ROMP−ATRP Block Copolymers Prepared from Monotelechelic Poly(oxa)norbornenes Using a Difunctional Terminating Agent

Novel block copolymers were prepared by combining ROMP and ATRP. Using the fast initiating ruthenium metathesis catalyst (H_2IMes)(Cl)_2(pyr)_2RuCHPh and (Z)-but-2-ene-1,4-diyl bis(2-bromopropanoate) as a terminating agent, three different monotelechelic poly(oxa)norbornenes were synthesized. Complete end-functionalization was shown by carrying out the ATRP of styrene and tert-butyl acrylate from the poly(oxa)norbornenes using a CuBr/PMDETA catalyst system. GPC showed no remaining homopolymer, and all block copolymers were found to have matching theoretical and observed molecular weights and low polydispersities