Atom transfer radical polymerization of n-butyl acrylate catalyzed by CuBr/N-(n-hexyl)-2-pyridylmethanimine

被引:49
|
作者
Zhang, HQ [1 ]
Van Der Linde, R [1 ]
机构
[1] Eindhoven Univ Technol, Fac Chem Engn & Chem, Lab Coatings Technol, NL-5600 MB Eindhoven, Netherlands
关键词
atom transfer radical polymerization (ATRP); N-(n-hexyl)-2-pyridylmethanimine; n-butyl acrylate; kinetics (polym.); block copolymers; random copolymers;
D O I
10.1002/pola.10460
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
The homogeneous atom transfer radical polymerization (ATRP) of n-butyl acrylate with CuBr/N-(n-hexyl)-2-pyridylmethanimine as a catalyst and ethyl 2-bromoisobutyrate as an initiator was investigated. The kinetic plots of ln([M](0)/[M]) versus the reaction time for the ATRP systems in different solvents such as toluene, anisole, N,N-dimethylformamide, and 1-butanol were linear throughout the reactions, and the experimental molecular weights increased linearly with increasing monomer conversion and were very close to the theoretical values. These, together with the relatively narrow molecular weight distributions (polydispersity index similar to 1.40 in most cases with monomer conversion > 50%), indicated that the polymerization was living and controlled. Toluene appeared to be the best solvent for the studied ATRP system in terms of the polymerization rate and molecular weight distribution among the solvents used. The polymerization showed zero order with respect to both the initiator and the catalyst, probably because of the presence of a self-regulation process at the beginning of the reaction. The reaction temperature had a positive effect on the polymerization rate, and the optimum reaction temperature was found to be 100 degreesC. An apparent enthalpy of activation of 81.2 kJ/mol was determined for the ATRP of n-butyl acrylate, corresponding to an enthalpy of equilibrium of 63.6 kJ/mol. An apparent enthalpy of activation of 52.8 kJ/mol was also obtained for the ATRP of methyl methacrylate under similar reaction conditions. Moreover, the CuBr/N-(n-hexyl)-2-pyridylmethanimine-based system was proven to be applicable to living block copolymerization and living random copolymerization of n-butyl acrylate with methyl methacrylate. (C) 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3549-3561, 2002.
引用
收藏
页码:3549 / 3561
页数:13
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