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.

Fluorinated copolymers with different compositions and geometric structures have been prepared from 1-trimethylsilyl-1-propyne and its fluorinated containing analogue 1-(3,3,3-trifluoropropyldimethylsilyl)-1-propyne and then studied. The copolymers combine resistance to different hydrocarbons with high permeability coefficients and high selectivity of n -butane separation from its mixture with the noncondensable hydrocarbon methane. High microporosity of the copolymers is confirmed by the results of the determination of the pore volume and pore surface area using low-temperature sorption of nitrogen and the investigation of the film surface by atomic force microscopy (AFM). It has been found that microporosity, which determines the transport properties of the copolymers, depends on both their comonomer composition and the microstructure formed at the stage of polymer synthesis catalyzed by a certain catalyst system. In particular, the copolymers produced in the presence of a TaCl 5 –Ph 3 Bi catalyst have a greater pore size and a larger pore surface area relative to copolymers with a similar composition formed in the presence of the NbCl 5 –Ph 3 SiH system. The high values of gas transport parameters of the obtained copolymers and their selectivity for recovery of condensable hydrocarbons from vapor–gas mixtures together with resistance to higher hydrocarbons make these copolymers promising membrane materials, e.g., for use in natural gas conditioning processes or separation of C 3+ hydrocarbons from associated petroleum gas.

The phase equilibrium and rheological properties of poly(1-trimethylsilyl-1-propyne) solutions obtained with tantalum catalysts are studied. For three polymers with different molecular masses, phase diagrams are determined in a number of solvents. From these diagrams, the Hansen solubility parameters of poly(1-trimethylsilyl-1-propyne) are calculated by the method proposed in this work. Dilute solutions of poly(1-trimethylsilyl-1-propyne) behave as Newtonian liquids, whereas the viscosity of viscoelastic concentrated systems decreases as the shear rate grows. The molecular and rheological characteristics of studied poly(1-trimethylsilyl-1-propyne) samples are compared with the samples prepared with NbCl5 catalysts. Poly(1-trimethylsilyl-1-propyne) obtained with a catalytic system involving tantalum pentachloride is characterized by high intrinsic viscosity and solution viscosity compared to poly(1-trimethylsilyl-1-propyne) prepared with niobium catalyst. The difference in properties is due to the dissimilar ratios of cis and trans units in the samples.

Using a NbCl5-based catalyst system, random copolymers of 1-(3,3,3-trifluoropropyldimethylsilyl)-1-propyne and 1-trimethylsilyl-1-propyne are synthesized in a wide range of comonomer contents. The dependences of gas-transport behavior on the composition and supramolecular organization of the copolymer are studied. Composition regions and conditions of preparing copolymers combining high permeability coefficients with resistance against nonpolar organic solvents are ascertained. The copolymers demonstrate a high selectivity in the separation of butane from a methane–butane mixture.

Разработан метод синтеза привитого сополимера поливинилтриметилсилан-прив-полиэтиленгликоль взаимодействием бромированного полимера с метиловым эфиром низкомолекулярного полиэтиленгликоля. По этой методике синтезированы образцы привитого сополимера с содержанием ПЭГ в составе сополимера до 79 мас. %. Исследованы свойства привитых сополимеров и смесей на их основе со специально синтезированным низкомолекулярным производным ПЭГ, имеющим концевую триметилсилильную группу. Создание физических смесей проведено с целью увеличения содержания этиленоксидных групп при сохранении пленкообразующих свойств в разрабатываемых композиционных материалах. С использованием структурных методов исследования установлено, что привитые сополимеры представляют собой аморфные однофазные системы, а смеси на их основе – это двухфазные дисперсные системы, в которых одна фаза обогащена поливинилтриметилсиланом, а другая ПЭГ. Изучение газо-транспортных свойств полученных образцов показало, что введение ПЭГ приводит к образованию материалов на основе ПВТМС селективных в пользу СО2 в смеси с Н2, в отличие от неселективного исходного.