Preparation of novel macromonomers and study of their polymerization

Novel macromonomers of polystyrene and poly(tert-butyl acrylate) containing a methacryloyl group as a polymerizable unit and two chains of the same length were prepared in two steps: the synthesis of the precursors through the atom transfer radical polymerization of styrene and tert-butyl acrylate initiated by 1-hydroxymethyl-1,1-di[(2-bromoisobutyryloxy)methyl] ethane and the esterification of the hydroxyl group in the precursors with methacryloyl chloride. The molecular weight and polydispersity of the macromonomers were controllable because of the living nature of the atom transfer radical polymerization. Gel permeation chromatography, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry, and hydrolysis confirmed the structure of the novel macromonomers. The homopolymerization and copolymerization of the macromonomers were investigated to prepare branched copolymers in which two chains were grafted from every repeating unit. (C) 2004 Wiley Periodicals, Inc.