Measurements for Addition Reaction Rate Constants of Organic Free Radicals to Maleic Anhydride by Means of Pulsed EPR Spectroscopy with Laser Excitation


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Abstract

Addition reaction of photo-generated organic radicals to maleic anhydride (MA), that is a common monomer in polymerization, was studied by time-resolved (TR)- and pulsed electron paramagnetic resonance (EPR) spectroscopic methods. The radicals examined are 2-hydroxypropyl (2Hy-Pr), diphenylphosphine oxide (DPPO) and hydroxycyclohexyl (Hy-CyH). Analysis of TR-EPR spectra gave the structures of adduct radicals. The addition rate constants of the radicals generated by the photolysis of initiators were measured by electron spin echo detection method. It was found that the addition reaction rate constants of 2Hy-Pr, DPPO and Hy-CyH radicals to MA show exceptionally smaller values than those estimated by the theoretical reaction model based on enthalpy and polar effects.

About the authors

Hirona Takahashi

Department of Chemistry, Faculty of Science, Okayama University of Science; Department of Chemistry, Graduate School of Science, Tokyo Institute of Technology

Author for correspondence.
Email: takahashi@chem.ous.ac.jp
ORCID iD: 0000-0003-2375-7084
Japan, 1-1 Ridaicho, Kita-ku, Okayama, 700-0005; 2-12-1 H-89, Ohokayama, Meguro-ku, Tokyo, 152-8551

Kenta Hagiwara

Department of Chemistry, Graduate School of Science, Tokyo Institute of Technology

Email: akawai@kanagawa-u.ac.jp
Japan, 2-12-1 H-89, Ohokayama, Meguro-ku, Tokyo, 152-8551

Akio Kawai

Department of Chemistry, Graduate School of Science, Tokyo Institute of Technology; Department of Chemistry, Faculty of Science, Kanagawa University

Author for correspondence.
Email: akawai@kanagawa-u.ac.jp
Japan, 2-12-1 H-89, Ohokayama, Meguro-ku, Tokyo, 152-8551; 2946 Tsuchiya, Hiratsuka-shi, Kanagawa, 259-1293


Copyright (c) 2018 Springer-Verlag GmbH Austria, part of Springer Nature

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