Membranes Based on Cellulose and Copolymers of Acrylonitrile Prepared from Joint Solutions.

Cellulose and copolymers of acrylonitrile (PAN) are characterized by their chemical resistance to several conventional solvents. Therefore, these polymers are often used to obtain membranes for the recovery of such solvents. In this work, for the first time, composite membranes formed from highly concentrated mixed solutions based on cellulose and PAN are considered (the total content of polymers is 18 wt.%). For mixed solutions, the morphology and rheological behavior were evaluated. It is shown that the resulting solutions are two-phase, and their morphology depends on the components' ratio and the system's history. The non-monotonous change in the viscosity with the PAN content indicates a specific interaction of cellulose and PAN in N-methylmorpholine-N-oxide solutions. The rheological behavior of mixed solutions allows for their processing in conditions identical to those of cellulose solutions. The introduction of PAN into the cellulose matrix promotes a decrease in the structural order in the system, affecting the membranes' transport properties. For composite membranes, it was found that with an increase in the content of the PAN phase, the retention of Remazol and Orange decreases, while the observed values are several times higher than those for cellulose membranes. The permeability of ethanol increases with increasing terpolymer content.

Stability of Porous Polymeric Membranes in Amine Solvents for Membrane Contactor Applications.

Membrane gas-liquid contactors have great potential to meet the challenges of amine CO2 capture. In this case, the most effective approach is the use of composite membranes. However, to obtain these, it is necessary to take into account the chemical and morphological resistance of membrane supports to long-term exposure to amine absorbents and their oxidative degradation products. In this work, we studied the chemical and morphological stability of a number of commercial porous polymeric membranes exposed to various types of alkanolamines with the addition of heat-stable salt anions as a model of real industrial CO2 amine solvents. The results of the physicochemical analysis of the chemical and morphological stability of porous polymer membranes after exposure to alkanolamines, their oxidative degradation products, and oxygen scavengers were presented. According to the results of studies by FTIR spectroscopy and AFM, a significant destruction of porous membranes based on polypropylene (PP), polyvinylidenefluoride (PVDF), polyethersulfone (PES) and polyamide (nylon, PA) was revealed. At the same time, the polytetrafluoroethylene (PTFE) membranes had relatively high stability. On the basis of these results, composite membranes with porous supports that are stable in amine solvents can be successfully obtained to create liquid-liquid and gas-liquid membrane contactors for membrane deoxygenation.

The Effect of Non-Solvent Nature on the Rheological Properties of Cellulose Solution in Diluted Ionic Liquid and Performance of Nanofiltration Membranes.

The weak point of ionic liquids is their high viscosity, limiting the maximum polymer concentration in the forming solutions. A low-viscous co-solvent can reduce viscosity, but cellulose has none. This study demonstrates that dimethyl sulfoxide (DMSO), being non-solvent for cellulose, can act as a nominal co-solvent to improve its processing into a nanofiltration membrane by phase inversion. A study of the rheology of cellulose solutions in diluted ionic liquids ([EMIM]Ac, [EMIM]Cl, and [BMIM]Ac) containing up to 75% DMSO showed the possibility of decreasing the viscosity by up to 50 times while keeping the same cellulose concentration. Surprisingly, typical cellulose non-solvents (water, methanol, ethanol, and isopropanol) behave similarly, reducing the viscosity at low doses but causing structuring of the cellulose solution and its phase separation at high concentrations. According to laser interferometry, the nature of these non-solvents affects the mass transfer direction relative to the forming membrane and the substance interdiffusion rate, which increases by four-fold when passing from isopropanol to methanol or water. Examination of the nanofiltration characteristics of the obtained membranes showed that the dilution of ionic liquid enhances the rejection without changing the permeability, while the transition to alcohols increases the permeability while maintaining the rejection.

Morphological Analysis of Poly(4,4'-oxydiphenylene-pyromellitimide)-Based Organic Solvent Nanofiltration Membranes Formed by the Solution Method.

Poly-(4,4'-oxydiphenylene) pyromellitimide or Kapton is the most widely available polyimide with high chemical and thermal stability. It has great prospects for use as a membrane material for filtering organic media due to its complete insolubility. However, the formation of membranes based on it, at the moment, is an unsolved problem. The study corresponds to the rediscovery of poly(4,4'-oxydiphenylene-pyromellitimide)-based soluble copoly(urethane-imides) as membrane polymers of a new generation. It is shown that the physical structure of PUI films prepared by the solution method becomes porous after the removal of urethane blocks from the polymer, and the pore size varies depending on the conditions of thermolysis and subsequent hydrolysis of the membrane polymer. The film annealed at 170 °C with a low destruction degree of polycaprolactam blocks exhibits the properties of a nanofiltration membrane. It is stable in the aprotic solvent DMF and has a Remasol Brilliant Blue R retention coefficient of 95%. After the hydrolysis of thermally treated films in acidic media, ultrafiltration size 66-82 nm pores appear, which leads to an increase in the permeate flow by more than two orders of magnitude. This circumstance provides opportunities for controlling the membrane polymer structure for further optimization of the performance characteristics of filtration membranes based on it. Thus, we proposed a new preparation method of ultra- and nanofiltration membranes based on poly(4,4'-oxydiphenylene-pyromellitimide) that are stable in aprotic solvents.

Selective Destruction of Soluble Polyurethaneimide as Novel Approach for Fabrication of Insoluble Polyimide Films.

Polymeric coatings and membranes with extended stability toward a wide range of organic solvents are practical for application in harsh environments; on the other hand, such stability makes their processing quite difficult. In this work, we propose a novel method for the fabrication of films based on non-soluble polymers. The film is made from the solution of block copolymer containing both soluble and insoluble blocks followed by selective decomposition of soluble blocks. To prove this concept, we synthesized copolymer [(imide)n-(polyurethane)]m, in which the imide blocks were combined with polyurethane blocks based on polycaprolactone. By selective hydrolysis of urethane blocks in the presence of acid, it was possible to obtain the insoluble polyimide film for the first time. It was shown that the combination of thermal and acid treatment allowed almost complete removal of urethane blocks from the initial copolymer chains. IR spectroscopy, TGA, DSC and DMA methods were used to study the evaluation of the structure and properties of polymeric material as a result of thermal oxidation and hydrolysis by acid. It was shown that the polymeric films obtained by controlled decomposition were not soluble in aprotic solvent, such as dimethylformamide, n-methylpyrrolidone and dimethyl sulfoxide, and showed very close similarity to the homopolymer consisting of the same imide monomer, poly-(4,4'oxydiphenylene)pyromellitimide, confirming the feasibility of the proposed concept and its perspectives for fabrication of organic solvent-resistant membranes.

Polymeric Membranes for Oil-Water Separation: A Review.

This review is devoted to the application of bulk synthetic polymers such as polysulfone (PSf), polyethersulfone (PES), polyacrylonitrile (PAN), and polyvinylidene fluoride (PVDF) for the separation of oil-water emulsions. Due to the high hydrophobicity of the presented polymers and their tendency to be contaminated with water-oil emulsions, methods for the hydrophilization of membranes based on them were analyzed: the mixing of polymers, the introduction of inorganic additives, and surface modification. In addition, membranes based on natural hydrophilic materials (cellulose and its derivatives) are given as a comparison.

Structure, Morphology, and Permeability of Cellulose Films.

The work is focused on the study of the influence of the cellulose type and processing parameters on the structure, morphology, and permeability of cellulose films. The free volume of the cellulose films was evaluated by the sorption of n-decane, which is a non-solvent for cellulose. The structural features of the membranes and their morphology were studied using X-ray diffraction, IR spectroscopy, SEM, and AFM methods. The characteristic features of the porous structure and properties of cellulose films regenerated from cellulose solutions in the N-methylmorpholine-N-oxide (NMMO) and cellophane films were compared. Generally, cellulose films obtained from solutions in NMMO have a higher permeability and a lower rejection (as measured using Orange II dye) as compared to cellophane films. It was also found that the cellulose films have a higher ultimate strength and modulus, whereas the cellophane films are characterized by higher elongation at break.

Morphology and transport properties of membranes obtained by coagulation of cellulose solutions in isobutanol.

The evolution of structural-morphological transformations of cellulose membranes obtained from solutions in N-methylmorpholine-N-oxide through various temperature isobutanol coagulation baths and subsequent treatment with water and their transport properties were studied. Using SEM, it was found that during coagulation in water and drying of the membranes, a uniform monolithic microheterogeneous texture was formed. The replacement of an aqueous precipitation bath with an isobutanol one leads to the formation of a porous structure with wide pore size and shape distributions. With an increase in precipitant temperature in the as-formed membrane, transverse tunnel cavities are formed with respect to the membrane-forming axis, which collapses when the membrane is washed with water, forming a dense texture with a non-uniform membrane volume. The mechanical properties of the obtained membranes were determined and a mechanism is proposed that allows their values to be correlated with structural-morphological and transport properties.