Permeation of solutes in water-swollen poly(vinyl alcohol-co-itaconic acid) membranes

Partition and permeability coefficients of urea, NaCl, and saccharose in water-swollen poly(vinyl alcohol-co-itaconic acid) membranes with various water contents (0.25 ? H ? 0.86) were measured. Partition coefficients and permeability ratios in freezing and nonfreezing water were estimated based on a parallel permeation model. It was suggested that at 25°C the permeation of saccharose in the nonfreezing water was nearly zero due to its negligible partition coefficient, while NaCl and urea were found to be able to permeate even the nonfreezing water. The activation energies of diffusion for three solutes were found to increase with the decrease of water content of the membranes. Since the fraction of nonfreezing water increased with the decrease of water content of the membranes, it is assumed that the increased activation energy of diffusion is due to the fact that the diffusion in nonfreezing water needs higher activation energy than in the pure bulk water.     

Preparation of monodisperse poly(vinyl alcohol) microspheres by heterogeneous surface saponification and iodine complex formation

Monodisperse poly(vinyl acetate) (PVAc) microspheres with high molecular weight obtained by suspension polymerization of vinyl acetate were saponified in alkaline aqueous solution to keep their spherical structure. The saponification was restricted on the surface of the PVAc microspheres and obtained particles had skin/core structure. Various poly(vinyl alcohol) (PVA) microspheres with different diameters and degrees of saponification (DSs) were obtained. The conversion of PVAc to PVA during the heterogeneous surface saponification time were examined by nuclear magnetic resonance spectroscopy and after 72 h hydrogel type PVA microspheres completely saponified were obtained. The crystal melting temperatures of the microspheres obtained by the saponification were measured a constant value of 238°C irrespective of varying DS, and the peaks became enlarged as reaction time. Iodine complexes were formed in saponified microspheres with DS of 41% and 99% by immersing them in I₂/KI aqueous solution and decomposed by the reduction of I₂ in the complexes to 2I^? using sodium sulfite to confirm whether the skin formed through the saponification was composed of PVA with high VA content. Obviously, characteristic blue color developments owing to I₅^?‐PVA complexes were observed in both saponified regions and a red in the PVAc core. Consequently, it was concluded that the PVA skins formed by heterogeneous surface saponification had high DSs. Such complexes endowed polymeric microspheres a good radiopacity which would be useful in clinical treatment of vascular diseases and were examined by X‐ray irradiation image. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation of poly(vinyl alcohol)-graft-N-isopropylacrylamide copolymer membranes and permeation of solutes through the membranes

Thermosensitive copolymers were prepared by graft copolymerization of N-isopropylacrylamide onto poly(vinyl alcohol) in dimethyl sulfoxide (DMSO) using potassium peroxodisulfate as an initiator. The phase transition temperature was measured by differential scanning calorimetry. The copolymers exhibited almost the same transition temperature (about 33°C) as that of poly(N-isopropylacrylamide) regardless of the composition of the copolymers. The copolymer membranes were obtained by evaporating solvent from the DMSO solution of the graft copolymers and were insolubilized by annealing the membranes at 120°C for 10 h. Permeation of the lithium ion and Methylene Blue through the membranes was investigated at various temperatures. The permeation of solutes was greatly affected by temperature, i.e., the permeation of the solutes could be controlled at temperatures below and above 33°C. © 1994 John Wiley & Sons, Inc.     

Structure and properties of poly(vinyl alcohol)–iodine complex formed in the crystal phase of poly(vinyl alcohol) films

The structure and optical properties of the complex formed in the crystal phase of PVA that is caused by soaking at very high iodine concentration are investigated. In the resonance Raman spectra of lightly and heavily iodinated specimens, two Raman shifts appeared at 109 and 161 cm^?1. The 109 cm^?1 peak due to the I mode was much stronger than the 161 cm^?1 peak in a heavily iodinated specimen, whereas the peak was comparable with the 161 cm^?1 peak in a lightly iodinated specimen. The complex formed in the crystal phase is identified as the I mode complex. It has an averaged iodine–iodine distance of 3.2 Å, which is different from the 3.08 Å of the I mode complex formed in the amorphous phase. The effect of KI concentration in the soaking solution on the formation of the complex is also examined. The increased KI concentration in the soaking solutions at a fixed iodine concentration increases the amount of the complex formed in the crystal phase. The change in the hydrogen-bonding state in the crystal phase with the complex formation can be evidenced by IR and NMR. © 1994 John Wiley & Sons, Inc.     

Gas permeation through water‐swollen polysaccharide/poly(vinyl alcohol) membranes

The effect of Na‐alginate content on the gas permeation properties of water‐swollen membranes prepared by varying Na‐alginate and poly(vinyl alcohol) (PVA) content in membranes was investigated. The influences of water content and crystallinity of the membranes on the gas permeation performance of the water‐swollen membranes were studied. The gas permeation rate and selectivity of Na‐alginate/PVA water‐swollen membranes were compared with those of the dry membranes. The permeation rates of nitrogen and carbon dioxide through water‐swollen membranes were in the range of 0.4–7.6 × 10^?7 to 3.7–8.5 × 10^?6 cm³ (STP)/cm² s^?1 cmHg^?1, which were 10,000 times higher than those of dry‐state membranes. The permeation rates of mixture gases through water‐swollen Na‐alginate/PVA membranes were found to increase exponentially with the increase of Na‐alginate content, whereas carbon dioxide concentration in permeates was decreased linearly. It was found that the gas permeance of the water‐swollen membranes increased with increasing the Na‐alginate content in the membrane. Gas permeation rates of the water‐swollen Na‐alginate/PVA membranes increased with increasing the water content in the membrane and decreasing the crystallinity of the membrane. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3225–3232, 2004     

Water stability of syndiotactic poly(vinyl alcohol)/iodine complex film

The desorption behavior of iodine in syndiotactic poly(vinyl alcohol) (s-PVA) with a syndiotactic diad content of 63.1% iodine film in water was investigated in relation to the solubility of s-PVA in water. Despite a low number-average degree of polymerization of 900, the degree of solubility of s-PVA film in water at 80°C was limited to about 10%, whereas atactic poly(vinyl alcohol) (a-PVA) film was completely soluble at a lower temperature, 50°C. The degree of iodine desorption of s-PVA/iodine film at a high temperature decreased remarkably compared with that of a-PVA/iodine film. The fastness of iodine of the drawn s-PVA/iodine film was far superior to that of the undrawn film. Over a draw ratio of 5, the iodine desorption was suppressed significantly with increasing drawing temperature rather than the draw ratio. In addition, the iodine desorption of postdrawn s-PVA/iodine film was lower than that of predrawn s-PVA/iodine film. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 108–113, 2001     

Characteristics of permeation and separation for propanol isomers through poly(vinyl alcohol) membranes containing cyclodextrin

Poly(vinyl alcohol) membranes containing cyclodextrin (CD–PVA membrane) were prepared and characteristics of permeation and separation for propanol (PrOH) isomers through the CD–PVA membranes were investigated by pervaporation and evapomeation. Evapomeation was more effective for the separation of PrOH isomers through the CD–PVA membrane than was pervaporation. The CD–PVA membrane more preferentially permeated n-PrOH than i-PrOH from their mixtures. In particular, the mixture of 10 wt % n-PrOH concentration was concentrated to about 45 wt % through the CD–PVA membrane. Both permeability and selectivity for n-PrOH were improved with an increase of CD content in the membrane. The results were supported by the fact that the affinity of CD for n-PrOH was stronger than that for i-PrOH. The permeation mechanism of PrOH isomers through the CD–PVA membrane is discussed based on the solution–diffusion theory. © 1994 John Wiley & Sons, Inc.     

Preparation of poly(vinyl alcohol)-graft-N-isopropylacrylamide copolymer membranes with triphenylmethane leucocyanide and permeation of solutes through the membranes

Thermo- and photosensitive hydrogel membranes were prepared by graft copolymerization of an N-isopropylacrylamide (NIPAAm) and triphenylmethane leucocyanide (LeCN) monomer onto poly(vinyl alcohol) (PVA). The yield of the graft copolymerization as well as the content of the poly(NIPAAm) segments grafted onto PVA was depressed by copolymerization of the LeCN monomer. The change in the permeation rate of poly(ethylene glycol)s through the hydrogel membranes was induced photochemically by dissociation of LeCN moieties in the membranes. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1931–1937, 1998     

Mechanochemistry and permeability of polyelectrolyte complex membranes composed of poly(vinyl alcohol) derivatives

Two polyanions and two polycations were prepared by the esterification of poly(vinyl alcohol). Properties of their neutral polyelectrolyte complex membranes were compared with those of polyelectrolyte membranes. The charged state on the membranes was related closely to the mechanochemical reaction, the salt rejection, and the solution permeability. Both the salt rejection and the water flux of neutral polyelectrolyte complex memberanes were lower than those of the corresponding acidic or basic complex membranes.     

Non-equilibrium electrolyte permeability in poly(vinyl alcohol) membranes

Permeability of poly(vinyl alcohol) membranes was studied as a function of exposure time in 45% aqueous potassium hydroxide and quantity of residual water in film. The presence of non-equilibrium and equilibrium periods in electrolyte permeability of PVA films containing aqueous KOH solution or residual water were found and were explained from the viewpoint of change in the diffusion mechanism of permeability. The influence of cross-linking on permeability of PVA films was examined.     

Effect of hygroscopic materials on water vapor permeation and dehumidification performance of poly(vinyl alcohol) membranes

In this study, two hygroscopic materials, inorganic lithium chloride (LiCl) and organic triethylene glycol (TEG) were separately added to poly(vinyl alcohol) (PVA) to form blend membranes for air dehumidification. Water vapor permeation, dehumidification performance and long‐term durability of the membranes were studied systematically. Membrane hydrophilicity and water vapor sorbability increased significantly with higher the hygroscopic material contents. Water vapor permeance of the membranes increased with both added hygroscopic material and absorbed water. Water permeation energy varied from positive to negative with higher hygroscopic content. This observation is attributed to a lower diffusion energy and a relatively constant sorption energy when hygroscopic content increases. Comparatively, PVA/TEG has less corrosive problems and is more environmentally friendly than PVA/LiCl. A membrane with PVA/TEG is observed to be highly durable and is suitable for dehumidification applications. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44765.     

Structure of poly(vinyl alcohol)-iodine complex formed in the amorphous phase of poly(vinyl alcohol) films

The effect of syndiotactivity of poly(vinyl alcohol) (PVA) both on the formation and thermal stability of the complex formed in the amorphous phase of PVA films is investigated, and then a model of the complex is presented. The amount of the complex formed in syndiotacticity-rich PVA is much larger than that formed in atactic PVA under a given iodine-soaking condition, and the former complex has a higher thermal stability in the soaking solution than the latter. The complex formed in the amorphous phase is proposed to have such a structure as that in which a linear polyiodine I₅^? or I₅^? with a 3.1 A? periodicity is enveloped by four PVA segments of syndiotactic configuration with extended conformation. In this model, these four PVA chains participating in a complex are supposed to be fixed by interchain hydrogen bonds. The observed X-ray meridional intensity curve of iodinated PVA film can be explained by a series of two I₅^?. © 1993 John Wiley & Sons, Inc.     

Formalized poly(vinyl alcohol) membranes for reverse osmosis

The permeation properties of formalized poly(vinyl alcohol) membranes are described. The interest of this work is centered on the properties relevant to desalination by reverse osmosis. These membranes, when properly prepared, showed reasonably high water permeability, high salt rejection, and stability in the presence of acids and alkalies.     

Poly(vinyl alcohol) and poly(vinyl amine) blend membranes for isopropanol dehydration

Blended membranes of hydrophilic polymers poly(vinyl alcohol) (PVA) and poly(vinyl amine) (PVAm) were prepared and crosslinked with glutaraldehyde. The prepared membranes were characterized using infrared (attenuated total reflection mode) spectroscopy, differential scanning calorimetry, X‐ray diffractometry, and scanning electron microscopy measurements. Pervaporation performances of the membranes were evaluated for the separation of water‐isopropanol (IPA) mixtures. As the PVAm content increased from PVAm0 to PVAm1.5, the flux through a 70 μm film increased from 0.023 to 0.10 kg/m² h at an IPA/water feed ratio of 85/15 at 30 °C. The driving force for permeation of water increased due to the temperature but it has no effect on IPA permeation. Activation energies for the permeation of IPA and water were calculated to be 17.11 and 12.46 kJ/mol, respectively. Controlling the thickness of the blend membrane could improve the permeation flux with only a marginal reduction in the separation factor. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45572.     

Separation of liquid mixtures by using polymer membranes. III. Grafted poly(vinyl alcohol) membranes in vacuum permeation and dialysis

A series of poly(vinyl alcohol) membranes were modifed by radiation-induced graft copolymerization with acrylic acid and methacrylic acid monomers. These grafted poly(vinyl alcohol) membranes were then tested for their separation and permeability characteristics in vacuum permeation and dialysis experiments. The permselectivity of the membranes toward methanol and water was studied on a vacuum permeation apparatus at 30, 40, and 50°C. The permeation process was found to be a temperature-activated process. The logarithm of the permeation rate varied linearly with the reciprocal of the absolute temperature. The permeability of the grafted membranes was found to increase with the degree of grafting, with no appreciable selectivity toward water in binary mixtures. The acrylic acid-grafted membranes generally showed greater improvement in permeability than the methacylic-grafted membranes. The permeability of the grafted membranes toward methanol, sodium chloride, urea, creatinine, and uric acid was studied in a dialyzer. In all cases, the grafted membranes showed an improved permeability toward these solutes over the commercial poly(vinyl alcohol) membranes. The dialysis results were then compared with those obtained for dialysis-grade cellophane membranes. For the case of sodium chloride, urea, and methanol, the permeability of the grafted membranes was comparable to that of cellophane. A comparison of commercial and grafted poly(vinyl alcohol) membranes in their permeability toward ionic solutes exhibited somewhat anomalous behavior in that the permeability of the commercial membranes was higher than that of the grafted membranes. This related to the ionic nature of the modified membrane. The permeability coefficients determined in the dialysis experiments were found to be directly related to the degree of hydration of the grafted membrane. This behavior was attributed to changes in the size and shape of voids within the membrane structure.     

Permeation characteristics of poly(vinyl alcohol)–poly(vinyl acetate) composite porous membranes

Poly(vinyl alcohol) (PVAc) composite porous membrane has been prepared from PVAc latex film by extraction with acetone. The PVAc latex was prepared by emulsion polymerization of vinyl acetate in the presence of PVA, employing the hydrogen peroxide–tartaric acid systemm as an initiator. The extraction degree of PVAc could be controlled in a wide range by changing the addition method of the initiator, and, acoordingly, PVA–PVAc omposite porous membranes which had variosu void volumes were obtained. The maximum void volume attained was ca. 90%. Permation characteristics of organic solvents wre investigated on the membranes whose extraction degrees were 95.6% and 80.7%. Thge feeds were benzene, n-hexane, cyclohexane, and their mixtures. neither swelling nor shrinkage in tje appearance size of the while benzene hardly permeated even at 20 kg/cm². The grafted PVAc in the mebrane was removed or converted into grafted PVA by treatment with sodium methylate, and then the depression of benzene permeation was lost. The grafted PVAc was suggested to be localizd on the cell wall and was found to function as a valve which closes with nenzene or a good solvent for PVAc and opens with n-haxane or a poor solvent for PVAc.     

On the poly(vinyl alcohol)–iodine complexes

The color development due to the complex formation of poly(vinyl alcohol) (PVA) with iodine increased with increasing syndiotacticity of PVA. Isotactic PVA showed no color development. The color development of syndiotacticity-rich PVA film decreased with increasing annealing temperature for films before complexization, whereas that of atactic (commercial) PVA increased with it. Lower temperatures, the elongation of complex film, and the presence of boric acid enhanced the absorbance at 600 nm due to I^?₅. The complexes are assumed to be made by incorporation of polyiodines into aggregates of syndiotactic sequences in PVA. The polarizability and electric conductivity of complex films are investigated. © 1993 John Wiley & Sons, Inc.     

Polyacrylonitrile-reinforced poly(vinyl alcohol) membranes: Mechanical and dialysis performance

Membranes used for hemodialysis should have good mechanical strength to withstand the maximum transmembrane pressure. Although crosslinked poly(vinyl alcohol) membrane has superior permeability to solutes, its wet breaking strength is low. Mechanical strength, dry and wet, of membranes made from crosslinked blendmers of poly(vinyl alcohol) and polyacrylonitrile was investigated. The possibilities of these membranes for the application as dialysis membranes were evaluated by estimating its solute permeabilities. The optimum membrane selected shows permeability and mechanical properties comparable with the commercial regenerated cellulose membrane. Polyelectrolyte grafting made the membrane more blood-compatible. © 1995 John Wiley & Sons, Inc.