Synthesis of poly(phenylacetylene)-block-poly(β-propiolactone) by use of Rh-catalyzed living polymerization of phenylacetylene

Synthesis of end-functionalized poly(phenylacetylene)s (poly(PA)s) and poly(PA)-block-poly(β-propiolactone) was investigated. Introduction of a t-BuMe2SiO group into Ph2CC(Ph)Li in the [(nbd)RhCl]2/Ph2CC(Ph)Li/Ph3P ternary catalyst system enabled the synthesis of poly(PA) having t-BuMe2SiO group at the initiating chain end. The t-BuMe2SiO group in the polymer was converted into OH group by treating with n-Bu4NF and then into ONa group with NaH. Polymerization of β-propiolactone (βPL) with the poly(PA) having ONa as a macroinitiator and the subsequent product separation by GPC provided poly(PA)-block-poly(βBL).