Synthesis of Colloids and Polymers
Topic:
Anionic Polymerization
And Macromolecular Engineering
Pierre J. LUTZ
5th Worhshop of the IRTG (International Research Training Group Soft
Condensed Matter)
Kontanz, April 3-5, 2006
Anionic Polymerization and Macromolecular Engineering
Some Problems that require well-defined Polymers
● How does the width of molar mass distribution influence the
mechanical properties of a polymer ?
● What is the effect of branching on polymer properties ?
● What protecting effect is exerted by soluble grafts on an insoluble
backbone in Graft Copolymers ?
● What is the size of a cyclic macromolecule as compared with that of
the linear homologue ?
● How does compositional heterogeneity affect the properties of a
Copolymer ?
● What are the conditions required for a block copolymer to exhibit
phase separation ?
Anionic Polymerization and Macromolecular Engineering
Some structures to be discussed
● LINEAR HOMOPOLYMERS or COPOLYMERS
● FUNCTIONAL POLYMERS or COPOLYMERS INCLUDING MACROMONOMERS
● BRANCHED POLYMERS
- GRAFT-COPOLYMERS
- STAR-SHAPED HOMO (CO-)POLYMERS
vaious cores: DVB, C60, Polygycerol, Sisesquioxanes
- COMB-LIKE POLYMERS HOMOPOLYMACROMONOMERS
● WELL-DEFINED POLYMERIC NETWORKS
● CYCLES or STRUCTURES derived from CYCLES
Anionic Polymerization and Macromolecular Engineering
Characterization Methods to be used to determine the structural parameters
or the behavior of Complex Macromolecular Architectures
● Static and Dynamic LIGHT SCATTERING To get Molar Mass,
Mw, and Radius of Gyration and Hydrodynamic Radius, …
● SIZE EXCLUSION CHROMATOGRAPHY (GPC)
Detectors required
* Differential Refractometry : to get c
* UV Spectrometry
to check for the presence of a chromophore
* Light scattering to get Mw
* Viscometry (necessary for universal calibration)
●
ELEMENTAL ANALYSIS
● DIFFERENTIAL REFRACTOMETRY / to get overall composition
● NMR, UV SPECTROMETRY (microstructure, composition, functionality)
● VISCOMETRY
● Maldi-TOF MS
● AFM,
● X-Ray measurements
In solution, in the bulk !
Anionic Polymerization and Macromolecular Engineering
Functionalization
Functionalization
Anionic Polymerization and Macromolecular Engineering
● Macromonomers well defined
polymers
- Low molar mass
- Polymerizable end-groups
- Accessible via anionic, cationic,
polymerization ATRP (FRP),
- PB, PE, PMMA, P2VP, PEO, PDMS
PS
Macromonomers
CH
CH 2
PS CH 2CCH 2
CH
CH2
CH2
CH 3
PS CH 2CH OCC CH 2
- Linear, block copolymer, star-shaped….
● Major interest
- Graft copolymers by (free) radical
copolymerization, branch length
- Access to new branched topolygies by
homopolymerization
Macromonomers by b-elimination reactions in coordination Polymerization
O
Anionic Polymerization / Macromolecular Eng.
Deactivation
(CH2)9
Macromonomer Synthesis
(CH 2 )9
Br
n
or
sec- BuLi
PS
toluene
Cl
+ THF
-78°C
w-allyl
+
n
(VBC)
Ph
PS (atactic):
undecenyl end group
Ph
Ph
w-undecenyl
Cl
n
PS
Ph
w-styrenyl
Characterization:
- Molar mass: SEC: Mn exp = Mn,th,
(1000 to 10 000 g.mol-1)
- Sharp molar mass distribution, no coupling
- Functionalization: 1H NMR
- Chemical Tritration
- Maldi-Tof
Anionic Polymerization / Macromolecular Eng.
Initiation
Macromonomer Synthesis
Anionic Polymerization of Oxirane
With K (and not Na or Li) RT
(CH2) 9
OH
(CH2) 9
Ø2CH- K+
+
O- K+
Diphenylmethyl potassium
10-undecene-1-ol
Initiation
O
(CH2) 9
-
+
O K
CH2
+
(CH2) 9
CH2
O- K+
O
Propagation
O
(CH2) 9
O-K+ + nCH2
O
CH2
(CH2) 9
]OK
[O
-
+
n
Termination
(CH2) 9
[O
]
O- K+ + HCl
n
(CH2) 9
[O
] OH
+ KCl
n
w-undecenyl, h ydroxy PEO
- Well functionalized
- Heterofunctional Polymer OH
- Deactivation also possible for PEO
Initiation not possible for
PS macromonomers
Anionic Polymerization / Macromolecular Engineering
GRAFT COPOLYMERS
Valuable polymeric materials constituted of a polymer backbone (Poly(A) carrying a
number of grafts of different chemical nature (Poly(B) distributed at random
PS
PEO
INTEREST: Arises from the incompatibility between backbone and grafts
● High segment density because of the branched structure
● High tendency to form intramolecular phase separation
● Micelles are formed in a preferential solvent of the grafts
(surface modification, compatibiliziers, micelles…. ) (enhancing or depressing surface
tension, making a surface hydrophobic or hydrophilic
In Graft Copolymers a variety of Molecular Parameters can be varied
- Main chain and side chain polymer type
- Degree of polymerization and polydispersities of the main and side chain
- Graft density (average spacing density between side chains)
- Distribution of the grafts (graft uniformity)
Anionic Polymerization / Macromolecular Engineering
GRAFT COPOLYMERS
Selected polymerization techniques can be used to tailor graft copolymers
on request : Well defined Graft copolymers
Ionic Polymerization
● grafting from : Grafting by anionic initiation from sites created on the backbone
● grafting onto : Anionic deactivation of living chains by electrophilic functions located on
a polymeric backbone
● grafting through : Use of dangling unsaturations to attach grafts onto a polymeric backbone
(Macromonomer free radical poly) .
Classical free radical polymerization not well adapted absence of control of molar mass and
polymolecularity (homopolymer, crosslinked material)
NEW DEVELOPMENTS : CFR POLYMERIZATION, COORDINATION POLYMERIZATION
Anionic Polymerization / Macromolecular Engineering
GRAFT COPOLYMERS
Graft copolymers via Macromonomers
Macromonomer/Comonomer Copolymerization Kinetics : free radical
In such copolymerizations, owing to the large differences in molar mass between
Macromonomer M and Comonomer A, the monomer concentration is always very
small : consequently the classical instantaneous copolymerization equation
[ A]( ra [ A]  [ M ]
d[ A]

d[ M ] [ M ]rM ([ M ]  [ A]
Reduces to
d[ A] ra [ A]

d[ M ] [ M ]
As in an « ideal » copolymerization the reciprocal of the radical reactivity of the
comonomer is a measure of the macromonomer to take part in the process
Controlled Free Radical Copolymerization
Anionic Polymerization / Macromolecular Engineering
Interest of branched Polymers
BRANCHED POLYMERS
- Compactness
- High segment density
● Statistical branching (free radical polymerization)
Branched pE’s
● Well defined branched polymers
- Homopolymerization of macromonomers
- Grafting onto or from (each monomer unit
of the main chain with a function)
● Star-shaped polymers
- « Arm-first » by deactivation, by copolymerization
- « Core-first » plurifunctional initiator
- In-out, heterostar … Miktoarm
● More complex star-shaped or branched architectures
Umbrella,
Anionic Polymerization / Macromolecular Engineering
PolyMacromonomers
• Anionic Polymerization
• (Controlled) free radical polymerization
• ROMP
• GTP
?
•Coordination Polymerization ?
• The Nature of the Unsaturation,
• The Chemical Environment of the Unsaturation
• The Length of the Macromonomer Chain
• The Thermodynamic Interactions between the
macromonomer and the backbone to be formed
• The Presence, the Amount of solvent
Bottlle brush structure DP > 80
Star-shaped DP < 80
Anionic Polymerization / Macromolecular Engineering
PolyMacromonomers
Some Catalysts Tested
Ar
Ti
Zr
Cl
Cl
Cl
Cl
Ti
Cl
Cl
Cl
H3C
Ti
H3C
Ti
F
F
MeO
OMe
OMe
BAr'4
Pd
Cl
N
Cl
Ar
n
Cl
Si
Ti
N
Zr
Cl
Cl
Cl
H3C CHCH3
3
Mn 1000 to 10 000g.mol-1
Activated with MAO
• Homopolymerization possible ! but never quantitative
M
40
PM
35
• Degree of Polymerization: DP Ti > DPZr around 7- 10
6h
10 h
22 h
40 h
30
25
• Polym. yield decreases with increasing PS molar mass, DPE
20
I
F
OMe
O
N
15
• Polym time increases, DP constant, conversion increases
10
5
0
• Highest DP obtained with CGC-Ti around 300
36
38
40
Elution volume
42
SEC
44
Dilute Solution characterization of PS poly(macromonomer)s
SEC: Smaller hydrodynamic volume
1400000
SEC: Transition comb-shaped / Star
7
1300000
1200000
1000000
6,5
Série6
Linear PS
log(Mw ddl)
900000
800000
700000
600000
500000
400000
Linear PS
6
5,5
Comb-shaped
5
Star(shaped)
300000
4,5
200000
100000
0
30
31
32
33
34
35
Elution volume (mL)
36
37
4
1,4
SEC: Smaller Radius of gyration
1,45
1,5
log (elution volume)
60
q2. I(q)
SANS
0,64
50
Rg = 0,0074.(Mw)
Linear PS
40
Rg (nm)
Mw (g/mol)
PS poly(macromonomer)
poly(macromonomer)
1100000
poly(macromonomer)
Linear PS
30
20
0,54
Rg=0,0126.(Mw)
10
2
R = 0,99
0
0
200000
400000
600000
Mw ddl (g/mol)
800000
1000000
1200000
Asymptotic Behavior of the particle
Scattering function of a PS PM (CP)
1,55
1,6
Anionic Polymerization / Macromolecular Engineering
PE stars by Arm-first Methods
BRANCHED / STARS
Anionic Polymerization / Macromolecular Engineering
Arm-first: Typical molecules used as core
BRANCHED / STARS
Anionic Polymerization / Macromolecular Engineering
BRANCHED / STARS
Arm-first Methods
● Synthesis of a w-living polymer (PS, PI)
● Core formation
-either by reacting it with a plurifunctional electrophile in stoechiometric amount
-or by using the carbanionic sites to initiate the polymerization a small amount of
biunsaturated monomer such as DVB, DEMA
PS, PI, PMMA
Advantages:
- Low fluctuations in molar mass
- Low composition heterogeneity (copo)
- Characterization of the individual branches
- Average number of branches accessible
Functionalization at the outer end of the branches not possible
Anionic Polymerization / Macromolecular Engineering
Arm-first Methods
● Synthesis of a w-living diblock polymer (PS-b-PI)
BRANCHED / STARS
Anionic Polymerization / Macromolecular Engineering
BRANCHED / STARS
Polyfunctional Initiators: CORE FIRST Method
- Metalorganic sites tend to strongly associate, even in aprotic polar solvents
- Aggregate formation is frequent : some sites may remain hidden
-As polymerization of the monomer proceeds gelation of the reaction medium is to be expected
- However Molar mass not directly accessible
From PolyDVB Cores
FIRST STEP: Preparation of a dilute
solution of living cores A solution of (DVB)
is added dropwise to a dilute solution of
Potassium naphtenide in THF
Conditions to be observed
to avoid microgel formation
- [DVB] / [K] ratio should be
below 2
- high dilution Avoid any
local excess of DVB
- efficient stirring
H2C CH2
O
OE: First the solution becomes turbid, After a few hours the
medium becomes biphasic Finally it gets homogeneous and
clear again when the branches are long enough to
contribute also to the solvatation of the cations
Anionic Polymerization / Macromolecular Engineering
BRANCHED / STARS
Polyfunctional Initiators: CORE FIRST Method
CMC Determination
2,0
Molar Mass and Viscosity
Sample 460
Sample 462
Sample 467
(Mn)br
Sample
(Mw)DDL
(g/mol)
f
(g/mol)
[  ]H2O
(mL/g)
[  ]MeOH
I1 / I3
1,9
1,8
(mL/g)
1,7
462
4800
116000
24
41.81
30.65
1,6
460
9100
417000
46
62.94
43.22
1,5
467
15900
986000
62
60.50
53.59
1,4
cmc
1,3
0
b
1,0
0.1%
0.2%
0.4%
0.5%
0,8
H(R h)
0,4
c
a
0,0
10
3
4
mol DVB/L (10
)
H(Rh)
1
2
4
0,6
0,2
1
Rh(nm)
100
1000
QELS measurements of core-first star-shaped PEO ’s
5
6
Anionic Polymerization / Macromolecular Engineering
BRANCHED / STARS
Polyfunctional Initiators: CORE FIRST Method
Other Multifunctional Iniatiators
Living poly(divinylbenzene) cores
Living poly(diisopropenylbenzene)
cores
Hydrophobic Core
more or less Polydisperse
+A
Bifunctional coupling agent
Other Initiators
Tris-alkoxides
Modified Carbosilane dendrimers
Polyglycerol cores
+B
Anionic Polymerization / Macromolecular Engineering
BRANCHED / STARS
PEO Stars Based on
Polyglycerol Cores
Controlled Polymerization of glycerol
O-POx-H
H-POx-O
O
O-POx-H
O
H-EOy-POx-O
O
O
~O
O-POx-EOy-H
O-POx-EOy-H
O-POx-EOy-H
O
O
O-POx-H
~O
O-POx-H
O
O
O-POx-EOy-H
O-POx-EOy-H
O
DPMP, kryptofix[2.2.2]
O
O
O
O
O-POx-H
O
O
~
O
O-POx-H
O-POx-EOy-H
O-POx-EOy-H
O-POx-H
H-POx-O
O-POx-H
O-POx-EOy-H
H-EOy-POx-O
Polyglycerol core
O-POx-EOy-H
O
O
O
O-POx-H
O
O
~
O
O
O
O
ethyleneoxide
O-POx-EOy-H
Star-shaped PEO
Anionic Polymerization / Macromolecular Engineering
Reference
core unit
PDcore Mn (calc.)a Mn (branch)b
Mn
PDstar
(SEC)c
BRANCHED / STARS
Yield
[%]
0,2
PG39
1.3
40,000
n.d.
8,000
2.0
95
P(G23PO3EO30)
P(G23PO3)
1.2
34,000
1,300
35,000
1.4
93
P(G23PO3EO48)
P(G23PO3)
1.2
55,000
2,100
53,000
1.4
95
P(G52PO3EO17)
P(G52PO3)
1.4
58,000
750
51,000
1.5
80
P(G52PO3EO39)
P(G52PO3)
1.4
95,000
1,700
100,000
2.2
85
P(G23PO3EO180)
P(G23PO3EO30)
1.4
220,000
7,600
180,000
1.4
80
52
3
)
17
M =51000 g/mol
n
0,1
a.i.
P(G39EO20)
SEC in water
P(G PO EO
0,0
-0,1
10
R.I. crude product
LALLS crude product
R.I. poly(glycerol-b-propylene oxide) educt
R.I. purified product
15
20
25
V
E
75
PEO linear
P(G PO EO )
52
3
36
viscosity
P(G PO EO )
52
50
3
15
P(G PO EO )
23
3
39
P(G PO EO )
23
3
30
35
[mL]
Purification via
fractional precipitation in THF/DE
fractional precipitation in
THF/Heptane
dialysis in H2O
dialysis in THF possible
26
25
PEO/POLYGLYCEROL STARS
0,01
0,02
0,03
conc. [g/mL]
0,04
0,05
Anionic Polymerization / Macromolecular Engineering
BRANCHED / STARS
« In-out » Star Polymers
● Use of a w-living seed polymer (PS, PI) as initiator (Protection and solubilization of the
poly(DVB) core
● Addition to the living core of another monomer exhibiting
higher electrophilicity (EO )
Typical Amphiphic behavior
-High solubility in many solvents
- Protection exerted by the hydrophilic
parts on the hydrophobic core
-High tendency to form stable
emulsions in water
-Tendency to phase separation in
concentrated media
Addition of styrene results in crosslinking (remaining double bond)
Anionic Polymerization / Macromolecular Engineering
BRANCHED / STARS
Living PS, PI, diblock
Well-defined star-shaped or related branched structures base
on anionic polymerization
But very time consuming synthesis, fractionated, interesting
morphologies
Anionic Polymerization / Macromolecular Engineering
BRANCHED / STARS
Star-shaped Polymers Based on Diphenylethylene Derivates
Quirk, Dumas
Anionic Polymerization / Macromolecular Engineering
BRANCHED / STARS
I - Addition of living polymers onto C60
6-6 bond 
 5-6 bond
C60 is constituted of 12 pentagons et 20
hexagons, 6 pyracylene units
Small molecule (d  10 Å) et plurifunctional (30
double bonds)
Model architectures :
* Control the number of grafts
* Control of the polymer chain :
-The chain end must be able to react with C60
- Control molar mass and polymolecularity
- Grafting of block copolymers..
 Anionic Polymerization
C. Mathis
Anionic Polymerization / Macromolecular Engineering
BRANCHED / STARS
Exemple : grafting of PSLi onot C60 in toluene
Toluene
BuLi + Styrene
CH2 CH- Li +
25°C
x PS Li +
+
Toluene
+
C 60
25°C
C
Ph
60
( PS ) C x ( Li +)
x
x
Anionic Polymerization / Macromolecular Engineering
BRANCHED / STARS
C60 being a conjugated molecule, charge (introduced by the carbanion present
at the living chain end) delocalizes. Therefore a second living chain cannot be
added onto pyracyclene units and hexagones h1 to h4. (addition to the 6-6
ring double bonds)
Anionic Polymerization / Macromolecular Engineering
BRANCHED / STARS
 hexafunctional Star-shaped polymers
Charge delocalisation and geometrical form of C60 limit the number of grafts to 6
(molar masses up to 2 106 g mol-1
Anionic Polymerization / Macromolecular Engineering
BRANCHED / STARS
II – Hexa-aducts can be used as plurifunctional initiator for the
anionic polymerization  Synthesis of Palmtree and Dumbbell
architectures
Anionic Polymerization / Macromolecular Engineering
BRANCHED / STARS
(PS)6C606-(Li+)6 + MMA  (PS)6C60(PMMA)2
[6PS + 2PMMA] “hetero-stars”
Anionic Polymerization / Macromolecular Engineering
BRANCHED / STARS
Synthesis of Palm tree or Dumbbell Architectures
(Li+)5
[6PSa + 1PSb] “palm-tree”
5-
PS-Li+
2 (PS)6C605-(Li+)5PSb-Li+ + BrCH2PhCH2Br  (PS)6C60PSb- CH2PhCH2-PSbC60(PS)6
Anionic Polymerization / Macromolecular Engineering
BRANCHED / STARS
POSS Polyoctaedralsilsesquioxanes New class of nanostructured materials:
-Higher thermal stability
-Higher mechanical properties
-Bette resistance to fire…
-Silsesquioxane: hydrophobic!
Non reactive Group
Eight corn
substituted cage

X

Further Chemical Reactions,
(co-) polymerization
Solubilization
R= H , OSi(CH3)2H
Function, epoxy,
alcohol, C=C

Stable Bond
- Functions: Chemical Modification or grafting of existing
polymers (modulation of the number of grafted chains ? ?)
- Polymerizable group (copolymerization with other monomers
via ATRP, Coordination Polymerization, ring opening…)
Anionic Polymerization / Macromolecular Engineering
Macromonomers:
New hybrid Materials
Well defined Polymers
Star-shaped Polymers
- Controlled functionality
- Controlled core
Mono, bifunctional,
- Controlled Molar Mass
Hydrosilylation
functionality
- Controlled branch
lenght
Allyl / SiH
H2PtCl6
- 8 SiH functions, cubic
BRANCHED / STARS
Networks or
Hydrogels
- Controlled
functionality of the
cross-linking points
- Controlled length of
the elastic chains
Silsesquioxanes:
Grafting of Monofunctional PEO macromonomers onto Silsesquioxanes
CH2=CH-CH2-O-(CH2-CH2-O)n-CH2-CH2-OCH3
+
8-10 fois molar
75°C
Toluene
H2PtCl6
POE w-allyle
or OH
( Hydrosilylation reaction )
Q8M8H
or OH
Star-shaped
Polymers
with 8 branches
(Q8M8PEO)
New Multifuntional
initiator
Extended to PS arms
Anionic Polymerization and Macromolecular Engineering
End-linking
Stoichiometric reaction betwenn a bifunctional linear polymer and a plurifunctional antagonist
compound
As result : the precursor chains become the elastically effective chains of the network
The plurifunctional compound becomes the branch points of the network
Ideal Network :
macrocopically homogenous
contains a known number of
elastic chains of known length
and branch points of known
functionality
However : some defects are
to be expected
CYCLIC POLYMERS
Introduction
• Synthesis of Cyclic Structures
- Ring-chain equilibria
- End-to-end Cyclization
• Properties of Cyclic Structures
- Dilute solution Behavior
- Influence of the nature of the preparation solvent
- Solid State
• Structures Derived from cyclic Polymers
Conclusion and Future
Anionic Polymerization and Macromolecular Engineering:
Cyclic Polymers
* MAY APPEAR AS A SUBJECT FOR PURE
MATHEMATICS OR THEORY NO ENDS
* TO COMPARE THE MOLECULAR DIMENSIONS OF WELLDEFINED CYCLIC AND LINEAR MACROMOLECULES
Same molar mass, Low polydispersity
in solution as well as in the bulk
* TO STUDY THE ABILITY OF CYCLIC) MACROMOLECULES TO
DIFFUSE IN A POLYMER MATRIX (REPTATION) OR IN
NETWORK
Accessible only by Anionic Polymerization ?
Introduction
Anionic Polymerization and Macromolecular Engineering:
Cyclic Polymers
* RING-CHAIN EQUILIBRIA
IN POLYCONDENSATION
Low molar mass CYCLES are formed preferentially
* BACK BITTING REACTIONS IN IONIC POLYMERIZATION
Reaction of a function on the chain with a functional link of the
same chain – an alkoxide with an ester function
-a Silanolate function with a siloxane bridge
- an oxonium with an ester bridge
- increase of the number of macromolecules
- decrease of their average molar mass
EX : Upon heating of a PDMS in the presence of some basic catalyst
implies the presence of a functional link in the chain
Synthesis of Cyclic Structures
Ring-chain equilibria
Cyclic Polymers
BACK
BITTING
POLYMERIZATION
REACTIONS
IN
CATIONIC
Reaction of a function on the chain with a functional link of the
same chain an oxonium with an ester bridge
Synthesis of Cyclic Structures
Ring-chain equilibria
Anionic Polymerization and Macromolecular Engineering:
Cyclic Polymers
SEC PDMS
Logarithmic plots of the root-square
radius of gyration
vs molar mass for linear and cyclic
PDMS fractions
After SEC Fractionation
Synthesis of Cyclic Structures
Semlyen et al.
Ring-chain equilibria
Anionic Polymerization and Macromolecular Engineering:
Cyclic Polymers
End-to-end Cyclization : effect of the concentration on the cyclization yield
Intramolecular reaction
Intermolecular reaction
Synthesis of Cyclic Structures
End-to-end Cylization
Cyclic Polymers
Synthesis via anionic polymerization
,w-difunctional
PS
K+ CHCH2
CH2 CH K+
Couplig agent
+
BrCH2
Cycle
chain extension
CH2 CHCH2
CHCH2
CH2 Br
CH2 CHCH2
CH2 CH
CH2
CH2
Cyclization
Chain extension
* Coupling reaction has to be fast, quantitative and free of side reactions
* Exact stoichiometry (balance active sites / functions)
* High dilution to favor intramolecular coupling with respect to intermolecular
coupling
* Efficient stirring to prevent local fluctuations in concentrations
Synthesis of Cyclic Structures
End-to-end Cylization
Cyclic Polymers
Experimental Procedure
Solvent •THF
Initial concentration 10 wt.-% after
dilution 0.1 wt.- %
Synthesis of Cyclic Structures
•Cyclohexane
• THF/Heptane
End-to-end Cyclization
Cyclic Polymers
SEC trace of the raw reaction product
SEC trace of cyclic and linear PS
Big difference in molar mass
Cycle
linear
Cycle
Chain
extension
Elution volume
Adequate separation of linear polycondensate from the
Elution volume
cycles
Cyclization yield from 20 to 50 wt-.% decreases with
increasing molar mass
Without dilution 2.5 wt.-% 20 % (2500)
Molar mass domain from 5000 to 200 000g.mol-1
Synthesis of Cyclic Structures
End-to-end Cylization
Cyclic Polymers
Synthesis of Cyclic Structures
End-to-end Cylization
Cyclic Polymers
Different strategies for the synthesis of block copolymer cycles
Synthesis of Cyclic Structures
Block copolymer cycles
Cyclic Polymers
Cyclization reactions based on unimolecular processes
Synthesis of Cyclic Structures
End-to-end Cylization
Cyclic Polymers
Reversible cyclization
Synthesis of Cyclic Structures
Reversible Cylization
Cyclic Polymers
SEC
SEC .M calibration
(Roovers)
RI
1/1a
Mapp.  []c 

Mw  []l 
Properties of Cyclic Structures
(0.66) 0.6 0.78
Dilute solution Behavior
Cyclic Polymers
Polymerization and cyclization in
a good solvent (ICS)
Synthesis in cyclohexane (near q
conditions) (Roovers)
Measurements on knoted rings ?
Theta temperature
28.29°C
May be due to to topological interactions
enhanced segment density,
independant of M ?
Stockmayer Fixmann treatment
Logarithmic plot of the limiting viscosity numbers
versus molar mass for linear and cyclic polystyrene,
measured in cyclohexane
Properties of Cyclic Structures
Dilute solution Behavior
Cyclic Polymers
Cycle in a good synthesized in good solvent only a
Cycle in a bad solvent
Cyclization
few knotes
Many knotes
Dimensions in a good solvent
?
Good Solvent
?
Qsolvent or
bad solvent
Properties of Cyclic Structures
Dilute solution Behavior
Cyclic Polymers
Properties of Cyclic Structures
Dilute solution Behavior
Cyclic Polymers
SEC
Sample
L
Mw LS
Elution
volume (ve)
14 300
39.95
PS 133
Hydrodynamic
behavior *
0.78
C
L
15 300
45 500
40 57
37.41
PS 204
0.79
C
L
43 500
69 000
38.16
35.66
C
L
70 700
115 300
36.37
34.55
PS 241
0.77
PS 243
0.83
C
113 500
Properties of Cyclic Structures
35.05
Dilute solution Behavior
Cyclic Polymers
Logarithmic plots of the root-square radius of gyration
vs molar mass for linear and cyclic Polystyrene fractions
Cycles prepared in THF O°C
Cycles prepared
in THF / heptane
Polystyrene fractions measured in d12
cyclohexane at 34 °C
Properties of Cyclic Structures
Dilute solution Behavior
Cyclic Polymers
Structures derived from cyclic polymers
Eight shaped Polymers
Cyclic Polymers
Structures derived from cyclic polymers
Rotaxane Catenane
Cyclic Polymers
Fe
J.P Sauvage, C. Diedrich
Structures derived from cyclic polymers
catenanes
Cyclic Polymers
Structures derived from cyclic polymers
Catenanes
Cyclic Polymers
* Well defined cyclic Polystyrenes are available up to
molar masses
of 200 000 g/mol
* Dilute solution properties are in good agreement with theoretical
expectations
hydrodynamic volume
limiting viscosity numbers
Radius of gyration
Translational diffusion coefficient
* Solid state properties
REPTATION CONCEPT
?
* Extension of the method to
Poly(2vinylpyridines)
Poly(ethylene oxide)
* Development of other cyclization methods and charged cycles
Conclusion
Cyclic Polymers
“Hydrodynamic Dimensions of Ring-shaped Macromolecules in a Good Solvent" M. Duval, P. Lutz. C. Strazielle Makromol. Chem., Rapid Commun. 6,
71-76 (1985)
"Solution Properties of Ring-shaped Polystyrenes“ P. Lutz, G.B. McKenna, P. Rempp, C. Strazielle Makromol. Chem., Rapid Commun. 7, 599-605 (1986)
"Synthesis and Solution Properties of Macrocyclic polymers"P. Lutz, C. Strazielle, P. Rempp
Recent Adv. in Anionic Polymerization ed. T.E. Hogen Esch, J. Smid, Elsevier Science Publishing, pp. 404-410 (1987) (Revue)
"Macrocyclic Polymers" P. Rempp, C. Strazielle, P. LutzEncyclopedia of Polymer Science and Engineering, 9, pp. 183-195 second Ed. John Wiley & Sons,
Inc. (1987) (Revue)
"Thermodynamic and Hydrodynamic Properties of Dilute Solutions of Cyclic and Linear Polystyrenes"
G. Hadziioannou, P.M. Cotts, G. ten Brinke, C.C. Han, P. Lutz, C. Strazielle, P. Rempp, A.J. KovacsMacromolecules 20, 493-497 (1987)
"Dilute Solution Characterization of Cyclic Polystyrene Molecules and Their Zero-shear Viscosity in the Melt"
G.B. McKenna, G. Hadziioannou, P. Lutz, G. Hild, C. Strazielle, C. Straupe, P. Rempp, A.J. KovacsMacromolecules 20, 498-512 (1987)
"Diffusion of Polymer Rings in Linear Polymer Matrices" P.J. Mills, J.W. Mayer, E.J. Kramer, G. Hadziioannou, P. Lutz, C. Strazielle, P. Rempp, A.J.
Kovacs , Macromolecules 20, 513-518 (1987)
"Polymer Topology and Diffusion: a Comparison of Diffusion in Linerar and Cyclic Macromolecules"
S.F. Tead, E.J. Kramer, G. Hadziioannou, M. Antonietti, H. Sillescu, P. Lutz, C. Strazielle, Macromolecules 25, 3942 (1992)
"Recent Developments in the Field of Star-shaped Polymers" D. Rein, P. Rempp, P.J. Lutz
Makromol. Chem., Macromol. Symp. 67, 237-249 (1993)
"Osmotic Pressure of Linear, Star, and Ring Polymers in Semi-dilute Solution". A comparison Between Experiment and Theory" G. Merkle, W. Burchard,
P.J. Lutz, K.F. Freed, J. Gao, Macromolecules 26, 2736-2742 (1993)
"Synthesis of Cyclic Macromolecules"
Y. Ederlé, K. Naraghi, P.J. Lutz
Materials Science and Technology, A Comprehensive Treatment, Volume Synthesis of Polymers, Ed. A.D. Schlüter, chapitre de livre, pp. 622-647, WileyVCH Weinheim-New-York (1999) (Revue)
J. Wittmer, et al. F. Isel, Equipe LLB (A. Lapp, F. Boué, J. Combet; M. Raviso , A. Rameau et al. …..
Acknowledgements