Synthesis and properties of photosensitive rubbers. II. Photosensitivity of cyclized polydienes and polypentenamer with pendent cinnamate groups

Photosensitivity of cyclized polydienes such as cis-1,4-polybutadiene, 1,2-polybutadiene, and polypentenamer having pendent cinnamate groups has been studied in terms of the influence of polymer structure. The photosensitivity, which was based on the photodimerization of cinnamate groups in these polymers, was greatly affected by the mobility of the cinnamate groups. The observed rates (k) could be estimated by using the reciprocal of the difference between an irradiated temperature (T) and a standardized temperature (Tg – 50), at which the free volume of the polymer could be considered as zero by taking the glass transition temperature (Tg) of the polymer as a standard. Furthermore, the photosensitivity of the cyclized rubber decreased with an increase in the amount of the cyclized units in the polymer. The overall rate of the photodimerization did not linearly correlate with the amount of the incorporated cinnamate groups, because the glass transition temperature of the cyclized rubber was not dependent on the small amount of the incorporated cinnamate groups, but on the amount of the cyclized units in the polymer. Theoretical treatment of the photodimerization reaction in the solid polymer was carried out, which was consistent with experimental results.