Abstract
Energy migration plays an important role in the photochemistry of polymers containing phenyl vinyl ketone (PPVK) and o-tolyl vinyl ketone (PTVK) units. The average residence time of the triplet excitation in any given chromophore is in the neighborhood of 30 ps. Triplet lifetimes are estimated as 55 ns for PPVK and 2 ns for PTVK and are intermediate for all the copolymers. Biradical lifetimes are 65 ns for PPVK and 200 ns for PTVK, reflecting the longer lifetime of the biradicals derived from the o-methylbenzoyl group. Photoenolization of the o-tolyl vinyl ketone moieties provides an energy sink, reducing the degree of photodegradation. For example, a copolymer of phenyl vinyl ketone and o-tolyl vinyl ketone containing 3% of the latter undergoes only 54% of the degradation undergone by PPVK.
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