This article describes a new technique for the preparation of hollow fiber (HF) membrane samples using an automatic manipulator unit. The manipulator uses a syringe needle to form a HF of a given geometry. The needle in automatic mode is sequentially immersed, first into the polymer solution and then into the coagulation bath. The possibility of using a manipulator to obtain HF samples was studied on the known polysulfone (PSf)/N-methylpyrrolidone (NMP)/pore-forming additive system. A series of HF membrane samples were made within 29 h from twelve 1 mL PSf casting solutions. This was 15 times faster than obtaining samples of HF membranes at the multifunctional research laboratory facility. From the point of view of the consumption of the components of the casting solution, the use of the manipulator was 30 times more economical, and the consumption of water for precipitation and washing was 8000 times less. The developed method made it possible to study samples of HF by scanning electron microscopy (SEM), ultrafiltration, and evaluate its mechanical properties without spinning the membranes. Using the new technique, the optimal composition of the casting solution for the wet spinning of HF PSf membranes was selected during two weeks. Thus, the manipulator makes it possible to significantly reduce the time of the new membrane preparation, reduce the volume of used polymer, and thus makes it promising to study expensive or new membrane materials.

In this work, PPSUs with different molecular weights were synthesized for the development of highly permeable ultrafiltration hollow fiber membranes for the first time. The M_W of the synthesized polymers was controlled by varying the monomers molar ratio within 1:1–1.15 under the same synthesis conditions. Based on the study of the rheological properties of polymer solutions, a high molecular weight PPSU (M_W = 102,000 g/mol) was chosen for the formation of hollow fiber membranes. The addition of PEG400 to the spinning solution led to an increase in viscosity, which makes it possible to work in the region of lower PPSU concentrations (18–20 wt. %) and to form membranes with a less dense porous structure. With the addition of PEG400 to the spinning solution, the membrane permeance increased sharply by more than two orders of magnitude (from 0.2 to 96 L/m²·h bar). At the same time, the membranes had high rejection coefficients (99.9%) of Blue Dextran model filtered substance (M_W = 69,000 g/mol).

For the first time, polysulfones (PSFs) were synthesized with chlorine and hydroxyl terminal groups and studied for the task of producing porous hollow fiber membranes. The synthesis was carried out in dimethylacetamide (DMAc) at various excesses of 2,2-bis(4-hydroxyphenyl)propane (Bisphenol A) and 4,4′-dichlorodiphenylsulfone, as well as at an equimolar ratio of monomers in various aprotic solvents. The synthesized polymers were studied by nuclear magnetic resonance (NMR), differential scanning calorimetry, gel permeation chromatography (GPC), and the coagulation values of 2 wt.% PSF polymer solutions in N-methyl-2-pyrollidone were determined. According to GPC data, PSFs were obtained in a wide range of molecular weights M_w from 22 to 128 kg/mol. NMR analysis confirmed the presence of terminal groups of a certain type in accordance with the use of the corresponding monomer excess in the synthesis process. Based on the obtained results on the dynamic viscosity of dope solutions, promising samples of the synthesized PSF were selected to produce porous hollow fiber membranes. The selected polymers had predominantly –OH terminal groups and their molecular weight was in the range of 55–79 kg/mol. It was found that porous hollow fiber membrane from PSF with M_w 65 kg/mol (synthesized in DMAc with an excess of Bisphenol A 1%) has a high helium permeability of 45 m³/m²∙h∙bar and selectivity α (He/N₂) = 2.3. This membrane is a good candidate to be used as a porous support for thin-film composite hollow fiber membrane fabrication.

In this work, membranes for organic solvents nanofiltration (OSN) based on a natural polymer, sodium alginate, were fabricated. They are chemically stable in organic solvents, including aprotic polar solvents. The unique advantage of these membranes is the absence of toxic reagents and solvents during their production. This ensures the safety and environmental friendliness of the production process. It has been shown that an operation as simple as changing the cation in alginate (Cu²⁺, Fe³⁺, Cr³⁺, Al³⁺, Zn²⁺, Ca²⁺) makes it possible to control the transport and separating properties of membranes, depending on the organic solvent being separated. Therefore, to isolate RemazolBrilliant Blue with MM = 626 g·mol⁻¹ from ethanol, membranes based on iron alginate with a rejection R = 97% and a permeability of 1.5 kg·m⁻²·h⁻¹·bar⁻¹ are the most efficient. For isolation of the same solute from DMF and MP, membranes based on calcium alginate with an R of about 90% and a permeability of 0.1–0.2 kg·m⁻²·h⁻¹·bar⁻¹ are the most efficient. The resulting membranes based on natural biodegradable sodium alginate are competitive compared to membranes based on synthetic polymers.

The scope of this work was to develop a thin-film composite (TFC) membrane for the separation of CO₂/CO mixtures, which are relevant for many processes of gas processing and gasification of carbon-based feedstock. Special attention was given to the development of highly permeable porous polysulfone (PSF) supports (more than 26,000 GPU for CO₂) since both the selective and support layers contribute significantly to the overall performance of the TFC membrane. The PSF porous support is widely used in commercial and lab-scale TFC membranes, and its porous structure and other exploitation parameters are set during the non-solvent-induced phase separation (NIPS) process. Since the casting solution properties (e.g., viscosity) and the interactions in a three-component system (polymer, solvent, and non-solvent) play noticeable roles in the NIPS process, polysulfone samples in a wide range of molecular weights (M_w = 76,000–122,000 g·mol⁻¹) with terminal hydroxyl groups were synthesized for the first time. Commercial PSF with predominantly terminal chlorine groups (Ultrason^® S 6010) was used as a reference. The PSF samples were characterized by NMR, DSC, and TGA methods, and the Hansen solubility parameters were calculated. It was found that increasing the ratio of terminal –OH over –Cl groups improved the “solubility” of PSF in N-methyl-2-pyrrolidone (NMP) and water. A direct dependence of the gas permeance of porous supports on the coagulation rate of the casting solution was identified for the first time. It was shown that the use of synthesized PSF (M_w = 76,000 g·mol⁻¹, M_w/M_n = 3.0, (–OH):(–Cl) ratio of 4.7:1) enabled a porous support with a CO₂ permeance of 26,700 GPU to be obtained, while the support formed from a commercial PSF Ultrason^® S 6010 (M_w = 68,000 g·mol⁻¹, M_w/M_n = 1.7, (–OH):(–Cl) ratio of 1:1.9) under the same conditions demonstrated 4300 GPU. The siloxane-based materials were used for the selective layer since the thin films based on rubbery polymers do not undergo the same accelerating physical aging as glassy polymers. Two types of materials were screened for the selective layer: synthesized polymethyltrifluoroethylacrylate siloxane-polydecylmethylsiloxane (50F3) copolymer, and polydimethylsiloxane (PDMS). 50F3 siloxane was studied for gas separation applications for the first time. It was shown that the permeance of composite membranes based on high-performance porous supports from the PSF samples synthesized was 3.5 times higher than that from similar composite membranes based on supports from a commercial Ultrason^® S 6010 PSF with a permeance value of 4300 GPU for CO₂. It was found that the enhanced gas permeance of composite membranes based on the highly permeable porous PSF supports developed was observed for both 50F3 polysiloxane and commercial PDMS. At the same time, the CO₂/CO selectivity of the composite membranes with a 50F3-selective layer (9.1–9.3) is 1.5 times higher than that of composite membranes with a PDMS-selective layer. This makes the F-containing 50F3 polysiloxane a promising polymer for CO₂/CO separation.

For the first time, copolymers of polyphenylene sulfone (PPSU) with cardo fragments of phenolphthalein (PP) were synthesized to develop highly permeable flat-sheet ultrafiltration membranes. By introducing cardo fragments into the polymer chain, we achieved a mechanical strength 1.3 times higher than the strength of commercial PPSU. It is shown that the introduction of the cardo monomer significantly increases the solubility of the polymer in aprotic solvents. The highest solubility is observed at the concentration of PP 50 mol.%. It is found that reduced viscosity of cardo polymer solutions leads to an increase in the coagulation rate. The permeance of asymmetric ultrafiltration membranes increases with PP concentration from 17.5 L/(m²·h·bar) (10 mol.% PP) to 85.2 L/(m²·h·bar) (90 mol.% PP). These data are in agreement with the results of a study of the coagulation rate of polymer solutions. Thus, for ultrafiltration membranes with 1.5–8 times higher permeance in comparison with PPSU due to the introduction of cardo fragments in the polymer chain, possessing high rejection of the model dye Blue Dextran (M_W = 70,000 g/mol), more than 99.2%, as well as high strength characteristics, were achieved.