Addition Polyalkylnorbornenes: A Promising New Class of Si-Free Membrane Materials for Hydrocarbons Separation.

Nanoporous glassy polymers are perspective materials for the fabrication of gas separation membranes, especially for the application of gaseous hydrocarbon separation. However, the drawback of such materials is the pronounced physical aging resulting in the dramatic drop of gas transport properties due to relaxation of high-free-volume fraction in time. Herein, a novel and readily available group of such glassy polymers is reported based on 5-alkylnorbornenes. These polymers are easily synthesized from dicyclopentadiene and α-olefins by Diels-Alder reaction and vinyl (addition) polymerization of the formed cycloadducts in the presence of ([(η3 -C3 H5 )PdCl]2 /PCy3 /Na+ [B(3,5-(CF3 )2 C6 H3 )4 ]- catalyst. The obtained polymers display low-fraction free volume, stable gas permeability over time, and possess a unique feature for the glassy polymers-solubility controlled permeation of hydrocarbons and enhanced C4 H10 /CH4 selectivity.

Effect of OH-Group Introduction on Gas and Liquid Separation Properties of Polydecylmethylsiloxane.

Membrane development for specific separation tasks is a current and important topic. In this work, the influence of OH-groups introduced in polydecylmethylsiloxane (PDecMS) was shown on the separation of CO2 from air and aldehydes from hydroformylation reaction media. OH-groups were introduced to PDecMS during hydrosilylation reaction by adding 1-decene with undecenol-1 to polymethylhydrosiloxane, and further cross-linking. Flat sheet composite membranes were developed based on these polymers. For obtained membranes, transport and separation properties were studied for individual gases (CO2, N2, O2) and liquids (1-hexene, 1-heptene, 1-octene, 1-nonene, heptanal and decanal). Sorption measurements were carried out for an explanation of difference in transport properties. The general trend was a decrease in membrane permeability with the introduction of OH groups. The presence of OH groups in the siloxane led to a significant increase in the selectivity of permeability with respect to acidic components. For example, on comparing PDecMS and OH-PDecMS (~7% OH-groups to decyl), it was shown that selectivity heptanal/1-hexene increased eight times.

Monoethanolamine (MEA) Degradation: Influence on the Electrodialysis Treatment of MEA-Absorbent.

The thermal-oxidative degradation of aqueous solutions of carbonized monoethanolamine (MEA, 30% wt., 0.25 mol MEA/mol CO2) was studied for 336 h at 120 °C. Based on the change in the color of the solution and the formation of a precipitate, the occurrence of thermal-oxidative degradation of the MEA solution with the formation of destruction products, including insoluble ones, was confirmed. The electrokinetic activity of the resulting degradation products, including insoluble ones, was studied during the electrodialysis purification of an aged MEA solution. To understand the influence of degradation products on the ion-exchange membrane properties, a package of samples of MK-40 and MA-41 ion-exchange membranes was exposed to a degraded MEA solution for 6 months. A comparison of the efficiency of the electrodialysis treatment of a model absorption solution of MEA before and after long-time contact with degraded MEA showed that the depth of desalination was reduced by 34%, while the magnitude of the current in the ED apparatus was reduced by 25%. For the first time, the regeneration of ion-exchange membranes from MEA degradation products was carried out, which made it possible to restore the depth of desalting in the ED process by 90%.

Pervaporation and Gas Separation Properties of High-Molecular Ladder-like Polyphenylsilsesquioxanes.

This paper presents the results of studies on the pervaporation properties (for benzene/hexane mixtures) and gas permeability (for He, H2, N2, O2, CO2, CH4, C2H6, and C4H10) of ladder-like polyphenylsesquioxanes (L-PPSQ) with improved physical and chemical properties. These polymers were obtained by condensation of cis-tetraphenylcyclotetrasiloxanetetraol in ammonia medium. The structure of L-PPSQ was fully confirmed by a combination of physicochemical analysis methods: 1H, 29Si NMR, IR spectroscopy, HPLC, powder XRD, and viscometry in solution. For the first time, a high molecular weight of the polymer (Mn = 238 kDa, Mw = 540 kDa) was achieved, which determines its improved mechanical properties and high potential for use in membrane separation. Using TGA and mechanical analysis methods, it was found that this polymer has high thermal (Td5% = 537 °C) and thermal-oxidative stability (Td5% = 587 °C) and good mechanical properties (Young's module (E) = 1700 MPa, ultimate tensile stress (σ) = 44 MPa, elongation at break (ε) = 6%), which is important for making membranes workable under various conditions. The polymer showed a high separation factor for a mixture of 10% wt. benzene in n-hexane (126) at a benzene flow of 33 g/(m2h).

Mitigation of Physical Aging of Polymeric Membrane Materials for Gas Separation: A Review.

The first commercial hollow fiber and flat sheet gas separation membranes were produced in the late 1970s from the glassy polymers polysulfone and poly(vinyltrimethyl silane), respectively, and the first industrial application was hydrogen recovery from ammonia purge gas in the ammonia synthesis loop. Membranes based on glassy polymers (polysulfone, cellulose acetate, polyimides, substituted polycarbonate, and poly(phenylene oxide)) are currently used in various industrial processes, such as hydrogen purification, nitrogen production, and natural gas treatment. However, the glassy polymers are in a non-equilibrium state; therefore, these polymers undergo a process of physical aging, which is accompanied by the spontaneous reduction of free volume and gas permeability over time. The high free volume glassy polymers, such as poly(1-trimethylgermyl-1-propyne), polymers of intrinsic microporosity PIMs, and fluoropolymers Teflon® AF and Hyflon® AD, undergo significant physical aging. Herein, we outline the latest progress in the field of increasing durability and mitigating the physical aging of glassy polymer membrane materials and thin-film composite membranes for gas separation. Special attention is paid to such approaches as the addition of porous nanoparticles (via mixed matrix membranes), polymer crosslinking, and a combination of crosslinking and addition of nanoparticles.

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.

Mitigating of Thin-Film Composite PTMSP Membrane Aging by Introduction of Porous Rigid and Soft Branched Polymeric Additives.

This work was focused on the mitigation of physical aging in thin-film composite (TFC) membranes (selective layer ~1 µm) based on polymer intrinsic microporosity (PTMSP) by the introduction of both soft, branched polyethyleneimine (PEI), and rigid, porous aromatic framework PAF-11, polymer additives. Self-standing mixed-matrix membranes of thicknesses in the range of 20-30 µm were also prepared with the same polymer and fillers. Based on 450 days of monitoring, it was observed that the neat PTMSP composite membrane underwent a severe decline of its gas transport properties, and the resultant CO2 permeance was 14% (5.2 m3 (STP)/(m2·h·bar)) from the initial value measured for the freshly cast sample (75 m3 (STP)/(m2·h·bar)). The introduction of branched polyethyleneimine followed by its cross-linking allowed to us to improve the TFC performance maintaining CO2 permeance at the level of 30% comparing with day zero. However, the best results were achieved by the combination of porous, rigid and soft, branched polymeric additives that enabled us to preserve the transport characteristics of TFC membrane as 43% (47 m3 (STP)/(m2·h·bar) after 450 days) from its initial values (110 m3 (STP)/(m2·h·bar)). Experimental data were fitted using the Kohlrausch-Williams-Watts function, and the limiting (equilibrium) values of the CO2 and N2 permeances of the TFC membranes were estimated. The limit value of CO2 permeance for neat PTMSP TFC membrane was found to be 5.2 m3 (STP)/(m2·h·bar), while the value of 34 m3(STP)/(m2·h·bar) or 12,600 GPU was achieved for TFC membrane containing 4 wt% cross-linked PEI, and 30 wt% PAF-11. Based on the N2 adsorption isotherms data, it was calculated that the reduction of the free volume was 1.5-3 times higher in neat PTMSP compared to the modified one. Bearing in mind the pronounced mitigation of physical aging by the introduction of both types of fillers, the developed high-performance membranes have great potential as support for the coating of an ultrathin, selective layer for gas separation.

Gas-Transport and the Dielectric Properties of Metathesis Polymer from the Ester of exo-5-Norbornenecarboxylic Acid and 1,1'-Bi-2-naphthol.

Polymers from norbornenes are of interest for applications in opto- and microelectronic (low dielectric materials, photoresists, OLEDs). Norbornenes with ester motifs are among the most readily available norbornene derivatives. However, little is known about dielectric properties and the gas-transport of polynorbornenes from such monomers. Herein, we synthesized a new metathesis polymer from exo-5-norbornenecarboxylic acid and 1,1'-bi-2-naphthol. The designed monomer was obtained via a two-step procedure in a good yield. This norbornene derivative with a rigid and a bulky binaphthyl group was successfully polymerized over the 1st generation Grubbs catalyst, affording high-molecular-weight products (Mw ≤ 1.5·106) in yields of 94-98%. The polymer is amorphous and glassy (Tg = 161 °C), and it shows good thermal stability. Unlike most, polyNBi is a classic low-permeable glassy polymer. The selectivity of polyNBi was higher than that of polyNB. Being less permeable than polyNB, polyNBi unexpectedly showed a lower value of dielectric permittivity (2.7 for polyNBi vs. 5.0 for polyNB). Therefore, the molecular design of polynorbornenes has great potential to obtain polymers with desired properties in a wide range of required characteristics. Further tuning of the gas separation efficiency can be achieved by attaching an appropriate substituent to the ester and aryl group.

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.

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.

Synthesis and Gas Transport Properties of Addition Polynorbornene with Perfluorophenyl Side Groups.

Polynorbornenes represent a fruitful class of polymers for structure-property study. Recently, vinyl-addition polynorbornenes bearing side groups of different natures were observed to exhibit excellent gas permeation ability, along with attractive C4H10/CH4 and CO2/N2 separation selectivities. However, to date, the gas transport properties of fluorinated addition polynorbornenes have not been reported. Herein, we synthesized addition polynorbornene with fluoroorganic substituents and executed a study on the gas transport properties of the polymer for the first time. A norbornene-type monomer with a C6F5 group, 3-pentafluorophenyl-exo-tricyclononene-7, was successfully involved in addition polymerization, resulting in soluble, high-molecular-weight products obtained in good or high yields. By varying the monomer concentration and monomer/catalyst ratio, it was possible to reach Mw values of (2.93-4.35) × 105. The molecular structure was confirmed by NMR and FTIR analysis. The contact angle with distilled water revealed the hydrophobic nature of the synthesized polymer as expected due to the presence of fluoroorganic side groups. A study of the permeability of various gases (He, H2, O2, N2, CO2, and CH4) through the prepared polymer disclosed a synergetic effect, which was achieved by the presence of both bulky perfluorinated side groups and rigid saturated main chains. Addition poly(3-pentafluorophenyl-exo-tricyclononene-7) was more permeable than its metathesis analogue by a factor of 7-21, or the similar polymer with flexible main chains, poly(pentafluorostyrene), in relation to the gases tested. Therefore, this investigation opens the door to fluorinated addition polynorbornenes as new potential polymeric materials for membrane gas separation.

Transport Properties of Thermoplastic R-BAPB Polyimide: Molecular Dynamics Simulations and Experiment.

The present work evaluates the transport properties of thermoplastic R-BAPB polyimide based on 1,3-bis(3,3',4,4'-dicarboxyphenoxy)benzene (dianhydride R) and 4,4'-bis(4-aminophenoxy)biphenyl (diamine BAPB). Both experimental studies and molecular dynamics simulations were applied to estimate the diffusion coefficients and solubilities of various gases, such as helium (He), oxygen (O2), nitrogen (N2), and methane (CH4). The validity of the results obtained was confirmed by studying the correlation of the experimental solubilities and diffusion coefficients of He, O2, and N2 in R-BAPB, with their critical temperatures and the effective sizes of the gas molecules, respectively. The solubilities obtained in the molecular dynamics simulations are in good quantitative agreement with the experimental data. A good qualitative relationship between the simulation results and the experimental data is also observed when comparing the diffusion coefficients of the gases. Analysis of the Robeson plots shows that R-BAPB has high selectivity for He, N2, and CO2 separation from CH4, which makes it a promising polymer for developing gas-separation membranes. From this point of view, the simulation models developed and validated in the present work may be put to effective use for further investigations into the transport properties of R-BAPB polyimide and nanocomposites based on it.