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Addition–fragmentation type initiation of cationic polymerization using allyloxy‐pyridinium salts
Author(s) -
Bacak Vildan,
Reetz Ivo,
Yagci Yusuf,
Schnabel Wolfram
Publication year - 1998
Publication title -
polymer international
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.592
H-Index - 105
eISSN - 1097-0126
pISSN - 0959-8103
DOI - 10.1002/(sici)1097-0126(199811)47:3<345::aid-pi67>3.0.co;2-5
Subject(s) - cationic polymerization , polymerization , chemistry , chain transfer , cobalt mediated radical polymerization , ionic polymerization , photochemistry , living free radical polymerization , cyclohexene oxide , radical , radical polymerization , reversible addition−fragmentation chain transfer polymerization , moiety , polymer chemistry , pyridinium , allylic rearrangement , ring opening polymerization , cyclohexene , organic chemistry , polymer , catalysis
Allyloxy‐pyridinium salts with various substituents on the allylic moiety are shown to be very efficient coinitiators in radical promoted cationic polymerization of cyclohexene oxide. Depending upon the radical initiator chosen, cationic polymerizations may be initiated by either heat or light. For the most part, the mechanism of initiation involves the addition of free radicals formed by the radical initiator, and a subsequent fragmentation of the energy‐rich intermediate yielding initiating pyridinium type radical cations. In addition– fragmentation polymerization, the substituent at the allylic moiety does not significantly influence the polymerization rate, thus implying that fragmentation is the rate determining step. In some cases, oxidation of the primarily formed free radicals contributes to the formation of initiating species. The salts under investigation are also able, to various extents, to initiate cationic polymerization upon external stimulation (heating or UV irradiation) without added radical initiators. © 1998 Society of Chemical Industry