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Solvay-a new PVC


Controlled Radical Polymerization of Vinyl
Vincent Bodart
SolVin Vinyls RD&T

Chloride: a first step toward a new PVC ?

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Outline
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? ? ?

Introduction Controlled Radical Polymerization : the basics Reverse Iodine Transfer Polymerization Cobalt Mediated Radical Polymerization Conclusion
2

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Introduction (1)
Why ? a new PVC ? ?
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PVC = a wonderful polymer with many outstanding properties
?

A huge number of very diversified applications

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Introduction (2)

But : we could dream of a new PVC, with still broadened applications
?

to enlarge the PVC market : injection, higher usage T to compete with other materials (PO, ABS, …)

?

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Introduction (3)

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Necessary to overcome some limitations, i.e.
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Limited thermal stability : ? dehydrochlorination Limited heat resistance : ? low crystallinity and low Tg

?

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Introduction (4)

Origin of these limitations : PVC molecular structure :
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Structural defects : initiation of the dehydrochlorination

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Introduction (5)

Thermal Stability DHC vs T pol
80 4

Kw
70 3.5

60

3

DHC (min)
50 2.5

40

2

30

1.5

Tertiary Cl (/1000 VC)
20 1

10

0.5

0 40 45 50 55 60 T pol (°C) 65 70 75 80 85

0

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Introduction (6)

Origin of these limitations : PVC molecular structure :
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Structural defects : initiation of the deshydrochlorination Low tacticity : ? low cristallinity

?

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Introduction (7)

Syndiotacticity & Cristallinity vs T pol
0.75 50 45 0.7 40 Syndiotatic fraction (NMR) 0.65 35

Commercial PVC domain
Crist. % 0.6 30 25 0.55 20 15 10 0.45 5 0.4 -100.00 0 100.00 Syndiotactic Fraction Cristallinity % (X ray diffr)

0.5

-80.00

-60.00

-40.00

-20.00

0.00 T pol (°C)

20.00

40.00

60.00

80.00

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Introduction (8)
Origin of these limitations : Both characteristics : Strongly related to the polymerization mechanism ? Free radical polymerization

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Introduction (9)

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Chain Transfer reactions (to the monomer and to the polymer) ? Structural defects (Labile Cl)

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Lack of stereocontrol of the propagation reaction ? Low tacticity level

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Introduction (10)

Two options to overcome those limitations : ? Play with the formulation (additives) ? the job of our customers (with our help !) ? Act on the PVC molecular structure ? our job as one of the top producers

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Introduction (11)

At Solvay : various research projects
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aiming at the modification of the polymerization mechanism mainly through Open Innovation approaches

?

Presentation of results for two of them, in the field of the Controlled Radical Polymerization
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Outline
? ? ? ? ? ? ? ? ?

Introduction Controlled Radical Polymerization (CRP) : the basics Reverse Iodine Transfer Polymerization Cobalt Mediated Radical Polymerization Conclusion
14

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CRP (1)

Free Radical (classical) Polymerization : Elementary reactions :
H Cl H A CH Cl ( ) n Cl
( Cl

Initiation Propagation Transfer Termination
A

A A

° 2 A

H

A

CH Cl

+

H H

Cl H A Cl

( Cl
) Cl

) n Cl
CH n

CH2 CH Cl

Cl

) n Cl

CH Cl

+2

H H

H A Cl Cl

(

CH2 Cl

+ Cl

CH Cl

(

2 A
Cl

) n Cl

( CH Cl A Cl

) n Cl Cl

+

( A Cl

) n Cl Cl

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CRP (2)

Free Radical (classical) Polymerization : Controlled Radical Polymerization Elementary reactions : Initiation Propagation Transfer Minimization of Termination
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CRP (3)

Dynamic equilibrium between dormant species
Z A Cl ( ) n Cl Cl Cl A Cl ( ) n Cl Cl CH Cl

and

propagating radicals
+
Z

H H

H Cl

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CRP (4)

Main characteristics of CRP (? FRP) :
?

Mn

Evolution of molecular weight with conversion Lower molecular weight polydispersity

Conv

?

?

Possibility of block copolymer synthesis

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Outline
? ? ? ? ? ? ? ? ?

Introduction Controlled Radical Polymerization (CRP) : the basics Reverse Iodine Transfer Polymerization (RITP) Cobalt Mediated Radical Polymerization Conclusion
19

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RITP (1)
Main characteristics of RITP :
? ?

Z = Iodine atom Equilibrium ? Degenerative Transfer
A Cl ( Cl ) n CH Cl

+

A Cl

( Cl

I ) n Cl

A Cl

( Cl

) n Cl

I

+

A Cl

( Cl

) n

CH Cl

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RITP (2)
Main characteristics of RITP :
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Iodinated compound synthesized in situ (reaction with iodine I2) :
I2 A2 2A M Pn Pn 2Pn AI Pm I 2AI in situ formation of the transfer agent during the inhibition period I2 2Pn I Pn I Pn I A M Pm Classical equilibrium of ITP process

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Can be straight implemented in current process (suspension)

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RITP (3)
Results :
H20/VC = 2.0 [DEPC] = 5.3 10 M [DEPC]/[I2] = 1.43 T=60°C
-4

PVC - DEPC - I2 - 60°C - Suspension in water
2.1

50

45

1.9

40

1.7

35

1.5 Iode/PDC Standard (PDC) Mn th Ip

30

1.3

25

1.1

20

15

0.9to Still transfer monomer 0.7

10 0 10 20 30 40 Con version (%) 50 60 70 80

0.5

Loss of I2 in H2O SOLVAY
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RITP (4)
Results : NMR
Initiator : CH3-CH2-O -CH2Cl (MB) + -CHCl-CH2Cl -CHCl-CH2Cl ---CH=CH-CH2Cl

FRP PVC

-CH2-CH2Cl

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RITP (5)
Results : NMR
Initiat or solvant Initiator : CH3 -C H2 -O -CH2-CH ClI -CHCl-CH2Cl ---CH=C H-CH 2Cl -C H2 Cl (MB) + -CHCl-CH2 Cl

RITP PVC

-CH2-CH 2Cl

-CHCl-CH=CH2

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RITP (6)

Conclusions :
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RITP leads to some control of the vinyl chloride polymerization (patented) RITP does not avoid Chain Transfer reactions RITP does not lead to a substantial improvement of the chemical structure

? ?

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Outline
? ? ? ? ? ? ? ? ?

Introduction Controlled Radical Polymerization (CRP) : the basics Reverse Iodine Transfer Polymerization (RITP) Cobalt Mediated Radical Polymerization (CMRP) Conclusion
26

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CMRP (1)
Main characteristics of CMRP :
?

H3C O
-

CH3 O Co O
2+ -

Z = Cobalt (II) complex
H3C

O

CH3

?
A

Equilibrium ? Reversible Termination
( Cl ) n Cl Cl Cl Cl Cl Co ( acac ) 2 A ( ) n Cl CH Cl

+

Co ( acac ) 2

H H

H Cl

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CMRP (2)

CMRP : very efficient for the vinyl acetate homopolymerization
(30°C, in bulk)
180000 150000 M n, SEC (g/mol) 2.5 M w /M n 120000 90000 60000 1.5 30000 0 0 10 20 30 40 50 conve rsion (%) 60 1.0 2.0
Debuigne, A.; Champouret, Y.; Jerome, R.; Poli, R.; Detrembleur, C. Chemistry--A European Journal 2008, 14, 4046-4059.

3.0

VAc reactivity similar to VC reactivity : so what about CMRP of VC ?
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CMRP (3)

CMRP of vinyl chloride :
?

as such (bulk, isotherm) : no polymerization

A Cl

(

) n Cl Cl Cl

Co ( acac ) 2

A Cl

(

) n Cl Cl

CH Cl

+

Co ( acac ) 2

H H

H Cl

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CMRP (4)

CMRP of vinyl chloride :
?

Better results if T increase or addition of H2O (patent application)
60 000 50 000 40 000 Mn 30 000 20 000 10 000 0 0% 10% 20% Conversion rate 30% 40% T increasing 40°C -> 80°C T= 40°C, Addition of water

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CMRP (5)

CMRP of vinyl chloride :
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Temperature increase and water addition lead to an equilibrium displacement towards the living species (C-Co bond reactivation)

?

allows the PVAc-b-PVC block copolymer synthesis

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CMRP (6)

CMRP of vinyl chloride :
?

NMR of CMRP PVC
-CHCl-CH2Cl ---CH=CH-CH2Cl

-CH2Cl (MB) + -CHCl-CH2Cl

-CH2-CH2Cl

-CHCl-CH=CH2

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CMRP (7)

Conclusions :
?

Modified CMRP leads to some control of the vinyl chloride polymerization (patent application) CMRP allows synthesis of VC-based block copolymers CMRP does not seem to modify the structure/concentration of the main chemical defects (still ongoing work on this topic)

? ?

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Outline
? ? ? ? ? ? ? ? ?

Introduction Controlled Radical Polymerization (CRP) : the basics Reverse Iodine Transfer Polymerization (RITP) Cobalt Mediated Radical Polymerization (CMRP) Conclusions
34

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Conclusions

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RITP and CMRP : two processes allowing controlled radical polymerization of vinyl chloride (in addition to SET) Open ways for new copolymer synthesis But do not show fundamental modifications of PVC molecular defects

? ?

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Aknowledgements

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RITP : B. Boutevin and P. Lacroix-Desmazes from the Ecole Nationale Supérieure de Chimie of Montpellier (France) CMRP : C. Detrembleur, A. Debuigne anf Y. Piette from the CERM (Liège University, Belgium)

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Thank you for your attention


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