Pervaporation of pyridine–water mixture through poly(acrylonitrile-co-4-styrene sulfonic acid) membrane

The modified polyacrylonitrile (PAN) membranes used in this study had sulfonic acid moiety to act as a specific functional group for the dehydration of pyridine aqueous solution. The in situ complex formed between pyridine in the feed and sulfonic acid moiety in the membrane could enhance the dehydration capacity of the modified PAN membranes. It was found that the pervaporation patterns were closely related to the content of the sulfonic acid in the modified PAN membranes. The effective in situ complex membrane can be prepared by controlling the content of sulfonic acid in the membrane. The in situ complex membrane shows an increase of permeation flux with a slight decrease in separation factor as operating temperature increase. © 1996 John Wiley & Sons, Inc.     

Infra-red study of poly(1-pentene) and poly(4-methyl-1-pentene)

The infra-red (i.r.) spectra of the two polymorphous forms (modification 1 and 2) of isotactic poly(1-pentene) are reported. Several absorption bands characteristic of the two modifications have been detected and attributed to the helical conformation of the polymer chains. The differences between the two modifications are reproducible, thus enabling their identification from i.r. spectroscopy. The infra-red spectra of isotactic poly(4-methyl-1-pentene) is also reported, and compared with that of the atactic polymer. General assignment of absorption bands is presented.     

Dehydration of acetic acid/water mixtures by pervaporation with a modified poly(4-methyl-1-pentene) membrane

The dehydration of acetic acid/water mixtures by pervaporation with a EVA/TPX membrane has been studied. The membrane exhibited water selectivity during all process runs. Investigations were focused on the effects of heat treatment temperature on membrane formation, membrane thickness, feed solution concentration, EVA content, and feed solution temperature. Compared with pure TPX membrane, the EVA/TPX blend membrane effectively improved the pervaporation performances. The permeation rate decreases with increasing heat treatment temperature during the membrane formation. Optimum pervaporation results were obtained by EVA/TPX membrane with 12.5 wt % EVA content, giving a separation factor of 606 and permeation rate of 215 g/m²h.     

Electrostatic polymer processing of isotactic poly(4-methyl-1-pentene) fibrous membrane

Isotactic poly(4-methyl-1-pentene) (P4M1P) is a widely used polymer in industrial applications and specifically, in medical products. Producing micro- or nanofibers would expand the usefulness of P4M1P to a broad range of medical applications. The choice and quality of solvent for the solution used for electrospinning can have a dramatic effect on the spinnability of fibers and on their morphological appearance. In this study, four solvent systems: cyclohexane, cyclohexane/acetone mixture, cyclohexane/dimethyl formamide (DMF) mixture and cyclohexane/acetone/DMF mixture have been investigated. As demonstrated by FE-SEM, electrospun fibers with different morphologies including round, twisted with a roughened texture, curled and twisted-ribbon shapes were formed. The fiber shape and morphology depended strongly on the type and amount of non-solvent used.     

Permeation and separation characteristics of alcohol–water mixtures through poly(dimethyl siloxane) membrane by pervaporation and evapomeation

Permeation and separation characteristics for aqueous alcoholic solutions such as methanol/water, ethanol/water and 1-propanol/water were studied using a poly(dimethyl siloxane) membrane by pervaporation and evapomeation. Poly(dimethyl siloxane) membrane preferentially permeated alcohol from aqueous alcoholic solutions in both methods. The concentration of alcohol in the permeate by evapomeation was higher than that by pervaporation. However, the permeation rate for the former method was smaller than that for the latter method. In evapomeation with a temperature difference between the feed solution and the membrane surroundings, when the temperature of the membrane surroundings was kept constant and the temperature of the feed solution was raised, both the permeation rate and the permselectivity for ethanol increased with increasing temperature of the feed solution. On the other hand, as the temperature of the feed solution was kept constant and the temperature of the membrane surroundings was changed, the permeation rate decreased, but the permselectivity for ethanol increased remarkably with dropping temperature in the membrane surrounding. Under permeation conditions of a feed solution of 40°C and a membrane surrounding temperature of ?30°C in evapomeation, an aqueous solution of 10 wt % ethanol in the feed was concentrated to about 90 wt % in the permeate. The permselectivity for alcohol was in the order of methanol <ethanol <1-propanol. The above permeation and separation characteristics are discussed from the viewpoint of the physicochemical properties of the poly(dimethyl siloxane) membrane and the permeating molecules.     

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.     

Pervaporation separation of an aqueous organic mixture through a poly(acrylonitrile‐co‐vinylphosphonic acid) membrane

Polyacrylonitrile (PAN)‐based copolymers containing phosphonic acid moiety were synthesized for dehydration of aqueous pyridine solution. The in situ complex, formed between the vinylphosphonic acid (VP) moiety in the membrane and the pyridine in the feed, enhanced separation capacity of poly(acrylonitrile‐co‐vinylphosphonic acid) (PANVP) membranes. All the PAN‐based membranes containing phosphonic acid were very selective toward water. The pervaporation performances of PANVP membranes depended on the content of the phosphonic acid moiety in the membrane and operating temperature. The pervaporation separation of water/pyridine mixtures using PANVP membranes exhibited over 99.8% water concentration in permeate and flux of 4–120 g/m²/h depending on the content of vinylphosphonic acid and operating temperature. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 83–89, 1999     

Effect of several dual solvents on the phase separation of poly(4-methyl-1-pentene)

Phase separation of isotactic poly(4-methyl-1-pentene) (PMP) from various solvents gives polymer masses which can be converted into foams that vary from crumbly powders to well-connected, strong, flexible solids. The composition of the solvent is an important parameter in determining the nature of the separated polymer phase. The influence of solvent (or non-solvent) on the temperature and character of the phase separation event and on the resulting foam structure is addressed in this paper. Thus differing ratios of two poor solvents for PMP, bibenzyl and paraffin, were found to give variable foam structures and surprising phase behaviour. Thermochromism is sometimes observed as the polymer separates.     

XPS characterization of surface fluorinated poly(4-methyl-1-pentene)

The fluorinated surface layer of poly(4-methyl-1-pentene) membranes exposed to a dilute stream of fluorine gas has been characterized with X-ray photoelectron spectroscopy. The concentration and profile of reacted fluorine as a function of exposure time is determined. A computer routine was employed to deconvolute the poorly resolved carbon spectra after various fluorine exposure times. The concentrations of mono-, di-, and trifluorocarbon groups thus determined were used to propose specific structures of PMP at the surface after 1 and 15 min of fluorination. The carbon spectra collected at electron takeoff angles of 15°, 30°, and 90° were also deconvoluted, giving insight into the placement of fluorine as a function of depth. Oxygen is incorporated into the polymer during the fluorination reaction, and the O1s spectra was deconvoluted to determine how the oxygen is bound.     

Pervaporation and solute separation through semi-interpenetrating and interpenetrating polymer network membranes prepared from poly(4-vinylpyridine) and poly(glycidyl methacrylate)

Semi-interpenetrating (SPN) and interpenetrating polymer network (IPN) membranes were prepared from a mixture system of poly(4-vinylpyridine) (P4VP) and poly(glycidyl methacrylate) (PGMA) by quaternizing crosslinking of P4VP with 1,4-dibromobutane (DBB) and by simultaneous crosslinking of P4VP with DBB and PGMA with tetraethylenepentamine (TEPA), respectively. The difference between SPN and IPN was demonstrated by IR, tensile strength, and dimension stability. The membrane performance in pervaporation (PV) for ethanol–water mixtures and reverse osmosis (RO) was investigated. The polymer mixture of 1 : 1 on a monomer base with 30 mol % DBB on the 4VP unit and 5.6–7.5 mol % (8–10 wt %) TEPA on the GMA unit gave an optimum membrane performance. Those crosslinked membranes were stronger than was the cellulose acetate membrane, mostly owing to the PGMA chains, and exhibited a high separation factor for the azeotropic feed in PV. IPN membranes generally showed a performance higher than that of the SPN ones. An attempt to improve the product rate was made by the addition of a water-soluble polymer to the membrane on casting. The separation factor for solubility in the membrane at the feed side dominated the overall separation factor, particularly for feeds of higher ethanol concentrations. © 1998 John Wiley & Sons, Inc. J Appl Polm Sci 69: 1953–1963, 1998     

Kinetics of the thermal oxidation of poly(4-methyl-1-pentene)

The kinetics of the thermal oxidation of isotactic and atactic poly(4-methyl-1-pentene) were studied in the bulk phase using infra-red (i.r.) spectroscopy. The rates of formation of the non-volatile products were assessed from the i.r. bands of the carbonyl groups at different temperatures and various oxygen concentrations. Reaction temperature varied from 120° to 185°C and oxygen concentrations from 10 to 100%, by volume. A general kinetic scheme and mathematical expressions, previously reported for the thermal oxidation of polyolefins, satisfactorily explained the experimental results. Single activation energies for the major oxidation stages in the scheme, were estimated from various Arrhenius plots.     

Pervaporation separation of water–isopropanol mixture using carboxymethylated poly(vinyl alcohol) composite membranes

The pervaporation separation of water–isopropanol mixtures was carried out using carboxymethylated poly(vinyl alcohol) (CMPVA) composite membranes. Carboxymethylated PVA (CMPVA) was synthesized by reacting PVA with various concentrations of monochloroacetic acid. Substitution efficiency of the CMPVA ranged from 12–32%. The cross‐sectional structure of the composite membrane for pervaporation was confirmed by scanning electron microscopy (SEM) exhibiting a 20‐μm active skin layer. Glass transition temperature of the CMPVA was in the range of 74–84°C, and decreased with increasing substitution efficiency. Degree of swelling and permeation flux for water–isopropanol in pervaporation increased with the substitution degree of carboxymethylation. CMPVA composite membrane, having 16% substitution efficiency, showed the following pervaporation performance; permeation flux of 831 g/m² h and separation factor of 362 measured at 80°C and 85 wt % feed isopropanol concentration. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 241–249, 1999     

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     

Pervaporation separation of aqueous organic mixtures through sulfated zirconia‐poly(vinyl alcohol) membrane

Sulfated zirconia‐poly(vinyl alcohol) membranes were prepared, and pervaporation performances for aqueous organic mixtures were investigated. These hydrophilic membranes were formed by crosslinking poly(vinyl alcohol) (PVA) with the solid acid of sulfated zirconia by an acid‐catalyzed reaction. The pervaporation performances were measured as a function of the content ratio of sulfated zirconia to PVA, which affected the degree of swelling for water and the crosslinking density of the membrane. The membrane selectivity in pervaporation of aqueous organic mixtures increased in order of acetic acid < ethanol < 2‐ethoxyethanol without sacrificing the permeation rate, depending on their feed compositions. The effects of feed temperature and concentration on the membrane performance were also significant. It was found that sulfated zirconia in the membrane preparation played an important role as a filler material as well as an effective crosslinking or insolubilization agent in improving and controlling the membrane performance, i.e., permeation rate and selectivity. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1450–1455, 2001     

Pervaporation separation of 1,1,2‐trichloroethane–water mixture through crosslinked acrylate copolymer composite membranes

The separation of a chlorinated hydrocarbon from a dilute aqueous solution through a crosslinked acrylate copolymer–porous substrate composite membrane by pervaporation was investigated. Poly(n‐butyl acrylate‐co‐acrylic acid) and poly(n‐butyl acrylate‐co‐2‐hydroxyethyl acrylate) were synthesized and composite membranes were prepared, which were made from the crosslinked polymer and a porous substrate. Pervaporation measurement was carried out for a dilute aqueous solution of 1,1,2‐trichloroethane at 25°C and under a vacuum on the permeate side (below 10 mmHg). The separation factor, overall flux, 1,1,2‐trichloroethane concentration in the membrane, and the degree of swelling decreased with increase in the acrylic acid or 2‐hydroxyethyl acrylate content of the acrylate copolymer. The influence of the crosslinking agent content on the pervaporation performance was small, and the separation factor and the overall flux showed a convex curve. The structure of the crosslinking agent had no effect on the separation. The influence of the pore size of the substrate and the thickness of the polymer layer on the separation of 1,1,2‐trichloroethane was observed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 983–994, 1999     

Pervaporation separation of styrene–ethylbenzene mixture using poly(hexamethylene sebacate)‐based polyurethane membranes

A series of poly(hexamethylene sebacate) (PHS), with molecular weight in a range of 890–2200, based polyurethanes (PU), were synthesized by solution polymerization with different kinds of isocyanate and chain extender and two kinds of polymerization methods. All the PHS‐based PU membranes exhibited selectivity towards styrene during the pervaporation of styrene–ethylbenzene mixtures, and the properties of sorption and pervaporation were related to the composition of the PU membranes. Membranes with a low hard‐segment content and by two‐stage polymerization method exhibited high permselectivity. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 753–761, 1999     

Pervaporation separation of water–isopropyl alcohol mixture by PVA/LiBr membrane

Hydrophilic polyvinyl alcohol membranes, modified by lithium bromide, were prepared with glutaraldehyde as a crosslinking reagent. The membranes were investigated for the pervaporation dehydration of a water–isopropyl systems. The effect of the feed temperature on permeation flux and membrane selectivity was studied. The characterization of modified membranes was performed using Fourier transform infrared spectroscopy (FT‐IR), differential scanning calorimeter (DSC) and X‐ray diffraction. It was observed that the crystallinity of membranes increased as lithium bromide was added to the polymer. High performance liquid chromatography (HPLC) was used to analyze water content and isopropyl alcohol in the feed and permeate samples The pervaporation tests also confirmed an enhancement in water permeability through adding LiBr to the polymer, because of the high hydrophilic properties of this salt. According to pervaporation experiments conducted at 50°C, the water flux increased from 0.1049 kg/ m² hr to 0.1114 kg/ m² hr as 0.5 wt% of LiBr was added to the polymer matrix. Furthermore, an addition of 1 wt% of LiBr compared to homogeneous PVA membrane increased selectivity from 76 to 779. POLYM. ENG. SCI., 59:E101–E111, 2019. © 2018 Society of Plastics Engineers     

An unusual branching in single crystals of isotactic poly(4-methyl-1-pentene)

Single crystals of low M_w poly(4-methyl-1-pentene) (P4MP1) in its form I display an unusual streaking of their diffraction pattern. The crystals also frequently give rise to composite diffraction patterns made of two patterns rotated by 37°. The streaking indicates a structural disorder, namely a shift of nearby layers along the a or b axis by one quarter of the unit-cell edge. The daughter crystals, rotated by 37°, are produced on the edges of the parent crystals via an epitaxial growth that is a direct consequence of the structural disorder.     

Crazelike features in deformation of hard elastic poly(4-methyl-1-pentene) film

A hard elastic film of poly(4-methyl-1-pentene) was investigated by using wide-angle X-ray diffraction, small-angle X-ray scattering (SAXS), and stress–strain measurements. The film showed somewhat hard elasticity above the glass transition temperature (T_g), while it showed a brittle nature below T_g. In the former case, the SAXS pattern of the stretched film was very analogous to that of usual crazed materials (crazelike feature), namely void scattering on the meridian and interference scattering due to microfibrils on the equator. The fibrillation was discussed in terms of deformability of the lamellae and, further, that of the hellcal chain. Our results were also compared with the model of ?a?kovi? and Hosemann for deformation of hard elastic crystalline materials.     

Melt spinning and characterization of hollow fibers from poly(4-methyl-1-pentene)

In this article, the melt spinning behavior of poly(4-methyl-1-pentene) (PMP) hollow fibers (HF) is examined. The melt spinning trials are carried out on a pilot scale melt spinning plant with different settings while a 10-hole 2c-shaped spinneret is used. It is found that the winding speed mainly affects the outer fiber diameter. The influence of different melt spinning parameters is investigated, in particular temperatures, take-up velocities, and the use of quench air. For this purpose, the shape and crystalline structure of the fibers are analyzed using a light microscope, a scanning electron microscope, and wide-angle X-ray scattering. The shape of the fibers is mainly influenced by the temperature settings in the melt spinning process. As a reasonable lower limit, a melt spinning temperature of 280°C is identified. Concerning the crystallinity, a saturation going along with a slight reduction of the polymer chain orientation is observed at elevated take-up velocities.