화학공학소재연구정보센터
Journal of Polymer Science Part A: Polymer Chemistry, Vol.35, No.1, 9-16, 1997
Preparation and Photochemical Study of Soluble Optically-Active Block Copolymethacrylates and Azo-Containing Random Copolymethacrylates
A series of soluble optically active block copolymers of trityl methacrylate (TrMA) and cyclohexyldiphenylmethyl methacrylate (CHDPMA) with methyl methacrylate (MMA) and n-butyl methacrylate (n-BuMA) were synthesized using the complex of 9-fluorenyllithium and (S,S)-(+)-2,3-dimethoxy-1,4-bis(dimethy as an initiator in toluene at -78 degrees C. Soluble optically active random copolymers derived from TrMA and ate methacrylates, 6-(4-phenylazophenoxy)hexyl methacrylate (PAHM) and 2-(4-phenylazophenoxy)ethyl methacrylate (PAEM), were obtained under similar anionic polymerization conditions. Optical activities of the copolymers largely depended on the weight percentage of TrMA or CHDPMA component in the polymer chains. Solubility and film formability were significantly improved for the copolymers. Irradiation of optically active TrMA-MMA and CHDPMA-MMA block copolymer films containing photoacid, diphenyl-p-tolylsulfonium triflate, causes the partial hydrolysis of bulky esters and results in the conformational randomization of helical chains, which in turn leads to a significant change in optical rotation of the films. Photoisomerization studies of ate-containing random copolymers indicate that the trans to cis isomerization induces the helical conformation racemization in solution.