Recent developments in photoinitiated radical polymerization

  • Decker C
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The author presents as a review (30 refs.) 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 polymn. kinetics was studied by real-time IR spectroscopy, which records conversion vs. 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 polymn. Acrylate monomers contg. 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 polymn. process. In both cases, the increase in reactivity was attributed to the presence of labile hydrogen atoms which favor chain transfer reactions. The copolymn. of donor-acceptor monomer systems, like vinyl ether maleate or vinyl ether maleimide, was shown to proceed readily upon UV irradn., even in the absence of added photoinitiator. Light-induced polymn. was also used to crosslink rapidly polymers functionalized with acrylate or vinyl double bonds, namely acrylated polyisoprene and a styrene-butadiene block copolymer. The addn. in small amts. (1%) of a trifunctional thiol was found to speed up drastically the crosslinking polymn., causing insolubilization of the thermoplastic elastomer to occur after a 0.1 s exposure.

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  • Christian Decker

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