Nonisocyanate Polyurethanes Systems
and Cyclic Carbonates
Oleg L. Figovsky,
D.Sc., Professor,
Academician of European Academy of Sciences,
Director R&D of Nanotech Industries, Inc. and
INRC Polymate,
Editor-in-chief of journals – ICMS (USA), SITA (Israel),
Chairman of the UNESCO Chair "Green Chemistry"
1
Polyurethanes
Polyurethanes (PUs) is a product of the addition polymerization
reaction between diisocyanates and diols. The demand in PUs has
continued to increase and it will attain in 2016 a production of 18
million tons (~US$66.4 bln) of which 75% are foam.
The main environmental issue of PU materials concerns the use
of isocyanate raw materials. In fact, these compounds are harmful
for human and environment. MDI and TDI, the most widely used
isocyanates in PU industry, are classified as CMR
(Carcinogen, Mutagen and Reprotoxic):
Merenyi S. REACH: regulation (EC) No 1907/2006: consolidated version
(June 2012) with an introduction and future prospects regarding the area of
Chemicals legislation. GRIN Verlag; 2012.
2
Among all methods of non-isocyanate synthesis of polyurethane,
reaction of cyclic carbonate with amine is the most attractive.
NIPU –
Non-Isocyanate PolyUrethane
HNIPU –
Hybrid Non-Isocyanate PolyUrethane
3
Historical inventions in the field of NIPU – HNIPU
Fundamentals for the practical application of NIPU on the basis of five-membered cyclic
carbonates (1,3-dioxolan-2-ones) in coatings, sealants, adhesives, etc. were largely developed
by L. Rappoport, O. Figovsky, V. Mikheev, V. Stroganov et al. in the 1970 – 1990’s
Soviet Union patents:
SU 351835, 1972 – Cyclic carbonate synthesis
SU 359255, 1972 – Polyhydroxyurethanes
SU 413824, 1983 – NIPU hardeners
SU 422262, 1978 – Polycyclic carbonate polydiens
SU 426493, 1978 – Polycyclic carbonate polydiens
SU 441805, 1978 – acrylic cyclic carbonate
SU 462478, 1975 – Dienehydroxyurethanes
SU 671318, 1984 – Cyclic carbonate synthesis
SU 707258, 1984 – Cyclic carbonate synthesis
RU 970856, 1996 – Polydienehydroxyurethanes
SU 1110783, 1984 – Cyclic carbonate synthesis
SU 1126569, 1984 – Cyclic carbonate synthesis
SU 529197, 1976 – Coating, sealant
SU 563396, 1977 – Polymer concrete
SU 628125, 1978 – Polymer concrete
SU 630275, 1978 – Coating, sealant
SU 659588, 1979 – Sealant
SU 518506, 1976 – Urethanediols
SU 812797, 1981 – Coating
SU 903340, 1982 – Polymer concrete
SU 908769, 1982 – Polymer concrete
RU 1770324, 1992 – NIPU foam
SU 1754747, 1992 – Coating
SU 1754748, 1992 – Coating
4
Non-amine curing of hybrid oligomer compositions
SU Patent 722206, Figovsky O.L. et al.
Hybrid anticorrosion composition on the base of epoxy
resin includes hydroxyphenyl ester of phosphoric acid
(OEPA).
OEPA is the reaction product of alkyl resorcinol fractions
shale phenols with orthophosphoric acid.
Hybrid composition cure at ambient temperatures
(+5 - +35o C)
5
Reaction of cyclocarbonates with amines has long been used in the
pharmaceutical:
Preparation of hydroxyaromatic esters of substituted carbamic acids
SU Patent 722082, Figovsky O.L. et al.
by reaction of aromatic amines with arylen cyclic carbonates
at temperatures 20-100o C
R1-Ar[NHCOO-Ph(o-OH)(R)]m
m = 1, 2, 3
R = H; -CH=CH-CH3; -OH; -C(CH3)3
R1 = -OH; -Cl; -COOC(CH3)-CH2-OOC-Ph-o-NH2
Ar = -Ph; naphtyl
6
Synthesis of cyclic carbonates
A plausible mechanism for catalyzed synthesis of cyclic carbonates
from epoxides and CO2
J Polymer Sci. Part A: Polymer Chemistry, 2013, V. 51, Issue 5, p. 1230-1242
7
Known role of Bu4NBr (TBAB) in cyclic carbonate synthesis
Bimetallic aluminum(salen) complex 1: [(salen)Al]2O
Angew. Chem. Int. Ed. 2009, 48, 2946-2948
8
Synthesis of cyclic carbonates from epoxides and CO2 at 1 atm and at ambient temperature:
complex 1 is used in conjunction with TBAB
rate = k [epoxide] [CO2] [1] [Bu4NBr]2
Eur. J. Inorg. Chem. 2007, 3323-3326
Angew. Chem. Int. Ed. 2009, 48, 2946-2948
9
Conversion of CO2 and epoxides into cyclic carbonates
Multilayered covalently supported ionic liquid
phase (mlc-SILP) materials synthesised by grafting
different bis-vinylimidazolium salts
on thiol-functionalised silica.
Catal. Sci. Technol., 2014, 4, 6, 1598-1607
10
One-pot coupling reaction of CO2, propylene oxide (PO) and bisepoxides
without the addition of external organic solvents by using
a nanolamellar zinc-cobalt double metal cyanide complex (Zn–Co(III) DMCC)
as the catalyst and
cetyltrimethyl-ammonium bromide (CTAB) as the co-catalyst.
RSC Adv., 2013, 3, 38, 17307-17313
11
Progress made in the use of ionic liquid catalysts and related systems
for cycloaddition reactions of carbon dioxide with epoxides
Catalysts range: from simple onium species including tetrabutylammonium bromide,
functionalized and simple imidazolium ionic liquids, to a plethora of supported ionic
liquid systems.
A range of supports: alumina, silica, carbon nanotubes, magnetic nanoparticles,
poly(ethyleneglycol), polystyrene, cellulose and chitosan
have been used with a variety of ionic groups.
Catal. Sci. Technol., 2014, 4, 6, 1513-1528
12
Alternative routes for the synthesis of cyclic carbonates
(Green Chem., 2010, 12, 1514–1539)
1. Cyclic carbonate synthesis via oxidative addition of CO2 to olefins
2. Carboxylative cyclization of propargyl alcohol with CO2
13
3. Cyclic carbonate synthesis from CO2 and 1,2-diols
4. Electrochemical synthesis of cyclic carbonates
14
Versatile dehydration systems have been developed,
which have drastically improved the yields of the target carbonates
Catal. Sci. Technol., 2014, 4, 9, 2830-2845
15
Direct synthesis of propylene carbonate from CO2 and 1,2-propanediol
in excellent yield (>99%)
using a carboxylation/hydration cascade catalyst of CeO2 with 2-cyanopyridine
ACS Catal., 2014, 4 (6), pp 1893–1896
16
Renewable Raw Materials
Regimes of carbonization
Raw materials: epoxidized fatty oils
Ref.
Catalyst
T, oC
Pg, atm
t, hours
Conversion, %
1
2
3
4
5
6
Tetrabutyl ammonium bromide (TBAB), 5 mol. %
TBAB
KI coupled with 18-crown-6
SnCl4 . 5H2O and TBAB, 3 mol. %
TBAB
TBAB (M = 322.4), 1-5 wt. %
94
100
98
65-90
63-100
50
63
TBAB 3.5% (or 3 mol.% halide per epoxy) and
silica-supported 4-pyrrolidino-pyridinium iodide,
SiO2–(I)
1
105
60
10
0-57
1
54
0; 10;
30
70
20-40
120
20
20-150
24
18
7
110
100
130
120
110-140
80
120
140
40, 70 and
100
1-200
8
1. J. Appl. Polym. Sci., 2004, 92 (2), 883-891; US Pat. 7045577, 2006.
2. Green Chem., 2005, 7 (12), 849-854; J. Agric. Food Chem., 2005, 53 (24), 9608-9614.
3. J. App. Polym. Sci., 2006, 102 (3), 2904-2914.
4. Catal Lett., 2008, 123 (3-4), 246-251;
5. J. Appl. Polym. Sci., 2008, 108 (6), 3867-3875.
6. J. Oleo Sci., 2007, 56 (12), 629-632.
7. Green Chem., 2012, 14, 2, 483-489.
8. Polym. Chem., 2012, 3, 2, 525-532.
17
Examples of cyclic carbonates
Monocyclic carbonates
Propylene carbonate
Glycerine carbonate
Propyl Carbonate Triethoxysilane
Allyl Glycerol carbonate
Glycerol carbonate methacrylate
Phenoxycarbonyloxymethyl
ethylene carbonate
18
Examples of cyclic carbonates
Dicyclic carbonates
Resorcinol Bis Carbonate
Alkyl Bis Carbonate
Bis Carbonate Terephtalate
Polydimethyl Siloxane Bis Carbonate
Cebacate Bis Carbonate
PPO Bis Carbonate
19
Examples of cyclic carbonates
Tricyclic and polycyclic carbonates
Propoxylated glycerine tricyclic carbonate
Trimethylolpropane tricyclic carbonate
Diaminodiphenylmethane tetracyclic carbonate
Aminophenol tricyclic carbonate
20
Examples of cyclic carbonates
Polyaromatic polycyclic carbonates
21
Examples of cyclic carbonates
Renewable plant-base raw materials
Carbonated epoxidized unsaturated fatty acid triglyceride
Vanillin Bis Carbonate
Poly Isosorbide Bis Carbonate
Limonene dicarbonate
22
Proprietary Chemistry of Nonisocyanate PU
★ NIPU networks are obtained through a
reaction between polycyclic carbonate oligomers
and aliphatic or cycloaliphatic polyamines with
primary amino groups. This forms a crosslinked
polymer with β-hydroxyurethane groups of
different structure resulting in a polyhydroxyurethane polymer.
★ Since NIPU is obtained without using highly
toxic isocyanates, the process of synthesis is
relatively safe for both humans and environment
in comparison to the production of the
conventional polyurethanes.
23
β-Hydroxyurethane moieties of nonisocyanate
polyurethanes:
(a) with secondary hydroxyl groups;
(b) with primary hydroxyl groups.
24
Stages of the hydroxyurethane formation process
Dok. Phys. Chem., 2003, Vol. 393, Nos. 1–3, pp. 289–292.
25
Activation of the cyclic carbonate group in proton-donor medium
Kinetic equation containing an uncatalysed and an autocatalysed reaction
-d[c]/dt = kl[C][a]p + k2[c][a]q[OH ]
[c] = concentration of cyclic carbonate
[a] = concentration of amine
[OH] = concentration of the product + initial concentration of OH
p~q~2
k2 >> kl
Polymer Bulletin, 1991, 27, 171-177.
26
Structures of the hydroxyurethane conformers and isomers
Russian Chem. Bull., Int. Edition, 2012, Vol. 61, No. 3, pp. 518-527.
27
Alternative synthesis of NIPU
(The Dow Chemical Company )
Recently a new isocyanate-free chemistry for the preparation of polyurethane materials
at ambient temperatures from the reaction of polyaldehydes with carbamate functional
polymers using an acid catalyst was proposed by Dow Chemical:
US Patent 8,653,174, February 18, 2014;
SSPC 2015. Isocyanate Free Polyurthane Coatings for Industrial Metal Applications
28
Alternative synthesis of NIPU
(The Dow Chemical Company )
Preferably the polyaldehyde is prepared by hydroformylating process with
hydrogen gas, carbon monoxide, and an olefin-containing starting compound.
The polycarbamates are acrylic carbamate functional polymers with a
molecular weight of ~15,000 in n-butyl acetate at ~70% solids by weight.
Isocyanates and phosgene are used on the preliminary stages for preparation of
the carbamate functional polymers.
Blocking agents (alcohols) are used for regulation of pot life.
As a result an additional allocation of water takes place.
US Patent 8,653,174, February 18, 2014;
SSPC 2015. Isocyanate Free Polyurthane Coatings for Industrial Metal Applications
29
NIPU is not sensitive to moisture in the surrounding
environment.
Hydroxyl groups formed at the β-carbon atom of the
urethane moiety increase adhesion properties.
Plurality of intra- and intermolecular hydrogen bonds
as well as an absence of unstable biuret and allophanate
units seem to be responsible for increased thermal
stability and chemical resistance to nonpolar solvents.
30
Advantages of HNIPU
HNIPU has superior properties in comparison to
conventional polyurethanes (PU)
 High hydrolytic stability
 Reduced permeability
3-4 time less than conventional PU
 Superior abrasive and chemical resistance
30-50% better than conventional PU
 Excellent adhesiveness
 Safer and easer application
Do not use the toxic isocyanate
 Wide spectrum of applications
31
Some recently achievements
in chemistry and technology of NIPU
(literature and patent data)
32
Five-membered cyclic carbonate polysiloxane compounds and
amine-modified polysiloxane compounds (Japan)
wherein A means
in which R1 means an alkylene group which has from 1 to 12 carbon atoms and may be linked via an
element of O, S or N and/or -(C2H4O)b-, R2 means a direct bond or an alkylene group having from 2 to 20
carbon atoms, R2 may be linked to an alicyclic group or aromatic group, b stands for a number of from 1
to 300, and a stands for a number of from 1 to 300.
33
The resulting polysiloxane-modified polyhydroxy polyurethane resins are very useful as a
raw material for various molding materials, synthetic leather and artificial leather materials,
fiber coating materials, surface treatment materials, thermal recording media, strippable
materials, paints, and a binder for printing inks; and, when added in epoxy resins, as a raw
material for various paints, adhesives, composite materials and sealants.
US Patents: 8,975,420, 2015; 8,951,933, 2015; US Patent 8,703,648, 2014.
34
A novel cyclic carbonate monomer comprising a reaction product of
(a) at least one divinylarene dioxide; and (b) carbon dioxide:
The poly(hydroxyurethane) compositions made from Divinylbenzene Dicarbonate and
polyamines forms a reactive intermediate that can be used for making, for example,
a poly(hydroxyurethane) foam product having an approximate volume expansion of 10.
US Patent Application 20140191156, DOW GLOBAL TECHNOLOGIES LLC
35
NIPU foams (France – Poland)
The obtained foamed mixtures were heated at 80 C for 12 h and 120 C for 4 h.
Apparent density of foam varies in the range 194-295 kg/m3.
Tension strain is 0.005-0.009 % at 35 % elongation.
European Polymer Journal, 2015, 66, 129–138
36
Synthesis of Terminal Bicarbonate Precursors from Plant Base Raw Materials
37
US Patent Application 20120259087
38
A method for preparing a compound
comprising a β-hydroxy urethane unit or a γ-hydroxy-urethane unit,
comprising reacting a compound A comprising a cyclocarbonate reactive unit
with a compound B comprising an amino reactive unit (-NH2)
in the presence of a catalyst, said method being characterized in that said catalyst comprises
an organometallic complex
and a cocatalyst selected from the group of
Lewis bases, or salts of tetra-alkyl ammonium.
US Patent Application 20140378648
39
Curing of epoxy resin compositions
comprising cyclic carbonates
using mixtures of amino hardeners and catalysts
US Patent 8,586,653, 2013, US Patent 8,877,837, 2014. BASF
40
Water-dispersible, cyclocarbonate-functionalized vinyl copolymer binder,
a process for the preparation of the binder, an aqueous dispersion containing the binder, a
system comprising the binder, water and an (amine) curing agent
and the use of the binder for the production of a hardened coating are proposed.
It was surprisingly found that this binder, in which the emulsifier groups
are incorporated in the polymer chain,
gives stable aqueous dispersions having a solids content of up to a 30% by weight.
US Patent 8,853,322, 2014
41
Method for preparing polyhydroxy-urethanes
from amino compounds and compounds carrying carbonate functions,
in particular cyclic carbonate functions.
US Patent 8,017,719, 2011. Rhodia.
42
Plasticizer Mixture of Epoxidized Fatty Acid Glycerin Carbonate Ester
and Epoxidized Fatty Acid Esters
wherein R1 is an epoxidized C7-23 hydrocarbon chain, represented by
wherein 1 ≤n ≤5 and 8 ≤ (m+3n+p+1) ≤ 23.
US Patent Application 20150057397
43
2-oxo-1,3-dioxolane-4-carboxamides (I)
in which R2 can be, inter alia, an
n-valent radical (n>1) which is
substituted with n-1 further 2oxo-1,3-dioxolane-4carboxamide groups of general
formula (II),
(I)
(II)
to processes for the preparation of these 2-oxo1,3-dioxolane-4-carboxamides, to processes
for the preparation of the 2-oxo-1,3-dioxolane4-carboxylic acids of formula (III),
which are suitable starting materials for the
above processes, and to the use of said 2-oxo1,3-dioxolane-4-carboxamides for the
preparation of (poly)hydroxyurethanes.
US Patent Application 20150051365
44
HYBRID POLYURETHANE SPRAY FOAMS MADE WITH
URETHANE PREPOLYMERS AND RHEOLOGY MODIFIERS
It was disclosed hybrid spray foams that use a urethane reactant, a
crosslinker, and an (optional) epoxy and/or acrylic resin, along with
a blowing agent and rheology modifier to produce a quick-setting
foam that remains in place until the foam forms and cures.
In some other formulations it was used the NIPU adducts of cyclic
carbonates and di- or polyamines, received from Polymate.
Unfortunately, the use of rheology modifiers in practice increases the
viscosity of the compositions and imparts to them a thixotropic
property, which significantly limits the use of this method for spray
foams.
US Patent Application 20120183694
45
Elaborations of novel NIPU – HNIPU products
and technologies
HCTI – Polymate
Cyclocarbonated Acrylic Oligomer
It was developed NIPU paint on the base of cyclocarbonated
acrylic oligomer cured by polyamines at 110-120 °C / 2-3 hours.
Paint has high water and weather stabilities but unfortunately we
need to use solvents for this composition.
46
Synthesis of polyaminofunctional hydroxyurethane oligomers
and hybrid polymers formed therefrom (EP 1070733, 2001)
Chemically resistant materials with high mechanical properties
are provided by using adducts of primary diamines (with
oligocyclocarbonate and epoxy compounds) and epoxy oligomers
with ended epoxy groups (or mixture of epoxy oligomers and
oligomercaptanes).
+
H2N-R2-NH2
→
47
Cyclocarbonate groups containing hydroxyamine oligomers
from epoxycylclic carbonates (US 6,407,198, 2002)
Chemically resistant materials with high mechanical properties
are provided by using polycyclic carbonates of special structure.
The polycyclic carbonates are prepared by the reaction of
oligocyclic carbonates containing ended epoxy groups with
primary aromatic diamine.
48
Hydroxyurethane-amine adducts as
hardeners for epoxy resins at RT
Scheme of hydroxyurethane modified amine
adduct for curing of epoxy resins
(US Patent Application 2010/0144966)
49
"HUMs" & "Uramines"
• > "Hydroxy Urethane Modifiers" (HUMs) are
the patented backbone technology of HNIPU
and are formulated as part of curing agents
under the name "Uramine" (Urethane Amines)
• > Developed for epoxides to enhance their
properties to the level of a polyurethane or
better
50
Hydroxyalkyl urethane modifier
(HUM)
HUM is obtained as a result of a reaction between a primary
amine and a cyclic carbonate compound at stoichiometric ratio,
and can be represented by the formula:
wherein R1 is a residue of the primary amine, R2 and R3 are the
same or different and are selected from the group consisting of H,
alkyl, hydroxyalkyl, and n satisfies the following condition: n ≥ 2
(US Patent 7,989,553, 2011).
51
Nano-structured non-isocyanate hybrid
epoxyurethane polymer
A novel non-isocyanate hybrid epoxyurethane composition contains alkoxysilane
units. The composition is highly curable at low temperatures with forming of
nanostructure under the influence of atmospheric moisture and the forming of
active, specific hydroxyl groups. The cured composition has excellent strengthstress properties, adhesion to a variety of substrates, appearance, and resistance to
weathering, abrasion, and solvents (US Patent 7,820,779 2010).
52
Radiation-curable biobased composition
A radiation-curable composition comprising (meth)acrylic monomers and/or
oligomers, photoinitiators, and a nonreactive composite additive, wherein the
nonreactive composite additive comprises a) a biobased hydroxyurethane
additive of formula (1):
R1[−NH−COO−CR2H−CR3H(OH)]2
(1)
wherein R1 is a residue of the biobased primary diamine, and R2 and R3 are the
same or different and are selected from the group consisting of H, alkyl, and
hydroxyalkyl; and b) a silane-based hydroxyurethane additive of formula (2):
(R6)3-n(OR5)nSi−R4−NH−COO−CR2H−CR3H(OH)
(2)
wherein R2 and R3 are the same as stated above, R4 is generally an aliphatic
group having from 1 to 6 carbon atoms, R5 and R6, independently, are
hydrocarbon radicals containing from 1 to 20 carbon atoms and selected from
the group consisting of aliphatic, cycloaliphatic, and aromatic groups or
combinations thereof, and n is equal to 1, 2, or 3 (US Application 14/160,297,
2014).
53
Hybrid nonisocyanate polyurethane grafted
polymers
Recently Polymate Ltd. develops a new hybrid epoxy-amine
hydroxyurethane network polymers with lengthy epoxy-amine
chains and pendulous hydroxyurethane units (US Application
14/296,478, 2014). The cured linear hybrid epoxy-amine
hydroxyurethane-grafted polymers by novel structure have a
controlled number of cross-links and combine increased
flexibility with well balanced physical-mechanical and physicalchemical properties of conventional epoxy-amine systems. In
particular, new materials have tensile strength up to 12 MPa and
elongation at break 70-275%. They may be used for various
applications, for example, for manufacturing of synthetic/
artificial leather, soft monolithic floorings and flexible foam.
54
Topological structure of polymer chains
The schematic structural formula of the novel polymer is the following:
where E―R`―E is a residue of a diglycidyl ether, which reacted with amine
hydrogens,
E is a converted epoxy group, i.e., –CH2–CH(OH)–CH2–O–,
N is a nitrogen atom,
A is a residue of a di-primary amine,
U(OH) is a hydroxyurethane group,
i.e., –R1–NH–CO–O–CH(R2)–CH(OH)–R3, and
=N―A―U(OH) is a residue of aminohydroxyurethane with the number of
free amine hydrogen atoms equal 2.
55
Creating a controlled number of cross-links
A schematic structural formula of the novel polymer with the directions of the
possible cross-links (shown by arrows) is the following:
,
where
is a residue of the polyfunctional epoxy resin, other
designations being the same as above. Polyamines with a number of free
amine hydrogen atoms more than 2 also may be used for cross-linking.
56
Some of perspective raw amines
PPGs amine terminated di- and tri-amines with MW up to 5000
Bio-based polyamines – idealized chemical structures
57
HNIPU FLOORING APPLICATION:
Indoor/Outdoor for Industrial & Commercial Buildings; Garages; Chemical Plants; Warehouses; Monolithic
Flooring for Civil, Industrial and Military Engineering, Marine Apps, etc.
PRODUCT NAME
FLI4W
FLI4W-FC
FLI4W-LP
FLI4W-B
FLIO6W
FLIO6S
FLI3
SPECIFIC PROPERTY
Increased chemical, wearing, light and humidity resistance plus
high sanitary-hygeinic properties. Application temperature: 5068 ˚F (10-20 ˚C)
Same as FLI4W but shorter curing time and pot life (10-30
minutes)
Same as FLI4W but longer pot life (2-3 hours)
Same as FLI4W but longer pot life (up to 4 hours)
Higher light resistance. Application temperature:
50-68 ˚F (10-20 ˚C)
Same as FLIO6W but increased "ultra" UV resistance
Low application temperature:
36-77 ˚F (2-25 ˚C), fast curing, high sanitary-hygienic properties
HNIPU PAINT APPLICATION:
Indoor/Outdoor for Industrial & Commercial Buildings; Chemical Plants; Marine Apps; Protective
Coatings Inside Pipes; Equipment for Liquid Fertilizer Delivery; Military Equip., etc.
PRODUCT NAME
SPECIFIC PROPERTY
PI9W
Paint for indoor light stable and chemical resistant applications.
Application temperature: 50-68 ˚F (10-20 ˚C)
PIO15W
Increased light resistance and high decorative properties. Application
temperature: 50-68 ˚F (10-20 ˚C)
PIO15S
Same as PIO15W but increased "ultra" UV resistance
Comparative properties of coatings
“cold curing”
Charackteristics
HNIPU
Conventional epoxy
Conventional PU
50-70
50-70
10-30
25-30
80-120
40-80
2
-1.4
51
-99
4
-5
Tensile strength, MPa
Abrasion resistance
(TABER, wheel CS17, 1000g), loss of
mass, mg/1000 cycles
Weatherability (QUVA testing, 1000 h)*:
color change, ΔE
gloss change, %
*Data of Sherwin-Williams
59
HNIPU foam
HNIPU foam is elaborated on the base of wide spectrum of
hydroxyurethanes.
Composition of polymeric matrix include up to 40 %
renewable components.
We have elaborated:
- sealant one-component foam;
- 2K sprayable foam insulation – rigid and semirigid;
- pourable rigid and semirigid foam;
- preliminary results on some types of soft and flexible foam
60
Non-isocyanate foam compositions related to hybrid systems
on the basis of epoxy, hydroxyurethane, acrylic, cyclic carbonate,
and amine raw materials in different combinations
Foamable, photopolymerizable liquid acrylicbased compositions
for sealing applications
US Patent 6,960,619 B2, 2005.
61
Hybrid non-isocyanate foams and coatings
on the basis of epoxies, acrylic epoxies, acrylic cyclocarbonates,
acrylic hydroxyurethane oligomers, and bifunctional amines
US Patent 7,232,877 B2, 2007.
62
Hybrid polyhydroxyurethane network
on a base of vegetable oil
Hybrid epoxy-hydroxyurethane compositions cross-linked at ambient
temperatures were obtained on the base of renewable raw materials.
Networks of hybrid polyhydroxyurethane were formed from
carbonated-epoxidized soybean oil, without the use of isocyanate
intermediates. Compositions can apply to the preparation of curable
polymeric foam and other materials (coatings, sealants, adhesives).
US Patent Application 2012/0208967.
63
Adaptation of hybrid nonisocyanate
composition for sprayable foam application
Provided is a method for the spray application of a nonisocyanate polymer foam
composition. The method comprises the steps of supplying dosed quantities of the
components of the nonisocyanate polymer composition to the mixing chamber,
transferring the foamable nonisocyanate polymer composition to the intermediate
chamber and continuously moving the composition through the intermediate
chamber for providing conditions most optimal for the spray application onto the
substrate.
US Patent Application 2015/0024138.
64
Principles of creating compositions
for polymer matrices
Varying oligomer raw materials (epoxy, hydroxyurethane, acrylic,
cyclic carbonate, and amine) in different combinations.
Using the hydroxyurethane components as comprising the main
chain, and as external dopants.
Using the renewable plant-based raw materials.
Blowing agents:
No impact on ozone layer depletion,
low Global Warming Impact (direct and indirect)
65
Blowing agents
Code and Name
Commercial Name
Boiling
point,
Tb, oC
Hydrofluorocarbons (HFCs)
HFC-227ea
FM-200, DuPont Fluoroproducts
1,1,1,2,3,3,3-Heptafluoropropane
HFC-236fa
SUVA® 236fa, DuPont Fluoroproducts
1,1,1,3,3,3-hexafluoropropane
HFC-245fa
Enovate® 3000, Honeywell
1,1,1,3,3-pentafluoropropane
HFC-365mfc
Forane® 365mfc, Arkema Inc.;
1,1,1,3,3-Pentafluorobutane
Solkane® 365mfc, Solvay Fluorides, Inc.
HFC-43-10mee
Vertrel® XF, DuPont Fluoroproducts
1,1,1,2,2,3,4,5,5,5-Decafluoropentane
HFC-1336mzz
Formacel® 1100, DuPont Fluoroproducts
1,1,1,4,4,4-hexafluoro-2-butene
Unsaturated hydrochlorofluorocarbon (HCFC)
HCFC-1233zd(E)
Solstice® LBA, Honeywell
trans-3,3,3-trifluoro-1-chloropropene
Hydrocarbons
n-Pentane
iso-Pentane
Cyclopentane
Chemical blowing agent
Polymethylhydrogensiloxane
Dow Corning 1107® Fluid, Dow Corning Corp.
–16.5
–1.4
15.3
40.2
55
33
19
36
28
49
66
Preliminary testing
of HNIPU sprayable foam
in Graco
67
68
69
70
RIGID HNIPU FOAM
Properties
Standard
Viscosity (Brookfield RVDV II, Spindle 29, 20
rpm) at 25ºC, cP
Base “A”
Base “B”
“A” + “B” (3-5 sec after mixing)
Pot life at: 25ºC (77 ºF), s
VOC
Gel time, s
Touch dry, s
Curing for transportation, min
Appearance of rigid foam
Compressive Properties of Rigid Cellular
Plastics, 24 hours, kg/mm2
ASTM D2196
Apparent Density of Rigid Cellular Plastics,
kg/m3
Thermal Resistance (R-value), hr•ft2•oF/BTU•in
Rigid Foam Insulation
ASTM D2369
2800 – 3200
3600-4100
≤3700
8-10
Compliant
2-4
30-40
15-20
White
ASTM D1621
0.02 – 0.04
ASTM D1622
30-40
C 518
4.5-5.0
71
Properties of preliminary flexible foam samples
Example No.
Properties
PP-1-77
PP-1-82
PP-1-88
PP-1-90
Brief description
Good foaming, not shrinkage flexible foam
Temperature of curing, oC
40
80
80
70
Cream time, sec
30
10
20
15
Touch dry, min
20
5
30
15
Density, kg/m3
45
40
38
38
Tensile Strength, MPa
0.028
0.026
0.03
0.12
Elongation at break, %
60
60
70
70
Sustainable raw materials
20-40 %
72