Measurements for Addition Reaction Rate Constants of Organic Free Radicals to Maleic Anhydride by Means of Pulsed EPR Spectroscopy with Laser Excitation
- Authors: Takahashi H.1,2, Hagiwara K.2, Kawai A.2,3
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Affiliations:
- Department of Chemistry, Faculty of Science, Okayama University of Science
- Department of Chemistry, Graduate School of Science, Tokyo Institute of Technology
- Department of Chemistry, Faculty of Science, Kanagawa University
- Issue: Vol 49, No 8 (2018)
- Pages: 813-824
- Section: Original Paper
- URL: https://journals.rcsi.science/0937-9347/article/view/248100
- DOI: https://doi.org/10.1007/s00723-018-1015-0
- ID: 248100
Cite item
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