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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
● 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 ?
Some Problems that require well-defined Polymers
Anionic Polymerization and Macromolecular Engineering
● 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
Some structures to be discussed
● Static and Dynamic LIGHT SCATTERING To get Molar MassMolar Mass, Mw, and Radius of Gyration and Hydrodynamic Radius, …
● SIZE EXCLUSION CHROMATOGRAPHY (GPC)Detectors required* Differential Refractometry : to get c* UV Spectrometryto 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
Characterization Methods to be used to determine the structural parameters or the behavior of Complex Macromolecular Architectures
Anionic Polymerization and Macromolecular Engineering Macromonomers
PS CH 2CCH 2 CH2CH
CH2CHCH 2PS
CH 3
CH 2CHOCC CH 2
O
PS
● Macromonomers well defined polymers - Low molar mass- Polymerizable end-groups
- Accessible via anionic, cationic, polymerization ATRP (FRP),- PB, PE, PMMA, P2VP, PEO, PDMS
- Linear, block copolymer, star-shaped….
● Major interest- Graft copolymers by (free) radical copolymerization, branch length
- Access to new branched topolygies by homopolymerization
Macromonomers by -elimination reactions in coordination Polymerization
Anionic Polymerization / Macromolecular Eng. Macromonomer Synthesis
-allyl
-undecenyl
-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
(CH2)9
Br
Ph
Ph
(CH2)9
n
PS Ph
PhCl
Cl
n
nPS
+ THF
-78°C
sec-BuLi
toluene +
or
(VBC)
PS (atactic):
undecenyl end group
Deactivation
Anionic Polymerization of OxiraneWith K (and not Na or Li) RT
Propagation
Termination
CH2 CH2
OCH2)9(
O- K+ +CH2)9(
OO-
K+
CH2)9(O
O- CH2 CH2
O
+ n K+ ]n
[CH2)9(O
O- K+
+ Ø2CH- K+CH2)9(OH
Initiation
CH2)9(O- K+
10-undecene-1-ol
-undecenyl, hydroxy PEO
+ HCl + KCl]n
[CH2)9(O
O-K+ ]n
[CH2)9(O
OH
Diphenylmethyl potassium
- Well functionalized - Heterofunctional Polymer OH- Deactivation also possible for PEO
Initiation
Anionic Polymerization / Macromolecular Eng. Macromonomer Synthesis
Initiation not possible for PS macromonomers
Valuable polymeric materials constituted of a polymer backbone (Poly(A) carrying a number of grafts of different chemical nature (Poly(B) distributed at random
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
PS
PEO
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
Selected polymerization techniques can be used to tailor graft copolymers on request : Well defined Graft copolymers
][]([r][
][][]([
][d
][d
M AMM
MArA
M
A a
Macromonomer/Comonomer Copolymerization Kinetics : free radical
In such copolymerizations, owing to the large differences in molar mass betweenMacromonomer M and Comonomer A, the monomer concentration is always verysmall : consequently the classical instantaneous copolymerization equation
Reduces to
][
][
][d
][d
M
Ar
M
A a
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 GRAFT COPOLYMERS
Graft copolymers via Macromonomers
Anionic Polymerization / Macromolecular Engineering BRANCHED POLYMERS
Interest of 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• (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
Zr
Cl ClCl
Ti
Cl ClCl
Ti
Cl ClCl
SiN Cl
ClTi
H3C
H3C
H3CCH3
CH3
TiMeO OMe
OMe
ZrCl
Cl
N
N
Pd
Ar
Ar
O
OMe
BAr'4
Some Catalysts Tested
• Homopolymerization possible ! but never quantitative • Degree of Polymerization: DP Ti > DPZr around 7- 10
• Polym. yield decreases with increasing PS molar mass, DPE
• Polym time increases, DP constant, conversion increases
• Highest DP obtained with CGC-Ti around 300
n
36 38 40 42 440
5
10
15
20
25
30
35
40
I
6 h 10 h 22 h 40 h
Activated with MAO
Mn 1000 to 10 000g.mol-1
Elution volume SEC
Ti
F FF
PM
M
Anionic Polymerization / Macromolecular Engineering PolyMacromonomers
Dilute Solution characterization of PS poly(macromonomer)s
4
4,5
5
5,5
6
6,5
7
1,4 1,45 1,5 1,55 1,6log (elution volume)
log(
Mw
ddl
)
PS poly(macromonomer)
Série6
Linear PS
Star(shaped)Comb-shaped
4
4,5
5
5,5
6
6,5
7
1,4 1,45 1,5 1,55 1,6log (elution volume)
log(
Mw
ddl
)
PS poly(macromonomer)
Série6
Linear PS
Star(shaped)Comb-shaped Star(shaped)Comb-shaped
0,54
60
1000000 1200000
poly(macromonomer)
Rg=0,0126.(Mw)
R2 = 0,99
Rg = 0,0074.(Mw)0,64
Linear PS
0
10
20
30
40
50
0 200000 400000 600000 800000
Mw ddl (g/mol)
Rg
(nm
)
Linear PS
0,54
60
1000000 1200000
poly(macromonomer)
Rg=0,0126.(Mw)
R2 = 0,99
Rg = 0,0074.(Mw)0,64
Linear PS
0
10
20
30
40
50
0 200000 400000 600000 800000
Mw ddl (g/mol)
Rg
(nm
)
Linear PS
Rg=0,0126.(Mw)
R2 = 0,99
Rg = 0,0074.(Mw)0,64
Linear PS
0
10
20
30
40
50
0 200000 400000 600000 800000
Mw ddl (g/mol)
Rg
(nm
)
Linear PS
0
100000
200000
300000
400000
500000
600000
700000
800000
900000
1000000
1100000
1200000
1300000
1400000
30 31 32 33 34 35 36 37
Elution volume (mL)
Mw
(g/m
ol)
poly(macromonomer)
Linear PS
0
100000
200000
300000
400000
500000
600000
700000
800000
900000
1000000
1100000
1200000
1300000
1400000
30 31 32 33 34 35 36 37
Elution volume (mL)
Mw
(g/m
ol)
poly(macromonomer)
Linear PS
SEC: Smaller hydrodynamic volume
SEC: Smaller Radius of gyration
SEC: Transition comb-shaped / Star
Asymptotic Behavior of the particle Scattering function of a PS PM (CP)
q2. I(q)SANS
Anionic Polymerization / Macromolecular Engineering BRANCHED / STARS
Arm-first: Typical molecules used as core
Anionic Polymerization / Macromolecular Engineering BRANCHED / STARS
Arm-first Methods
● Synthesis of a -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 BRANCHED / STARS
Arm-first Methods
● Synthesis of a -living diblock polymer (PS-b-PI)
Anionic Polymerization / Macromolecular Engineering BRANCHED / STARS
H2C CH2
O
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
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
I1 /
I3
0 1 2 3 4 5 61,3
1,4
1,5
1,6
1,7
1,8
1,9
2,0
cmc
Sample 460 Sample 462 Sample 467
mol DVB/L (104 )
Sample(Mn)br
(g/mol)
(Mw)DDL
(g/mol)f
[ ]H2O
(mL/g)
[ ]MeOH
(mL/g)
462 4800 116000 24 41.81 30.65
460 9100 417000 46 62.94 43.22
467 15900 986000 62 60.50 53.59
CMC Determination
Molar Mass and Viscosity
Anionic Polymerization / Macromolecular Engineering BRANCHED / STARS
Polyfunctional Initiators: CORE FIRST Method
1 10 100 1000
0,0
0,2
0,4
0,6
0,8
1,0
c
b
a
0.1% 0.2% 0.4% 0.5%
H(R
h)
Rh(nm)
H(Rh)
QELS measurements of core-first star-shaped PEO ’s
+ A
+ B
Other Multifunctional Iniatiators
Living poly(divinylbenzene) coresLiving poly(diisopropenylbenzene) cores
Hydrophobic Core more or less Polydisperse
Other Initiators
Tris-alkoxidesModified Carbosilane dendrimers
Polyglycerol cores
Bifunctional coupling agent
Anionic Polymerization / Macromolecular Engineering BRANCHED / STARS
Polyfunctional Initiators: CORE FIRST Method
O
O O
O
O
O
O
OO
OO-POx-H
O
O
H-POx-O O-POx-H
O-POx-H
O-POx-H
H-POx-O
O-POx-H O-POx-H
O
O O-POx-H
O-POx-H
O-POx-H
~
~
O
O O
O
O
O
O
OO
OO-POx-EOy-H
O
O
H-EOy-POx-O O-POx-EOy-H
O-POx-EOy-H
O-POx-EOy-H
H-EOy-POx-O
O-POx-EOy-HO-POx-EOy-H
O-POx-EOy-H
O O-POx-EOy-H
O-POx-EOy-H
O-POx-EOy-H
~
~
DPMP, kryptofix[2.2.2]
ethyleneoxide
Polyglycerol core Star-shaped PEO
Anionic Polymerization / Macromolecular Engineering BRANCHED / STARS
PEO Stars Based on Polyglycerol Cores
Controlled Polymerization of glycerol
Reference core unit PDcore Mn (calc.)a Mn (branch)b Mn
(SEC)c
PDstar Yield
[%]
P(G39EO20) 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
PEO/POLYGLYCEROL STARS
Anionic Polymerization / Macromolecular Engineering BRANCHED / STARS
10 15 20 25 30 35
-0,1
0,0
0,1
0,2SEC in waterP(G
52PO
3EO
17)
Mn=51000 g/mol
R.I. crude product LALLS crude product
a.i.
VE [mL]
R.I. poly(glycerol-b-propylene oxide) educt R.I. purified product
0,01 0,02 0,03 0,04 0,05
25
50
75
PEO linear P(G
52PO
3EO
36)
P(G52
PO3EO
15)
P(G23
PO3EO
39)
P(G23
PO3EO
26)
visc
osity
conc. [g/mL]
Purification viafractional precipitation in THF/DEfractional precipitation in THF/Heptanedialysis in H2Odialysis in THF possible
Anionic Polymerization / Macromolecular Engineering BRANCHED / STARS
« In-out » Star Polymers
● Use of a -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 )
Addition of styrene results in crosslinking (remaining double bond)
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
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
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 bondC60 is constituted of 12 pentagons et 20
hexagons, 6 pyracylene units
Small molecule (d 10 Å) et plurifunctional (30 double bonds)
* 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
Model architectures :
Anionic Polymerization / Macromolecular Engineering BRANCHED / STARS
C. Mathis
PSToluene
25°C
25°C
Toluene
x +Li +- C60
BuLi + Styrene CH CH Li
Ph
+-2
)(xC
60x-
x)( Li +PS
+ C
Exemple : grafting of PSLi onot C60 in toluene
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
Charge delocalisation and geometrical form of C60 limit the number of grafts to 6
(molar masses up to 2 106 g mol-1
hexafunctional Star-shaped polymers
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
2 (PS)6C605-(Li+)5PSb
-Li+ + BrCH2PhCH2Br (PS)6C60PSb- CH2PhCH2-PSbC60(PS)6
Synthesis of Palm tree or Dumbbell Architectures
PS-Li+
5-(Li+)5
Anionic Polymerization / Macromolecular Engineering BRANCHED / STARS
[6PSa + 1PSb] “palm-tree”
Stable Bond
X
Further Chemical Reactions,(co-) polymerization
Non reactive Group
- 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…)
Solubilization
Function, epoxy, alcohol, C=C
R= H , OSi(CH3)2H
Eight corn substituted cage
POSS Polyoctaedralsilsesquioxanes New class of nanostructured materials: -Higher thermal stability-Higher mechanical properties-Bette resistance to fire…-Silsesquioxane: hydrophobic!
Anionic Polymerization / Macromolecular Engineering BRANCHED / STARS
Well defined PolymersWell defined Polymers
- - Controlled functionalityControlled functionality
Mono, bifunctional, Mono, bifunctional,
- Controlled Molar Mass- Controlled Molar Mass
Silsesquioxanes::
Star-shaped PolymersStar-shaped Polymers
- Controlled core Controlled core functionalityfunctionality
- Controlled branch Controlled branch lenghtlenght
New hybrid MaterialsNew hybrid Materials
- 8 SiH functions, cubic- 8 SiH functions, cubic
HydrosilylationHydrosilylation
Macromonomers:Macromonomers:
Allyl / SiHAllyl / SiH
HH2PtClPtCl6
Networks or Networks or HydrogelsHydrogels
- Controlled Controlled functionality of the functionality of the cross-linking pointscross-linking points
- Controlled length of - Controlled length of
the elastic chainsthe elastic chains
Anionic Polymerization / Macromolecular Engineering BRANCHED / STARS
8-10 fois molar
75°CToluene H2PtCl6
( Hydrosilylation reaction )
++
QQ88MM88HH
POE POE -allyle-allyle
Star-shaped Star-shaped Polymers Polymers with 8 brancheswith 8 branches(Q(Q88MM88
PEOPEO))
or OHor OH
or OHor OH
Grafting of Monofunctional PEO macromonomers onto SilsesquioxanesGrafting of Monofunctional PEO macromonomers onto Silsesquioxanes
CHCH2=CH-CH=CH-CH2-O-(CH-O-(CH2-CH-CH2-O)-O)nn-CH-CH2-CH-CH2-OCH-OCH3
New Multifuntional New Multifuntional initiatorinitiator
Extended to PS arms
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
Anionic Polymerization and Macromolecular Engineering End-linking
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
* MAY APPEAR AS A SUBJECT FOR PURE
MATHEMATICS OR THEORY NO ENDS
* TO COMPARE THE MOLECULAR DIMENSIONS OF WELL-DEFINED 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
Anionic Polymerization and Macromolecular Engineering: Cyclic Polymers
Synthesis of Cyclic Structures Ring-chain equilibria
Cyclic Polymers
Synthesis of Cyclic Structures Ring-chain equilibria
BACK BITTING REACTIONS IN CATIONIC POLYMERIZATION
Reaction of a function on the chain with a functional link of the same chain an oxonium with an ester bridge
Anionic Polymerization and Macromolecular Engineering: Cyclic Polymers
Synthesis of Cyclic Structures Ring-chain equilibria
SEC PDMS
After SEC Fractionation
Logarithmic plots of the root-square radius of gyration vs molar mass for linear and cyclic PDMS fractions
Semlyen et al.
End-to-end Cyclization : effect of the concentration on the cyclization yield
Intramolecular reaction
Intermolecular reaction
Anionic Polymerization and Macromolecular Engineering: Cyclic Polymers
Synthesis of Cyclic Structures End-to-end Cylization
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
CHCH2 CH2CH K+CH2BrBrCH2
CH2CHCH2 CH2CHCH2
CH2CHCHCH2
CH2 CH2
Cycle chain extension
+K+
PS -difunctional Couplig agent
Synthesis via anionic polymerization
Cyclic Polymers
Synthesis of Cyclic Structures End-to-end Cylization
Experimental Procedure
Initial concentration 10 wt.-% after dilution 0.1 wt.- %
Cyclic Polymers
Synthesis of Cyclic Structures End-to-end Cyclization
Solvent •THF
•Cyclohexane
• THF/Heptane
SEC trace of the raw reaction product SEC trace of cyclic and linear PS
Big difference in molar mass
Adequate separation of linear polycondensate from the
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
Cycle
Chain extension
Elution volume
Elution volume
Cyclelinear
Cyclic Polymers
Synthesis of Cyclic Structures End-to-end Cylization
Different strategies for the synthesis of block copolymer cycles
Cyclic Polymers
Synthesis of Cyclic Structures Block copolymer cycles
Cyclization reactions based on unimolecular processes
Cyclic Polymers
Synthesis of Cyclic Structures End-to-end Cylization
Cyclic Polymers
Properties of Cyclic Structures Dilute solution Behavior
SEC
RI
780660 60
11
.).(][][. .
/
a
lc
MwMapp
SEC .M calibration
(Roovers)
Logarithmic plot of the limiting viscosity numbers
versus molar mass for linear and cyclic polystyrene,
measured in cyclohexane
Polymerization and cyclization in a good solvent (ICS)
Synthesis in cyclohexane (near 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
Cyclic Polymers
Properties of Cyclic Structures Dilute solution Behavior
Properties of Cyclic Structures Dilute solution Behavior
Cyclic Polymers
Cyclization Dimensions in a good solvent
Good Solvent
solvent or bad solvent
Cycle in a good synthesized in good solvent only a few knotesCycle in a bad solvent Many knotes
?
?
Sample Mw LS Elution
volume (ve) Hydrodynamic
behavior * L PS 133 C
14 300
15 300
39.95
40 57
0.78
L PS 204 C
45 500
43 500
37.41
38.16
0.79
L PS 241 C
69 000
70 700
35.66
36.37
0.77
L PS 243 C
115 300
113 500
34.55
35.05
0.83
Cyclic Polymers
Properties of Cyclic Structures Dilute solution Behavior
SEC
Cyclic Polymers
Polystyrene fractions measured in d12 cyclohexane at 34 °C
Logarithmic plots of the root-square radius of gyration vs molar mass for linear and cyclic Polystyrene fractions
Cycles prepared in THF / heptane
Properties of Cyclic Structures Dilute solution BehaviorProperties of Cyclic Structures Dilute solution Behavior
Cycles prepared in THF O°C
* 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
Cyclic Polymers
Conclusion
Cyclic Polymers
Acknowledgements
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"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, Wiley-VCH 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. …..