Synthesis and properties of copolymers from diphenylacetylene having a hexaphenylbenzene moiety

Copolymerization of diphenylacetylene having a hexaphenylbenzene group, 1-[ p-(pentaphenyl)phenyl] -2-phenylacetylene (1), with a few other diphenylace tylene derivatives (i.e., diphenylacetylene, 1-phenyl-2-[p-(trimethyl silyl )phenyl] acetylene, 1-phenyl-2- [p-n-octylphenyl] acetylene, (2a-c, respect ively) and properties of the formed copolymers were investigated. No polyme r was obtained in homopolymerization of 1 with TaCl5-n-Bu4Sn catalyst owing to steric hindrance. On the other hand, copolymerization with 2a-c proceed ed at various feed ratios to give copolymers in moderate yields. Copoly(1/2 a) (feed ratio 25/75) was soluble in toluene and CHCl3 and its weight-avera ge molecular weight (M-w) was ca. 31x10(4) and relatively high. Copoly(1/2b ) and copoly(1/2c) (both feed ratios 5/95) were soluble in common organic s olvents, and had a large Mw up to ca. 1x10(6). These copolymers were yellow to orange solids. Oxidative cyclodehydrogenation of hexaphenylbenzene grou ps in copoly(1/2a) was attempted in order to convert them into more conjuga ted groups.