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.     

Rejection of phenolic derivatives in aqueous solution by an interpolymer anionic composite reverse osmosis membrane

Reverse osmosis separation for 23 phenollic derivatives was examined by an anionic charged composite membrane. The solute permeation was carried out in single-solute aqueous solution (200 mg/L) under applied pressure of 3.92–7.85 MPa at 25°C. The correlation between the solute rejection and polar parameters for phenolic derivatives has been investigated. For p-alkylphenols, the solute rejection increased with molecular weight and/or molecular branching. In undissociated state, the rejection of phenolic derivatives was closely related with the Taft's number and the Hammett's number of substituents. Also rejections of phenolic derivatives depended upon the pH value of feed soultion and the polar effect of substituted groups. For example, rejections of aminophenols showed the minimum value at a certain pH value and on either side of the minimum point, the rejection of aminophenol increased. From these facts, the main factors in reverse osmosis serparation by an anionic composite membrane were discussed.     

The rejection of polar organic solutes in aqueous solution by an interpolymer anionic composite reverse osmosis membrane

Reverse osmosis separation for many kinds of polar organic solutes (alcohols, phenols, monocarboxylic acids, amines, and ketones) was examined by an anionic charged composite membrane. The solute permeation was carried out in single-solute aqueous solution (200 mg/L) under applied pressure of 7.88 MPa at 25°C. The correlation between the solute rejection and polar parameters for these organic solutes have been investigated. For n-alkyl alcohols, monocarboxylic acids, and ketones, the solute rejection increases with molecular weight and/or molecular branching. For undissociable polar organic solutes such as alcohols and ketones, solute rejections are closely related with the Taft's number. For dissociable polar organic solutes, solute rejections depend greatly upon the dissociation constant and the degree of dissociation of solute. This membrane showed higher rejection (80%) for phenol in an undissociated state at a 98% rejection level of NaCl. Also, rejections of phenolic derivatives depend upon the pH value of the feed solution and the polar effect of substituted groups. For acetic acid and methylamine, the solute rejection increases proportionally to the degree of dissociation of solute. From these facts, the main factors in reverse-osmosis separation by an anionic composite membrane are discussed.     

Investigation of the interpolymer association between poly(vinyl alcohol) and poly(sodium styrene sulfonate) in aqueous solution

A viscosimetric method has been used to study the interpolymer association between poly(vinyl alcohol) (PVA) and poly(sodium styrene sulfonate) (PSSNa) in aqueous solution. At constant molecular weight of PSSNa, it was found that, the PVA and PSSNa associations were improved with the decrease of molecular weight of PVA and the decrease of its hydrolysis degree. The measurement of intrinsic viscosity [η] and the determination of Huggins associative coefficient K_H of different PVA samples were used to select the most appropriate PVA sample, which leads to homogeneous polymer–polymer mixtures (PVA with hydrolysis degree 87–89%, molecular weight 124,000–186,000 g/mol, intrinsic viscosity [η] = 1.02 dL/g, and Huggins associative coefficient K_h.ass = 0.76). The obtained results show that the interpolymer association between PVA and PSSNa, in aqueous solution, is mainly due to intermolecular hydrogen bonds between hydroxyl groups of PVA and sulfonate groups of PSSNa. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and structure of poly(vinyl alcohol)–poly(vinyl acetate) composite porous membrane

The preparation of poly(vinyl alcohol) (PVA)–poly(vinyl acetate) (PVAc) composite porous membrane was investigated by extracting PVAc with solvent from films of PVAc lattices which were obtained by the emulsion polymerization of vinyl acetate (VAc) in the presence of PVA. The formation of the porous membrane depended upon whether or not PVAc in the latex film was easily extracted with solvent. In the case of using hydrogen peroxide (HPO)–tartaric acid (TA) as an initiator, in the film of the latex which was produced from the batch method in which all ingredients of the batch were put into the reaction vessel before starting polymerization, PVAc could be extracted over 90% of total PVAc with common organic solvents. In the film of the latex which was produced from the dropwise addition method of VAc and initiator, the PVAc extraction was about 20-30%. On the other hand, in the case of using ammonium persulfate as an initiator, the desired porous membrane was not obtained. The structure of the porous membrane obtained from the latex of the batch method by using HPO—TA consisted of spherical cells which were made up of PVA and grafted PVAc or insoluble PVAc like microgels, which were not extracted with organic solvent and were connected by small pores. The PVA—PVAc composite porous membrane is permeated by n-hexane with 5.58 × 10² mL/cm²·s at 0.5 kg/cm², by benzene with only 1.33 × 10^?3mL/cm²·s even at 60 kg/cm².     

Thermally crosslinkable poly(styrene sulfonic acid-co-maleic acid) (PSSA-MA)/polyvinyl alcohol (PVA) ion-exchange fibers

The aim of this study was to prepare poly(styrene sulfonic acid-co-maleic acid) (PSSA-MA)/polyvinyl alcohol (PVA) ion-exchange fibers using the electrospinning technique and a post-thermal treatment. First, intermediate PSSA-MA/PVA fibers were prepared from solutions of PSSA-MA/PVA combined at ratios of 0.2/1 to 1/1; the fibers were subsequently crosslinked at 80–150 °C for 0.25–7 h. The effect of the crosslinking time, the temperature and the PSSA-MA/PVA ratio on various properties of the obtained ion-exchange fibers was investigated. When the PSSA-MA/PVA ratios were greater than 0.4/1, bead formation was observed. Thus, only smooth fibers without beads prepared from PSSA-MA/PVA mixed in ratios up to 0.4/1 were subjected to the thermal crosslinking treatment. When the crosslinking time and temperature were increased, the degree of crosslinking increased, which caused a decrease in the water solubilization and water uptake and an increase in the Young’s modulus. These parameters also appeared to significantly affect the ion-exchange capacity value. The temperature and time for successful crosslinking were 120–140 °C and 1–7 h, respectively.     

Mechanical properties of films of poly(vinyl alcohol) derived from vinyl trifluoroacetate

In order to study the influence of the stereoreguralities of polymer chains on the mechanical properties of films of poly(vinyl alcohol) (PVA)_(VTFA) derived from vinyl trifluoroacetate, the strength of the film was measured. In the case of undrawn PVA_(VTFA) films, Young's modulus and strength at break were the smallest at the annealing temperature of about 100°C. It is considered to be due to the melt of small microcrystals and the increase in mobility of chains in amorphous parts. Young's moduli of undrawn PVA_(VTFA) films were in the range of 1.50–3.75 GPs and the values were higher than that (0.17–0.36 GPa) of undrawn film of commercial PVA with the low concentration of syndiotacticity and the high concentration of head-to-head bounds. In the case of drawn, annealed PVA_(VTFA) films, the maximum Young's modulus was about 20 GPa.     

Properties of poly(4-vinylpyridine-co-methyl vinyl ketone) membranes for reverse osmosis

The copolymer prepared from 4-vinylpyridine and methyl vinyl ketone could form a dense and tough membrane which is stronger than cellulose acetate when crosslinked with malonyl dihydrazide (MD) or 2-phenyl-4,6-dihydrazino-s-triazine (PDT), showing a fair performance in reverse osmosis for NaCl and CoCl₂ feed. The relationship between the content of MD or PDT and the membrane performance was investigated. An increase in MD or PDT led to an increase in membrane thickness and water content as well as the performance. A maximum rejection was obtained at ca. 30 mol % MD and ca. 13 mol % PDT based on MVK, and a maximum membrane strength at 20–30 mol % crosslinking agent. A membrane of a lower NaCl rejection tended to be permselective due to the complexation of the CoCl₂ with membrane. About 1:1 copolymer gave membranes of a higher rejection, which may be related to monomer arrangement in the copolymer chain. There methods for the flux improvement were presented and discussed: preparation of a copolymer blend membrane containing a hydrophilic monomer, crosslinking quaternization of membranes with diiodobutane, and oximation of the membrane material in order to introduce hydrophilic groups.     

Hybrid composite based on poly(vinyl alcohol) and fillers from renewable resources

Hybrid composite laminates consisting of polyvinyl alcohol (PVA) as continuous phase (33% by weight) and lignocellulosic fillers, derived from sugarcane bagasse, apple and orange waste (22% by weight) were molded in a carver press in the presence of water and glycerol such as platicizers agents. Corn starch was introduced as a biodegradation promoter and gluing component of the natural filler and synthetic polymeric matrix in the composite (22% by weight). The prepared laminates were characterized for their mechanical properties and degradative behavior in simulated soil burial experiments. The fibers type and content in composite impacted mechanical properties. Materials based on PVA and starch with apple wastes and sugarcane bagasse fillers were much harder (Young's Modulus respectively, 57, 171 MPa) than materials prepared with orange wastes (17 Mpa). Respirometric test revealed that soil microbes preferentially used natural polymers and low molecular weight additive as a carbon source compared to biodegradable synthetic polymer. The presence of PVA in formulations had no negative effect on the degradation of lignocellulosic fibers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Characterization of reverse osmosis membranes prepared from the oxime of poly(4-vinylpyridine-co-methyl vinyl ketone)

The copolymer (4VK) of 4-vinylpyridine (4VP) and methyl vinyl ketone (MVK) was nearly quantitatively converted into an oxime (4VKX) which could be complexed with various metal salts. 4VKX was compared with 4VK in their membrane performance. When crosslinked with divinyl sulfone (DVS), the 4VKX membrane showed a higher strength than cellulose acetate (CA) membrane and a higher performance than 4VK membrane crosslinked with dihydrazine derivatives. The most adequate DVS content and copolymer composition were found to be 25 mol % based on MVK oxime and 1:1, respectively. A metal salt taken up by the membrane in a much larger amount tended to be highly rejected. The crosslinking quaternization of 4VKX with diisobutane (DIB) very effectively improved water permeability, as did 4VK, and gave a membrane performance superior to that of 4VK. The most appropriate charge ratio of DIB was 15–20 mol % based on 4VP. Some transport characteristics and compaction in a long-term operation were investigated and discussed.     

Embedding poly(styrene sulfonic acid) into PVDF matrix—a new type of proton electrolyte membrane

Hydrophilic polymer segments, consisting of styrene sulfonic acid (SSA) units, were uniformly embedded into hydrophobic poly(vinylidene fluoride) (PVDF) matrix through the mediation of poly(methyl methacrylate) (PMMA) segments, with which SSA segments form a copolymer. Discrete domains (∼100 nm) assembled by the SSA segments have been identified throughout the matrix of the membrane, which was prepared through blending of the copolymer P(MMA-SSA) and the PVDF. The thermal stability of the SSA was largely boosted in such hydrophobic environment. This unique matrix structure offers proton conductivity of as high as 10⁻³ S/cm at a low SSA equivalent (0.6 mmol -SO₃H/g of membrane), which is accompanied with a low level of water uptake (26%) at ambient temperature. Using this type of polymer membrane as electrolyte, the electrochemical cell possesses obvious capacitive resistance when the membrane is in the anhydride form according to the impedance analysis. However, the capacitive character vanishes when the membrane is hydrated; this response is attributed to the existence of highly dispersed SSA domains in the membrane. This work also analyzes the impedance spectra of the membranes at different hydrated states or with different SSA contents by using an equivalent electrical circuit.     

可溶于水的导电性聚苯乙烯磺酸掺杂聚苯胺的合成

以苯胺（An)为单体,过硫酸铵（APS）为氧化剂,在聚苯乙烯磺酸（PSSA）的水溶液中合成了可完全溶于水的导电性聚苯乙烯磺酸掺杂聚苯胺。结果表明,当APS与An的摩尔比为1：2,PSSA的浓度为0．19mol/L,APS溶液的滴加时间为3h,反应温度为14℃,产物电导率的最高值为0．13S/cm,而且可完全溶于水,形成稳定的墨绿色溶液。     

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.     

Synthesis of chemically bonded poly(vinyl alcohol)-starch composite

Poly(vinyl alcohol) (PVA) was grafted on hydrolysed starch through introduction of the chemically reactive bifunctional compound N-methylolacrylamid (N-MAm). The grafting reaction was carried out in two separate reaction steps. The first step was the reaction of PVA with N-MAm in alkaline medium. The reaction mechanism and reaction conditions such as alkali concentration, temperature, reaction time as well as N-MAm concentration were studied. According to the results obtained, the most appropriate conditions for the preparation of this reactive PVA are: treating PVA with N-MAm (1.25 mol/mol PVA) in the presence of NaOH (6% based on solution volume) at 20°C for 8 h. Second step was the reaction of this reactive PVA (N-MAm-PVA) with hydrolysed starch in the presence of NH₄Cl. The latter was carried out under different conditions including temperature, reaction time, catalyst concentration as well as N-MAm-PVA/hydrolysed starch ratio. The results obtained show that the extent of the grafting reaction is governed by each of these factors. Furthermore, GPC data showed that the molecular weight distribution and the apparent viscosity of PVA-N-MAm-starch composite depend on the initial molecular weight of both PVA and hydrolysed starch used.     

An overview of poly(vinyl alcohol) and poly(vinyl pyrrolidone) in pharmaceutical additive manufacturing

Recently, drug personalization has received noticeable attention. Problems arising from standard generalized drug treatments have aroused over the years, particularly among pediatric and geriatric patients. The growing awareness of the limitations of the “one-size-fits-all” approach has progressively led to a rethinking of the current medicine's development, laying the basis of personalized medicine. Three-dimensional printing is a promising tool for realizing personalized therapeutic solutions fitting specific patient needs. This technology offers the possibility to manufacture drug delivery devices with tailored doses, sizes, and release characteristics. Among additive manufacturing techniques, fused deposition modeling (FDM) is the most studied for oral drug delivery device production due to its high precision and cheapness. By playing with factors such as drug loading method, filament production, and printing parameters, the medication release profile of a drug delivery device produced by 3D printing can be tailored depending on the patient's requirements. This review focuses on the applications of FDM in drug fabrication using poly(vinyl alcohol) (PVA) and poly(vinyl pyrrolidone) (PVP) as drug-loaded matrices. The authors aim to provide an overview of the current trends in this research field, with special attention to the effect of the printing parameters, tablet shape, and drug distribution and concentration on drug customization and personalized drug release.     

Wetting behavior of electrospun poly(L‐lactic acid)/poly(vinyl alcohol) composite nonwovens

Poly(L ‐lactic acid) (PLLA) fibers have been extensively studied for various applications. In this work, PLLA and poly(vinyl alcohol) (PVA) were prepared by coelectrospinning to form composite nonwoven materials. The structures and diameter distribution of the electrospun PLLA/PVA composite nonwovens were examined by atomic force microscopy (AFM) and scanning electronic microscope (SEM). The wetting behavior of the electrospun PLLA/PVA composite nonwovens was also investigated using static contact angles and dynamic water adsorption measurements. It was observed that the addition of PVA in the electrospun PLLA/PVA composite nonwovens significantly alerted the contact angles and water adsorption of the composite materials. It was also found that the increase in the content of PLLA led to the increase in the surface contact angle and decrease in water adsorption of the electrospun PLLA/PVA nonwoven materials. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis of poly(vinyl benzal) from poly(vinyl alcohol) in nonaqueous medium

Poly(vinyl alcohol) (PVA) is soluble only in water and so some important derivatives like esters cannot be prepared from PVA. The 100% conversion of PVA to acetal is also elusive as there is strong intermolecular and intramolecular hydrogen bonding. However, PVA can be dissolved in a nonaqueous medium in the presence of a small amount of C₂H₅NO₃ · DMSO(EN · DMSO) and so a maximum extent of conversion may be possible. Here, we report the preparation of poly(vinyl benzal) (PVB) by acid-catalyzed homogeneous acetalization of PVA with benzaldehyde in a nonaqueous medium. The formation of PVB was confirmed by IR and ¹H-NMR spectra. The molecular mass of the polymer was determined by the GPC method. The PVB prepared had a degree of acetalization of 95 mol%. The glass transition temperature, T_g was measured from differential scanning calorimetric (DSC) thermograms. Thermal stabilities were checked by thermogravimetric analysis (TGA) and differential thermogravimetry (DTG). A possible mechanism of three-step thermal decomposition of PVB is proposed. © 1996 John Wiley & Sons, Inc.     

Hydrophilic interpolymer membranes from crosslinked blends of poly(vinylalcohol), poly(styrene sodium sulfonate) and poly(vinyl methyl ether–alt–maleic anhydride)

Interpolymer ion exchange membranes were prepared from a compatible casting solution that contained poly(styrene sodium sulfonate), poly(vinyl methyl ether–alt–maleic anhydride), and poly(vinyl alcohol). Crosslinking of the films was accomplished through the formation of ester linkages that were stable in aqueous environments. Membrane properties (water content, capacity, concentration potential, equivalent conductivity) were measured over a wide range of membrane compositions. Ultrafiltration was carried out with a feed solution that was 0.01N in KCI and 15 ppm in erythrosin. Rejection and hydraulic permeability data were reported as a function of membrane composition.     

Conductivity studies of poly (vinyl alcohol)-iodine complex membrane

Summary The conductivities of polymers like poly (vinyl alcohol) (PVA) and its iodine complex membranes are reported here. PVA-iodine complex membrane was prepared by dipping PVA film into an I₂–KI solution. The formation of the complex membrane was confirmed by IR spectra. Conductivities were determined from 30 to 300 °C with a frequency ranges from 42 Hz to 500 KHz in solid state. It was observed that iodine is known to act as a catalyst for dehydration of PVA. A possible mechanism for the dehydration of PVA catalyzed by iodine is also explained.