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Synthesis, Structure and Properties of Poly(1-trimethylsilyl-1-propyne) Obtained with NbBr5- and TaBr5-Based Catalytic Systems

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Abstract

In this work, the polymerization of 1-trimethylsilyl-1-propyne [TMSP] using catalytic systems based on pentabromide Nb(V) and Ta(V) with organometallic cocatalysts Ph3Bi, Ph4Sn, Bu4Sn, Ph3SiH, and Et3SiH was investigated. The use of NbBr5-based catalytic systems has strongly marked cis-stereospecificity and gives highly cis-enriched poly(1-trimethylsilyl-1-propyne) [PTMSP] (content of cis-units above 70%), whereas the use of TaBr5-based catalytic systems leads to the formation of PTMSP with mixed cis-/trans-composition (content of cis-units from 50 to 65%).With increasing cis-content, solvent resistance of PTMSP increases significantly. PTMSP with a content of cis-units above 70% obtained on NbBr5-containing systems in cyclohexane acquires resistance to aliphatic and aromatic hydrocarbons, and cis-regular PTMSP obtained on NbBr5-based systems in toluene is totally insoluble in any of the organic solvents. The results of wide-angle X-ray diffraction indicate an increase in the packing density of the polymer during the transition from a mixed configuration to a cis-regular one. Durable PTMSP film membranes exhibit ultra-high permeability coefficients for individual gases (e.g., \({{P}_{{{{{\text{O}}}_{{\text{2}}}}}}}\) = 8500–11000 barrer, \({{\alpha }_{{{{{\text{O}}}_{{\text{2}}}}{\text{/}}{{{\text{N}}}_{{\text{2}}}}}}}\) = 1.5–1.9). According to the low-temperature Ar sorption, PTMSP synthesized with NbBr5- and TaBr5-based catalytic systems has high BET surface areas in the range of 870–1050 m2/g, high intrinsic microporosity, and higher gas permeability coefficients of PTMSP correlate with BET surface area growth.

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Funding

This work was supported by the Russian Science Foundation (project no. 18-13-00334).

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Authors and Affiliations

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

    S. M. Matson, A. A. Kossov, V. P. Makrushin, I. S. Levin, N. A. Zhilyaeva, E. G. Litvinova & V. S. Khotimskiy

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  1. S. M. Matson
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  2. A. A. Kossov
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  3. V. P. Makrushin
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  4. I. S. Levin
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  6. E. G. Litvinova
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  7. V. S. Khotimskiy
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Correspondence to S. M. Matson.

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Matson, S.M., Kossov, A.A., Makrushin, V.P. et al. Synthesis, Structure and Properties of Poly(1-trimethylsilyl-1-propyne) Obtained with NbBr5- and TaBr5-Based Catalytic Systems. Polym. Sci. Ser. C 61, 76–85 (2019). https://doi.org/10.1134/S1811238219010120

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