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Recent developments in photoinitiated radical polymerization
Author(s) -
Decker Christian
Publication year - 1999
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/masy.19991430106
Subject(s) - polymer chemistry , photoinitiator , polymerization , copolymer , monomer , acrylate , chain transfer , vinyl ether , photopolymer , materials science , reactivity (psychology) , radical polymerization , photochemistry , chemistry , polymer , organic chemistry , medicine , alternative medicine , pathology
This article presents the progress made in the development of high‐speed photocurable resins and reports the performance of some novel radical‐type photoinitiators, acrylate monomers and telechelic oligomers. The polymerization kinetics has been studied by real‐time infrared spectroscopy, which records conversion versus time curves for reactions occurring in a fraction of a second. Phosphine oxides are among the most efficient photoinitiators and proved to be particularly well suited for the photocuring of pigmented systems and for solar‐assisted polymerization. Acrylate monomers containing a heterocyclic oxygen in their structural unit exhibit an unexpectedly high reactivity. The introduction of an amino group in the chain of a telechelic acrylate‐polyester causes a substantial acceleration of the polymerization process. In both cases, the increase in reactivity was attributed to the presence of labile hydrogen atoms which favor chain transfer reactions. The copolymerization of donor‐acceptor monomer systems, like vinyl ether‐maleate or vinyl ether maleimide, was shown to proceed readily upon UV irradiation, even in the absence of added photoinitiator. Light‐induced polymerization was also used to crosslink rapidly polymers functionalized with acrylate or vinyl double bonds, namely acrylated polyisoprene and a styrene‐butadiene block copolymer. The addition in small amounts (1 wt%) of a trifunctional thiol was found to speed up drastically the crosslinking polymerization, causing insolubilization of the thermoplastic elastomer to occur after a 0.1 s exposure.