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Synthesis and Gas-Separation Properties of New Silacyclopentane-Containing Polynorbornenes

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Abstract

Previously, it was shown that the presence of bulky silicon-containing substituents in the monomer unit of metathesis polynorbornenes hinders the postmodification and, in particular, exhaustive gem-difluorocyclopropanation of main-chain double bonds. In order to reduce the double bonds shielding by substituents, a new polynorbornene with a dimethylsilacyclopentane fragment in the monomer unit, poly(4,4-dimethyltricyclo[5.2.1.02,6]-4-siladec-8-ene) (PNBCP), is synthesized, in which the silylmethyl group is moved further from the double bonds. In order to achieve this, the monomer 4,4-dimethyltricyclo[5.2.1.02,6]-4-siladec-8-ene (NBCP) is first obtained via the diene condensation of 1,3-cyclopentadiene and 1,1-dichlorosilacyclopent-3-ene with following methylation of Si-Cl bonds. NBCP is polymerized by the ring-opening metathesis scheme in the presence of the first-generation Grubbs catalyst, Cl2(PCy3)2Ru=CHPh. The new polymer PNBCP is obtained in a yield of 99–100% and characterized. The gem-difluorocyclopropanation of PNBCP with difluorocarbene, generated during the thermolysis of sodium chlorofluoroacetate, is studied; the conditions for exhaustive replacement of double bonds by gem-difluorocyclopropane are found. It is shown that PNBCP is more active in postmodification compared to poly(5-trimethylsilyl)norbornene but is less active than unsubstituted polynorbornene. It is demonstrated that the introduction of the silacyclopentane fragment into the monomer unit of the metathesis polynorbornene and its subsequent difluorocyclopropanation lead to increase in gas permeability and diffusion and cause a slight decrease in ideal separation selectivities. It is found that gem-difluorocyclopropanation increases the glass transition temperature of PNBCP by 60°C and makes its films stable when stored in air.

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ACKNOWLEDGMENTS

The structure of the obtained compounds was studied using the equipment of the Shared Research Center of the Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences and the Center for Molecular Studies of the Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences.

We are grateful to Dr. A.S. Peregudov for his help in determining the structure of the monomer and polymers, G.A. Shandryuk for DSC and TGA studies, and S.А. Korchagina for GPC analysis.

Funding

The study was performed under the State Program of the Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences.

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Authors and Affiliations

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

    V. A. Zhigarev, A. A. Morontsev, R. Yu. Nikiforov, M. L. Gringolts, N. A. Belov & E. Sh. Finkelshtein

  2. State Scientific Research Institute of Chemistry and Technology of Organoelement Compounds (GNIIChTEOS), 105118, Moscow, Russia

    N. G. Komalenkova & V. G. Lakhtin

Authors
  1. V. A. Zhigarev
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  2. A. A. Morontsev
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  3. R. Yu. Nikiforov
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  4. M. L. Gringolts
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  5. N. A. Belov
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  6. N. G. Komalenkova
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  7. V. G. Lakhtin
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  8. E. Sh. Finkelshtein
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Corresponding author

Correspondence to A. A. Morontsev.

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Translated by V. Avdeeva

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Zhigarev, V.A., Morontsev, A.A., Nikiforov, R.Y. et al. Synthesis and Gas-Separation Properties of New Silacyclopentane-Containing Polynorbornenes. Polym. Sci. Ser. C 61, 107–119 (2019). https://doi.org/10.1134/S1811238219010181

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  • DOI: https://doi.org/10.1134/S1811238219010181

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