Block copolymerization of tert-butyl methacrylate with α,ω-difunctionalized polystyrene macroiniferter and hydrolysis to amphiphilic block copolymer

The block copolymerization of tert-butyl methacrylate (tBMA) with a difunctionalized polystyrene (PS) macroinitiator it as investigated. The polymerizations were performed under UV light irradiation using PS bearing alpha- and omega -functionalized end groups containing diethyldithiocarbamyl groups as a macroiniferter. Kinetic studies indicate the molecular weights of triblock copolymers increased linearly with the conversion. Block copolymers with different lengths of PtBMA segments were easily prepared by varying the ratio of tBMA and PS macroiniferter or by controlling the monomer conversion. The formations of block copolymers were characterized by gel permeation chromatographic, H-1 NMR, and DSC analyses. PtBMA segments of the triblock copolymer were subsequently hydrolyzed quantitatively to poly(methacrylic acid) segments using concentrated HCl as a catalyst in a refluxing solution of dioxane, and then an amphiphilic ABA triblock copolymer was produced. (C) 2001 John Wiley & Sons, Inc.