Triplet-Sensitized Reactions of Some Main Chain Liquid-Crystalline Polyaryl Cinnamates

P. Subramanian, University of Southern Mississippi
David Creed, University of Southern Mississippi
Charles E. Hoyle, University of Southern Mississippi
Krishnan Venkataram, University of Southern Mississippi

Abstract

Thin films of a liquid crystalline polyaryl cinnamate have been irradiated at (lambda) > 400 nm in the presence of ketocoumarin triplet sensitizers. The aryl cinnamate chromophore disappears upon irradiation with concomitant loss of solubility attributed to cross-linking by interchain cyclobutane photoproduct formation. Competing loss of sensitizer absorption also occurs during irradiation. Up to ca. 80% of the aryl cinnamate chromophores in amorphous films can be destroyed using high weight percentages (>= 5%) of sensitizer. At low concentrations of sensitizer (0.5 wt.%), approximately 80 cinnamate chromophores are photolyzed for each sensitizer molecule initially present, despite the competing photolysis of sensitizer during the course of irradiation. The ketocoumarins are insoluble in the glassy (frozen) nematic films of the polymer and thus are ineffective in sensitizing photolysis in this more organized phase.