Self-Organization of Polyurethane Ionomers Based on Organophosphorus-Branched Polyols.

Based on organophosphorus branched polyols (AEPAs) synthesized using triethanolamine (TEOA), ortho-phosphoric acid (OPA), and polyoxyethylene glycol with MW = 400 (PEG), vapor-permeable polyurethane ionomers (AEPA-PEG-PUs) were obtained. During the synthesis of AEPAs, the reaction of the OPA etherification with polyoxyethylene glycol was studied in a wide temperature range and at different molar ratios of the starting components. It turned out that OPA simultaneously undergoes a catalytically activated etherification reaction with triethanolamine and PEG. After TEOA is fully involved in the etherification reaction, excess OPA does not react with the terminal hydroxyl groups of AEPA-PEG or the remaining amount of PEG. The ortho-phosphoric acid remaining in an unreacted state is involved in associative interactions with the phosphate ions of the AEPA. Increasing the synthesis temperature from 40 °C to 110 °C leads to an increase in OPA conversion. However, for the AEPA-PEG-PU based on AEPA-PEG obtained at 100 °C and 110 °C, ortho-phosphoric acid no longer enters into associative interactions with the phosphate ions of the AEPA. Due to the hydrophilicity of polyoxyethylene glycol, the presence of phosphate ions in the polyurethane structure, and their associative binding with the unreacted ortho-phosphoric acid, the diffusion of water molecules in polyurethanes is enhanced, and high values of vapor permeability and tensile strength were achieved.

Microporous Block Copolymers Modified with Cu(II)-Coordinated Polyethylene Oxide-Substituted Silicas for Analytical Sensors.

The influence of stable-to-self-condensation Cu(II)-coordinated polyoxyethylene-substituted silicas (ASiP-Cu-0.5) on the synthesis of microporous block copolymers (OBCs) whose structural feature is the existence of coplanar polyisocyanate blocks of acetal nature (O-polyisocyanates) and a flexible-chain component of amphiphilic nature was studied. The use of ASiP-Cu-0.5 increased the yield of O-polyisocyanate blocks and the microphase separation of OBC. The resulting OBCs turned out to be effective sorbents for the analytical reagents PAN and PHENAZO, which, being in the micropore cavity, interacted with copper(II) and magnesium ions. To reduce the thickness of the selective OBC layer ten-fold and simplify the technology for obtaining analytical test systems, polyethylene terephthalate was used as a substrate for applying OBC. It was found that the increased sensitivity of the resulting test systems was due to the fact that in thin reaction layers, the efficiency of the formation of O-polyisocyanate blocks noticeably increased.

Silicas with Polyoxyethylene Branches for Modification of Membranes Based on Microporous Block Copolymers.

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.

Pervaporation Polyurethane Membranes Based on Hyperbranched Organoboron Polyols.

On the basis of aminoethers of boric acid (AEBA), polyurethane vapor-permeable and pervaporative membranes were obtained. AEBAs, the structure of which is modified by bulk adducts (EM) of diphenylol propane diglycidyl ether and ethanolamine, were studied. It turned out that AEBA exists in the form of clusters, and the use of EM as a result of partial destruction of associative interactions leads to a significant decrease in the size of AEBA-EM particles and their viscosity compared to unmodified AEBA. The introduction of EM into the composition of AEBA leads to a threefold increase in the vapor permeability of polyurethanes obtained on their basis. The observed effect is explained by the fact that a decrease in the size of clusters leads to loosening of their dense packing. Areas of clustering due to associative interactions of hydroxyl groups, together with the hydrophilic nature of polyoxyethylene glycol, create channels through which water molecules can penetrate. The increase in vapor permeability is accompanied by a multiple increase in the permeability coefficients in the pervaporative dehydration of isopropanol.

Catalytic Etherification of ortho-Phosphoric Acid for the Synthesis of Polyurethane Ionomer Films.

The etherification reaction of ortho-phosphoric acid (OPA) with polyoxypropylene glycol in the presence of tertiary amines was studied. The reaction conditions promoting the catalytic activity of triethanolamine (TEOA) and triethylamine (TEA) in the low-temperature etherification of OPA were established. The catalytic activity of TEOA and TEA in the etherification reaction of phosphoric acid is explained by the hydrophobic-hydrophilic interactions of TEA with PPG, leading, as a result of collective interactions, to a specific orientation of polyoxypropylene chains around the tertiary amine. When using triethylamine, complete etherification of OPA occurs, accompanied by the formation of branched OPA ethers terminated by hydroxyl groups and even the formation of polyphosphate structures. When triethanolamine is used as a catalyst, incomplete etherification of OPA with polyoxypropylene glycol occurs and as a result, part of the phosphate anions remain unreacted in the composition of the resulting aminoethers of ortho-phosphoric acid (AEPA). In this case, the hydroxyl groups of triethanolamine are completely involved in the OPA etherification reaction, but the catalytic activity of the tertiary amine weakens due to a decrease in its availability in the branched structure of AEPA. The kinetics of the etherification reaction of OPA by polyoxypropylene glycol catalyzed by TEOA and TEA were studied. It was shown that triethanolamine occupies a central position in the AEPA structure. The physico-mechanical and thermomechanical properties of polyurethane ionomer films obtained on the basis of AEPA synthesized in a wide temperature range were studied.

Optically Transparent Polydimethylsiloxane-Ethylene Oxide-Propylene Oxide Multiblock Copolymers Crosslinked with Isocyanurates as Organic Compound Sorbents.

New crosslinked (polydimethylsiloxane-ethylene-propylene oxide)-polyisocyanurate multiblock copolymers (MBCs) were synthesized, and their supramolecular structure and sorption characteristics were studied. It was found that the interaction of PPEG and D4 leads to polyaddition of D4 initiated by potassium-alcoholate groups. The use of the amphiphilic silica derivatives associated in an oligomeric medium (ASiPs) leads to structuring of the MBC due to the transetherification reaction of the terminal silanol groups of the MBC with ASiPs. It was established that the supramolecular structure of an MBC is built according to the "core-shell" structure. The obtained polymers were tested as sorbents for the development of new methods for the concentration and determination of inorganic compounds. The efficiency of sorption of reagents increased with an increase in the "thickness" of the polydimethylsiloxane component of the "shell" and with a decrease in the size of the polyisocyanurate "core". The use of the obtained polymers as adsorbents of organic reagents is promising for increasing the efficiency of field methods of chemical testing and inorganic analysis, including the determination of the elemental composition and the detection of traces of contamination.

Amphiphilic Poly(dimethylsiloxane-ethylene-propylene oxide)-polyisocyanurate Cross-Linked Block Copolymers in a Membrane Gas Separation.

Amphiphilic poly(dimethylsiloxane-ethylene-propylene oxide)-polyisocyanurate cross-linked block copolymers based on triblock copolymers of propylene and ethylene oxides with terminal potassium-alcoholate groups (PPEG), octamethylcyclotetrasiloxane (D4) and 2,4-toluene diisocyanate (TDI) were synthesized and investigated. In the first stage of the polymerization process, a multiblock copolymer (MBC) was previously synthesized by polyaddition of D4 to PPEG. The usage of the amphiphilic branched silica derivatives associated with oligomeric medium (ASiP) leads to the structuring of block copolymers via the transetherification reaction of the terminal silanol groups of MBC with ASiP. The molar ratio of PPEG, D4, and TDI, where the polymer chains are packed in the "core-shell" supramolecular structure with microphase separation of the polyoxyethylene, polyoxypropylene and polydimethylsiloxane segments as the shell, was established. Polyisocyanurates build the "core" of the described macromolecular structure. The obtained polymers were studied as membrane materials for the separation of gas mixtures CO2/CH4 and CO2/N2. It was found that obtained polymers are promising as highly selective and productive membrane materials for the separation of gas mixtures containing CO2, CH4 and N2.

Synthesis and Characterization of Novel Nanoporous Gl-POSS-Branched Polymeric Gas Separation Membranes.

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.

Synthesis and Study of Gas Transport Properties of Polymers Based on Macroinitiators and 2,4-Toluene Diisocyanate.

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 СН4. 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.