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Cationic polymerization of butadiene with isomerization of the initiator structure

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Abstract

Cationic polymerization of butadiene using AlEt2Cl–isobutyl chloride initiating system was studied for the first time. It was found using NMR spectroscopy that head units of the synthesized polybutadiene macromolecules are tert-butyl groups connected with the 1,4-trans units of the polybutadiene. It has been established that tert-butyl units are formed as a result of isomerization of the isobutyl cation into tert-butyl cation, which is the true initiator of the polymerization process of butadiene. The resulting polybutadiene is a fully soluble solid thermoplastic polymer characterized by reduced unsaturation, high glass transition temperature and high softening point.

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Authors and Affiliations

  1. Institute of Ecology of Volga River Basin, Russian Academy of Sciences, Samara Federal Research Scientific Center, Russian Academy of Sciences, 10 ul. Komzina, 445003, Togliatti, Russian Federation

    V. A. Rozentsvet, D. M. Ulyanova & N. A. Sablina

  2. Department of Chemistry, St. Petersburg State University, 7–9 Universitetskaya nab., 199034, St. Petersburg, Russian Federation

    P. M. Tolstoy

  3. State Research Institute of Chemistry and Technology of Organoelement Compounds, 38 shosse Entuziastov, 111123, Moscow, Russian Federation

    M. G. Kuznetsova

Authors
  1. V. A. Rozentsvet
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  2. D. M. Ulyanova
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  3. N. A. Sablina
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  4. P. M. Tolstoy
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  5. M. G. Kuznetsova
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Corresponding authors

Correspondence to V. A. Rozentsvet, P. M. Tolstoy or M. G. Kuznetsova.

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The authors declare no competing interests.

Additional information

The authors are grateful to T. A. Popova, leading chemical engineer of the Scientific and Technical Center of Tolyattikauchuk LLC, for carrying out the GPC analysis of isobutyl chloride.

The work was carried out within the framework of the state assignment No 1021060107217-0-1.6.19 and State Task No AAAA-A19-119091190094.

No human or animal subjects were used in this study.

Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, Vol. 72, No. 9, pp. 2180–2190, September, 2023.

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Rozentsvet, V.A., Ulyanova, D.M., Sablina, N.A. et al. Cationic polymerization of butadiene with isomerization of the initiator structure. Russ Chem Bull 72, 2180–2190 (2023). https://doi.org/10.1007/s11172-023-4014-8

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  • DOI: https://doi.org/10.1007/s11172-023-4014-8

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