氯甲基化/季铵化新型聚芳醚砜酮超滤膜的研制

本文对含二氮杂萘结构聚芳醚砜酮进行改性制得氯甲基化聚芳醚砜酮。选用N-甲基一2-吡咯烷酮作制膜溶剂，依据正交设计方法制得了一系列氯甲基化聚芳醚砜酮超滤膜。考察了聚合物浓度、添加剂种类和添加量以及制膜蒸发时间等对膜性能的影响。将氯甲基化聚芳醚砜酮超滤膜浸入三甲胺溶液进行季铵化反应，得季铵化聚芳醚砜酮超滤膜。并考察了膜的抗污染性。     

Nanofiltration membranes based on PA6/EVOH with variable composition and morphology

Nanofiltration PA6/EVOH membranes were prepared through a nonsolvent induced phase separation technique. The effects of polymer concentration in the solution and solvent evaporation time on the performance and morphology of the resulting membranes were investigated by cloud point titration, permeation, and scanning electron microscopy (SEM). Experimental cloud point data for various prepared membranes suggested that polymer solutions with higher concentrations of PA6/EVOH need a less content of nonsolvent. SEM observations show that an increase in polymer concentration leads to formation of a thin dense layer on the surface of the membrane thanks to pore size reduction. However, dense top layer of membrane becomes thicker as polymer concentration increases from 15 wt% to 20 wt%. The performance of membranes reveals a decrease with polymer concentration in casting solution. By contrast, Polyamide/Poly(ethylene‐co‐vinyl alcohol) membranes show an optimal performance with various formic acid evaporation times. J. VINYL ADDIT. TECHNOL., 25:E28–E34, 2019. © 2018 Society of Plastics Engineers     

Primary study of novel poly(acrylic sodium)/poly(ether sulfone) composite ultrafiltration membranes (I) the preparation of composite membrane

The poly(acrylic sodium) (PAS)/poly(ether sulfone) (PES) composite ultrafiltration membranes were prepared by coating PAS membrane solution on PES support membrane. The effects of substrate membrane, the composition of PAS solution such as PAS concentration, the choice of the solvent and the additive, and the thickness of PAS active layer on the performance of the composite membranes were extensively investigated. The experimental results have indicated the optimal PAS/PES composite membranes, containing a PES substrate with MWCO of 70,000, together with a PAS top layer having a thickness of about 20 μm, were tested at room temperature and under the pressure of 0.6 MPa with the mass concentration of 0.005 g/L poly(ethylene glycol) (PEG) (Mw = 1000 g/mol) solution, a flux of 32.6 L/(m² h) and a rejection of 92.2% were obtained, which are superior to those of the common commercial membranes reported.     

A rationale for the preparation of asymmetric pervaporation membranes

Pervaporation is carried out primarily with homogeneous membranes. An improvement in permeation rate can be achieved by using asymmetric or composite membranes. In order to maintain a high selectivity, very dense top layers are needed. The formation of asymmetric pervaporation membranes will be discussed in terms of the model proposed by our group: formation of the top layer by gelation; formation of the porous sublayer by liquid–liquid phase separation followed by gelation of the concentrated polymer phase. To obtain very dense top layers the following factors are important: the ratio of nonsolvent inflow and solvent outflow, polymer concentration, location of the liquid–liquid demixing gap, and location of the gel region. Asymmetric membranes have been prepared by varying these factors, and the obtained membranes have been tested on ethanol/water mixtures.     

Effect of solvents on performance of polyethersulfone ultrafiltration membranes: Investigation of metal ion separations

The new polyethersulfone (PES) based ultrafiltration membranes were formed using a two stage process of dry and wet phase inversion in non solvent coagulation bath. The effects of three different solvents such as, N,N-dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP) and Dimethyl sulphoxide (DMSO) of 82.5% and 85% concentrations on the performance of final membranes were extensively investigated. Scanning electron microscopy (SEM) image results proved that PES membranes with an asymmetric structure were successfully formed. The number of pores formed on the top layer of PES membranes using above-mentioned three solvents was the result of the combined effect of the thermodynamic properties of the system (composition, concentrations, and phase behaviour) and membrane formation kinetics, whereas, the formation of the macroporous sub layer of those membranes was controlled by the diffusion rate of solvent–nonsolvent. The flux of pure water, membrane resistance, mechanical stability, molecular weight cut-off (MWCO) and separation performance of the PES membranes were studied. Separation of metal ions from aqueous solutions was studied for Ni(II), Cu(II) and Cr(III) using two complexing polymer ligands: polyvinyl alcohol (PVA) and poly(diallyldimethylammonium chloride) (PDDA).The separation and permeate rate (flux) efficiencies of the new membranes are compared using different solvents and different PES/solvent compositions.     

Verbesserte Hydrophilie von Hohlfasermembranen mittels funktionalisierter Trennschicht für die Ultrafiltration

Dual layer hollow fiber membranes, based on poly(ether sulfone), were fabricated to achieve hydrophilic membranes with improved fouling resistance. A new triblock copolymer, consisting of two hydrophilic poly(ethylene oxide) blocks and an inner poly(ether sulfone) block, was chosen for the functionalization of the inner layer. The most promising membrane of this study was characterized by an improved hydrophilicity, and a performance in the ultrafiltration studies of 2000 L m⁻²h⁻¹bar⁻¹ and retention of 100 kDa.     

Preparation and gas separation properties of asymmetric polysulfone membranes by a dual bath method

Defect-free skinned asymmetric gas separation membranes were prepared by a dual bath coagulation method that is a wet/wet phase inversion technique. The membranes were cast from a polysulfone/N,N-dimethylacetamide solution. In two sequent nonsolvent baths, the first bath using iso-propanol (IPA) leads to the formation of a dense skin top layer and the second bath using water makes the actual polymer precipitation. The top skin layer thickness was governed by changing the immersion time of the first IPA bath. We suggest that the growth rate of the skin layer is to be determined by a diffusion process.     

Sulfonated poly(ether ether ketone)‐induced porous poly(ether sulfone) blend membranes for the separation of proteins and metal ions

Asymmetric ultrafiltration (UF) membranes were prepared by the blending of poly(ether sulfone) (PES) and sulfonated poly(ether ether ketone) (SPEEK) polymers with N,N′‐dimethylformamide solvent by the phase‐inversion method. SPEEK was selected as the hydrophilic polymer in a blend with different composition of PES and SPEEK. The solution‐cast PES/SPEEK blend membranes were homogeneous for all of the studied compositions from 100/0 to 60/40 wt % in a total of 17.5 wt % polymer and 82.5 wt % solvent. The presence of SPEEK beyond 40 wt % in the casting solution did not form membranes. The prepared membranes were characterized for their UF performances, such as pure water flux, water content, porosity, and membrane hydraulic resistance, and morphology and melting temperature. We estimated that the pure water flux of the PES/SPEEK blend membranes increased from 17.3 to 85.6 L m^?2 h^?1 when the concentration of SPEEK increased from 0 to 40 wt % in the casting solution. The membranes were also characterized their separation performance with proteins and metal‐ion solutions. The results indicate significant improvement in the performance characteristics of the blend membranes with the addition of SPEEK. In particular, the rejection of proteins and metal ions was marginally decreased, whereas the permeate flux was radically improved. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of Casting Solution on Morphology and Performance of PVDF Microfiltration Membranes

The effects of preparation‐influencing parameters such as polymer concentration, thickness of casting solution, and type of solvent on morphology and performance of poly(vinylidene difluoride) (PVDF) microfiltration membranes for the treatment of emulsified oily wastewater were investigated. Flat‐sheet membranes were prepared from a casting solution of polymer and additive in various solvents by immersing the prepared films in nonsolvent‐containing mixtures of water and 2‐propanol. The membranes were characterized using scanning electron microscopy. Increasing the polymer concentration and membrane thickness significantly affected the pore size, leading to permeate flux decrease. An attempt was made to correlate the effect of the solvent on membrane morphology and performance employing solubility parameters between solvent and nonsolvent).     

Micro‐ and ultrafiltration film membranes from poly(ether ether ketone) (PEEK)

Film membranes from the thermoplastic poly(ether ether ketone) (PEEK) have been extruded and tested for their microfiltration and ultrafiltration performance. High‐performance asymmetric membranes have been obtained by extruding polymer blends of PEEK, polysulphone, and a small molecule solvent mixture, and then by removing the polysulphone and solvent in a subsequent extraction step. The process for making ultrafiltration membranes differs from microfiltration membranes only in the relative blend components, and the temperature of the film pick‐up rolls. Processing parameters with important effects on the membrane performance have been identified. Microfiltration membranes are characterized by their pore‐size distributions and SEM, and ultrafiltration membranes by their rejection of bovine serum albumin, bubble point, and SEM. Composite membrane for nanofiltration utilizing the PEEK ultrafiltration membrane as a substrate performed similarly to a commercial membrane for the same purpose. This work details the best method for making PEEK film membranes published to date. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1146–1155, 1999     

Diffusive and bulk flow transport in polymers

The transport properties of polymer membranes in various forms which have a wide variety of practical applications, such as ultrafiltration, dialysis and blood oxygenation, depend upon the structure (homogeneous or heterogeneous) and the transport characteristics of the membrane material. Among many possible driving forces of transport, the pressure gradient and the concentration gradient are considered to be the most general forces encountered in practical use of polymer membranes. The transport of various permeants (gas, dissolved gas, liquid solvent, and solute) through porous and homogeneous (nonporous) polymer membranes under these driving forces is discussed. In the absence of a pressure gradient, the transport of permeants can be described as diffusion, regardless of the permeant phase and the membrane structure. In the presence of a pressure gradient, the transport of permeants may occur by diffusion and/or bulk flow of the permeants, depending upon the membrane structure and the nature of the permeant. In homogeneous membranes, many noninteracting permeants such as gases and nonsolvent vapors permeate by diffusion under applied pressure gradient: however, solvent in homogeneously swollen membranes moves by bulk flow and the diffusion depending on the degree of swelling of the membrane. In heterogeneous membranes under applied pressure, most permeants move by bulk flow.     

非溶剂对浇铸SPEEK膜性能的影响

首次采用磺化聚醚醚酮/N,N-二甲基甲酰胺(SPEEK/DMF)和非溶剂(四氯乙烯或对二甲苯)组成的铸膜液制备了SPEEK膜.采用交流阻抗法和隔膜扩散法分别考察了膜的质子传导性和透水性能.结果表明,由于在SPEEK/DMF中添加非溶剂,膜的透水率增加了约30％,质子导电率提高了50％左右.非溶剂的加入影响了铸膜液中聚合物的形态、尺寸和团聚情况,从而影响了成膜后膜的性能.本研究提出的控制膜微相结构的新方法将有助于提高SPEEK膜燃料电池性能.     

Synthesis and characterization of poly(ether‐block‐amide) membranes for the pervaporation of organic/aqueous mixtures

We made poly(ether‐block‐amide) membranes by casting a solution on a nonsolvent surface. The effects of the solvent ratio (n‐butanol/isopropyl alcohol), temperature, and polymer concentration on the quality of the membranes were studied. The results show that the film quality was enhanced with increasing isopropyl alcohol ratio in the solvent. This behavior was related to the reduction of the solution surface tension and the interfacial tension between the solution and nonsolvent. Uniform films were made at a temperature range of 70–80°C and a polymer concentration of 4–7 wt %. The morphology of the membranes was investigated with scanning electron microscopy. The qualities of the films improved with increasing isopropyl alcohol ratio in the solvent. With these membranes, the pervaporation of ethyl butyrate (ETB)/water and isopropyl alcohol/water mixtures was studied, and high separation performance was achieved. For ETB/water mixtures, with increasing ETB content, both the permeation flux and separation factor increased. However, for isopropyl alcohol/water mixtures, with increasing isopropyl alcohol content, the permeation flux increased, but the separation factor was diminished. Increasing temperature in a limited range resulted in a decreasing separation factor and an increasing permeation flux. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation of defect-free asymmetric membranes for gas separations

A technique was developed to prepare defect-free, asymmetric, polymer membranes for gas separation. The preparation method eliminates the need for coatings, which are usually required to render asymmetric, polymer based, membranes gas selective. In this method, a casting solution containing a polymer, solvent, and salt additive is given a desired shape and immersed in a coagulation bath containing a nonsolvent. The nonsolvent is selected to have a low affinity for both the solvent and salt additive. After the complete coagulation of the membrane, the additive salt is leached out in a second bath. This leads to the formation of an asymmetric membrane that has a well-interconnected porous network. The fine membrane structure is preserved by solvent exchange before it is finally dried. Polyetherimide (PEI) (Ultem® 1000) membranes were prepared from casting solutions containing 23, 25, and 26.5% (wt) PEI, various amounts of lithium nitrate and N-methyl-2-pyrrolidinone (NMP). Membrane performance was determined for the separation of oxygen from air. The effects of polymer concentration, additive salt concentration and the drying process on oxygen permeance, and the actual separation factor of the membrane are discussed. The addition of a small amount of solvent to the coagulation bath improved the leaching of the salt additive and produced membranes with a more open structure. A polymer concentration of 23% produced membranes with the highest performance. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1471–1482, 1999     

Morphology and performance of poly(vinylidene fluoride) flat sheet membranes: Thermodynamic and kinetic aspects

In this study, poly(vinylidene fluoride) (PVDF) membranes were prepared using two different solvents with various polymer concentrations to investigate the predominant kinetic or thermodynamic aspects of membrane preparation in a phase separation process. For this purpose, dimethyl sulfoxide (DMSO) as a weak solvent and N‐2‐methylpyrrolidone (NMP) as a strong solvent were used with polymer concentrations between 8 and 15 wt %. Scanning electron microscopy and water content, contact angle, and pore size measurements were used to assess the factors affecting the physicochemical properties of the prepared membranes. The results showed that in the case of NMP, the membrane structure is mainly controlled by thermodynamic parameters, while when using DMSO, kinetic parameters are predominant. According to the results, the prepared PVDF‐based membranes with DMSO exhibited a relatively denser top layer and less permeation compared to the NMP/PVDF membranes. The difference between the viscosities of the casting solutions with equal polymer concentrations in DMSO and NMP was considered to be the main effective factor in solvent/nonsolvent exchange, resulting in denser top layers in the DMSO/PVDF membranes. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46419.     

Determination of solvent/polymer interaction parameters of moderately concentrated polymer solutions by vapor pressure osmometry

The paper describes the application of vapor pressure osmometry (VPO) to determine solvent/polymer interaction parameters for various polymer solutions containing high-molecular weight polymers in the semi-diluted concentration range. The theoretical basis for the data evaluation is the Flory–Huggins (FH) model and a virial expansion up to the third virial term. For validation already well characterized polymer/solvent systems poly(vinylpyrrolidone)/water, polysulfone/N,N-dimethylformamide (DMF), and poly(ether sulfone)/DMF were investigated. In the second part interaction parameters of poly(ether imide) (PEI) in solvents with technical relevance for membrane formation (DMF, N-methylpyrrolidone (NMP), N,N-dimethylacetamide (DMAc)) were examined at different concentrations and temperatures. The results document that VPO is a fast and promising method for characterization of semi-diluted polymer solutions containing polymers with higher molecular weight. Results confirm the decrease of solvent power for PEI in the series: NMP > DMAc > DMF.     

有机超滤膜的制备及在工业废水处理中的应用进展

重点对一些常用高分子有机膜材料,特别是对聚醚砜(PES)、聚偏氟乙烯(PVDF)、聚乙烯醇(PVA)、壳聚糖(CS)和醋酸纤维素(CA)膜材料的制备和改性进行了论述,并就超滤膜在废水处理中的最优分离操作条件的设计进行了阐述,同时对超滤技术在水污染防治中的研究与应用前景进行了展望.     

The behavior of the tracer diffusion coefficient of polystyrene in isorefractive “solvents” composed of poly(vinyl methyl ether) ando-Fluorotoluene

Summary In this paper, we describe and use a relatively new technique — dynamic light scattering from refractive index-matched ternary solutions-to study a quantity very closely related to the self-diffusion coefficient in binary systems. We refer to this quantity as the tracer diffusion coefficient. This tracer diffusion coefficient is expected to behave in much the same way as the self-diffusion coefficient, in terms of its concentration and molecular weight dependencies. In this study, we use two compatible polymers, polystyrene and poly(vinyl methyl ether), and a solvent, o-fluorotoluene, chosen specifically because its refractive index matches that of the poly(vinyl methyl ether). The technique is advantageous in that it allows the experimenter to vary independently the molecular weight of both the probe and “invisible” matrix polymers, their individual molecular topologies, and the overall polymer concentration with relative ease. No special chemical tagging is required, although it must be borne in mind that we are not measuring self-diffusion but the diffusion of a dissimilar tracer. Our experiments probe the diffusion of linear polystyrenes in matrices composed of linear poly(vinyl methyl ether)/o-fluorotoluene. Our results show a crossover from non-free draining (Zimm) to free draining (Rouse) hydrodynamic behavior of polystyrene as the concentration of the invisible poly(vinyl methyl ether) making up the matrix is increased.     

Polyelectrolyte multilayer modified nanofiltration membranes for the recovery of ionic liquid from dilute aqueous solutions

The feasibility of nanofiltration membranes fabricated by static polyelectrolyte layer‐by‐layer deposition of poly(styrene sulfonate) and poly(allylamine hydrochloride) on poly(ether sulfone) ultrafiltration and alumina microfiltration membranes for the recovery of ionic liquid from low molecular weight sugar was investigated. The surface properties of these modified membranes were correlated with their performances. The selectivity for 1‐butyl‐3‐methylimidazolium chloride over cellobiose and glucose was found to be as high as 50.5/2.3 for modified alumina and 32.3/3.5 for modified poly(ether sulfone) membranes with optimized number of bilayers. The values for membrane permeance were 4.8 and 2.5 L m^?1 h² bar^?1, respectively. For low depositions, the separation mechanism was predominantly governed by size‐exclusion. For higher depositions, the enhanced negative zeta potential of the modified membranes suggested preferred dominating electrostatic interactions, resulting in high selectivity of ionic liquids over low molecular weight sugars. At very high depositions, the molecular weight cut‐off of the membrane becomes constricting for size‐exclusion effect. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45349.