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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.

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Acknowledgements

The authors express their thanks to Mr. Yasuo Nakajima (Furukawa Electric Corporation) for his kind advice and suggestions. This study was supported in part by Cross-ministerial Strategic Innovation Promotion Program, Structural Materials for Innovation, No. (a)A09 from Cabinet Office, Government of Japan, and by Grants-in-Aid for Scientific Research No. 16K13926 from the Ministry of Education, Culture, Sports, Science and Technology, Japan.

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Authors and Affiliations

  1. Department of Chemistry, Faculty of Science, Okayama University of Science, 1-1 Ridaicho, Kita-ku, Okayama, 700-0005, Japan

    Hirona Takahashi

  2. Department of Chemistry, Graduate School of Science, Tokyo Institute of Technology, 2-12-1 H-89, Ohokayama, Meguro-ku, Tokyo, 152-8551, Japan

    Hirona Takahashi, Kenta Hagiwara & Akio Kawai

  3. Department of Chemistry, Faculty of Science, Kanagawa University, 2946 Tsuchiya, Hiratsuka-shi, Kanagawa, 259-1293, Japan

    Akio Kawai

Authors
  1. Hirona Takahashi
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  2. Kenta Hagiwara
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  3. Akio Kawai
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Corresponding authors

Correspondence to Hirona Takahashi or Akio Kawai.

Electronic supplementary material

Literature values of additional reaction rate constants used in Fig. 6 were summarized in Tables S1 and S2. These tables may be found in the online version of this article at the publisher's web-site.

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Supplementary material 1 (PDF 284 kb)

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Takahashi, H., Hagiwara, K. & Kawai, A. Measurements for Addition Reaction Rate Constants of Organic Free Radicals to Maleic Anhydride by Means of Pulsed EPR Spectroscopy with Laser Excitation. Appl Magn Reson 49, 813–824 (2018). https://doi.org/10.1007/s00723-018-1015-0

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  • DOI: https://doi.org/10.1007/s00723-018-1015-0

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