Synthesis of Thermoresponsive Mixed Arm Star Polymers by Combination of RAFT and ATRP from a Multifunctional Core and Its Self-Assembly in Water

Abstract

Mixed arm star copolymers of poly(N,N-dimethylacrylamide) (PDMA) and poly(N-isopropylacrylamide) (PNIPAm) were synthesized by a sequential reversible addition−fragmentation chain transfer (RAFT) and atom transfer radical polymerization (ATRP) from a multi-initiator-functionalized hyperbranched polyglycerol (MI-HPG) core. The MI-HPG core was synthesized from an amine-functionalized polyglycerol, modified successively with 2-chloropropionamide groups (ATRP initiator) and 4,4′-azobis(4-cyanovaleric acid) (azo initiator). N,N-Dimethylacrylamide was polymerized from MI-HPG core by the RAFT method using S,S′-bis(α,α′-dimethyl-α′′-acetic acid)trithiocarbonate as a chain transfer agent (CTA) in acetic acid/sodium acetate aqueous buffer solutions. The ratio of [CTA]/[azo initiator] was critical in controlling the molecular weight of the PDMA grafts from MI-HPG core (HPG-g-PDMA). Controlled synthesis of mixed arm star copolymers was achieved by cografting PNIPAm on to the HPG-g-PDMA macroinitiator by ATRP. The temp...