Synthesis and characterization of double hydrophilic block copolymers containing semi‐rigid and flexible segments

Abstract

ABSTRACT3‐Methyl‐(E)‐stilbene (3MSti) and 4‐(diethylamino)‐(E)‐stilbene (DEASti) monomers are synthesized and polymerized separately with maleic anhydride (MAn) in a strictly alternating fashion using reversible addition‐fragmentation chain transfer (RAFT) polymerization techniques. The optimal RAFT chain transfer agents (CTAs) for each copolymerization affect the reaction kinetics and CTA compatibilities. Psuedo‐first order polymerization kinetics are demonstrated for the synthesis of poly((3‐methyl‐(E)‐stilbene)‐alt‐maleic anhydride) (3MSti‐alt‐MAn) with a thiocarbonylthio CTA (methyl 2‐(dodecylthiocarbonothioylthio)−2‐methylpropionate, TTCMe). In contrast, a dithioester CTA (cumyl dithiobenzoate, CDB) controls the synthesis of poly((4‐(diethylamino)‐(E)‐stilbene)‐alt‐maleic anhydride) (DEASti‐alt‐MAn) with pseudo‐first order polymerization kinetics. DEASti‐alt‐MAn is chain extended with 4‐acryloylmorpholine (ACMO) to synthesize diblock copolymers and subsequently converted to a double hydrophilic polyampholyte block copolymers (poly((4‐(diethylamino)‐(E)‐stilbene)‐alt‐maleic acid))‐b‐acryloylmorpholine) (DEASti‐alt‐MA)‐b‐ACMO) via acid hydrolysis. The isoelectric point and dissociation behavior of these maleic acid‐containing copolymers are determined using ζ‐potential and acid–base titrations, respectively. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 219–227