Gas and vapor permeability of perfluoroalkylated polymers

Summary Three polymers bearing benzene rings: polystyrene, poly(2,6-dimethyl-p-phenylene oxide) and poly(diphenylacetylene), were chemically modified with bis(heptafluorobutyryl) peroxide. The heptafluoropropylated products have higher gas permeabilities than the parent polymers. In the pervaporation of aqueous ethanol, modified poly(diphenylacetylene) showed ethanol permselectivity.     

Synthesis and Gas Permeability of Novel Poly(diphenylacetylenes) Having Polyethylene Glycol Moieties

4-Trimethylsilyldiphenylacetylenes with methyl group or bromine atom (Me₃SiC₆H₄C≡CC₆H₄R, R = m-CH₃, p-CH₃, m-Br, p-Br, 1a–d, respectively) were polymerized with TaCl₅/ n-Bu₄Sn to afford poly(diphenylacetylene) derivatives (2a–d). The polymers (2a–d) had high molecular weight over 5×10⁵, and gave free-standing membranes by solution casting method. Chlorination of the obtained poly[1-(3-methylphenyl)-2-(4-trimethylsilyl)phenylacetylene] was carried out by using sulfuryl chloride, and then substitution of polyethylene glycol was performed to give poly(diphenylacetylene) possessing polyethylene glycol moieties. Its carbon dioxide permeability (P_{CO 2}) and permselectivity (P_{CO 2}/P_{N 2}) were 2,970 barrers and 9.0, respectively.     

Effect of Fumed Silica Nanoparticles on the Gas Permeation Properties of Substituted Polyacetylene Membranes

Summary The gas permeability of three substituted polyacetylenes, poly(1-chloro-2-phenylacetylene) (PClPA), poly[1-phenyl-2-(4-trimethylsilyl)phenylacetylene] (PTMSDPA), and poly[1-(trimethylsilyl)-1-propyne] (PTMSP), increased systematically with increasing content of nonporous fumed silica (FS) nanoparticles. For instance, the oxygen permeability coefficient (PO₂) of PClPA containing 30 wt % FS was 86 barrers, which was 10 times higher than that of the unfilled polymer (PO₂=8.6 barrers). The extent of permeability increase with the addition of FS was smaller when the permeability of the original polymer was higher. The order of the permeability increase in FS-filled polymers was as follows: PClPA > PTMSDPA > PTMSP. The addition of FS resulted in the decrease of O₂/N₂ permselectivity of these polymers. The H₂/CH₄ permselectivity largely decreased with increasing FS content in PClPA, while it hardly changed with FS loading in PTMSP. The gas solubility of PClPA was practically independent of FS content, and the increase in gas permeability in filled PClPA resulted from an increase in diffusivity with the addition of FS.     

Pervaporation properties of polypyrrolidinone‐based membranes for EtOH/ETBE mixtures separation

The separation of ethanol/ethyl‐tertiobutylether mixtures by pervaporation was studied with new membranes prepared from N‐vinyl‐pyrrolidinone (NVP) and N‐[3‐(trimethylamoniopropyl)]methacrylamidemethylsulfate) (TMA). The pervaporation results showed that highly EtOH selective membranes could be obtained from PVP blends and from pyrrolidinone‐based crosslinked copolymers. The influences of the polymer blend composition and the role of the polymer microstructures on the membrane properties were investigated. Whatever the exact NVP/TMA composition used, the membranes strongly favored the pervaporation of ethanol. The ethanol selectivity was higher for the lower PVP/TMA ratio. On the one hand, these results were ascribed to the high pyrrolidinone residues content, which is responsible of the enhanced EtOH sorption affinity. The observed permeation selectivity was in agreement with the swelling data also recorded with the different polymers, showing higher affinity for ethanol with PVP‐enriched materials compared with TMA ones. This is a direct consequence of the Lewis base feature of pyrrolidinone sites towards EtOH molecules. On the other hand, the TMA residues improved the overall stability and selectivity of the membranes thanks to crosslinking reactions, which were induced by thermal treatment. A close comparison made between polymer blend and copolymer pervaporation results helped to clarify the TMA role of the membrane transport properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99:3622–3630, 2006     

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.     

Vapor Permeation and Pervaporation of Aqueous 2‐Propanol Solutions through the Torlon® Poly(amide imide) Membrane

Abstract

In the present study, vapor permeation and pervaporation of aqueous 2‐propanol mixtures were investigated using Torlon^® poly(amide imide) as a membrane material. Torlon membranes preferentially permeated H₂O from aqueous 2‐PrOH mixtures both by vapor permeation and pervaporation. Diffusion experiments led to the conclusion that both solubility selectivity and diffusivity selectivity showed a preference for H₂O. Solubility selectivity is by far the dominant factor governing permselectivity, and as a result, Torlon membranes showed permselectivity toward water in vapor permeation and pervaporation. The present study showed that Torlon^® poly(amide imide) is a membrane material potentially applicable to the dehydration of water miscible organics.     

Water–ethanol permseparation by pervaporation through photocrosslinked poly(vinyl alcohol) composite membranes

Water–ethanol permselectivity was investigated by pervaporation through composite membranes which were prepared by coating photocrosslinkable poly(vinyl alcohol) containing pendant styrylpyridinium group (0.86–3.93 mol %) on porous films. These membranes were water-permselective, and the selectivity was dependent on the state of membranes; namely, incorporation ratio of styrylpyridinium group on poly(vinyl alcohol), molecular weight of the base polymer, coating thickness of a photopolymer, etc. Photocrosslinkable styrylpyridinium group showed, of course, the ionic character by a pyridinium moiety to work on permseparation of water effectively as well as preventing the dissolution of membranes by crosslinking. Membranes based on the higher molecular weight poly(vinyl alcohol) (P = 1700) gave the higher permselectivity of water in general than those of lower molecular weight (P = 500) one. Swelling of the polymers reached 160%, and permeation rate through the membranes increased with the increase of swelling. Selective diffusion of water was found to take place in swelling, and to play a part in the water-permseparation through the membranes.     

Synthesis of poly(ɛ-caprolactone-b-isobutylene) diblock copolymer and poly(ɛ-caprolactone-b-isobutylene-b-ɛ-caprolactone) triblock copolymer

Summary Poly(isobutylene-b-ɛ-caprolactone) diblock and poly(ɛ-caprolactone-b-isobutylene-b-ɛ-caprolactone) triblock copolymers have been prepared and characterized. The synthesis involved the living cationic polymerization of IB, followed by capping with 1,1-diphenylethylene or 1,1-p-ditolylethylene and end-quenching with 1-methoxy-1-trimethylsiloxy-2-methyl-propene to yield methoxycarbonyl functional PIB. Hydroxyl end-functional PIB polymers were quantitatively obtained by the subsequent reduction of methoxycarbonyl end-functional PIB with LiAlH₄. The structure of hydroxyl end-functional PIBs was confirmed by ¹H NMR and IR spectroscopy. Poly(ɛ-caprolactone-b-isobutylene) diblock copolymers and poly(ɛ-caprolactone-b-isobutylene-b-ɛ-caprolactone) triblock copolymers were synthesized by the living cationic ring-opening polymerization of ɛ-caprolactone with hydroxyl end-functional PIB as macroinitiator in the presence of HCl•Et₂O via the “activated monomer mechanism”. The block copolymers exhibited close to theoretical M_ns and narrow molecular weight distributions. Received: 30 January 2002/Revised version: 19 February 2002/ Accepted: 19 February 2002     

Cellulose–poly(acrylamide or acrylic acid) interpenetrating polymer network membranes for the pervaporation of water–ethanol mixtures

A new type of interpenetrating polymer network (IPN) pervaporation membranes based on cellulose and synthetic polymers was developed. They were prepared by free-radical polymerization of acrylamide or acrylic acid in the presence (or absence) of the crosslinking agent (allyldextran or N,N′-methylenebisacrylamide) within cellophane films swollen in the reaction mixture. The swelling behavior of these membranes in water–ethanol solutions and their separation characteristics were investigated depending on the polyacrylamide (PAAm) or poly(acrylic acid) (PAA) content in the IPN (C_p) and for ionic cellulose–PAA membranes depending on the degree of neutralization of carboxylic groups and on the type of counterions. IPN membranes were selective over a wide range of ethanol concentration in the feed. The separation factor (α) and the permeation rate (P) significantly improved with increasing C_p in IPN membranes, especially for the cellulose–PAA(K⁺ form) membranes (for 86% EtOH feed at 50°C, and α and P values reached 1500 and 1.6 kg/m² h, respectively). The results for ionic and nonionic IPN membranes were compared. The separation characteristics of membranes were in good correlation with their swelling behavior. The α values of the membranes depended on the affinity of the IPN polymer chains functional groups for water. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 761–769, 1998     

Pervaporation separation of binary organic–aqueous liquid mixtures using crosslinked PVA membranes. III. Ethanol–water mixtures

The application of the pervaporation process in biotechnology is rapidly growing. A two stage pervaporation process could be applied to the downstream processing of ethanol fermentation. In this paper, the second stage process—a water-selective process—was investigated in detail using the crosslinked poly(vinyl alcohol) membranes with the low molecular weight of poly(acrylic acid) as the crosslinking agent. The ratio of poly(vinyl alcohol) and poly(acrylic acid) in the membrane was 90/10, 85/15, and 80/20 by weight. The prepared membranes were tested to separate the various compositions of the water–ethanol mixtures, specially 50/50 solution at 60°C and 30/70, 20/80, 10/90, and 4.4/95.6 solutions at 60, 70, and 75°C. For water: ethanol = 50 : 50 solution, the separation factor α_w/e = 260 at 75°C was obtained by using a PVA/PAA = 80/20 membrane. The permeation rate and the separation factor at the azeotropic point of a water–ethanol mixture showed 30 g/m²/h and 5800 at 75°C, respectively, when a PVA/PAA = 80/20 membranes was used. © 1995 John Wiley & Sons, Inc.     

Mixed Matrix Silicone and Fluorosilicone/Zeolite 4A Membranes for Ethanol Dehydration by Pervaporation

The ability of homogeneous and mixed matrix membranes prepared using standard silicone rubber, poly(dimethylsiloxane) (PDMS), and fluorosilicone rubber, poly(trifluoropropylmethylsiloxane) (PTFPMS), to dehydrate ethanol by pervaporation was evaluated. Although PDMS is generally considered to be the benchmark hydrophobic membrane material in pervaporation, water/ethanol molar permselectivity of a pure PDMS membrane was found to be 0.89 for a feed containing 80/20 w/w ethanol/water at 50°C, indicating a slight selectivity for water. Fluorinated groups in PTFPMS improved the water-ethanol permselectivity to 1.85, but decreased the water permeability from 9.7 × 10^?12 kmol · m/m² · s · kPa in PDMS to 5.1 × 10^?12 kmol · m/m² · s · kPa (29,000 and 15,200 Barrer, respectively). These water permeabilities are attractive, particularly since the rubbery materials should not experience the steep declines in water permeability observed with most standard dehydration membranes as water concentration in the feed decreases. However, the water selectivity is lower than desired for most applications. Particles of hydrophilic zeolite 4A were loaded into both PDMS and PTFPMS matrices in an effort to boost water selectivity and further improve water permeability. Water-ethanol permselectivities as high as 11.5 and water permeabilities as high as 23.2 × 10^?12 kmol · m/m² · s · kPa were observed for the PTFPMS/zeolite 4A mixed matrix membranes?6 times higher than for the unfilled PTFPMS membrane.     

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     

PVA/PEG/TEOS杂化膜制备及性能研究

以聚乙烯醇(PVA)与聚乙二醇(PEG)共混,并与正硅酸乙酯(TEOS)进行交联反应制备杂化膜。FTIR证实杂化溶胶液发生交联反应形成共价键Si—O—C,WXRD观察表明加入TEOS改变了膜结晶度,加入PEG提高了PVA膜对乙醇/水溶液的渗透通量,但分离因子下降,随着TEOS的加入,膜的分离因子提高。在TEOS质量分数为10%时,杂化膜的分离因子达到最大。提高退火温度可以提高膜的分离因子,但通量下降。在100℃下退火12 h的杂化膜对乙醇质量分数为85%的乙醇/水溶液的分离性能最佳。     

Pervaporation of methanol/methyl tert‐butyl ether mixtures through agarose/hydroxyethylcellulose blended membranes

In this study, we investigated methanol (MeOH)/methyl tert‐butyl ether (MTBE) separation with hydroxyethylcellulose (HEC)/agarose blended membranes by applying a pervaporation technique. The membranes permeated MeOH in preference to MTBE from MeOH/MTBE mixtures. From pervaporation and sorption data, the permselectivity of HEC/agarose blended membrane was dominantly due to solubility selectivity. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3408–3411, 2002     

Poly(p-substituted phenylacetylene) with perfluoroalkyloxydimethylsilyl side groups for oxygen and ethanol permselective membrane

Summary p-(1H,1H,2H,2H-perfluorodecyloxydimethylsilyl)phenylacetylene(ACf8) and p-(1H,1H,2H,2H-Perfluorohexyloxydimethylsilyl)phenylacetylene(ACf4) were synthesized and copolymerized with p-trimethylsilylphenylacetylene(ASi). The resulting copolymers, copoly(ACf8/ASi) and copoly(ACf4/ASi), were fabricated to tough membranes showing high oxygen permeabilities(Po ₂) of 10^-8 cc(STP)·cm/cm²·s·cmHg and high oxygen permselectivities(=Po ₂/Pn ₂) of more than 2.7. In particular, a copoly(ACf4/ASi) containing 15.1 mol% of ACf4 unit showed the best result: Po ₂=3.51x10^-8 cc(STP)·cm/cm²·s·cmHg and =3.04. The values were in a top level and very close to those of upper bound line in an -Po ₂ plot of data in the literature. In addition, copoly(ACfn/ASi) membranes were ethanol permselective owing to water repellency of the perfluoroalkyl groups. Copoly(ACf4/ASi) membranes showed better oxygen and ethanol permselectivity than copoly(ACf8/ASi) membranes.     

Selective separation of water from aqueous alcohol mixtures through functionalized syndiotactic poly(styrene‐co‐4‐methylstyrene) membranes by pervaporation

The pervaporation performances of a series of functionalized syndiotactic poly(styrene‐co‐4‐methylstyrene) (SPSM) membranes for various alcohol mixtures were investigated. The syndiotactic polystyrene copolymers, poly(styrene‐co‐4‐methylstyrene) (SPSM), were prepared by styrene with 4‐methylstyrene using a Cp*Ti(OCH₃)₃/methyl aluminoxane (metallocene/MAO) catalyst. The effect of functionalization on the thermal properties and polymer structure of the SPSM membranes were also investigated. The crystallinity of the functionalized SPSM membrane is lower than that of the unfunctionalized SPSM membranes. The water molecules preferentially permeate through the SPSM membranes. Compared with unfunctionalized SPSM membranes, the functionalized SPSM membrane effectively increases the membrane formation performances and the pervaporation performances. The optimun pervaporation performance (a separation factor of 510 and permeation rate of 220 g/m²h) was obtained by the bromination of SPSM (SPSMBr) membrane with a 90 wt % aqueous ethanol solution. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2247–2254, 2002     

Pervaporation characteristics and structure of poly(vinyl alcohol)/poly(ethylene glycol)/tetraethoxysilane hybrid membranes

Poly(vinyl alcohol) (PVA) blended with poly(ethylene glycol) (PEG) was crosslinked with tetraethoxysilane (TEOS) to prepare organic–inorganic PVA/PEG/TEOS hybrid membranes. The membranes were then used for the dehydration of ethanol by pervaporation (PV). The physicochemical structure of the hybrid membranes was studied with Fourier transform infrared spectra (FT‐IR), wide‐angle X‐ray diffraction WXRD, and scanning electron microscopy (SEM). PVA and PEG were crosslinked with TEOS, and the crosslinking density increased with increases in the TEOS content, annealing temperature, and time. The water permselectivity of the hybrid membranes increased with increasing annealing temperature or time; however, the permeation fluxes decreased at the same time. SEM pictures showed that phase separation took place in the hybrid membranes when the TEOS content was greater than 15 wt %. The water permselectivity increased with the addition of TEOS and reached the maximum at 10 wt % TEOS. The water permselectivity decreased, whereas the permeation flux increased, with an increase in the feed water content or feed temperature. The hybrid membrane that was annealed at 130°C for 12 h exhibited high permselectivity with a separation factor of 300 and a permeation flux of 0.046 kg m^?2 h^?1 in PV of 15 wt % water in ethanol. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Transport Phenomena of Chitosan Membrane in Pervaporation of Water-Ethanol Mixture

ABSTRACT

The pervaporation transport process of H₂O-EtOH solution was studied on a chitosan membrane and on a H₂SO₄ crosslinked chitosan membrane. The influence of concentration, temperature, and crosslinking was also studied. The dependence of permeation fluxes on feed concentration showed strong coupling effects existed in the permeation process. That the thermodynamic swelling—distribution relationship changed with the feed concentration also showed that a strong coupling effect existed in the thermodynamic swelling process. The permeation fluxes and thermodynamic swelling processes showed analogous relationships versus the concentration in the feed. The high swelling ratio and the high selectivity of the membrane in the thermodynamic swelling distribution process was the basis ofhigh flux and high permselectivity of pervaporation. With an increase of temperature, the permeation fluxes increased quickly, but the swelling ratio of water and EtOH in the membrane scarcely changed. This showed that an increase of temperature promoted the diffusion process but had little influence on permselectivity. The permselectivity of pervaporation depended strongly on the thermodynamic swelling process.     

Modification of cation exchange membrane by grafted poly(4-vinyl-N-methylpyridinium-iodide)

It is well known that cation exchange membranes, having a very thin layer of a cationic polyelectrolyte on the membrane surface, have preferential permselectivity for monovalent cations in a monovelent-divalent cations system. We studied the relationship between preferential permselectivity and molecular structure of the cationic polyelectrolyte. Grafted poly(4-vinyl-N-methylpyridinium-iodide) was used and was compared with poly(4-vinyl-N-methylpyridiniumiodide). The backbone polymers were poly(styrene-co-p-benzylstyrene) and poly(benzyl), onto which 4-vinylpyridine was grafted by anionic polymerization and then quaternized with CH₃I. The grafted poly(4-vinyl-N-methylpyridinium-iodide) is effective in making the cation exchange membrane preferentially permselevtive for Na⁺ - Ca²⁺ system and is more preferable than poly(4-vinyl-N-methylpyridinium-iodide) in terms of electric resistance of the membrane. However, the relationship between the molecular structure of the cationic polyelectrolyte and the durability of the preferential permselectivity is not clear.     

Separation of alcohol–water mixture by pervaporation through a reinforced polyvinylpyridine membrane

A membrane consisted of cross-linked poly(4-vinylpyridine) and reinforced by a nonwoven cloth made of poly(ethylene terephthalate) was prepared by copolymerization of 4-vinylpyridine with divinylbenzene in the presence of the nonwoven cloth. Pervaporation performance of this polyvinylpyridine membrane was examined at several feed alcohol concentrations and temperatures. The membrane showed water selectivity, and the permselectivity, α_W/_A, for the alcohol–water mixture was in the order isopropyl > propyl > tert-butyl > ethyl > methyl. The membrane showed a large permeability, and the pervaporation flux, ?, for the ethanol–water mixture was 7–13 kg/h per square meter of the membrane in pervaporation with sweeping of carbon dioxide under atmospheric pressure and at 40°C. The membrane was durable and long lasting for a prolonged-period, and permselectivity and permeability of the membrane did not fall off even after repeated use for 1000 h. © 1993 John Wiley & Sons, Inc.