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Intrinsic and Catalyzed Photochemistry of Phenylvinylketone for Wavelength‐Sensitive Controlled Polymerization
Author(s) -
Reeves Jennifer A.,
De Alwis Watuthanthrige Nethmi,
Boyer Cyrille,
Konkolewicz Dominik
Publication year - 2019
Publication title -
chemphotochem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.13
H-Index - 18
ISSN - 2367-0932
DOI - 10.1002/cptc.201900052
Subject(s) - photopolymer , photochemistry , polymerization , chain transfer , photodegradation , polymer , photocatalysis , kinetics , polymer chemistry , tetraphenylporphyrin , materials science , chemistry , porphyrin , radical polymerization , catalysis , organic chemistry , physics , quantum mechanics
Reversible addition‐fragmentation chain transfer (RAFT) photopolymerization of phenylvinylketone (PVK) is investigated. The polymerization is investigated both in the presence of two photocatalysts (iridium tris(phenylpyridine (Ir(ppy) 3 ) and zinc tetraphenylporphyrin (ZnTPP)). The polymerization was efficient in the absence of photocatalyst, and accelerated by Ir(ppy) 3 , whereas ZnTPP was found to lead to retardation of polymerization. In all cases, well‐controlled polymers were synthesized with linear growth in M n with conversion and narrow molecular weight distributions. The observed photopolymerization kinetics were consistent with a Norrish Type 1 reaction of PVK to give two radicals. The polymerization kinetics were investigated as a function of wavelength, with the reaction rate being fastest with blue irradiation (440 nm), which is surprisingly far from the absorption maximum of PVK and Ir(ppy) 3 . Photodegradation of PVK was observed under UV irradiation, but the polymers were stable against visible light.