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Copolymerizations of macromonomer prepared by addition-fragmentation chain transfer polymerization of methyl acrylate trimer
Authors:Yamada  Bunichiro  Hirano  Tomoyuki
Affiliation:(1) Department of Applied and Bioapplied Chemistry, Graduate School of Engineering, Osaka City University, Osaka 558-8585, Japan, E-mail: yamada@a-chem.eng.osaka-cu.ac.jp Tel.:+81-6-6605-2797, JP
Abstract:Summary An oligomer of the methyl acrylate unsaturated trimer bearing 2-carbomethoxy-2-propenyl ω-end group (M n = 1300, M w/M n = 1.7, and functionality > 0.7) was copolymerized as a macromonomer (0.02 mol/L) with styrene (1.0 mol/L) in benzene at 60 °C. The amounts of monomer and macromonomer in the feed simultaneously decreased with increasing time to indicate copolymer formation, and the macromonomer was found to be as reactive as styrene toward poly(styrene) radicals. The M ns of the copolymers were 13900–22000 depending on conversion. No resonance due to the unsaturated <ω-end group bound to the poly(styrene) chain was detected by 1H-NMR spectroscopy, indicating that no fragmentation of adduct radical of the end group to expel the poly(methyl acrylate trimer) radical. Polymerization of ethyl methacrylate (1.0 mol/L) in the presence of the macromonomer (0.02 mol/L) resulted in a mixture of the unreacted macromonomer and homopolymer of ethyl methacrylate. No end group bound to the poly(ethyl methacrylate) was detected by 1H-NMR spectroscopy, excluding the possibility of addition fragmentation chain transfer to the macromonomer to expel an oligomer radical of the methyl acrylate trimer. Addition of the poly(methacrylate) radical to the macromonomer is extremely slow under the present conditions of copolymerization. Received: 27 March 2003/Revised version: 30 April 2003/ Accepted: 30 April 2003 Correspondence to Bunichiro Yamada
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