Development of Experimental Method for Kinetics Research −Kinetics of Radical Polymerizations Based on Electron Spin Resonance Spectroscopy−

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  • 化学反応の速度を調べる手法の開発 ─ 電子スピン共鳴分光を基礎としたラジカル重合反応の速度論 ─

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Abstract

Steady-state electron spin resonance （SS ESR） spectroscopy has been applied for kinetics studies of radial polymerizations, especially determination of propagation rate constants （kp) based on observed spectra of propagating radicals in the actual polymerization systems. Time-resolved ESR （TR ESR) spectra allowed direct observation of transient radicals (chain initiating radical) obtained by the addition reaction of a diphenylphosphinoyl radical to monomers. The addition rate constants (k2) of diphenylphosphinoyl radical to the monomers （initiation rate constants) were determined by the monomer concentration dependence of the decay rate of the diphenylphosphinoyl radical. A combination of SS ESR and TR ESR provided information on the kinetics both of initiation and propagation processes in radical polymerization of various monomers.

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