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Group Transfer Polymerization: A Critical Review of Its Mechanism and Comparison with Other Methods for Controlled Polymerization of Acrylic Monomers

  • Owen W. Webster
Part of the Advances in Polymer Science book series (POLYMER, volume 167)

Abstract

Group transfer polymerization (GTP) was announced 20 years ago by DuPont as a method for synthesis of acrylic block polymers. It operates at high enough temperatures to allow reactor cooling by water-cooled reflux condensers, rather than more costly refrigeration units. GTP uses 1-methoxy-1-(trimethylsiloxy)-2-methylprop-1-ene (MTS) as initiator and a carboxylic acid salt as catalyst. The number of growing polymer chains corresponds to the amount of MTS used. Chain growth stops when the monomer is depleted. Addition of a new monomer at this point starts chain growth again to produce a block polymer. DuPont sells pigmented inks containing GTP block polymer dispersing agents.

Initial mechanism studies pointed to a trimethylsilyl transfer process that now appears to be incorrect. Strong evidence is presented for a dissociative anionic process. Reactivation of silylated chain ends by the alkoxide eliminated during end group cyclization is proposed as the reason GTP works at 80 °C.

A comparison of GTP with other methods for block polymer synthesis is presented.

Keywords

Group transfer polymerization Polymethacrylates Polyacrylates Living polymerization GTP mechanism Living anionic polymerization of MMA 

List of Abbreviations

Ac

Acetate

ATRP

Atom transfer polymerization

BMA

Butyl methacrylate

Bz

Benzoate

CCT

Catalytic chain transfer

DP

Degree of polymerization

GTP

Group transfer polymerization

MA

Methyl acrylate

MMA

Methyl methacrylate

MTS

1-Methoxy-1-(trimethylsiloxy)-2-methylprop-1-ene

Mn

Number average molecular weight

Mw

Weight average molecular weight

MWD

Molecular weight dispersity, Mw/Mn

MW

Molecular weight

P

Polymer

P5

Tetrakis[tris(dimethylamino)phosphoranyliden-amino]phosphonium

PBMA

Poly(butyl methacrylate)

PMA

Poly(methyl acrylate)

PMMA

Poly(methyl methacrylate)

RAFT

Reversible addition fragmentation transfer

S

Styrene

SFRP

Stable free radical polymerization

TAS

Trisdimethylaminosulfonium

TBA

Tetrabutylammonium

tol

Tolyl

TEMPO

2,2,6,6-Tetramethyl-1-piperidinyloxy

TMS

Trimethylsilyl

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Notes

Acknowlegments

The bulk of the DuPont work described herein was conducted by research workers in the Automotive Finishes and Central Research Departments. I wish to especially thank Dotsi Sogah, Wally Hertler, Bill Farnham, T.V. RajanBabu, and Professors Jack Roberts and Barry Trost for many hours of discussion on various aspects of GTP technology.

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Copyright information

© Springer-Verlag 2003

Authors and Affiliations

  1. 1.Chadds FordUSA

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