期刊
MACROMOLECULAR CHEMISTRY AND PHYSICS
卷 203, 期 16, 页码 2281-2289出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/macp.200290002
关键词
MADIX; MALDI; molecular weight distribution; radical polymerization; xanthates
Control of the free-radical polymerization of styrene was achieved using a series of eight xanthates of the general structure R-A(C=A)OEt as reversible addition fragmentation chain-transfer agents. The influence of the nature of the R leaving group was explored. It was found that the transfer ability of the xanthate is markedly improved with increasing stability of R and its steric hindrance. Group R strongly influences the M-n evolution profile during polymerization, but only influences the polydispersities to a small extent. The cyanoisopropyl group was shown to be the best leaving group, leading to an increase in the molecular weight during polymerization that was close to linearity. The living character of the polymerization and the high purity of the chain structures were supported by matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometry and C-13 NMR spectroscopy. A zero-order dependence of the kinetics of polymerization on the xanthate concentration was observed.
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