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The effect of the stereoregularity of poly(1-trimethylsilyl-1-propyne) [PTMSP] (cis-content from 50 to 90%) on physical aging was investigated by measurement of the gas permeability. Films from pure PTMSP as well as those with the addition of the antioxidant Irganox 1076 were exposed to the air. The permeability of pure PTMSP films increases with an increase in cis-stereoregularity and correlates with an increase in interchain distances (according to X-ray analysis). For pure PTMSP films, the most significant aging (up to 50% of permeability drop) was observed for polymers with mixed microstructure, and the slowest aging (10–30% of permeability drop) was observed for polymers with cis-regular structure. For PTMSP films with added Irganox 1076, some decrease in permeability with time is also observed. The addition of Irganox 1076 to PTMSP in mixed as well as cis-enriched configurations visibly slows down aging. In the case of cis-regular PTMSP with a slow aging rate, the introduction of an antioxidant does not provide any advantages. The high stability of cis-regular PTMSP demonstrates the possibility of obtaining more stable membrane materials with the highest equilibrium state of the polymer selective layer prepared by casting solution.

Poly(1-trimethylsilyl-1-propyne) modified with quaternary ammonium salts is synthesized. The introduction of salts into the polymer structure is carried out using a two-step method consisting in the bromination of the starting polymer followed by the addition of tertiary alkylamines—trimethylamine and triethylamine. The presence of ammonium salts is confirmed by the data of organometallic analysis and IR spectroscopy. X-ray diffraction analysis is used to study the supramolecular structure of the materials obtained. The TGA data indicate their high thermal and thermo-oxidative stability. The permeability, solubility, and diffusion coefficients of the poly(1-trimethylsilyl-1-propyne) samples containing trimethylamine and triethylamine salts for individual CO2, N2, and CH4 gases are determined. An increased ideal selectivity for the separation of gas pairs CO2/N2 and CO2/CH4 in modified poly(1-trimethylsilyl-1-propyne) is achieved owing to the increased selectivity of the dissolution of CO2 in quaternary ammonium salts.

This work is devoted to the chemical modification of the polymers of 1,2-disubstituted acetylenes for the creation of gas-separation membranes possessing enhanced stability to aliphatic hydrocarbons and CO2 selectivity. The feasibility of obtaining polyacetylenes containing chlorine atoms in the side substituents of poly(1-trimethylsilyl-1-propyne) (PTMSP) and poly(4-methyl-2-pentyne) (PMP) by radical chlorination with N-chlorosuccinimide has been shown. The reaction has been carried out under mild conditions to minimize the possibility of polymer degradation and other side reactions. The obtained polymers exhibit good mechanical and film-forming properties as well as high thermal stability. Chlorinated PTMSP possesses enhanced stability to alicyclic and aliphatic C5–C12 hydrocarbons. It has been shown that in the case of introduction of chlorine into the structure of PTMSP and PMP, the CO2/N2 and CO2/CH4 selectivities increase, with the high level of permeability being retained.

The modification of highly permeable films of brominated 1,2-disubstituted polyacetylene, poly(4-methyl-2-penthyne), via incorporation of in situ formed butylimidazolium bromide is reported for the first time. Principal possibility and efficiency of supercritical CO2 and CHF3 use as reaction media for the corresponding process, namely for quaternization of butylimidazole by brominated polymer are revealed. As a result, we prepared new membrane materials possessing promising properties such as stability toward organic solvents, good mechanical properties and significantly improved CO2-selectivity while maintaining gas permeability at high values. Comparative analysis of the results allowed us to determine content and conditions for the incorporation of butylimidazolium groups optimal for most efficient separation of CO2 from industrial gas mixtures. These results are of interest for the designing of new CO2 selective membranes.

The modification of highly permeable films of brominated 1,2-disubstituted polyacetylene, poly(4-methyl-2-penthyne), via incorporation of in situ formed butylimidazolium bromide is reported for the first time. Principal possibility and efficiency of supercritical CO2 and CHF3 use as reaction media for the corresponding process, namely for quaternization of butylimidazole by brominated polymer are revealed. As a result, we prepared new membrane materials possessing promising properties such as stability toward organic solvents, good mechanical properties and significantly improved CO2-selectivity while maintaining gas permeability at high values. Comparative analysis of the results allowed us to determine content and conditions for the incorporation of butylimidazolium groups optimal for most efficient separation of CO2 from industrial gas mixtures. These results are of interest for the designing of new CO2 selective membranes.

The work is devoted to the chemical modification of a polymer that is promising for the creation of gas separation membranes, aimed at increasing the selectivity with respect to CO2. The introduction of ionic liquids into the structure of poly(1-trimethylsilyl-1-propyne) is realized by a two-step process: bromination of the initial polymer with N-bromosuccinimide and subsequent addition of tertiary amine (N-butylimidazole) to it. Depending on the process conditions, the method allows polymers with different contents of the ionic liquid to be obtained. The obtained polymers show good film-forming properties and thermal stability. Depending on the content of the ionic liquid in the polymer matrix, the resistance to aliphatic alicyclic to the majority of halogenated, as well as aromatic hydrocarbons, increases. With an increase of the ionic liquid content in the polymer, the ideal selectivities of CO2/N2 and CO2/CH4 gas pairs increases while maintaining a high level of permeability.