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Free radical accelerated cationic polymerizations
Author(s) -
Crivello James V.,
Rajaraman Surésh,
Mowers William A.,
Liu Saoshi
Publication year - 2000
Publication title -
macromolecular symposia
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.257
H-Index - 76
eISSN - 1521-3900
pISSN - 1022-1360
DOI - 10.1002/1521-3900(200007)157:1<109::aid-masy109>3.0.co;2-y
Subject(s) - cationic polymerization , vinyl ether , epoxide , monomer , polymer chemistry , polymerization , chemistry , ring opening polymerization , living cationic polymerization , ether , anionic addition polymerization , chain transfer , ionic polymerization , living free radical polymerization , radical polymerization , photochemistry , organic chemistry , catalysis , polymer
The simultaneous photoinitiated cationic polymerizations of epoxides and vinyl ethers in the presence of diaryliodonium salt photoinitiators results in an acceleration of the ring‐opening epoxide polymerization and a deceleration of the vinyl ether polymerization. These effects are seen both in mixtures of the two monofunctional monomers as well as in hybrid monomers which bear vinyl ether and epoxide groups in the same molecule. A combination of two mechanisms have been proposed to account for these effects. The reversible conversion of alkoxycarbenium to oxiranium ions results in a two‐stage reaction in which first, the epoxide, then the vinyl ether polymerization takes place. Free radical chain induced decomposition of the diaryliodonium salt produces a large incremental number of carbenium ion species which results in the acceleration effect.