The scheme of ASiP formation.

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.

Organosubstituted silica derivatives were synthesized and investigated as modifiers of block copolymers based on macroinitiator and 2,4-toluene diisocyanate. A peculiarity of the modified block copolymers is the existence in their structure of coplanar rigid polyisocyanate blocks of acetal nature (O-polyisocyanates). Organosubstituted silica derivatives have a non-additive effect on high-temperature relaxation and α-transitions of modified polymers and exhibit the ability to influence the supramolecular structure of block copolymers. The use of the developed modifiers leads to a change in the gas transport properties of block copolymers. The increase of the permeability coefficients is due to the increase of the diffusion coefficients. At the same time, the gas solubility coefficients do not change. An increase in the ideal selectivity for a number of gas pairs is observed. An increase in the selectivity for the CO2/N2 gas pair (from 25 to 39) by 1.5 times demonstrates the promising use of this material for flue gases separation.

We have synthesized cubic and linear polysiloxanes containing polyoxyethylene branches (ASiP-Cu) using tetraethoxysilane, polyoxyethylene glycol, and copper chloride as precursors; the products are stable to self-condensation. The effect of copper chloride content on the chemical structure of ASiP-Cu has been established. A special study was aimed at defining the modifying effect of ASiP-Cu on the sorption characteristics of membranes based on microporous, optically transparent block copolymers (OBCs). These OBCs were produced using 2,4-toluene diisocyanate and block copolymers of ethylene and propylene oxides. The study demonstrated significantly increased sorption capacity of the modified polymers. On the basis of the modified microporous block copolymers and 1-(2-pyridylazo)-2-naphthol (PAN) analytical reagent, an analytical test system has been developed. Additionally, the modified OBCs have the benefit of high diffusion permeability for molecules of organic dyes and metal ions. It has been shown that the volume of voids and structural features of their internal cavities contribute to the complex formation reaction involving PAN and copper chloride.