticles for
dual targeting of montelukast in prevention of in-stent restenosis. RSC Adv. 2016, 6, 12337–12347. [CrossRef]
Pomin, S.P.; Lima, I.A.d.; Pezarini, R.R.; Cavalcanti, O.A. Evaluation of rosin gum and Eudragit®RS PO as a
functional film coating material. AAPS PharmSciTech 2017, 18, 2854–2861. [CrossRef]
Moustafa, H.; El Kissi, N.; Abou-Kandil, A.I.; Abdel-Aziz, M.S.; Dufresne, A. PLA/PBAT bionanocomposites
with antimicrobial natural rosin for green packaging. ACS Appl. Mater. Interfaces 2017, 9, 20132–20141.
[CrossRef]
Nirmala, R.; Woo-il, B.; Navamathavan, R.; Kim, H.Y.; Park, S.-J. Preparation and characterizations of rosin
based thin films and fibers. J. Nanosci. Nanotechnol. 2015, 15, 4653–4659. [CrossRef] [PubMed]
Nirmala, R.; Woo-il, B.; Navamathavan, R.; Kalpana, D.; Lee, Y.S.; Kim, H.Y. Influence of antimicrobial
additives on the formation of rosin nanofibers via electrospinning. Colloid Surf. B 2013, 104, 262–267.
[CrossRef] [PubMed]
Nirmala, R.; Baek, W.; Navamathavan, R.; Kim, T.W.; Kalpana, D.; Park, M.; Kim, H.Y.; Park, S.-J. Bactericidal
efficacy of electrospun rosin/poly(ε-caprolactone) nanofibers. Macromol. Res. 2014, 22, 139–145. [CrossRef]
Nirmala, R.; Kalpana, D.; Navamathavan, R.; Park, M.; Kim, H.Y.; Park, S.-J. Antimicrobial activity of
electrospun polyurethane nanofibers containing composite materials. Korean J. Chem. Eng. 2014, 31, 855–860.
[CrossRef]
Bayer, I.S.; Tiwari, M.K.; Megaridis, C.M. Biocompatible poly(vinylidene fluoride)/cyanoacrylate composite
coatings with tunable hydrophobicity and bonding strength. Appl. Phys. Lett. 2008, 93, 173902. [CrossRef]
Sharma, L.; Singh, C. Composite film developed from the blends of sesame protein isolate and gum rosin
and their properties thereof. Polym. Compos. 2018, 39, 1480–1487. [CrossRef]
Park, J.Y.; Lee, Y.K.; Lee, D.-S.; Yoo, J.-E.; Shin, M.-S.; Yamabe, N.; Kim, S.-N.; Lee, S.; Kim, K.H.; Lee, H.-J.;
et al. Abietic acid isolated from pine resin (Resina Pini) enhances angiogenesis in HUVECs and accelerates
cutaneous wound healing in mice. J. Ethnopharmacol. 2017, 203, 279–287. [CrossRef]
Sakamoto, K.; Suzuki, Y.; Yamamura, H.; Ohya, S.; Muraki, K.; Imaizumi, Y. Molecular mechanisms
underlying pimaric acid-induced modulation of voltage-gated K+ channels. J. Pharmacol. Sci. 2017, 133,
223–231. [CrossRef]
Kim, N.-H.; Son, Y.; Jeong, S.-O.; Hur, J.M.; Bang, H.S.; Lee, K.-N.; Kim, E.-C.; Chung, H.-T.; Pae, H.-O.
Tetrahydroabietic acid, a reduced abietic acid, inhibits the production of inflammatory mediators in raw264.7
macrophages activated with lipopolysaccharide. J. Clin. Biochem. Nutr. 2010, 46, 119–125. [CrossRef]
Filippov, L.O.; Foucaud, Y.; Filippova, I.V.; Badawi, M. New reagent formulations for selective flotation of
scheelite from a skarn ore with complex calcium minerals gangue. Miner. Eng. 2018, 123, 85–94. [CrossRef]
Molecules 2019, 24, 1651
57.
58.
59.
60.
61.
62.
63.
64.
65.
66.
67.
68.
69.
70.
71.
72.
73.
74.
75.
76.
77.
42 of 52
Peng, H.; Shan, X.; Kang, J.; Ling, X.; Wang, D. Influence of rotary disk configurations on droplets
characteristics in molten slag granulation for waste heat recovery. Appl. Therm. Eng. 2018, 135, 269–279.
[CrossRef]
Huang, F.; Li, H.; Yi, Z.; Wang, Z.; Xie, Y. The rheological properties of self-compacting concrete containing
superplasticizer and air-entraining agent. Constr. Build. Mater. 2018, 166, 833–838. [CrossRef]
Patel, V.K.; Rawat, N. Physico-mechanical properties of sustainable Sagwan-teak wood flour/polyester
composites with/without gum rosin. Sustain. Mater. Technol. 2017, 13, 1–8. [CrossRef]
Li, X.; Ge, S.; Yang, J.; Chang, R.; Liang, C.; Xiong, L.; Zhao, M.; Li, M.; Sun, Q. Synthesis and study the
properties of StNPs/gum nanoparticles for salvianolic acid B-oral delivery system. Food Chem. 2017, 229,
111–119. [CrossRef]
Domene-López, D.; Guillén, M.M.; Martin-Gullon, I.; García-Quesada, J.C.; Montalbán, M.G. Study of the
behavior of biodegradable starch/polyvinyl alcohol/rosin blends. Carbohydr. Polym. 2018, 202, 299–305.
[CrossRef]
Kato, H.; Nakamura, A.; Matsubara, K. Dynamics and role of rosin acid molecules for preparation of
well-dispersed CaCO3 colloidal suspensions. J. Nanopart. Res. 2012, 14, 950. [CrossRef]
Sifontes, Á.B.; Gutierrez, B.; Mónaco, A.; Yanez, A.; Díaz, Y.; Méndez, F.J.; Llovera, L.; Cañizales, E.; Brito, J.L.
Preparation of functionalized porous nano-γ-Al2O3 powders employing colophony extract. Biotechnol. Rep.
2014, 4, 21–29. [CrossRef]
Huang, X.; Qian, X.; Li, J.; Lou, S.; Shen, J. Starch/rosin complexes for improving the interaction of mineral
filler particles with cellulosic fibers. Carbohydr. Polym. 2015, 117, 78–82. [CrossRef]
Soltes, J.; Zinkel, D.F. Chemistry of rosin. In Naval Stores: Production, Chemistry, Utilization; Pulp Chemicals
Association: New York, NY, USA, 1989; ISBN 978-0-685-30903-2.
Nakamura, Y.; Sakai, Y.; Imamura, K.; Ito, K.; Fujii, S.; Urahama, Y. Effects of the compatibility of a polyacrylic
block copolymer/tackifier blend on the phase structure and tack of a pressure-sensitive adhesive. J. Appl.
Polym. Sci. 2012, 123, 2883–2893. [CrossRef]
Zhang, M.; Luo, Z.; Zhang, J.; Chen, S.; Zhou, Y. Effects of a novel phosphorus–nitrogen flame retardant on
rosin-based rigid polyurethane foams. Polym. Degrad. Stab. 2015, 120, 427–434. [CrossRef]
Ding, K.; John, A.; Shin, J.; Lee, Y.; Quinn, T.; Tolman, W.B.; Hillmyer, M.A. High-performance pressuresensitive adhesives from renewable triblock copolymers. Biomacromolecules 2015, 16, 2537–2539. [CrossRef]
Ahn, B.K.; Sung, J.; Kim, N.; Kraft, S.; Sun, X.S. UV-curable pressure-sensitive adhesives derived from
functionalized soybean oils and rosin ester. Polym. Int. 2013, 62, 1293–1301. [CrossRef]
Arrieta, M.P.; Samper, M.D.; Jiménez-López, M.; Aldas, M.; López, J. Combined effect of linseed oil and gum
rosin as natural additives for PVC. Ind. Crop Prod. 2017, 99, 196–204. [CrossRef]
Guo, P.; Danish, M.; Du, P.; Kong, Z.; Guan, R. Viscoelastic and adhesive properties of polystyrenehydrogenated (3,4-polyisoprene and 1,4-polyisoprene)-polystyrene and polymethyl methacrylate-polybutyl
acrylate-polymethyl methacrylate-based HMPSA. J. Adhes. Sci. Technol. 2014, 28, 417–433. [CrossRef]
Lee, S.; Lee, K.; Kim, Y.-W.; Shin, J. Preparation and characterization of a renewable pressure-sensitive
adhesive system derived from ε-decalactone, l-lactide, epoxidized soybean oil, and rosin ester. ACS Sustain.
Chem. Eng. 2015, 3, 2309–2320. [CrossRef]
Zhang, K.; Shang, S.; Sun, P.; Shen, M.; Wang, D. Hydrogenated rosin ester latexes/waterborne polyacrylate
blends for pressure-sensitive adhesives. J. Appl. Polym. Sci. 2016, 133, 42965. [CrossRef]
Gao, L.; Zheng, G.; Zhou, Y.; Hu, L.; Feng, G. Thermal performances and fire behaviors of rosin-based rigid
polyurethane foam nanocomposites. J. Therm. Anal. Calorim. 2015, 119, 411–424. [CrossRef]
Gao, L.; Zheng, G.; Zhou, Y.; Hu, L.; Feng, G.; Zhang, M. Synergistic effect of expandable graphite, diethyl
ethylphosphonate and organically-modified layered double hydroxide on flame retardancy and fire behavior
of polyisocyanurate-polyurethane foam nanocomposite. Polym. Degrad. Stab. 2014, 101, 92–101. [CrossRef]
Lee, H.J.; Choi, I.; Kim, K.; Kim, H.S.; Choi, W.M.; Oh, E.S. Performance of various rosin-derivatives as binder
additives for lithium titanium oxide anodes. J. Electroanal. Chem. 2016, 782, 241–244. [CrossRef]
Moyano, M.A.; París, R.; Martín-Martínez, J.M. Assessment of the compatibility in hot melts by using
different thermoanalytical methods. Ethylene/n-butyl acrylate (EBA) hot melts containing tackifiers of
different nature. J. Therm. Anal. Calorim. 2017, 129, 1495–1503. [CrossRef]
Molecules 2019, 24, 1651
78.
79.
80.
81.
82.
83.
84.
85.
86.
87.
88.
89.
90.
91.
92.
93.
94.
95.
96.
97.
98.
99.
43 of 52
Moyano, M.A.; París, R.; Martín-Martínez, J.M. Changes in compatibility, tack and viscoelastic properties of
ethylene n-butyl acrylate (EBA) copolymer-pentaerythritol rosin ester blend by adding microcrystalline wax,
Fischer-Tropsch wax and mixture of waxes. Int. J. Adhes. Adhes. 2016, 65, 47–53. [CrossRef]
Yamamura, K.; Shitajima, K.; Fujii, S.; Nakamura, Y.; Hamada, Y.; Hagiwara, S.; Kishi, H.; Urahama, Y.;
Sasaki, M. Temperature dependence of tack and pulse NMR analysis of polystyrene block copolymer/tackifier
system. J. Adhes. Sci. Technol. 2013, 27, 2727–2740. [CrossRef]
Chu, H.-H.; Chiang, W.-L.; Chuang, K.S. Viscoelastic and adhesive properties of PMMA-b-PtBA with tackifier.
Int. J. Adhes. Adhes. 2012, 38, 89–94. [CrossRef]
Atta, A.M.; Al-Lohedan, H.A. Influence of nonionic rosin surfactants on surface activity of silica particles
and stability of oil in water emulsions. J. Surfactant. Deterg. 2014, 17, 1043–1053. [CrossRef]
Liu, X.; Xin, W.; Zhang, J. Rosin-based acid anhydrides as alternatives to petrochemical curing agents.
Green Chem. 2009, 11, 1018–1025. [CrossRef]
Liu, X.Q.; Huang, W.; Jiang, Y.H.; Zhu, J.; Zhang, C.Z. Preparation of a bio-based epoxy with comparable
properties to those of petroleum-based counterparts. Express Polym. Lett. 2012, 6, 293–298. [CrossRef]
Liu, X.; Zhang, J. High-performance biobased epoxy derived from rosin. Polym. Int. 2010, 59, 607–609.
[CrossRef]
Li, P.; Wang, T.; Lei, F.; Tang, P.; Tan, X.; Liu, Z.; Shen, L. Rosin-based molecularly imprinted polymers
as the stationary phase in high-performance liquid chromatography for selective separation of berberine
hydrochloride. Polym. Int. 2014, 63, 1699–1706. [CrossRef]
Yu, C.L.; Zhang, F.A.; Gong, Q.H. Preparation of maleic rosin-based macromonomer and copolymerization
with styrene and methyl methacrylate. Adv. Mater. Res. 2011, 236–238, 728–731. [CrossRef]
Li, X.; Li, M.; Li, J.; Lei, F.; Su, X.; Liu, M.; Li, P.; Tan, X. Synthesis and characterization of molecularly
imprinted polymers with modified rosin as a cross-linker and selective SPE-HPLC detection of basic orange
II in foods. Anal. Methods 2014, 6, 6397–6406. [CrossRef]
Ma, Q.; Liu, X.; Zhang, R.; Zhu, J.; Jiang, Y. Synthesis and properties of full bio-based thermosetting resins
from rosin acid and soybean oil: The role of rosin acid derivatives. Green Chem. 2013, 15, 1300–1310.
[CrossRef]
Lu, Y.; Zhao, Z.; Bi, L.; Chen, Y.; Wang, J.; Xu, S. Synthesis of a multifunctional hard monomer from rosin: the
relationship of allyl structure in maleopimarate and UV-curing property. Sci. Rep. 2018, 8, 2399. [CrossRef]
Wang, J.; Yu, J.; Liu, Y.; Chen, Y.; Wang, C.; Tang, C.; Chu, F. Synthesis and characterization of a novel
rosin-based monomer: Free-radical polymerization and epoxy curing. Green Mater. 2013, 1, 105–113.
[CrossRef]
Si, H.; Liu, H.; Shang, S.; Song, J.; Liao, S.; Wang, D.; Song, Z. Maleopimaric acid-modified two-component
waterborne polyurethane for coating applications. J. Appl. Polym. Sci. 2016, 133, 43292. [CrossRef]
Li, R.; Zhang, P.; Liu, T.; Muhunthan, B.; Xin, J.; Zhang, J. Use of hempseed-oil-derived polyacid and
rosin-derived anhydride acid as cocuring agents for epoxy materials. ACS Sustain. Chem. Eng. 2018, 6,
4016–4025. [CrossRef]
Zhang, X.; Wu, Y.; Wei, J.; Tong, J.; Yi, X. Curing kinetics and mechanical properties of bio-based composite
using rosin-sourced anhydrides as curing agent for hot-melt prepreg. Sci. China Technol. Sci. 2017, 60,
1318–1331. [CrossRef]
Liu, X.; Xin, W.; Zhang, J. Rosin-derived imide-diacids as epoxy curing agents for enhanced performance.
Bioresour. Technol. 2010, 101, 2520–2524. [CrossRef]
Mustata, F.; Tudorachi, N.; Bicu, I. Thermosetting resins obtained via sequential photo and thermal
crosslinking of epoxy resins. Curing kinetics, thermal properties and morphology. Compos. Part B 2013, 55,
470–478. [CrossRef]
Li, S.; Zou, T.; Liu, X.; Tao, M. Synthesis and characterization of benzoxazine monomers from rosin and their
thermal polymerization. Des. Monomers Polym. 2014, 17, 40–46. [CrossRef]
Wang, H.; Liu, X.; Liu, B.; Zhang, J.; Xian, M. Synthesis of rosin-based flexible anhydride-type curing agents
and properties of the cured epoxy. Polym. Int. 2009, 58, 1435–1441. [CrossRef]
Jaswal, S.; Gaur, B. Structure-property correlation study of bio-based multifunctional vinyl ester resin in
presence of methacrylated lignin model compounds. Polym. Sci. Ser. B 2015, 57, 417–433. [CrossRef]
Qin, J.; Liu, H.; Zhang, P.; Wolcott, M.; Zhang, J. Use of eugenol and rosin as feedstocks for biobased epoxy
resins and study of curing and performance properties. Polym. Int. 2014, 63, 760–765. [CrossRef]
Molecules 2019, 24, 1651
44 of 52
100. Zhai, Z.; Yan, X.; Song, Z.; Shang, S.; Rao, X. Annular and threadlike wormlike micelles formed by a bio-based
surfactant containing an extremely large hydrophobic group. Soft Matter 2018, 14, 499–507. [CrossRef]
101. Lin, H.; Yang, M.; Tian, C.; Han, C.; Song, J.; Duan, J.; Jiang, J. Design of diversified self-assembly systems based
on a natural rosin-based tertiary amine for doxorubicin delivery and excellent emulsification. Colloid Surf. B
2018, 165, 191–198. [CrossRef]
102. Zhai, Z.; Yan, X.; Xu, J.; Song, Z.; Shang, S.; Rao, X. Phase behavior and aggregation in a catanionic system
dominated by an anionic surfactant containing a large rigid group. Chem. Eur. J. 2018, 24, 9033–9040.
[CrossRef]
103. Li, J.; Zhang, G.; Shang, T.; Zhu, J. Synthesis, characterization and application of a dispersant based on rosin
for coal-water slurry. Int. J. Min. Sci. Technol. 2014, 24, 695–699. [CrossRef]
104. Atta, M.A.; El-Mahdy, A.G.; Dyab, K.F.A.; Allohedan, A.H. Application of highly surface active cationic
surfactants based on rosin as corrosion inhibitor for tubing steel during acidization of petroleum oil and gas
wells. Int. J. Electrochem. Sci. 2013, 8, 9629–9643.
105. Lin, G.-S.; Dong, S.-Q.; Duan, W.-G.; Cen, B.; Xu, X.-T.; Yang, Z.-Q. Synthesis and biological activities of
maleated rosin-based dithiourea compounds. Holzforschung 2013, 68, 549–554. [CrossRef]
106. Yao, G.; Ye, M.; Huang, R.; Li, Y.; Zhu, Y.; Pan, Y.; Liao, Z.-X.; Wang, H. Synthesis and antitumor activity
evaluation of maleopimaric acid N-aryl imide atropisomers. Bioorg. Med. Chem. Lett. 2013, 23, 6755–6758.
[CrossRef]
107. Wang, H.; Wang, H.; Zhou, G. Synthesis of rosin-based imidoamine-type curing agents and curing behavior
with epoxy resin. Polym. Int. 2011, 60, 557–563. [CrossRef]
108. Xing, Y.; Zhang, W.; Song, J.; Zhang, Y.; Jiang, X.; Wang, R. Anticancer effects of a novel class rosin-derivatives
with different mechanisms. Bioorg. Med. Chem. Lett. 2013, 23, 3868–3872. [CrossRef]
109. Xu, X.; Song, Z.; Shang, S.; Cui, S.; Rao, X. Synthesis and properties of novel rosin-based water-borne
polyurethane. Polym. Int. 2011, 60, 1521–1526. [CrossRef]
110. Si, H.; Liu, H.; Shang, S.; Song, J.; Liao, S.; Wang, D.; Song, Z. Preparation and properties of maleopimaric
acid-based polyester polyol dispersion for two-component waterborne polyurethane coating. Prog. Org.
Coat. 2016, 90, 309–316. [CrossRef]
111. Xu, X.; Shang, S.; Song, Z.; Cui, S.; Wang, H.; Wang, D. Preparation and characterization of rosin-based
waterborne polyurethane from maleopimaric acid polyester polyol. Bioresources 2011, 6, 2460–2470.
112. Liu, H.; Cui, S.; Shang, S.; Wang, D.; Song, J. Properties of rosin-based waterborne polyurethanes/cellulose
nanocrystals composites. Carbohydr. Polym. 2013, 96, 510–515. [CrossRef]
113. Wu, Q.; Yao, G.; Zhang, Y.; Wang, H.; Yang, L.; Zhu, Y.; Pan, Y. In situ synthesis of rosin derived chiral
derivatizing agents for 31P NMR assays of amine and alcohol enantiomers. Chem. Res. Chin. Univ. 2013, 29,
894–899. [CrossRef]
114. Yu, J.; Xu, N.; Liu, Z.; Wang, L. Novel one-component positive-tone chemically amplified i-line molecular
glass photoresists. ACS Appl. Mater. Interfaces 2012, 4, 2591–2596. [CrossRef]
115. Tan, W.-X.; Lin, Z.-T.; Bu, H.-T.; Tian, Y.; Jiang, G.-B. Nano-micelles based on a rosin derivative as potent
sorbents and sinking agents with high absorption capabilities for the removal of metal ions. RSC Adv. 2012,
2, 7279–7289. [CrossRef]
116. Xu, T.; Liu, H.; Song, J.; Shang, S.; Song, Z.; Zou, K.; Yang, C. Synthesis and characterization of maleated
rosin-modified fluorosilicone resin and its fluorosilicone rubber. J. Appl. Polym. Sci. 2015, 132, 41888.
[CrossRef]
117. Ha, Y.B.; Jin, M.Y.; Oh, S.S.; Ryu, D.H. Synthesis of an environmentally friendly phenol-free resin for printing
ink. Bull. Korean Chem. Soc. 2012, 33, 3413–3416. [CrossRef]
118. Yang, M.; Chen, X.; Li, J.; Lin, H.; Zhang, S.; Han, C. Preparation of wood with better water-resistance
properties by a one-step impregnation of maleic rosin. J. Adhes. Sci. Technol. 2018, 1–13. [CrossRef]
119. Yang, M.; Chen, X.; Lin, H.; Han, C.; Zhang, S. A simple fabrication of superhydrophobic wood surface by
natural rosin based compound via impregnation at room temperature. Eur. J. Wood Prod. 2018, 76, 1417–1425.
[CrossRef]
120. Li, H.; Lin, R.; He, J.; Long, H.; Liao, W.; Chen, Q. Effect of pretreatment on the enzymatic synthesis of rosin
acid starch. New J. Chem. 2016, 40, 2856–2862. [CrossRef]
121. Tudorachi, N.; Mustaţă, F.; Bicu, I. Thermal decomposition of some Diels–Alder adducts of resin acids: study
of kinetics process. J. Anal. Appl. Pyrol. 2012, 98, 106–114. [CrossRef]
Molecules 2019, 24, 1651
45 of 52
122. Deng, L.; Ha, C.; Sun, C.; Zhou, B.; Yu, J.; Shen, M.; Mo, J. Properties of bio-based epoxy resins from rosin
with different flexible chains. Ind. Eng. Chem. Res. 2013, 52, 13233–13240. [CrossRef]
123. Mandal, M.; Borgohain, P.; Begum, P.; Deka, R.C.; Maji, T.K. Property enhancement and DFT study of wood
polymer composites using rosin derivatives as co-monomers. New J. Chem. 2018, 42, 2260–2269. [CrossRef]
124. Yu, C.; Wang, X.; Chen, C.; Zhang, F. Preparation of polystyrene microspheres using rosin–acrylic acid diester
as a cross-linking agent. Ind. Eng. Chem. Res. 2014, 53, 2244–2250. [CrossRef]
125. Yan, X.; Zhai, Z.; Song, Z.; Shang, S.; Rao, X. Synthesis and properties of polyester-based polymeric surfactants
from diterpenic rosin. Ind. Crop. Prod. 2017, 108, 371–378. [CrossRef]
126. Li, T.; Liu, X.; Jiang, Y.; Ma, S.; Zhu, J. Bio-based shape memory epoxy resin synthesized from rosin acid.
Iran. Polym. J. 2016, 25, 957–965. [CrossRef]
127. Deng, L.; Shen, M.; Yu, J.; Wu, K.; Ha, C. Preparation, characterization, and flame retardancy of novel
rosin-based siloxane epoxy resins. Ind. Eng. Chem. Res. 2012, 51, 8178–8184. [CrossRef]
128. Lin, H.X.; Yang, M.S.; Li, J.; Chen, X.Y.; Jiang, J.X.; Han, C.R. A novel bola-type rosin-based functional
surfactant and its synergistic effect with natural surfactant saponin. J. Surfactant. Deterg. 2017, 20, 1205–1212.
[CrossRef]
129. Gao, Y.; Li, L.; Chen, H.; Li, J.; Song, Z.; Shang, S.; Song, J.; Wang, Z.; Xiao, G. High value-added application
of rosin as a potential renewable source for the synthesis of acrylopimaric acid-based botanical herbicides.
Ind. Crop. Prod. 2015, 78, 131–140. [CrossRef]
130. Gao, Y.; Li, J.; Song, Z.; Song, J.; Shang, S.; Xiao, G.; Wang, Z.; Rao, X. Turning renewable resources into
value-added products: Development of rosin-based insecticide candidates. Ind. Crop Prod. 2015, 76, 660–671.
[CrossRef]
131. Li, J.; Li, S.; Li, S.; Wang, J.; Liu, D. Synthesis of a rosin amide and its inhibition of wood decay fungi.
Adv. Mater. Res. 2010, 113–116, 2232–2236. [CrossRef]
132. Liu, G.; Chen, C.; Wu, G.; Kong, Z. Preparation and antimicrobial activity of rosin-based carbamate
group-containing quaternary ammonium salt derivatives. Bioresources 2013, 8, 4218–4226. [CrossRef]
133. Chen, Z.; Li, S.; Tian, B.; Liang, T.; Jin, Y. Synthesis and characterization of a rosin gemini surfactant. Mater. Sci.
Forum 2011, 685, 285–290. [CrossRef]
134. Liang, T.; Li, S.; Li, S.; Zhang, L. Synthesis of N-(3-rosin acyloxy-2-hydroxyl) propyl-N,N diethanolamine
and its anti-fungal activity. Adv. Mater. Res. 2011, 280, 124–127. [CrossRef]
135. Jin, Y.; Li, S.; Liang, T.; Chen, Z. Synthesis of quaternary ammonium salt from rosin and its inhibition to some
wood decay fungi. Mater. Sci. Forum 2011, 685, 291–297. [CrossRef]
136. Li, S.; Wang, J.; Li, S.; Chen, Z.; Tian, B.; Wang, D. Synthesis and characterization of bisN-(3-rosin
acyloxy-2-hydroxyl) propyl-N,N dimethylamine. Adv. Mater. Res. 2010, 113–116, 2197–2200. [CrossRef]
137. Li, M.; Zhang, J.; Huang, K.; Li, S.; Jiang, J.; Xia, J. Mixed calcium and zinc salts of dicarboxylic acids derived
from rosin and dipentene: preparation and thermal stabilization for PVC. RSC Adv. 2014, 4, 63576–63585.
[CrossRef]
138. Mustata, F.; Bicu, I. A novel route for synthesizing esters and polyesters from the Diels–Alder adduct of
levopimaric acid and acrylic acid. Eur. Polym. J. 2010, 46, 1316–1327. [CrossRef]
139. Mustata, F.R.; Tudorachi, N.; Bicu, I. Biobased epoxy matrix from diglycidyl ether of bisphenol A and
epoxidized corn oil, cross-linked with Diels–Alder adduct of levopimaric acid with acrylic acid. Ind. Eng.
Chem. Res. 2013, 52, 17099–17110. [CrossRef]
140. Li, J.; Lin, H.X.; Chen, X.Y.; Zhu, J.R.; Yang, M.S.; Yang, J.; Han, C.R. Self-assembled structures and excellent
surface properties of a novel anionic phosphate diester surfactant derived from natural rosin acids. J. Colloid
Interface Sci. 2017, 486, 67–74. [CrossRef] [PubMed]
141. Gu, W.; Wang, S. Synthesis and antimicrobial activities of novel 1H-dibenzo[a,c]carbazoles from
dehydroabietic acid. Eur. J. Med. Chem. 2010, 45, 4692–4696. [CrossRef]
142. Lu, C.; Yu, J.; Wang, C.; Wang, J.; Chu, F. Fabrication of UV-absorbent cellulose-rosin based thermoplastic
elastomer via “graft from” ATRP. Carbohydr. Polym. 2018, 188, 128–135. [CrossRef]
143. Li, W.; Xie, D.; Song, B.; Feng, L.; Pei, X.; Cui, Z. Synthesis and characterization of ordered mesoporous silica
using rosin-based gemini surfactants. J. Mater. Sci. 2018, 53, 2434–2442. [CrossRef]
144. Zhang, H.; Yang, Y.; Shen, M.; Shang, S.; Song, J.; Jiang, J.; Song, Z. Soybean oil-based thermoset reinforced
with rosin-based monomer. Iran. Polym. J. 2018, 27, 405–411. [CrossRef]
Molecules 2019, 24, 1651
46 of 52
145. Zheng, Y.; Yao, K.; Lee, J.; Chandler, D.; Wang, J.; Wang, C.; Chu, F.; Tang, C. Well-defined renewable polymers
derived from gum rosin. Macromolecules 2010, 43, 5922–5924. [CrossRef]
146. Ding, W.; Wang, S.; Yao, K.; Ganewatta, M.S.; Tang, C.; Robertson, M.L. Physical Behavior of Triblock
Copolymer Thermoplastic Elastomers Containing Sustainable Rosin-Derived Polymethacrylate End Blocks.
ACS Sustain. Chem. Eng. 2017, 5, 11470–11480. [CrossRef]
147. Yao, K.; Wang, J.; Zhang, W.; Lee, J.S.; Wang, C.; Chu, F.; He, X.; Tang, C. Degradable rosin-ester-caprolactone
graft copolymers. Biomacromolecules 2011, 12, 2171–2177. [CrossRef]
148. Yu, J.; Liu, Y.P.; Wang, C.P.; Chen, Y.; Wang, J.F.; Chu, F.X. Preparation and characterization of novel naturally
renewable resin acid based monomer. Adv. Mater. Res. 2013, 712–715, 139–146. [CrossRef]
149. Zhang, H.; Jiang, J.; Shang, S.; Song, Z.; Song, J. Novel, rosin-based, hydrophobically modified cationic
polyacrylamide for kaolin suspension flocculation. J. Appl. Polym. Sci. 2018, 135, 46637. [CrossRef]
150. Gu, W.; Qiao, C.; Wang, S.-F.; Hao, Y.; Miao, T.-T. Synthesis and biological evaluation of novel N-substituted
1H-dibenzo[a,c]carbazole derivatives of dehydroabietic acid as potential antimicrobial agents. Bioorg. Med.
Chem. Lett. 2014, 24, 328–331. [CrossRef] [PubMed]
151. Luo, D.; Ni, Q.; Ji, A.; Gu, W.; Wu, J.; Jiang, C. Dehydroabietic acid derivative QC4 induces gastric cancer cell
death via oncosis and apoptosis. BioMed Res. Int. 2016, 2016, 2581061. [CrossRef]
152. Gowda, R.; Madhunapantula, S.V.; Kuzu, O.F.; Sharma, A.; Robertson, G.P. Targeting multiple key signaling
pathways in melanoma using leelamine. Mol. Cancer Ther. 2014, 13, 1679–1689. [CrossRef] [PubMed]
153. Kuzu, O.F.; Gowda, R.; Sharma, A.; Robertson, G.P. Leelamine mediates cancer cell death through inhibition
of intracellular cholesterol transport. Mol. Cancer Ther. 2014, 13, 1690–1703. [CrossRef] [PubMed]
154. Gowda, R.; Madhunapantula, S.V.; Sharma, A.; Kuzu, O.F.; Robertson, G.P. Nanolipolee-007, a novel
nanoparticle-based drug containing leelamine for the treatment of melanoma. Mol. Cancer Ther. 2014, 13,
2328–2340. [CrossRef]
155. Singh, K.B.; Ji, X.; Singh, S.V. Therapeutic potential of leelamine, a novel inhibitor of androgen receptor and
castration-resistant prostate cancer. Mol. Cancer Ther. 2018, 17, 2079–2090. [CrossRef] [PubMed]
156. Li, C.; Liu, X.; Zhu, J.; Zhang, C.; Guo, J. Synthesis, characterization of a rosin-based epoxy monomer and its
comparison with a petroleum-based counterpart. J. Macromol. Sci. A 2013, 50, 321–329. [CrossRef]
157. Liu, X.; Zhang, R.; Li, T.; Zhu, P.; Zhuang, Q. Novel Fully Biobased Benzoxazines from Rosin: Synthesis and
Properties. ACS Sustainable Chem. Eng. 2017, 5, 10682–10692. [CrossRef]
158. Wang, P.; Chen, S.X.; Zhao, Z.D.; Wang, Z.; Fan, G. Synthesis of ordered porous SiO2 with pores on the border
between the micropore and mesopore regions using rosin-based quaternary ammonium salt. RSC Adv. 2015,
5, 11223–11228. [CrossRef]
159. Song, F.; Wang, P.; Chen, S.; Wang, Z.; Fan, G. Ordered lamellar supermicroporous titania templating by
rosin-derived quaternary ammonium salt. PLoS ONE 2017, 12, e0180178. [CrossRef] [PubMed]
160. Liu, Y.; Li, C.; Dai, J.; Jiang, Y.; Liu, X.; Zhu, J. Synthesis of multifunctional monomers from rosin for the
properties enhancement of soybean-oil based thermosets. Sci. China Technol. Sci. 2017, 60, 1332–1338.
[CrossRef]
161. Yang, Y.; Shen, M.; Huang, X.; Zhang, H.; Shang, S.; Song, J. Synthesis and performance of a thermosetting
resin: Acrylated epoxidized soybean oil curing with a rosin-based acrylamide. J. Appl. Polym. Sci. 2017, 134,
44545. [CrossRef]
162. Huo, L.; Wang, D.; Liu, H.; Jia, P.; Gao, J. Cytoxicity, dynamic and thermal properties of bio-based rosin-epoxy
resin/ castor oil polyurethane/ carbon nanotubes bio-nanocomposites. J. Biomater. Sci. Polym. Ed. 2016, 27,
1100–1114. [CrossRef] [PubMed]
163. El-Ghazawy, R.A.; El-Saeed, A.M.; Al-Shafey, H.I.; Abdul-Raheim, A.-R.M.; El-Sockary, M.A. Rosin based
epoxy coating: Synthesis, identification and characterization. Eur. Polym. J. 2015, 69, 403–415. [CrossRef]
164. Brocas, A.-L.; Llevot, A.; Mantzaridis, C.; Cendejas, G.; Auvergne, R.; Caillol, S.; Carlotti, S.; Cramail, H.
Epoxidized rosin acids as co-precursors for epoxy resins. Des. Monomers Polym. 2014, 17, 301–310. [CrossRef]
165. Mantzaridis, C.; Brocas, A.-L.; Llevot, A.; Cendejas, G.; Auvergne, R.; Caillol, S.; Carlotti, S.; Cramail, H.
Rosin acid oligomers as precursors of DGEBA-free epoxy resins. Green Chem. 2013, 15, 3091–3098. [CrossRef]
166. Liu, Y.; Yao, K.; Chen, X.; Wang, J.; Wang, Z.; Ploehn, H.J.; Wang, C.; Chu, F.; Tang, C. Sustainable
thermoplastic elastomers derived from renewable cellulose, rosin and fatty acids. Polym. Chem. 2014, 5,
3170–3181. [CrossRef]
Molecules 2019, 24, 1651
47 of 52
167. Wang, J.; Yuan, L.; Wang, Z.; Rahman, M.A.; Huang, Y.; Zhu, T.; Wang, R.; Cheng, J.; Wang, C.; Chu, F.; et al.
Photoinduced metal-free atom transfer radical polymerization of biomass-based monomers. Macromolecules
2016, 49, 7709–7717. [CrossRef]
168. An, S.Y.; Hong, S.H.; Tang, C.; Oh, J.K. Rosin-based block copolymer intracellular delivery nanocarriers with
reduction-responsive sheddable coronas for cancer therapy. Polym. Chem. 2016, 7, 4751–4760. [CrossRef]
169. Wang, J.; Yao, K.; Korich, A.L.; Li, S.; Ma, S.; Ploehn, H.J.; Iovine, P.M.; Wang, C.; Chu, F.; Tang, C. Combining
renewable gum rosin and lignin: Towards hydrophobic polymer composites by controlled polymerization.
J. Polym. Sci. A 2011, 49, 3728–3738. [CrossRef]
170. Wilbon, P.A.; Zheng, Y.; Yao, K.; Tang, C. Renewable rosin acid-degradable caprolactone block copolymers by
atom transfer radical polymerization and ring-opening polymerization. Macromolecules 2010, 43, 8747–8754.
[CrossRef]
171. Wang, J.-F.; Lin, M.-T.; Wang, C.-P.; Chu, F.-X. Study on the synthesis, characterization, and kinetic of bulk
polymerization of disproportionated rosin (β-acryloxyl ethyl) ester. J. Appl. Polym. Sci. 2009, 113, 3757–3765.
[CrossRef]
172. Duan, W.; Chen, C.; Jiang, L.; Li, G.H. Preparation and characterization of the graft copolymer of chitosan
with poly[rosin-(2-acryloyloxy)ethyl ester]. Carbohydr. Polym. 2008, 73, 582–586. [CrossRef] [PubMed]
173. Liu, B.; Nie, J.; He, Y. From rosin to high adhesive polyurethane acrylate: Synthesis and properties. Int. J.
Adhes. Adhes. 2016, 66, 99–103. [CrossRef]
174. Do, H.-S.; Park, J.-H.; Kim, H.-J. Synthesis and characteristics of photoactive-hydrogenated rosin epoxy
methacrylate for pressure sensitive adhesives. J. Appl. Polym. Sci. 2009, 111, 1172–1176. [CrossRef]
175. Yan, X.; Zhai, Z.; Song, Z.; Shang, S.; Rao, X. Synthesis of comb-like polymeric surfactants with a tricyclic
rigid core and their use as dispersants in pymetrozine water suspension concentrates. RSC Adv. 2017, 7,
55741–55747. [CrossRef]
176. Do, H.-S.; Park, J.-H.; Kim, H.-J. UV-curing behavior and adhesion performance of polymeric photoinitiators
blended with hydrogenated rosin epoxy methacrylate for UV-crosslinkable acrylic pressure sensitive
adhesives. Eur. Polym. J. 2008, 44, 3871–3882. [CrossRef]
177. Lu, Y.; Zhao, Z.; Chen, Y.; Wang, J.; Xu, S.; Gu, Y. Synthesis of allyl acrylpimarate by microwave irradiation
and phase-transfer catalytic reaction and its UV-curing reactions as a new monomer. Prog. Org. Coat. 2017,
109, 9–21. [CrossRef]
178. Li, T.; Liu, X.; Jiang, Y.; Ma, S.; Zhu, J. Synthesis of epoxy curing agents containing different ring structures
and properties investigation of the cured resins. J. Appl. Polym. Sci. 2016, 133, 44219. [CrossRef]
179. Qin, J.; Chen, X.; Yu, J.; Wang, Y.; Tian, Y.; Wu, S. Nonisothermal crystallization kinetics of isotactic
polypropylene containing nucleating agent and dispersant. J. Appl. Polym. Sci. 2010, 117, 1047–1054.
[CrossRef]
180. Wang, J.; Dou, Q. Crystallization behavior and optical and mechanical properties of isotactic polypropylene
nucleated with rosin-based nucleating agents. Polym. Int. 2008, 57, 233–239. [CrossRef]
181. Lu, Y.; Wang, M.; Zhao, Z.; Chen, Y.; Xu, S.; Wang, J.; Bi, L. Facile synthesis of allyl resinate monomer in an
aqueous solution under microwave irradiation. J. Chem. Sci. 2015, 127, 1183–1190. [CrossRef]
182. Lu, Y.; Zhao, Z.; Gu, Y.; Chen, Y.; Bi, L. Synthesis of rosin allyl ester and its UV-curing characteristics. Polym. J.
2011, 43, 869–873. [CrossRef]
183. Wang, H.; Liu, B.; Liu, X.; Zhang, J.; Xian, M. Synthesis of biobased epoxy and curing agents using rosin and
the study of cure reactions. Green Chem. 2008, 10, 1190–1196. [CrossRef]
184. Wang, H.; He, C.; Pan, Y.; Yao, G.; Wu, Q.; Deng, H. Synthesis and amines enantiomeric recognition ability of
binaphthyl-appended 22-crown-6 ethers derived from rosin acid. J. Incl. Phenom. Macrocycl. Chem. 2012, 73,
177–183. [CrossRef]
185. Mustata, F.R.; Tudorachi, N. Epoxy resins cross-linked with rosin adduct derivatives. Cross-linking and
thermal behaviors. Ind. Eng. Chem. Res. 2010, 49, 12414–12422. [CrossRef]
186. Zhang, L.; Jiang, Y.; Xiong, Z.; Liu, X.; Na, H.; Zhang, R.; Zhu, J. Highly recoverable rosin-based shape
memory polyurethanes. J. Mater. Chem. A 2013, 1, 3263–3267. [CrossRef]
187. Pietrzak, K.; Kirpluks, M.; Cabulis, U.; Ryszkowska, J. Effect of the addition of tall oil-based polyols on the
thermal and mechanical properties of ureaurethane elastomers. Polym. Degrad. Stab. 2014, 108, 201–211.
[CrossRef]
Molecules 2019, 24, 1651
48 of 52
188. Zhan, S.H.; Jiang, X.H.; Li, J.; Meng, Z.; Chen, L.L.; Han, C.R. Controlled synthesis of hydroxyapatite using a
novel natural rosin-based surfactant. Nano 2017, 12, 1750098. [CrossRef]
189. Liang, T.; Zhang, Y.; Li, S.; Nguyen, T.T.H. Synthesis, characterization, and bioactivity of rosin quaternary
ammonium salt derivatives. Bioresources 2013, 8, 735–742. [CrossRef]
190. Li, J.; Gao, Y.; Shang, S.; Rao, X.; Song, J.; Wang, Z. Synthesis and quantitative structure–activity relationship
(QSAR) studies of novel rosin-based diamide insecticides. RSC Adv. 2014, 4, 58190–58199. [CrossRef]
191. Atta, A.; El-Mahdy, G.; Al-Lohedan, H.; Al-Hussain, S.; Atta, A.M.; El-Mahdy, G.A.; Al-Lohedan, H.A.;
Al-Hussain, S.A. Synthesis of environmentally friendly highly dispersed magnetite nanoparticles based
on rosin cationic surfactants as thin film coatings of steel. Int. J. Mol. Sci. 2014, 15, 6974–6989. [CrossRef]
[PubMed]
192. Atta, A.M.; El-Saeed, A.M.; El-Mahdy, G.M.; Al-Lohedan, H.A. Application of magnetite nano-hybrid epoxy
as protective marine coatings for steel. RSC Adv. 2015, 5, 101923–101931. [CrossRef]
193. Ishtikhar, M.; Rahisuddin; Khan, M.V.; Khan, R.H. Anti-aggregation property of thymoquinone induced
by copper-nanoparticles: A biophysical approach. Int. J. Biol. Macromol. 2016, 93, 1174–1182. [CrossRef]
[PubMed]
194. Ishtikhar, M.; Chandel, T.I.; Ahmad, A.; Ali, M.S.; Al-lohadan, H.A.; Atta, A.M.; Khan, R.H. Rosin surfactant
QRMAE can be utilized as an amorphous aggregate inducer: a case study of mammalian serum albumin.
PLoS ONE 2015, 10, e0139027. [CrossRef] [PubMed]
195. Ishtikhar, M.; Usmani, S.S.; Gull, N.; Badr, G.; Mahmoud, M.H.; Khan, R.H. Inhibitory effect of copper
nanoparticles on rosin modified surfactant induced aggregation of lysozyme. Int. J. Biol. Macromol. 2015, 78,
379–388. [CrossRef]
196. Wang, H.; Nguyen, T.T.H.; Li, S.; Liang, T.; Zhang, Y.; Li, J. Quantitative structure–activity relationship of
antifungal activity of rosin derivatives. Bioorg. Med. Chem. Lett. 2015, 25, 347–354. [CrossRef]
197. Chen, Z.; Li, S.; Tian, B.; Liang, T.; Jin, Y. Synthesis of a rosin gemini surfactant and its properties. Environ. Eng.
Sci. 2011, 29, 606–610. [CrossRef]
198. Wang, P.; Zhao, Z.D.; He, L.Z.; Bi, L.W.; Chen, Y.X. Fabrication of mesoporous ZrO2 by using rosin-based
quaternary ammonium salt. Adv. Mater. Res. 2011, 239–242, 3257–3261. [CrossRef]
199. Deng, W.; Zhang, Y.; Zhong, Y.; Peng, J. Synthesis and thermodynamic properties of rosin-based cationic
gemini surfactants. J. Surfactant. Deterg. 2014, 17, 453–458. [CrossRef]
200. Liu, G.; Wu, G.; Chen, J.; Kong, Z. Synthesis, modification and properties of rosin-based non-isocyanate
polyurethanes coatings. Prog. Org. Coat. 2016, 101, 461–467. [CrossRef]
201. Wang, H.; Tian, X.; Yang, D.; Pan, Y.; Wu, Q.; He, C. Synthesis and enantiomeric recognition ability of
22-crown-6 ethers derived from rosin acid and BINOL. Tetrahedron Asymmetry 2011, 22, 381–386. [CrossRef]
202. Nong, W.J.; Chen, X.P.; Liang, J.Z.; Wang, L.L.; Tong, Z.F.; Huang, K.L.; Wu, R.; Xie, Q.R.; Jia, Y.H.; Li, K.X.
Isolation and characterization of abietic acid. Adv. Mater. Res. 2014, 887–888, 551–556. [CrossRef]
203. Zhang, G.; Jiang, C.; Wang, Z.; Chen, W.; Gu, W.; Ding, Y. Dehydroabietic acid derivative QC2 induces
oncosis in hepatocellular carcinoma cells. Biomed Res. Int. 2014, 2014, 682197. [CrossRef]
204. Li, J.; Song, J.; Shang, S.-B.; Rao, X.-P.; Gao, Y.-Q. Syntheses and antibacterial activity of Schiff bases
from 16-isopropyl-5, 9-dimethyltetracyclo [10.2.2.01, 10.04, 9] hexadec-15-ene-5, 14-dicarboxylic acid.
Nat. Prod. Res. 2013, 27, 702–710. [CrossRef] [PubMed]
205. Li, J.; Rao, X.; Shang, S.; Gao, Y.; Song, J. Synthesis and antibacterial activity of amide derivatives from
acrylopimaric acid. Bioresources 2012, 7, 1961–1971. [CrossRef]
206. Shi, Z.; Wang, Y.; Nie, Y.; Yao, X. Synthesis and characterization of glucose dehydroabietate. Adv. Mater. Res.
2012, 396–398, 1260–1264. [CrossRef]
207. Liu, Y.; Li, L.; Liu, S.; Xie, C.; Yu, S. The selective hydrogenation of rosin to hydroabietic content using
Pd/SBA-15 as catalysts. Res. Chem. Intermed. 2017, 43, 1211–1221. [CrossRef]
208. Huang, Y.; Wang, L.; Chen, X.; Wei, X.; Liang, J.; Li, W. Intrinsic kinetics study of rosin hydrogenation on a
nickel catalyst supported on spent equilibrium catalyst. RSC Adv. 2017, 7, 25780–25788. [CrossRef]
209. Wang, M.M.; Liu, S.W.; Li, L.; Yu, S.T.; Xie, C.X.; Song, Z.Q. Hydrogenation of rosin over PVP-stabilized Pd
nanoparticles in aqueous/organic biphasic system. Res. Chem. Intermed. 2016, 42, 6181–6190. [CrossRef]
210. Zhang, D.; Zhou, D.; Wei, X.; Liang, J.; Chen, X.; Wang, L. Green catalytic conversion of hydrogenated rosin
to glycerol esters using subcritical CO2 in water and the associated kinetics. J. Supercrit. Fluid. 2017, 125,
12–21. [CrossRef]
Molecules 2019, 24, 1651
49 of 52
211. Bernas, A.; Salmi, T.; Murzin, D.Y.; Mikkola, J.-P.; Rintola, M. Catalytic transformation of abietic acid to
hydrocarbons. Top. Catal. 2012, 55, 673–679. [CrossRef]
212. Wang, L.; Huang, C.; Chen, J.; Wei, X.; Chen, X.; Liang, J. Catalyst-free biodiesel production from industrial
rosin residue (dark-grade rosin) using supercritical methanol. Waste Biomass Valori. 2018, 9, 1191–1198.
[CrossRef]
213. Kulikov, A.B.; Onishchenko, M.I.; Maksimov, A.L.; Lysenko, S.V.; Karakhanov, E.A. Hydroconversion of rosin
acids in the presence of Pt-containing Al–HMS mesoporous aluminosilicate. Pet. Chem. 2016, 56, 717–723.
[CrossRef]
214. Huang, Y.; Chen, X.; Deng, Y.; Zhou, D.; Wang, L. A novel nickel catalyst derived from layered double
hydroxides (LDHs) supported on fluid catalytic cracking catalyst residue (FC3R) for rosin hydrogenation.
Chem. Eng. J. 2015, 269, 434–443. [CrossRef]
215. Tong, D.S.; Zheng, Y.M.; Yu, W.H.; Wu, L.M.; Zhou, C.H. Catalytic cracking of rosin over acid-activated
montmorillonite catalysts. Appl. Clay Sci. 2014, 100, 123–128. [CrossRef]
216. Bicu, I.; Mustata, F. Polymers from a levopimaric acid–acrylonitrile Diels–Alder adduct: Synthesis and
characterization. J. Polym. Sci. A 2005, 43, 6308–6322. [CrossRef]
217. Atta, A.; Al-Lohedan, H.; Al-Hussain, S.; Atta, A.M.; Al-Lohedan, H.A.; Al-Hussain, S.A. Functionalization
of magnetite nanoparticles as oil spill collector. Int. J. Mol. Sci. 2015, 16, 6911–6931. [CrossRef]
218. Atta, A.M.; Akl, Z.F. Removal of thorium from water using modified magnetite nanoparticles capped with
rosin amidoxime. Mater. Chem. Phys. 2015, 163, 253–261. [CrossRef]
219. Li, M.; Jiang, J.; Zhang, J.; Yang, X.; Zhang, Y.; Li, S.; Song, J.; Huang, K.; Xia, J. Preparation of a new liquid
thermal stabilizer from rosin and fatty acid and study of the properties of the stabilized PVC. Polym. Degrad.
Stab. 2014, 109, 129–136. [CrossRef]
220. Chen, P.; Zeng, X.; Li, H.; Liu, X.; Liu, D.; Li, X. Preparation and characterization of polyacrylate/polymerized
rosin composite emulsions by seeded semicontinuous emulsion polymerization. J. Appl. Polym. Sci. 2012,
124, 4694–4701. [CrossRef]
221. Chen, P.; Zeng, X.; Li, H.; Liu, X.; Liu, D.; Li, X. Effect of polymerized rosin on polymer microstructure and
adhesive properties in tackified acrylate emulsions. Polym. Plast. Technol. Eng. 2012, 51, 122–127. [CrossRef]
222. Foreiter, M.B.; Gunaratne, H.Q.N.; Nockemann, P.; Seddon, K.R.; Stevenson, P.J.; Wassell, D.F. Chiral
thiouronium salts: Synthesis, characterisation and application in NMR enantio-discrimination of chiral
oxoanions. New J. Chem. 2013, 37, 515–533. [CrossRef]
223. Guo, X.-T.; Sha, F.; Wu, X.-Y. Highly enantioselective Michael addition of α,α-disubstituted aldehydes to
nitroolefins. Res. Chem. Intermed. 2016, 42, 6373–6380. [CrossRef]
224. Reddy, B.V.S.; Swain, M.; Reddy, S.M.; Yadav, J.S. Enantioselective Michael addition of
2-hydroxy-1,4-naphthoquinone and 1,3-dicarbonyls to β-nitroalkenes catalyzed by a novel bifunctional
rosin-indane amine thiourea catalyst. RSC Adv. 2013, 3, 8756–8765. [CrossRef]
225. Zhang, G.; Zhang, Y.; Jiang, X.; Yan, W.; Wang, R. Highly enantioslective synthesis of multisubstituted
polyfunctional dihydropyrrole via an organocatalytic tandem michael/cyclization sequence. Org. Lett. 2011,
13, 3806–3809. [CrossRef]
226. Reddy, B.V.S.; Swain, M.; Reddy, S.M.; Yadav, J.S.; Sridhar, B. Asymmetric Michael/hemiketalization
of 5-hydroxy-2-methyl-4H-pyran-4-one to β,γ-unsaturated α-ketoesters catalyzed by a bifunctional
rosin–indane amine thiourea catalyst. RSC Adv. 2014, 4, 42299–42307. [CrossRef]
227. Jiang, X.; Zhang, Y.; Wu, L.; Zhang, G.; Liu, X.; Zhang, H.; Fu, D.; Wang, R. Doubly stereocontrolled
asymmetric aza-Henry reaction with in situ generation of N-Boc-imines catalyzed by novel rosin-derived
amine thiourea catalysts. Adv. Synth. Catal. 2009, 351, 2096–2100. [CrossRef]
228. Zhang, H.-R.; Xue, J.-J.; Chen, R.; Tang, Y.; Li, Y. A bifunctional rosin-derived thiourea catalyzed asymmetric
tandem reaction and its new mechanism. Chin. Chem. Lett. 2014, 25, 710–714. [CrossRef]
229. Jiang, X.; Wang, Y.; Zhang, G.; Fu, D.; Zhang, F.; Kai, M.; Wang, R. Enantioselective synthesis of cyclic
thioureas via mannich reaction and concise synthesis of highly optically active methylthioimidazolines:
discovery of a more potent antipyretic agent. Adv. Synth. Catal. 2011, 353, 1787–1796. [CrossRef]
230. Jiang, X.; Fu, D.; Zhang, G.; Cao, Y.; Liu, L.; Song, J.; Wang, R. Highly diastereo- and enantioselective Mannich
reaction of lactones with N-Boc-aldimines catalyzed by bifunctional rosin-derived amine thiourea catalysts.
Chem. Commun. 2010, 46, 4294–4296. [CrossRef]
Molecules 2019, 24, 1651
50 of 52
231. Jiang, X.; Wu, L.; Xing, Y.; Wang, L.; Wang, S.; Chen, Z.; Wang, R. Highly enantioselective Friedel–Crafts
alkylation reaction catalyzed by rosin-derived tertiary amine–thiourea: synthesis of modified chromanes
with anticancer potency. Chem. Commun. 2011, 48, 446–448. [CrossRef]
232. Jiang, X.; Zhang, Y.; Liu, X.; Zhang, G.; Lai, L.; Wu, L.; Zhang, J.; Wang, R. Enantio- and diastereoselective
asymmetric addition of 1,3-dicarbonyl compounds to nitroalkenes in a doubly stereocontrolled manner
catalyzed by bifunctional rosin-derived amine thiourea catalysts. J. Org. Chem. 2009, 74, 5562–5567.
[CrossRef]
233. Zhao, X.; Kang, T.; Shen, J.; Sha, F.; Wu, X. Enantioselective allylic amination of morita-baylis-hillman acetates
catalyzed by chiral thiourea-phosphine. Chin. J. Chem. 2015, 33, 1333–1337. [CrossRef]
234. Zhu, H.; Jiang, X.; Li, X.; Hou, C.; Jiang, Y.; Hou, K.; Wang, R.; Li, Y. Highly enantioselective synthesis of
N-protected β-amino malonates catalyzed by magnetically separable heterogeneous rosin-derived amino
thiourea catalysts: a stereocontrolled approach to β-amino acids. ChemCatChem 2013, 5, 2187–2190. [CrossRef]
235. Lin, N.; Long, X.W.; Chen, Q.; Zhu, W.R.; Wang, B.C.; Chen, K.B.; Jiang, C.W.; Weng, J.; Lu, G. Highly
efficient construction of chiral dispirocyclic oxindole/thiobutyrolactam/chromanone complexes through
Michael/cyclization cascade reactions with a rosin-based squaramide catalyst. Tetrahedron 2018, 74, 3734–3741.
[CrossRef]
236. Cao, Y.; Jiang, X.; Liu, L.; Shen, F.; Zhang, F.; Wang, R. Enantioselective Michael/cyclization reaction sequence:
Scaffold-inspired synthesis of spirooxindoles with multiple stereocenters. Angew. Chem. Int. Ed. 2011, 50,
9124–9127. [CrossRef]
237. Pan, D.; Wu, A.; Li, P.; Xu, H.; Lei, F.; Shen, L. Palladium-loaded renewable polymer as a green heterogeneous
catalyst for cross-coupling reactions under microwave irradiation. J. Chem. Res. 2014, 38, 715–718. [CrossRef]
238. Morkhade, D.M.; Nande, V.S.; Barabde, U.V.; Patil, A.T.; Joshi, S.B. PEGylated rosin derivatives: Novel
microencapsulating materials for sustained drug delivery. AAPS PharmSciTech 2007, 8, E134. [CrossRef]
239. Morkhade, D.M.; Nande, V.S.; Barabde, U.V.; Joshi, S.B. Study of biodegradation and biocompatibility of
PEGylated rosin derivatives. J. Bioact. Compat. Polym. 2017, 32, 628–640. [CrossRef]
240. Morkhade, D.M.; Nande, V.S.; Barabde, U.V.; Patil, A.T.; Joshi, S.B. Design and evaluation of dental films
of PEGylated rosin derivatives containing sparfloxacin for periodontitis. Drug. Dev. Ind. Pharm. 2018, 44,
914–922. [CrossRef]
241. El-Mahdy, G.A.; Atta, A.M.; Al-Lohedan, H.A. Water soluble nonionic rosin surfactants as corrosion inhibitor
of carbon steel in 1 M HCl. Int. J. Electrochem. Sci. 2013, 8, 5052–5066.
242. Chen, Y.; Wilbon, P.A.; Chen, Y.P.; Zhou, J.; Nagarkatti, M.; Wang, C.; Chu, F.; Decho, A.W.; Tang, C.
Amphipathic antibacterial agents using cationic methacrylic polymers with natural rosin as pendant group.
RSC Adv. 2012, 2, 10275–10282. [CrossRef]
243. Kaith, B.S.; Jindal, R.; Sharma, R. Synthesis of a gum rosin alcohol-poly(acrylamide) based adsorbent and its
application in removal of malachite green dye from waste water. RSC Adv. 2015, 5, 43092–43104. [CrossRef]
244. Jindal, R.; Kaith, B.S.; Sharma, R. Central composite design model to study swelling of GrA-cl-poly(AAm)
hydrogel and kinetic investigation of colloidal suspension. J. Polym. Environ. 2018, 26, 999–1011. [CrossRef]
245. Ganewatta, M.S.; Ding, W.; Rahman, M.A.; Yuan, L.; Wang, Z.; Hamidi, N.; Robertson, M.L.; Tang, C.
Biobased plastics and elastomers from renewable rosin via “living” ring-opening metathesis polymerization.
Macromolecules 2016, 49, 7155–7164. [CrossRef]
246. Rahman, M.A.; Lokupitiya, H.N.; Ganewatta, M.S.; Yuan, L.; Stefik, M.; Tang, C. Designing block copolymer
architectures toward tough bioplastics from natural rosin. Macromolecules 2017, 50, 2069–2077. [CrossRef]
247. Choi, S.J.; Yim, T.; Cho, W.; Mun, J.; Jo, Y.N.; Kim, K.J.; Jeong, G.; Kim, T.-H.; Kim, Y.-J. Rosin-embedded
poly(acrylic acid) binder for silicon/graphite negative electrode. ACS Sustain. Chem. Eng. 2016, 4, 6362–6370.
[CrossRef]
248. Carbonell-Blasco, P.; Antoniac, I.V.; Martín-Martínez, J.M. New polyurethane sealants containing rosin for
non-invasive disc regeneration surgery. Key Eng. Mater. 2014, 583, 67–79. [CrossRef]
249. Carbonell-Blasco, P.; Martín-Martínez, J.M.; Antoniac, I.V. Synthesis and characterization of polyurethane
sealants containing rosin intended for sealing defect in annulus for disc regeneration. Int. J. Adhes. Adhes.
2013, 42, 11–20. [CrossRef]
250. Atta, A.M.; Elsaeed, A.M. Use of rosin-based nonionic surfactants as petroleum crude oil sludge dispersants.
J. Appl. Polym. Sci. 2011, 122, 183–192. [CrossRef]
Molecules 2019, 24, 1651
51 of 52
251. Atta, A.M.; Ramadan, A.M.; Shaffei, K.A.; Nassar, A.M.; Ahmed, N.S.; Fekry, M. Synthesis and properties of
nonionic surfactants from rosin-imides maleic anhydride adduct. J. Disper. Sci. Technol. 2009, 30, 1100–1110.
[CrossRef]
252. Kaith, B.S.; Jindal, R.; Sharma, R. Study of ionic charge dependent salt resistant swelling behavior and removal
of colloidal particles using reduced gum rosin-poly(acrylamide)-based green flocculant. Iran. Polym. J. 2016,
25, 349–362. [CrossRef]
253. Jindal, R.; Sharma, R.; Maiti, M.; Kaur, A.; Sharma, P.; Mishra, V.; Jana, A.K. Synthesis and characterization
of novel reduced gum rosin-acrylamide copolymer-based nanogel and their investigation for antibacterial
activity. Polym. Bull. 2017, 74, 2995–3014. [CrossRef]
254. Li, Q.; Huang, X.; Liu, H.; Shang, S.; Song, Z.; Song, J. Properties Enhancement of Room Temperature
Vulcanized Silicone Rubber by Rosin Modified Aminopropyltriethoxysilane as a Cross-linking Agent.
ACS Sustain. Chem. Eng. 2017, 5, 10002–10010. [CrossRef]
255. Li, Q.; Huang, X.; Liu, H.; Shang, S.; Song, Z.; Song, J. Preparation and properties of room temperature
vulcanized silicone rubber based on rosin-grafted polydimethylsiloxane. RSC Adv. 2018, 8, 14684–14693.
[CrossRef]
256. Xu, T.; Liu, H.; Song, J.; Shang, S.-B.; Song, Z.-Q.; Chen, X.-J.; Yang, C. Synthesis and characterization of
imide modified poly(dimethylsiloxane) with maleopimaric acid as raw material. Chin. Chem. Lett. 2015, 26,
572–574. [CrossRef]
257. Lin, R.; Li, H.; Long, H.; Su, J.; Huang, W. Structure and characteristics of lipase-catalyzed rosin acid starch.
Food Hydrocoll. 2015, 43, 352–359. [CrossRef]
258. Lin, R.; Li, H.; Long, H.; Su, J.; Huang, W. Synthesis of rosin acid starch catalyzed by lipase. BioMed Res. Int.
2014, 2014, 647068. [CrossRef]
259. De Castro, D.O.; Bras, J.; Gandini, A.; Belgacem, N. Surface grafting of cellulose nanocrystals with natural
antimicrobial rosin mixture using a green process. Carbohydr. Polym. 2016, 137, 1–8. [CrossRef]
260. Niu, X.; Liu, Y.; Song, Y.; Han, J.; Pan, H. Rosin modified cellulose nanofiber as a reinforcing and
co-antimicrobial agents in polylactic acid /chitosan composite film for food packaging. Carbohydr. Polym.
2018, 183, 102–109. [CrossRef]
261. George, M.; Mussone, P.G.; Bressler, D.C. Utilization of tall oil to enhance natural fibers for composite
applications and production of a bioplastic. J. Appl. Polym. Sci. 2016, 133, 44327. [CrossRef]
262. Sacripante, G.G.; Zhou, K.; Farooque, M. Sustainable polyester resins derived from rosins. Macromolecules
2015, 48, 6876–6881. [CrossRef]
263. Yuan, L.; Hamidi, N.; Smith, S.; Clemons, F.; Hamidi, A.; Tang, C. Molecular characterization of biodegradable
natural resin acid-substituted polycaprolactone. Eur. Polym. J. 2015, 62, 43–50. [CrossRef]
264. Wang, J.; Chen, Y.P.; Yao, K.; Wilbon, P.A.; Zhang, W.; Ren, L.; Zhou, J.; Nagarkatti, M.; Wang, C.; Chu, F.; et al.
Robust antimicrobial compounds and polymers derived from natural resin acids. Chem. Commun. 2011, 48,
916–918. [CrossRef]
265. Ma, G.; Zhang, T.; Wu, J.; Hou, C.; Ling, L.; Wang, B. Preparation and properties of glycerin ester of tung oil
modified rosin. J. Appl. Polym. Sci. 2013, 130, 1700–1706. [CrossRef]
266. Wu, J.; Zhang, T.; Ma, G.; Li, P.; Ling, L.; Wang, B. Synthesis of a tung oil–rosin adduct via the diels–alder
reaction: Its reaction mechanism and properties in an ultraviolet-curable adhesive. J. Appl. Polym. Sci. 2013,
130, 4201–4208. [CrossRef]
267. Yu, C.; Chen, C.; Gong, Q.; Zhang, F.-A. Preparation of polymer microspheres with a rosin moiety from rosin
ester, styrene and divinylbenzene. Polym. Int. 2012, 61, 1619–1626. [CrossRef]
268. Huang, J.F.; Shi, Q.S.; Feng, J.; Chen, M.J.; Li, W.R.; Li, L.Q. Facile pyrolysis preparation of rosin-derived
biochar for supporting silver nanoparticles with antibacterial activity. Compos. Sci. Technol. 2017, 145, 89–95.
[CrossRef]
269. Wang, L.; Shi, Y.; Wang, Y.; Zhang, H.; Zhou, H.; Wei, Y.; Tao, S.; Ma, T. Composite catalyst of rosin
carbon/Fe3O4: Highly efficient counter electrode for dye-sensitized solar cells. Chem. Commun. 2014, 50,
1701–1703. [CrossRef]
270. Ruan, Z.; Wu, J.; Huang, J.F.; Lin, Z.T.; Li, Y.F.; Liu, Y.-L.; Cao, P.-Y.; Fang, Y.-P.; Xie, J.; Jiang, G.-B.
Facile preparation of rosin-based biochar coated bentonite for supporting α-Fe2O3 nanoparticles and its
application for Cr(VI) adsorption. J. Mater. Chem. A 2015, 3, 4595–4603. [CrossRef]
Molecules 2019, 24, 1651
52 of 52
271. Zeng, C.; Lin, Q.; Fang, C.; Xu, D.; Ma, Z. Preparation and characterization of high surface area activated
carbons from co-pyrolysis product of coal-tar pitch and rosin. J. Anal. Appl. Pyrol. 2013, 104, 372–377.
[CrossRef]
272. Liu, H.; Du, S.; Chen, Y. Preparing mesoporous carbon and silica with rosin-silica composite gel. J. Nanosci.
Nanotechnol. 2009, 9, 799–802. [CrossRef]
© 2019 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).