Abstract

Free volume distribution of poly (methyl methacrylate) was determined with a photo-reactive probe technique. Fairly large part of the free volume in PMMA has been found to be the more reactive than the reaction in solution using azobenzene as the photochromic probe, while there is some free volume fraction where quantum yield of photoreaction is restricted to zero. Information on the bulk region is clearly observed using a novel photochromic probe, which is obtained by connecting azobenzene to PMMA polymer chain. Effect of polymer relaxation on the quantum yield distribution shows contrast between azobenzene and polymer-connected azobenzene, which reflects the information on vacant or bulk region, respectively. Information on the free volume where the space is crowed by the probe molecule is also obtained by using azobenzene dimer as the photo reactive probe, showing the decrease in the photoreactivity and homogenous quantum yield distribution.

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