GROUP TRANSFER

POLYMERIZATION (GTP)
BY
DR. DIPAK PINJARI
ICT, MUMBAI.
 OUTLINE
• Discovery of Method
• Synthetic Routes
• Mechanisms:Then and Now
• Applications
• Pros and Cons
 DISCOVERY OF GTP
• Webster et al at DuPont’s Central R&D
• Needed a method for controlled “living” polymerizations of acrylates and
methacrylates
• Name suggested by Trost
• Aiming for methods of synthesizing “pigment dispersing agents” and “rheology
control”
• First production of PMMA by group transfer polymerization with ZnBr2 catalyst
• Printer Inks
DESIRED CHARACTERISTICS

• Workable Temp. range (50-80ºC)

• Can synthesize blocks
• Cheap production ($5>/lb.)
• Good PDIs and MWs (~20,000 Da)
• Nontoxic, colorless, no bad odors, etc.
SYNTHETIC ROUTES
• Always start with conjugate addition of silyl ketene acetal
initiators
• Monomer: Methacrylates, Acrylates, Ketones,
Nitriles, Carboxamides
O CH3
• Catalysts: Two choices
-Nucleophilic Anions O
Si
-Lewis Acids
 SYNTHESIS: CATALYSTS
• Nucleophilic Anions tried by Webster: KHF2
• TASHF2 =Tris(dimethylamino)-sulfonium
Nucleophilic Anions Lewis Acids F H
H 3C CH3
KHF2 ZnB2 N F
TASHF2B ZnI2 H 3C N
S
ZnCl2 N CH3
u4NF F Me Me
(i-Bu2Al)2O CH3 CH3
TASCN O
Si
Me O Me Si Me
Et4NCN i-Bu2AlCl Me F
TASN3 Et2AlCl O Me
O Me
SYNTHESIS: CATALYST
• Later Variations:
• Bu4NPhCO2HO2CPh = TBA Bibenzoate
• Bis(triphenylphosphoranylidene)ammonium
bifluoride
F H

F O
P P O O
N K
O O

• Potassium 18-crown-6 O
ANY EVIDENCE FOR ASSOCIATIVE MECHANISM?
• Yes!
• Excellent Double-Label Experiment by
Farnham and Sogah

Sogah, D.Y.; Farnham, W.B. Polym. Prepr. Am. Chem. Soc. Div. Polym. Chem. 1986, 27, 167.
 GTP:THE TRUTH
• So, actually an anionic living polymerization
• “Anionic initiators for MMA can act as catalysts for GTP”
• Caveat: Back-biting not an issue with this anionic living
polymerization
APPLICATIONS

• Pigment Dispersant H2O H2O

• Emulsion Stabilizers
• AB block co-polymer
A = Hydrophilic Block B = H2O

Hydrophobic Block
H2O
 PROS & CONS

• Advantages • Disadvantages
1. Good for making blocks of acrylates and methacrylate's 1. Cannot be done in presence of
water
2. Can be done at RT and elevated T
2. Initiator still costly
3. Excellent architectural control (stars, blocks, etc.)
3. Cannot use monomers with acidic or
4. Low PDIs (can get down to 1.03!)
active hydrogen functional groups
5. No metallic or halide impurities left over

6. No bad odors!
CONCLUSION

• Relatively new ‘living’ polymerization technique

• Full of potential, still room for improvement
• Best method around for block polymers of methacrylate
derivatives