synthesis of colloids and polymers topic: anionic polymerization and macromolecular engineering...

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


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 !


Characterization Methods to be used to determine the structural parameters or the behavior of Complex Macromolecular Architectures

Anionic Polymerization and Macromolecular Engineering Functionalization

Functionalization

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


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


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

PE stars by Arm-first Methods


Arm-first: Typical molecules used as core


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


Arm-first Methods

● Synthesis of a -living diblock polymer (PS-b-PI)


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


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


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


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


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


« 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


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


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 :


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


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)


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


II – Hexa-aducts can be used as plurifunctional initiator for the anionic polymerization Synthesis of Palmtree and Dumbbell architectures


(PS)6C606-(Li+)6 + MMA (PS)6C60(PMMA)2

[6PS + 2PMMA] “hetero-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


[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!


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


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


Synthesis of Cyclic Structures Ring-chain equilibria

Cyclic Polymers


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



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


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


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


Cyclic Polymers


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


Reversible cyclization

Cyclic Polymers

Synthesis of Cyclic Structures Reversible 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



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

?

?

Cyclic Polymers


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


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

Cyclic Polymers

Structures derived from cyclic polymers Eight shaped Polymers

Cyclic Polymers

Structures derived from cyclic polymers Rotaxane Catenane

Cyclic Polymers

Structures derived from cyclic polymers catenanes

Fe

J.P Sauvage, C. Diedrich

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

Cyclic Polymers

Conclusion

Cyclic Polymers

Acknowledgements

“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, 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. …..

synthesis of colloids and polymers topic: anionic polymerization and macromolecular engineering...

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