Free-radical propagation rate coefficients of dodecyl methacrylate deduced from electron spin resonance experiments

被引：34

作者：

Buback, M

Kowollik, C

Kamachi, M

Kajiwara, A

机构：

[1] Univ Gottingen, Inst Phys Chem, D-37077 Gottingen, Germany

[2] Osaka Univ, Grad Sch Sci, Dept Macromol Sci, Osaka 5600043, Japan

来源：

MACROMOLECULES | 1998年 / 31卷 / 21期

关键词：

D O I：

10.1021/ma980542p

中图分类号：

O63 [高分子化学（高聚物）];

学科分类号：

070305 ; 080501 ; 081704 ;

摘要：

Propagation rate coefficients (k(p)) for the free-radical polymerization of dodecyl methacrylate (DMA) in solution in toluene have been measured via electron spin resonance (ESR) spectroscopy in the temperature range 0 to 50 degrees C. The polymerization is photochemically induced at different initiator concentrations of di-tert-butyl peroxide (DTBP). Free-radical concentration under steady-state conditions is deduced from double integration of the well-resolved ESR spectra, consisting of 13 lines in the initial period of the polymerization reaction and 9 lines at enhanced degrees of monomer conversion. The hp values from ESR analysis are in excellent agreement with the corresponding data from pulsed laser polymerization (PLP)/size-exclusion chromatography (SEC), the IUPAC-recommended procedure for reliable k(p) measurement. The activation energy associated with the ESR k(p) data, E-A = 21.7 +/- 2.0 kJ mol(-1), is in full agreement with E-A (k(p)) results from recent PLP-SEC studies.

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页码：7208 / 7212

页数：5

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