Linear and Comb-Like Acrylonitrile/N-Isopropylacrylamide Copolymers Synthesized by the Combination of RAFT Polymerization and ATRP

We describe the synthesis of three novel thermoresponsive copolymers of acrylonitrile (AN) with N-isopropylacrylamide (NIPAM) by a combination of reversible addition-fragmentation chain transfer (RAFT) polymerization and atom transfer radical polymerization (ATRP). Linear copolymer polyacrylonitrile (PAN)-b-PNIPAM was directly prepared by RAFT polymerization. Comb-like copolymers were synthesized by ATRP using brominated AN/2-hydroxyethyl methacrylate copolymers as macroinitiators, which were prepared by RAFT polymerization. FT-IR, NMR, and GPC were employed to characterize the synthesized copolymers. Results indicate that the polymerization processes can be well controlled and the resultant copolymers have well-defined structures as well as narrow polydispersity. Then dense films were fabricated from these thermoresponsive copolymers and the surface wettability was evaluated by water contact angle measurements at different temperatures. It is found that the surface wettability is temperature-dependant and both the transition temperature and decrement of water contact angle are affected by the copolymer shapes as well as the length of PNIPAM blocks. Considering the excellent fiber- and membrane-forming properties of PAN-based copolymers, the obtained thermoresponsive copolymers are latent materials for functional fibers and membranes. (c) 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 92-102, 2009