Microporous polymers based on anionic macroinitiator and toluene 2,4-diisocyanate were used as a support for 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF₆]) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([emim][Tf₂N]) immobilization. The polymeric support was modified by using silica particles associated in oligomeric media, and the influence of the modifier used on the polymeric structure was studied. The supported ionic liquid membranes (SILMs) were tested for He, N₂, NH₃, H₂S, and CO₂ gas separation and ideal selectivities were calculated. The high values of ideal selectivity for ammonia-based systems with permanent gases were observed on polymer matrixes immobilized with [bmim][PF₆] and [emim][Tf₂N]. The modification of SILMs by nanosize silica particles leads to an increase of NH₃ separation relatively to CO₂ or H₂S.

It is shown that the water vapor permeability of polyurethanes obtained on the basis of sterically hindered aminoethers of boric acid is due to the peculiarities of the chemical structure of AEBA.

Optically transparent mesoporous polymers have been synthesized through the anionic polymerization of 2,4-toluene diisocyanate initiated by anionic macroinitiators. The influence of the molecular weight of the macroinitiators on the formation behavior of amphiphilic block copolymers has been considered along with the role of substituted urea in the stabilization of the O-polyisocyanate blocks. The features of the supramolecular organization of mesoporous polymers have been studied. It has been shown that an increase in the proportion of O-polyisocyanate blocks in the coplanar trans configuration in the polymers is accompanied by a significant decrease in their volume electrical resistivity values. The preferential formation of amphiphilic block copolymers is reflected in the formation of highly ordered domains and perfection of the supramolecular cellular geometry of mesoporous polymers. It has been found that the mesoporous polymer structuring enables the immobilization of organic chromophores. It has been shown that luminophores in the cavities of mesopores generate laser radiation and exhibit high resistance to high-power laser radiation.

Novel nanoporous Gl-POSS-branched polymers based on the macroinitiator of anionic nature, 2,4-toluene diisocyanate, and octaglycidyl polyhedral oligomeric silsesquioxane (Gl-POSS) were obtained as gas separation membranes. The synthesis of polymers was carried out using various loads of Gl-POSS. It was found that the main reaction proceeding with 2,4-toluene diisocyanate is the polyaddition, accompanied by the isocyanate groups opening of the carbonyl part. This unusual opening of isocyanate groups leads to the formation of coplanar acetal nature polyisocyanates (O-polyisocyanate). The terminal O-polyisocyanate links initiate the subsequent opening of the epoxide rings in Gl-POSS. As a result, Gl-POSS serves as a hard and bulky branching agent and creates the specific framing supramolecular structure, which leads to the formation of nanopores in the polymer, where the flexible polyether components are located inside the cavities. Thermal, mechanical, physical, and chemical properties of the obtained polymers were studied at various Gl-POSS contents in the polymer matrix. It was found that these polymers show high selectivity of gas transport properties for pure ammonia relative to nitrogen and hydrogen at ambient temperature. Measurements showed that the gas permeability coefficients and the values of ideal selectivity were in a non-additive dependence to the Gl-POSS content.

Self-organization and arrangement of supramolecular structures from block-copolymers are some of the ways used for the development of nanoporous and mesoporous polymers. Herein, reactive olygomers can play the key role in the design of supramolecular arranging of polymers. Optically transparent mesoporuos block-copolymers with adjusted free volume are obtained by the polyaddition of 2,4-toluene diisocyanate (TDI) to anionic macroinitiators. The mechanism of polyaddition of TDI to an anionic macroinitiator in various chemical solvents was studied by infrared spectroscopy. It is established that the reaction of forming polyisocyanate blocks of acetal nature (O-polyisocyanate) and stabilization of end O-polyisocyanate chains are based on the formation of voids in polymer. The formation of voids is conditioned by the geometry of self-organization of block-copolymers containing end potassium-O-polyisocyanates stabilized by crown ether fragments. The formation of urea with the participation of isocyanate groups of ortho-location of TDI is one of the main factors of the stabilization of O-polyisocyanate blocks. The investigation of the polymer sorption properties was carried out by electron spectroscopy. As an adsorbed dye Rhodamine 6G was used. The ability of Rhodamine 6G to sorb depended on the content of the O-polyisocyanate component in the polymer. Mesoporous polymers demonstrated high efficiency as an optically transparent matrix for laser-active media with high radiation stability. Rhodamine 6G in mesoporous polymers retains spectral luminescent properties and generates laser radiation during excitation by the second harmonic of Nd:YAG laser.

Nowadays, block copolymers hold great promise for the design of novel membranes to be applied for the membrane gas separation. In this regard, microporous block copolymers based on a macroinitiator with an anionic nature, such as potassium-substituted block copolymers of propylene oxide and ethylene oxide (PPEG) and 2,4-toluene diisocyanate (TDI), were obtained and investigated as effective gas separation membranes. The key element of the macromolecular structure that determines the supramolecular organization of the studied polymers is the coplanar blocks of polyisocyanates with an acetal nature (O-polyisocyanate). In the present research, the influence of the content of peripheral polyoxyethylene (POE) blocks in PPEG on the supramolecular structure processes and gas transport characteristics of the obtained polymers based on PPEG and TDI was investigated. According to the study of polymers if the POE block content is 15 wt %, the polyoxypropylene segments are located in the internal cavity of voids formed by O-polyisocyanate blocks. When the POE block content is 30 wt %, the flexible chain component forms its own microphase outside the segregation zone of the rigid O-polyisocyanate blocks. The permeability for polar molecules, such as ammonia or hydrogen sulfide, significantly exceeds the permeability values obtained for non-polar molecules He, N₂ and CH₄. A relatively high permeability is also observed for carbon dioxide. At the same time, the content of POE blocks has a small effect on the permeability for all studied gases. The diffusion coefficient increases with an increase in the POE block content in PPEG for all studied gases.