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Polymer Science, Series C

, Volume 61, Issue 1, pp 76–85 | Cite as

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

  • S. M. MatsonEmail author
  • A. A. Kossov
  • V. P. Makrushin
  • I. S. Levin
  • N. A. Zhilyaeva
  • E. G. Litvinova
  • V. S. Khotimskiy
Article
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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.

Notes

FUNDING

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

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Copyright information

© Pleiades Publishing, Ltd. 2019

Authors and Affiliations

  • S. M. Matson
    • 1
    Email author
  • A. A. Kossov
    • 1
  • V. P. Makrushin
    • 1
  • I. S. Levin
    • 1
  • N. A. Zhilyaeva
    • 1
  • E. G. Litvinova
    • 1
  • V. S. Khotimskiy
    • 1
  1. 1.A.V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of SciencesMoscowRussia

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