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Synthesis and Metathesis Polymerization of New Monomer 7-Trimethylsilyltricyclo[4.2.2.02,5]deca-3,9-diene

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Abstract

The reaction of 1,3,5,7-cyclooctatetraene with silicon-substituted ethylenes has been studied for the first time. It is shown that vinyltrimethylsilane is inactive in the reaction, and vinyltrichlorosilane forms 7-trichlorosilyltricyclo[4.2.2.02,5]deca-3,9-diene in up to 12% yield. A new silicon-substituted monomer 7‑trimethylsilyltricyclo[4.2.2.02,5]deca-3,9-diene containing 92% of the endo-isomer has been synthesized by methylation of the chloroadduct. The metathesis polymerization of the final monomer mediated by the Grubbs Ru catalysts of the first and second generations is studied. A new poly(7-trimethylsilyltricyclo[4.2.2.02,5]deca-3,9-diene) containing a bulky bicyclic fragment and predominantly trans-double bonds in the main chain (up to 94%) is obtained in 90–96% yields. The polymer is characterized by the highest glass transition point (187°C) in the series of monotrimethylsilyl-substituted polynorbornenes. The double bonds present in the monomer unit open up prospects for further modification.

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ACKNOWLEDGMENTS

The structure of the compounds obtained was studied using equipment from the Center for Collective Use Analytical Center of Problems for Advanced Refining of Oil and Petrochemistry, Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, and Center of Investigation of Molecule Structure, Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences.

We are grateful to R.S. Borisov, Ya.I. Derikov, and G.A. Shandryuk (Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences) for assistance in analysis of polymers and A.S. Peregudov (Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences) for 13C NMR and 29Si NMR spectrum registration and two-dimensional NMR spectra.

Funding

The reported study was funded by RFBR according to the research project no. 20-33-90158.

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Authors and Affiliations

  1. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 119991, Moscow, Russia

    V. A. Zhigarev, M. L. Gringolts, M. P. Filatova & E. Sh. Finkelshtein

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  1. V. A. Zhigarev
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  2. M. L. Gringolts
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  3. M. P. Filatova
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  4. E. Sh. Finkelshtein
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Correspondence to V. A. Zhigarev.

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Translated by K. Aleksanyan

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Zhigarev, V.A., Gringolts, M.L., Filatova, M.P. et al. Synthesis and Metathesis Polymerization of New Monomer 7-Trimethylsilyltricyclo[4.2.2.02,5]deca-3,9-diene. Polym. Sci. Ser. B 63, 470–479 (2021). https://doi.org/10.1134/S1560090421050195

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