Group Transfer Polymerization

Concept
Getting to know your Silicon

Group Transfer Polymerization

Concept
Getting to know your Silicon

R FR R Si W FR R

F Si W R

-1 FFR R

F F Si W R

-2

Group Transfer Polymerization

Concept
R FR R Si W W FR R Si R F -1

Si

F-

W-

Si

Group Transfer Polymerization

Concept

R FR R Si W FR R

F Si W R

-1 F
-

F R R Si W F R

-2

F-

Five coordinate Silicon has greater Lewis acidity a. Because of charge or b. Because of greater resonance stabilization of six coordinate silicon

Group Transfer Polymerization

Initiator

Si
Si + H

O OR

O OR

Silyl ketene acetal

Group Transfer Polymerization

Mechanism: Propagation

OSi(CH3)3

OCH3
X- (X = F, RCOO, etc) OCH3 -

X Si(CH 3)3

Group Transfer Polymerization

Mechanism: Propagation
OCH3 X Si(CH 3)3 O -

MMA OCH3 OCH3 O O X Si(CH 3)3

Group Transfer Polymerization

Mechanism: Propagation
OCH3 OCH3 O O X Si(CH3)3

OCH3 OCH3 O O

X Si(CH3)3

Group Transfer Polymerization

Mechanism: Propagation
OCH3 OCH3 O O X Si(CH3)3

OCH3 OCH3 O O

X Si(CH3)3

Group Transfer Polymerization

Mechanism: Propagation

OCH3 OCH3 O O

OCH3 X Si(CH3)3 OCH3 O OCH 3 O O X Si(CH3)3

Group Transfer Polymerization

Mechanism: Propagation

OCH3 OCH3 O OCH3 O O X Si(CH3)3

OCH3 OCH3 O OCH3 O O X Si(CH3)3

Group Transfer Polymerization

Mechanism: Propagation

OCH3 OCH3 O OCH3 O O X Si(CH3)3

OCH3 OCH3 O OCH3 O O X Si(CH3)3

Group Transfer Polymerization

Mechanism: Termination
OCH3 OCH3 O OCH3 O O X H Si(CH3)3 Cl OCH3 OCH3 O OCH3 O OH X + Cl Si(CH3)3

OCH3 OCH3 O OCH3 O O

Advantages of GTP

Group Transfer Polymerization

1. Living (PDI 1) 2. Can do this reaction at room temperature (ionic requires low temp) 3. Can make telechelic polymers 4. Obtain random copolymers (reactivity ratios less of a consideration) 5. Air stable (but not water stable) 6. Can use DMF as solvent 7. Tolerant of other functional groups, especially vinyl side chains that would polymerize during radical polymerizations. Cant use acids (MAA)
O

Group Transfer Polymerization

Disadvantages of GTP
1. Only use for acrylate or methacrylate monomers (or aldehyde as discussed next) 2. More expensive than radical, 3. Requires water free conditions (pure reagents)

Group Transfer Polymerization

Aldol GTP: Things to know

1. Should use less than 5% anionic catalyst (F- , or CH3COO-) to avoid total catalyst displacement 2. Rates slower than radical polym. (by approx an order of magnitude) 3. Can get competing radical polymerization.

Group Transfer Polymerization

Aldol GTP-Initiation

OSiMe2t-Bu O ZnBr2

ZnBr2 SiMe2t-Bu
O

Group Transfer Polymerization

Aldol GTP: Initiation and Propagation

ZnBr2 SiMe2t-Bu
O O

ZnBr2 SiMe2t-Bu
O

O O

SiMe2t-Bu ZnBr2

ZnBr2 SiMe2t-Bu
O

Group Transfer Polymerization

Aldol GTP

O O

SiMe2t-Bu ZnBr2 SiMe2t-Bu

O

O O

SiMe2t-Bu SiMe2t-Bu ZnBr2

Group Transfer Polymerization

Aldol GTP

109 Si

X-

90 Si

Group Transfer Polymerization

Aldol GTP
New catalyst-free initiator

Si

OCH3