Synthesis and Solid-State Polymerization of Butadiyne Derivatives with Trialkoxyphenylurethane Groups

Abstract

Abstract 3,4,5-Trialkoxyphenyl isocyanate derivatives, in which alkoxy was dodecyloxy or methoxy, reacted with 4,6-decadiyn-1,10-diol and 5,7-dodecadiyn-1,12-diol, and four butadiyne derivatives with (N-trialkoxyphenyl)urethane groups were successfully synthesized. Their solid-state polymerization stimulated by UV or γ-ray irradiation was investigated. All monomers in crystals were found to be polymerizable. However, conversion was different depending on the compounds. The derivatives from 5,7-dodecadiyn-1,12-diol showed better conversion, suggesting that they have more favorable monomer arrangement for the solid-state polymerization. Polymers of dodecyloxy derivatives could be partially dissolved in chloroform and they showed solvatochromism when hexane was added to the solution. As was expected from the structure of tridodecyloxyphenyl groups introduced, dodecyloxy derivatives gave organogels in various organic solvents in the concentration less than 2 wt %. However, these gels could not be polymerized by UV irradiation, and the monomer alignment was found to be different between crystalline and gel states.