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Autopolymerization of 2-bromo-3-methoxythiophene, analysis of reaction products and estimation of polymer structure

Polymer Journal volume 53, pages 429–438 (2021)Cite this article

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Abstract

The study concerning the physical and chemical properties of thiophene derivatives has received much attention because they are incorporated in natural products, medicines, functional materials, and photoresponsive dyes. The autopolymerization reaction is one of the synthesis methods of polythiophenes using halogenated thiophene derivatives. In this paper, we analyzed the products and reaction mechanism of the polymerization reaction of 2-bromo-3-methoxythiophene by investigating the gas, liquid, and solid states using UV-Vis, electron spin resonance (ESR), gas chromatography/mass spectrometry (GC/MS), elemental analysis, NMR, and FT-IR spectroscopy. Consequently, we found a side reaction of the autopolymerization reaction and estimated that the polymerization reaction mechanism occurred in multiple steps. When we employed the brominated alkoxythiophene as a monomer, hydrogen bromide gas was generated to act not only as a catalyst of the polymerization reaction but also as an acid to cleave the alkoxyl group. The results provide useful information for the design of monomers via autopolymerization.

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Acknowledgements

The authors are grateful to Dr T. Kamitanaka for the GC/MS spectroscopy measurement and Mr I. Kobayashi and Prof Dr T. Nakaoki for the 13C NMR measurement in the solid state. This work was supported by the CREST program (JPMJCR17N2) of the Japan Science and Technology Agency, and the Ministry of Education, Culture, Sports, Science and Technology, Japan (MEXT) as a Supported Program for the Strategic Research Foundation at Private Universities, JSPS KAKENHI Grant Number JP18J20078 in the JSPS Research Fellow.

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Authors and Affiliations

  1. Department of Materials Chemistry, Faculty of Science and Technology, Ryukoku University, Seta, Otsu, Shiga, 520-2194, Japan

    Ryo Nishimura, Yohei Hattori, Masako Akazawa, Jun-ichiro Kitai & Kingo Uchida

  2. RIKEN Cluster for Science, Technology and Innovation Hub, Nakamura Laboratory, 2-1 Hirosawa, Wako, Saitama, 351-0198, Japan

    Shinichiro Okude, Yuki Sakamoto & Shinichiro Nakamura

  3. Department of Chemistry, Graduate School of Science, Tokyo Metropolitan University, Room 568, 8th Building, 1-1 Minami-Osawa, Hachioji-shi, Tokyo, 192-0397, Japan

    Seiji Yamazoe

  4. School of Pharmacy, Tokyo University of Pharmacy and Life Sciences, 1432-1 Horinouchi, Hachioji, Tokyo, 192-0392, Japan

    Satoshi Yokojima

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  1. Ryo Nishimura
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Nishimura, R., Hattori, Y., Akazawa, M. et al. Autopolymerization of 2-bromo-3-methoxythiophene, analysis of reaction products and estimation of polymer structure. Polym J 53, 429–438 (2021). https://doi.org/10.1038/s41428-020-00435-1

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