Synthesis of hydrophilic/CO2-philic poly(ethylene oxide)-b-poly (1,1,2,2-tetrahydroperfluorodecyl acrylate) block copolymers via controlled/living radical polymerizations and their properties in liquid and supercritical CO2

Hydrophilic/CO2-philic poly(ethylene oxide)-b-poly(1,1,2,2-tetrahydroperfluorodecyl acrylate) block copolymers were synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization, iodine transfer polymerization (ITP), and atom transfer radical polymerization (ATRP) in the presence of either degenerative transfer agents or a macroinitiator based on poly(ethylene oxide). In this work, both RAFT and ATRP showed higher efficiency than ITP for the preparation of the expected copolymers. More detailed research was carried out on RAFT, and the living character of the polymerization was confirmed by an ultraviolet (UV) analysis of the -SC(S)Ph or -SC(S)S-C12H25 end groups in the polymer chains. The quantitative (UV) analysis of the copolymers indicated a number-average molecular weight in good agreement with the value determined by H-1 NMR analysis. The properties of the macromolecular surfactants were investigated through the determination of the cloud points in neat liquid and supercritical CO2 and through the formation of water-in-CO2 emulsions. (C) 2004 Wiley Periodicals, Inc.