EPR Analysis of n-Butyl Acrylate Radical Polymerization

被引：56

作者：

Barth, Johannes ^{[1
]}

Buback, Michael ^{[1
]}

Hesse, Pascal ^{[1
]}

Sergeeva, Tatiana ^{[1
]}

机构：

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

来源：

MACROMOLECULAR RAPID COMMUNICATIONS | 2009年 / 30卷 / 23期

关键词：

backbiting; butyl acrylate; ESR/EPR; kinetics (polym.); mid-chain radical; PULSED-LASER POLYMERIZATION; ELECTRON-SPIN-RESONANCE; SP-PLP-ESR; MIDCHAIN RADICALS; RATE COEFFICIENTS; POLY(NORMAL-BUTYL ACRYLATE); PHOTOCHEMICAL PROCESSES; TERMINATION KINETICS; CHAIN TRANSFER; METHACRYLATE;

D O I：

10.1002/marc.200900531

中图分类号：

O63 [高分子化学（高聚物）];

学科分类号：

070305 ; 080501 ; 081704 ;

摘要：

Via electron paramagnetic resonance (EPR) spectroscopy, concentrations of secondary propagating radicals (SPRs) and tertiary mid-chain radicals (MCRs) in n-butyl acrylate solution polymerization were measured. The EPR spectrum is dominated by the 4-line spectrum of SPRs at -50 degrees C and by the 7-line spectrum of MCRs at +70 degrees C. At intermediate temperatures, a third spectral component is seen, which is assigned to an MCR species with restricted rotational mobility. The MCR components are produced by 1,5-hydrogen shift (backbiting) of SPRs. The measured ratio of MCRs to SPRs U allows for estimating the rate coefficient k(p)(t) for monomer addition to a mid-chain radical. For 70 degrees C, k(p)(t) is obtained to be 65.5 L . mol(-1) . s(-1).

引用

页码：1969 / 1974

页数：6

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