Miscibility enhancement of poly(vinyl chloride)/polystyrene blend: Application to membrane separation of benzene from benzene/cyclohexane mixture by pervaporation

In order to improve the miscibility of poly(vinyl chloride)/polystyrene (PVC/PS) system and to use the prepared material as a membrane to separate benzene from benzene/cyclohexane mixture by pervaporation technique, two poly(styrene-co-N-vinylpyrrolidone) (PSVP) copolymers containing 6.67 and 13.55 mol% of N-vinylpyrrolidone (N-VP) contents were synthesized through a radical polymerization. A comparative study of the miscibility of the PVC/PSVP blends with different compositions was carried out using differential scanning calorimetry, viscosimetry and Fourier transform infrared spectroscopy methods in which the interaction parameters between the two components were widely investigated. To improve the pervaporative flux of PVC membrane to separate benzene from benzene/cyclohexane mixture, a preliminary test of swelling and sorption was performed on PVC/PSVP7 membranes using an azeotropic benzene/cyclohexane mixture. It was revealed that the PVC/PSVP7 membrane containing 10 wt% of PSVP7 showed the best performance and the diffusion behaviour of this mixture through PVC and PVC/PCVP7 membranes has a Fickian behaviour. The pervaporation parameters of this membrane support those of the swelling and selective sorption data and reveal that this membrane could enhance the total flux without significantly affecting its selectivity to benzene.     

Chelate membrane from poly(vinyl alcohol)/poly(N-salicylidene allyl amine) blend. III. Effect of Mn(II) and Co(II) on oxygen/nitrogen separation

Facilitated transport of oxygen through Co(II) and Mn(II) chelate membranes from poly(vinyl alcohol)/poly(N-salicylidene allyl amine) was investigated. As the membranes became chelated, oxygen diffusivity decreased and the solubility toward oxygen was enhanced. The oxygen permeability of the base poly(vinyl alcohol)/poly(N-salicylidene allyl amine) membrane was 2.6 × 10⁻³ cm³(STP)cm/cm² cm Hg sec (barrer), and the selectivity toward oxygen was 2.2. As Co(II) was introduced into this membrane, oxygen permeability and oxygen selectivity increased to 2.82 × 10⁻² barrer and 8.5, respectively. The permeability and selectivity of Mn(II) chelate membrane were 3.28 × 10⁻² and 5, respectively. A major reason for the increased selectivity was the enhanced solubility of oxygen in chelate membrane upon chelation. The transport behavior of chelate membranes followed a dual-mode transport, and the parameters were estimated and compared between Co(II) and Mn(II) membranes. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 483–490, 1997     

Specialty polymeric membranes, 7. Pervaporation separation of benzene/cyclohexane mixtures with nylon 6-graft-poly(oxyethylene) membranes

Novel membrane materials for pervaporation separation of benzene/cyclohexane mixtures were prepared by the introduction of oligo(oxyethylene)s, such as diethylene glycol, poly(ethylene glycol) 200 (PEG200) and poly(ethylene glycol) 400 (PEG400) onto Nylon 6. The polymeric membranes from modified Nylon 6 thus prepared showed permselectivity toward benzene. Some membranes exclusively permeated benzene from benzene/cyclohexane mixture.     

Pervaporation characteristics of methyl methacrylate–methacrylic acid copolymer membranes ionically crosslinked with metal ions for a benzene/cyclohexane mixture

Methyl methacrylate–methacrylic acid copolymer (MMA–MAA) membranes ionically crosslinked with Fe³⁺ and Co²⁺ ions (MMA–MAA–Fe³⁺ and –Co²⁺) were prepared, and characteristics of permeation and separation for a benzene/cyclohexane mixture of 50 wt % benzene through these membranes in pervaporation (PV) were studied. Although the introduction of the metal ions to the MMA–MAA membrane enhanced both benzene permselectivity and permeability for a benzene/cyclohexane mixture, the PV characteristics between the MMA–MAA–Fe³⁺ and –Co²⁺ membranes were significantly different. The difference in the PV characteristics between these membranes was strongly governed by the difference of these membrane structures based on the glass transition temperature, contact angle to methylene iodide, degree of swelling, and mixture composition absorbed in the membrane, and so on. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 233–241, 1999     

Pervaporation Separation of Benzene/Cyclohexane Mixtures by Poly(vinyl chloride) Membranes

Sorption and pervaporation of benzene/cyclohexane mixtures were studied by using poly(vinyl chloride) (PVC) polymer. The effects of composition of benzene/cyclohexane mixture and temperature on sorption and pervaporation characteristics were determined at 30, 40, and 50 °C for the membranes containing 8 wt% PVC polymer. Liquid feed composition effects on the flux and the selectivity were determined for two different membranes at 30 °C. The membranes that were prepared from the solutions containing 4 wt% and 8 wt% PVC polymer have thicknesses of 30 μm and 50 μm, respectively. Membrane thickness changes with polymer content as expected. Total sorption increased with increasing concentration of benzene. Increasing the concentration of benzene resulted in increasing flux as well as decreasing selectivity also. Fluxes were increased and selectivity decreased with increasing temperature. The selectivity was not affected significantly with varying amounts of polymer in the casting solution but the flux decreased with increasing amount of polymer in the casting solution.     

Preparation and characterizaton of poly(dimethyl amino ethyl methacrylate) modified poly(vinyl alcohol) membrane by UV radiation for the permeation of 5‐fluorouracil

Poly(vinyl alcohol) was modified by UV radiation with dimethyl amino ethyl methacrylate (DMAEMA) monomer to get poly(dimethyl amino ethyl methacrylate) modified poly(vinyl alcohol) (PVADMAEMA) membrane. The PVADMAEMA membranes were characterized by Fourier transform infrared spectroscopy. The tensile strength and elongation of PVADMAEMA membranes were measured by Universal Testing Machine. The results of X‐ray diffraction (XRD) and differential scanning calorimetry (DSC) showed that (1) the crystalline area in PVADMAEMA decreased with increasing the content of poly(dimethyl amino ethyl methacrylate) in the membrane. (2) Only one glass transition temperature (T_g) was found for the various PVADMAEMA membranes. It means that poly(dimethyl amino ethyl methacrylate) and PVA are compatible in PVADMAEMA membrane. (3)The T_g of the membrane is reduced with increasing the content of poly(dimethyl amino ethyl methacrylate) in the membrane. The water content on the PVADMAEMA membranes was determined. It was found that the water content on the PVADMAEMA membrane increased with increasing the content of poly(dimethyl amino ethyl methacrylate). The changes of properties enhanced the permeability of 5‐Fluorouracil (5‐Fu) through the PVADMAEMA membranes. A linear relationship between the permeability and the weight percent of poly(dimethyl amino ethyl methacrylate) in the PVADMAEMA membrane is found. It is expressed as P (cm/s) = (9.6 ± 0.4) × 10^?5 + (8.8 ± 0.6) × 10^?5 W _x , where P is the permeability of 5‐Fu through the membrane and W_x is the weight percent of poly(dimethyl amino ethyl methacrylate) in the PVADMAEMA membrane. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Specialty polymeric membranes. XIV. Pervaporation of benzene/cyclohexane mixtures through modified polyamide membranes

Methyl methacrylate, ethyl methacrylate, propyl methacrylate, and styrene were graft‐polymerized onto the amorphous polyamide poly(hexamethylene terephthalamide/isophthalamide) (SELAR). Membranes were prepared from the modified SELAR and unmodified SELAR. The membranes were permeated benzene in preference to cyclohexane from benzene/cyclohexane mixtures by pervaporation. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 183–188, 2003     

Synthesis,characterization, and pervaporation properties of segmented poly(urethane‐urea)s

Poly(urethane‐urea)s (PUUs) from 2,4‐tolylene diisocyanate (2,4‐TDI), poly(oxytetramethylene)diols (PTMO) or poly(butylene adipate)diol (PBA), and various diamines were synthesized and characterized by Fourier transform infrared spectroscopy, gel permeation chromatography, differential scanning calorimetry, and density measurements. Transport properties of the dense PUU‐based membranes were investigated in the pervaporation of benzene–cyclohexane mixtures. It was shown that the pervaporation characteristics of the prepared membranes depend on the structure and length of the PUU segments. The PBA‐based PUUs exhibit good pervaporation performance along with a very good durability in separation of the azeotropic benzene–cyclohexane mixture. They are characterized by the flux value of 25.5 (kg μm m⁻² h⁻¹) and the separation factor of 5.8 at 25°C, which is a reasonable compromise between the both transport parameters. The PTMO‐based PUUs display high permeation flux and low selectivity in separation of the benzene‐rich mixtures. At the feed composition of 5% benzene in cyclohexane, their selectivity and flux are in the range of 3.2 to 11.7 and 0.4 to 40.3, respectively, depending on the length of the hard and soft segments. The chemical constitution of the hard segments resulting from the chain extender used does not affect the selectivity of the PUU membranes. It enables, however, the permeability of the membranes to be tailored. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1615–1625, 1999     

Separation of benzene/cyclohexane by pervaporation through chelate poly(vinyl alcohol)/poly(allyl amine) blend membrane

Summary Chelate poly(vinyl alcohol)/poly(allyl amine) blend membrane was prepared and used for the separation of benzene/cyclohexane mixture by pervaporation processes. The coordination of benzene in the feed with cobalt in the membrane plays a major role in the separation of the mixture. Chelate poly(vinyl alcohol)/poly(allyl amine) blend membrane showed a preferential sorption toward benzene and was found to be more effective for permeating benzene in the benzene/cyclohexane mixture than an original Schiff base poly(vinyl alcohol)/poly(allyl amine) membrane.     

Pervaporation of benzene/cyclohexane and benzene/n-hexane mixtures through PVA membranes

Poly(vinyl alcohol) (PVA) membranes (both homogeneous and asymmetric) were studied for the pervaporation separation of benzene/n-hexane and benzene/cyclohexane mixtures. The asymmetric PVA membrane with skin and porous layers was prepared through the phase inversion technique. Both asymmetric and homogeneous membranes were benzene-selective for all the feed compositions. The benzene separation factor of homogeneous PVA membrane was smaller than three, and the total permeation flux was several g/m²/h. The benzene selectivity of the asymmetric PVA membrane was much higher than that of the homogeneous membrane; weight fraction of benzene in the permeate side was larger than 90% for all the feed compositions. On the other hand, the total flux was almost unchanged compared with that of the homogeneous membrane. These results indicate that the density of the skin layer of the asymmetric membrane should be much higher than that of the homogeneous membrane. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1061–1065, 1997     

Filled poly(2,6-dimethyl-1,4-phenylene oxide) dense membranes by silica and silane modified silica nanoparticles: characterization and application in pervaporation

The effects of silica and silane modified silica fillers on the pervaporation properties of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) dense membranes have been studied. Crystallinity, thermal and mechanical properties of unfilled and filled PPO membranes with silica and silane modified silica nanoparticles were investigated. The surface energy together with the solubility parameters of the membranes and the nanoparticles were determined. Pervaporation separation of methanol/methyl tert butyl ether (MTBE) mixtures over the entire range of concentration were carried out using both filled and unfilled membranes. The results are discussed in terms of the solubility and the diffusivity of each liquid component in the membranes. Flory-Huggins theory was used to predict the sorption methanol selectivity. Compared to the unfilled PPO membrane, the filled PPO membranes exhibit higher methanol selectivity and lower permeability. For methanol concentration in liquid feed mixture lower than 50 wt%, methanol selectivity of the filled PPO membranes with silane modified silica is better than that of the silica filled and unfilled PPO membranes.     

Pervaporation of benzene–cyclohexane mixture by poly(γ-methyl L-glutamate) membrane and synergetic effect of their mixture on diffusion rate

The pervaporation of binary liquids mixture of benzene and cyclohexane was examined by use of poly(γ-methyl L -glutamate) (PMLG) membrane. The permeation rate–time curve for each of benzene and cyclohexane from their mixtures changed to the longer times side by increasing the cyclohexane in the mixtures. t_1/2 (the time required to reach a half-value of the steady state permeation rate) for the each component increased exponentially with increasing of cyclohexane, which has a smaller plasticizing effect on PMLG membrane than benzene, in the mixtures. The apparent diffusion coefficients, obtained from the steady state permeation and the sorption experiments, for benzene–PMLG and cyclohexane–PMLG are dependent exponentially on the sorbed amounts of benzene. This result was explained on the bases that the diffusion of cyclohexane was enhanced synergetically with benzene coexisting in the system. This effect influenced negatively the separation of the liquids mixture by pervaporation.     

Pervaporation separation of a water–ethanol mixture by PSF–PEG membrane

For dehydrating a water–ethanol mixture by pervaporation, a polysulfone–And poly(ethylene glycol)(PSF–PEG) membrane was prepared. The separation performance of water and ethanol was found to strongly depend on the diffusion selectivity of permeates. On the other hand, the solubility selectivity of water to ethanol showed only minor change with an increasing PEG composition of the PSF–PEG membrane. This study found that the PEG content in a PSF–PEG membrane showed mobility enhancement of pervaporation properties and that the diffusion difference of permeates increased with increasing PEG content. The effect of PEG content on separation performance was a result of the improvement of the permeate diffusion properties of the PSF/PEG membrane. The diffusion difference in the membrane, not the solubility of water–ethanol in the membrane, was the dominant factor for the separation. Suitable PEG content in PSF/PEG membranes can prepare a high‐performance pervaporation membrane. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2158–2164, 2003     

Membranes based on polyimide–polyaniline nanocomposites for pervaporation of organic mixtures

Polyimide–polyaniline nanocomposites were obtained by mixing poly{[4,4′‐bis(4″‐N‐phenoxy)diphenylsulfone]imide‐1,3‐bis(3,4‐dicarboxyphenoxy)benzene} (PI) and polyaniline (PANI) solutions in N‐methylpyrrolidone. These solutions were used for the preparation of homogeneous and composite membranes. Uniform distribution of PANI particles in the membranes, resulted from interactions between macromolecules, was confirmed by transmission electron microscopy. Membranes based on PI and PI–PANI were tested in pervaporation of binary organic mixtures: methanol/toluene and methanol/cyclohexane and showed a remarkable selectivity with respect to methanol. In both pervaporation processes, selectivity was improved in PANI‐containing membranes. Interactions between membrane polymers and liquid penetrants (methanol, toluene, and cyclohexane) were studied by measurements of surface tension, sorption, and pervaporation parameters. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Pervaporation membranes based on imide‐containing poly(amic acid) and poly(phenylene oxide)

Three imide‐containing poly(amic acids) were synthesized and used for homogeneous and composite membrane preparation. The transport properties of composite membranes consisting of an imide‐containing poly(amic acid) top layer on an asymmetric porous poly(phenylene oxide) support were studied in the pervaporation of aqueous solutions of organic liquids (ethanol, isopropanol, acetone, and ethylacetate) and organic/organic mixtures (ethylacetate/ethanol, methanol/cyclohexane). For most of the aqueous/organic mixtures, the composite membranes exhibited dehydration properties. Dilute aqueous solutions of ethylacetate were an exception. In these solutions, the composite membranes exhibited organophilic properties, high permeability, and selectivity with respect to ethylacetate. In the pervaporation of methanol/cyclohexane mixtures, methanol was removed with very high selectivity. To account for specific features of pervaporation on the composite membranes, the sorption and transport properties of homogeneous membranes prepared from polymers comprising the composite membrane [imide‐containing poly(amic acids) and poly(phenylene oxide)] were studied. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2361–2368, 2003     

Preparation of novel ZSM‐5 zeolite‐filled chitosan membranes for pervaporation separation of dimethyl carbonate/methanol mixtures

Novel mixed matrix membranes were prepared by incorporating ZSM‐5 zeolite into chitosan polymer for the pervaporative separation of dimethyl carbonate (DMC) from methanol. These membranes were characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and X‐ray diffraction (XRD) to assess their morphology, intermolecular interactions, and crystallinity. Sorption studies indicated that the degree of swelling for zeolite‐filled membranes increased with zeolite content in the membrane increasing and the separation selectivity of DMC/methanol was dominated by solubility selectivity rather than diffusivity selectivity. The characteristics of these membranes for separating DMC/methanol mixtures were investigated by varying zeolite content, feed composition, and operating temperature. The pervaporation separation index (PSI) showed that 5 wt % of ZSM‐5 zeolite‐filled membrane gave the optimum performance in the PV process. From the temperature‐dependent permeation values, the Arrhenius activation parameters were estimated. The resulting lower activation energy values obtained for zeolite‐filled membranes contribute to the framework of the zeolite. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Nonequilibrium nanoblend membranes for the pervaporation of benzene/cyclohexane mixtures

Immiscible blends of polymers were cast from solution, and the rate of evaporation was controlled relative to the rate of phase separation to produce different morphologies; upon crosslinking, stable nonequilibrium nanoblends were realized. This process of forced assembly produced useful membrane materials that could be designed for solubility selectivity with the group contribution methodology. Crosslinked ternary blends of nitrile butadiene rubber (NBR), poly(methyl methacrylate) (PMMA), and a tercopolymer of ethylene oxide/epichlorohydrin/allyl glycidyl ether (Hydrin) were examined for use in the separation of benzene from cyclohexane by pervaporation. For a 50 : 50 wt % benzene/cyclohexane feed, blend 811 (containing 80 wt % NBR, 10 wt % Hydrin, and 10 wt % PMMA) gave a separation factor of 7.3 and a normalized flux of 28 kg μm/m² h; such a performance is unmatched in the literature, with the flux being very high for the reported separation factor. Among the samples tested, the flux of the membrane increased as the amount of NBR in the ternary blend decreased; however, the separation factor was not largely affected. Blended samples showed no sign of deformation after 48 h at the operating temperature as compared to pure NBR, which did show evidence of creep. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Permeation and sorption properties of benzene, cyclohexane, and n-hexane vapors in poly[bis(2,2,2-trifluoroethoxy)phosphazene] (PTFEP) membranes

The permeability and solubility of benzene, cyclohexane, and n-hexane (C-6 compounds) in poly[bis(2,2,2-trifluoroethoxy)phosphazene] (PTFEP) membranes were determined experimentally, and the corresponding diffusivity was obtained by analyzing the data with the solution-diffusion model. The permeability of benzene ranged from several hundreds to several thousands Barrers, and that of cyclohexane and n-hexane ranged from several decades to several hundreds Barrers. All the permeabilities increased exponentially with the vapor activity and increased with temperature. The sorption isotherms of those C-6 compounds were well described by the Henry's law relationship, and constant solubility at each temperature could be determined from the linear correlation. The solubility seems to be inversely proportion to the molecular size of the penetrant when there is not much strong polymer-penetrant interaction. The diffusivity of those C-6 compounds ranged from 10⁻⁷ to 10⁻⁹ cm²/s, and the values of benzene were much larger than those of cyclohexane and n-hexane at the same temperature and vapor activity. The diffusivities of those C-6 compounds also increased exponentially with the vapor activity, and the relative magnitude of the diffusivity is determined by the molecular size (collision diameter) of them. The diffusivities of those C-6 compounds increased with temperature and their activation energies of diffusion were very similar possibly due to the same energy characteristic of polymer main chain movement.     

Characterization and pervaporation of chlorinated hydrocarbon–water mixtures with fluoroalkyl methacrylate‐grafted PDMS membrane

It is desirable to enhance the selectivity of a polydimethylsiloxane (PDMS) membrane for chlorinated hydrocarbons. In this study, the PDMS membranes were improved by graft polymerization of 1H,1H,9H‐hexadecafluorononyl methacrylate (HDFNMA), which has the effect of increasing the selectivity for chlorinated hydrocarbons. The PDMS membrane and HDFNMA were irradiated simultaneously by a ⁶⁰Co source. The grafted membranes had a microphase‐separated structure, that is, a separated structure of PDMS and grafted HDFNMA. In the grafted PDMS membrane, a great separation performance for a TCE–water mixture was shown due to the introduction of the hydrophobic polymer, poly(HDFNMA). For the permeation of the grafted PDMS membrane, the permeability of molecules in the PDMS phase was significantly great, and that in the poly(HDFNMA) phase was too low to affect the whole permeation of the grafted PDMS membrane directly. However, the permeation of molecules at the interface of poly(HDFNMA) and PDMS played an important role because poly(HDFNMA) had a much stronger affinity for TCE than water. At a low feed concentration of the TCE solution, the diffusivity of TCE molecules must be much lower than that of water due to the larger molecular size of TCE. At a high concentration of TCE solution, TCE was sufficiently sorbed into the membrane so that the diffusion of water was prevented by TCE molecules; in turn, the permselectivity of TCE was increased significantly. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 273–287, 1999     

Development of methanol selective membranes for separation of methanol–methyl tertiary butyl ether mixtures by pervaporation

Several copolymers of acrylonitrile (AN) were synthesized. Methanol selective membranes were prepared from these copolymers of AN. The other monomers in the copolymers were selected on the basis of their solubility parameter values relative to those of methanol. These were hydroxyethyl methacrylate, methacrylic acid, and vinyl pyrrolidone. Thus, pervaporative separation of methanol from its mixture with methyl tertiary butyl ether over the entire concentration range of 0–100% methanol was studied using these copolymer membranes of AN. For each copolymer of AN three different membranes with different copolymer compositions were prepared. Copolymers of AN with hydroxyethyl methacrylate and methacrylic acid showed high selectivity and moderate flux for methanol (2561, 773, 0.057, and 0.045 kg/m² h, respectively, with a membrane of 50‐μm thickness for a feed mixture containing 5% methanol at 30°C). A copolymer of AN with vinyl pyrrolidone showed comparable flux, but methanol selectivity of this membrane was poor. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2645–2659, 1999