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Radical telomerization of vinyl acetate with chloroform. Application to the synthesis of poly(vinyl acetate)‐ block ‐polystyrene copolymers by consecutive telomerization and atom transfer radical polymerization
Author(s) -
Destarac Mathias,
Pees Bernard,
Boutevin Bernard
Publication year - 2000
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/1521-3935(20000701)201:11<1189::aid-macp1189>3.0.co;2-c
Subject(s) - telomerization , polymer chemistry , copolymer , vinyl acetate , atom transfer radical polymerization , chemistry , polystyrene , chloroform , styrene , living free radical polymerization , reversible addition−fragmentation chain transfer polymerization , polymerization , radical polymerization , monomer , chain transfer , organic chemistry , catalysis , polymer
This paper demonstrates that radical telomerization and atom transfer radical polymerization (ATRP) can be combined in a two‐step procedure to prepare poly‐(vinyl acetate)‐ block ‐polystyrene (PVOAc‐ b ‐PSt) diblock copolymers. The first step consists in telomerizing VOAc with chloroform, leading to trichloromethyl‐terminated VOAc telomers CCl 3 (VOAc) n H. A detailed 1 H NMR analysis shows that nearly pure telomer structures are obtained over a broad range of DP n values (up to at least 60 units). When ATRP of styrene is initiated with a model telomer adduct (CCl 3 CH 2 CH 2 OAc), molecular weights increase linearly with monomer conversion and match theoretical values. Moreover, polydispersities are consistently low (1.22 < M w / M n < 1.38) throughout polymerization. Similarly, VOAc telomers ( DP n = 9 and 62) are good ATRP macroinitiators. The high purity of the resulting diblock copolymers is confirmed by GPC using RI/UV dual detection.