Thin-film composite crosslinked polythiosemicarbazide membranes for organic solvent nanofiltration (OSN)

In this work we report a new class of solvent stable thin-film composite (TFC) membrane fabricated on crosslinked polythiosemicarbazide (PTSC) as substrate that exhibits superior stability compared with other solvent stable polymeric membranes reported up to now. Integrally skinned asymmetric PTSC membranes were prepared by the phase inversion process and crosslinked with an aromatic bifunctional crosslinker to improve the solvent stability. TFC membranes were obtained via interfacial polymerization using trimesoyl chloride (TMC) and diaminopiperazine (DAP) monomers. The membranes were characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and contact angle measurement.The membranes exhibited high fluxes toward solvents like tetrahydrofuran (THF), dimethylformamide (DMF) and dimethylsulfoxide (DMSO) ranging around 20 L/m² h at 5 bar with a molecular weight cut off (MWCO) of around 1000 g/mol. The PTSC-based thin-film composite membranes are very stable toward polar aprotic solvents and they have potential applications in the petrochemical and pharmaceutical industry.     

Fabrication and investigation of phosphoric acid doped imidazolium siloxane crosslinked poly(2,6‐dimethyl‐1,4‐phenylene oxide) for high temperature polymer electrolyte membranes

A series of high temperature polymer electrolyte membranes were fabricated based on imidazolium poly(2,6‐dimethyl‐1,4‐phenylene oxide) (PPO) using methylimidazole (MeIm) and triethoxysilylpropyldihydroimidazole (SiIm) as quaternization reagents via the S_N2 nucleophilic substitution. Meanwhile SiIm was also employed as a crosslinking agent and the crosslinked Si–O–Si network was constructed through a hydrolysis procedure of SiIm in an acid medium. Compared with the PPO‐100%MeIm membrane without the crosslinking structure, the imidazolium siloxane crosslinked PPO‐x%SiIm‐y%MeIm membranes exhibited increased acid doping contents, enhanced dimensional stabilities, improved mechanical properties and higher conductivities. The PPO‐30%SiIm‐70%MeIm/(198 wt% phosphoric acid) membrane displayed a conductivity of 0.08 S cm^?1 at 180 °C without humidifying and a tensile strength of 6.4 MPa at room temperature. © 2019 Society of Chemical Industry     

Positively charged hollow‐fiber composite nanofiltration membrane prepared by quaternization crosslinking

Poly(N,N‐dimethylaminoethyl methacrylate) (PDMAEMA) can be crosslinked by interfacial polymerization to develop a positively charged dense network structure. According to this mechanism, a positively charged hollow‐fiber composite nanofiltration (NF) membrane was prepared by quaternization to achieve a crosslinked PDMAEMA gel layer on the outer surface of polysulfone hollow‐fiber ultrafiltration (UF) membranes with a PDMAEMA aqueous solution as a coating solution and p‐xylylene dichloride as an agent. The preparation conditions, including the PDMAEMA concentration, content of additive in the coating solution, catalyzer, alkali, crosslinking temperature, and hollow‐fiber substrate membrane, were studied. Fourier transform infrared spectroscopy and scanning electron microscopy were used to characterize the structure of the membranes. This membrane had a rejection to inorganic salts in aqueous solution. The rejection of MgSO₄ (2 g/L aqueous solution at 0.7 MPa and 25°C) was above 98%, and the flux was about 19.5 L m^?2 h^?1. Moreover, the composite NF membranes showed good stability in the water‐phase filtration process. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Polymer electrolyte membranes prepared by EB‐crosslinking of sulfonated poly(ether ether ketone) with 1,4‐butanediol

Crosslinked sulfonated poly(ether ether ketone) (SPEEK) membranes were prepared through the electron beam (EB)‐irradiation crosslinking of SPEEK/1,4‐butanediol under various irradiation conditions and used as a proton exchange membrane (PEM) for fuel cell applications. The crosslinked membranes were characterized by gel fraction, a universal testing machine (UTM), dynamic mechanical analysis (DMA), and small‐angle X‐ray scattering (SAXS). The gel fraction of the crosslinked membranes was used to estimate the degree of crosslinking, and the gel fraction was found to be increased with an increase of the crosslinker content and EB‐absorbed dose. The UTM results indicate that a brittle EB‐crosslinked membrane becomes more flexible with an increase in the crosslinker content. The DMA results show that the EB‐crosslinked membranes have well‐developed ionic aggregation regions and the cluster T_g of membranes decrease with an increase in the 1,4‐butanediol crosslinker content. The SAXS results show that the Bragg and persistence distance of crosslinked membranes increase with an increase in the crosslinker content. The proton conductivities of the EB‐crosslinked membranes were more than 9 × 10^?2 S/cm. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41760.     

Crosslinked anion exchange membrane with improved membrane stability and conductivity for alkaline fuel cells

As a core component of anion exchange membrane (AEM) fuel cells, it has practical significance to improve the performance of AEMs. However, it is difficult to obtain AEM with both good stability and high conductivity. In this study, a series of AEMs were prepared by chloromethylation, quaternization, and crosslinking reactions. The quaternization reaction was carried out first to ensure that there are abundant quaternary ammonium groups on AEM and enhance the conductivity of membrane. N,N,N′,N′-tetramethylethylenediamine was used as a crosslinker to improve membrane stability and mechanical property. A simple, mild, and cost-effective AEM synthetic route was developed. This strategy achieves a certain balance of electrochemical and physical properties. The effect of the crosslinking reactions on the property of membrane was evaluated. Crosslinked membranes have better dimensional stability (water uptake: 20.2% and swelling ratio: 2.1%), mechanical properties (55.84 MPa), and alkaline stability because crosslinked structures result in large steric hindrance. The mutually independent quaternization and crosslinking reaction do not affect the electrochemical performance of membranes; in the crosslinking reaction stage, crosslinker also reacted as quaternization agent and increased the number of reactive groups in AEM. Thus, the resulting crosslinked AEM exhibits higher ion exchange capacity and ionic conductivities (46.4 mS cm⁻¹). © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48169.     

Positively charged composite nanofiltration membrane prepared by poly(N,N‐dimethylaminoethyl methacrylate)/polysulfone

Poly(N,N‐dimethylaminoethyl methacrylate) (PDMAEMA) can be crosslinked by quaternization to develop a positively charged dense network structure. According to this mechanism, PDMAEMA/polysulfone (PSF) positively charged nanofiltration membrane was developed by interfacial crosslinking polymerization using PSF plate microfiltration membrane as support layer, PDMAEMA aqueous solution as coating solution, and p‐xylylene dichloride/n‐heptane as crosslinking agent. Technique and condition of developing membrane such as concentration of coating solution, coating time, pH value of coating solution, content of low molecular weight additive in coating solution, concentration of crosslinking agent, crosslinking time, and number of coatings were studied. FTIR, SEM, and X‐ray photoelectron spectroscopy were used to characterize the structure of membranes. This membrane had rejection to inorganic salts in water solution, the rejection rate to MgSO₄ (1 g/L water solution at 0.8 MPa and 30°C) was about 90%, and permeation flux was about 10–20 L m^?2 h^?1. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2721–2728, 2004     

Novel,positively charged membrane from a blending,crosslinking, and coagulation procedure

A novel, positively charged membrane was prepared through a blending, crosslinking, and coagulation procedure in which poly(N,N‐dimethylaminoethyl methacrylate) (PDM) and polyacrylonitrile (PAN) were used as the functional and substrate component, respectively. Because 1,4‐dibromobutane (DBT) was used as the crosslinker and quaternizing agent, PDM was crosslinked and quaternized simultaneously. The effects of PDM content, polymer concentration, and additive dosage of the casting solution on the membrane performances are discussed in detail, and differences between the PAN membrane, PDM/PAN blend membrane, and crosslinked PDM/PAN blend membrane are also discussed. We also studied the adsorption behaviors of the membranes to a positively charged dye and a negatively charged dye. Environmental scanning electron microscopy observation showed that the resulting positively charged membrane from such a blending, crosslinking, and coagulation procedure possessed a unique and uniform structure. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1847–1854, 2005     

Enhancement of flux and solvent stability of Matrimid® thin‐film composite membranes for organic solvent nanofiltration

The development of high flux and solvent‐stable thin‐film composite (TFC) organic solvent nanofiltration (OSN) membranes was reported. A novel cross‐linked polyimide substrate, consisting of a thin skin layer with minimum solvent transport resistance and a sponge‐like sublayer structure that could withstand membrane compaction under high‐pressure was first fabricated. Then the solvent flux was significantly enhanced without compromising the solute rejection by the coupling effects of (1) the addition of triethylamine/camphorsulfonic acid into the monomer solution, and (2) the combined post‐treatments of glycerol/sodium dodecyl sulphate immersion and dimethyl sulfoxide (DMSO) filtration. Finally, the long‐term stability of the TFC membrane in aprotic solvents such as DMSO was improved by post‐crosslink thermal annealing. The novel TFC OSN membrane developed was found to have superior rejection to tetracycline (MW: 444 g/mol) but was very permeable to alcohols such as methanol (5.12 lm^?2h^?1bar^?1) and aprotic solvents such as dimethylformamide (3.92 lm^?2h^?1bar^?1) and DMSO (3.34 lm^?2h^?1bar^?1). © 2014 American Institute of Chemical Engineers AIChE J, 60: 3623–3633, 2014     

Properties and pervaporation performance of poly(vinyl alcohol) membranes crosslinked with various dianhydrides

In this work, three dianhydrides with similar chemical structures, 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride (BTDA), 4,4′‐oxydiphthalic anhydride (ODPA), and pyromellitic dianhydride (PMDA), are employed for the crosslinking modification of poly(vinyl alcohol) (PVA) membranes for ethanol dehydration via pervaporation. The changes in crosslinking degree, surface hydrophilicity, and glass‐transition temperature are investigated and compared. Compared to the pure PVA membrane, all crosslinked membranes show higher fluxes but lower separation factors, because of the higher fractional free volume and the lower hydrophilicity by the crosslinking of the PVA matrix, respectively. In addition, all crosslinked PVA membranes exhibit similar flux, and the separation factor presents a decreasing order of PVA/PMDA‐2 > PVA/ODPA‐2 > PVA/BTDA‐2, which is in the reverse order of their hydrophilicity, probably because of the reduction in the swelling resistance. With the PMDA content increasing from 0.01 to 0.04 mol/(kg PVA) in the PVA/PMDA crosslinked membranes, the crosslinking degree is enhanced and the hydrogen bonding is weakened, resulting in a flux increase from 120.2 to 190.8 g m^?2 h^?1, but the separation factor declines from 306 to 58. This work is believed to provide useful insight on the chemical modification of PVA membranes for pervaporation and other membrane‐based separation applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46159.     

Microwave‐Assisted Preparation of Hydrogel‐Forming Microneedle Arrays for Transdermal Drug Delivery Applications

A microwave (MW)‐assisted crosslinking process to prepare hydrogel‐forming microneedle (MN) arrays was evaluated. Conventionally, such MN arrays are prepared using processes that includes a thermal crosslinking step. Polymeric MN arrays were prepared using poly(methyl vinyl ether‐alt‐maleic acid) crosslinked by reaction with poly(ethylene glycol) over 24 h at 80 °C. Polymeric MN arrays were prepared to compare conventional process with the novel MW‐assisted crosslinking method. Infrared spectroscopy was used to evaluate the crosslinking degree, evaluating the area of the carbonyl peaks (2000–1500 cm^?1). It was shown that, by using the MW‐assisted process, MN with a similar crosslinking degree to those prepared conventionally can be obtained in only 45 min. The effects of the crosslinking process on the properties of these materials were also evaluated. For this purpose swelling kinetics, mechanical characterisation, and insertion studies were performed. The results suggest that MN arrays prepared using the MW assisted process had equivalent properties to those prepared conventionally but can be produced 30 times faster. Finally, an in vitro caffeine permeation across excised porcine skin was performed using conventional and MW‐prepared MN arrays. The release profiles obtained can be considered equivalent, delivering in both cases 3000–3500 μg of caffeine after 24 h.

     

Palladium and platinum sorption on a thiocarbamoyl‐derivative of chitosan

Novel proton exchange membranes are solvent‐cast from N,N‐dimethylacetamide (DMAc) solutions of the crosslinked poly(arylene ether ketone) copolymer with pendant carboxylic acid group (C‐SPAEK) via poly(ethylene glycol) (PEG) with different amounts. These membranes are formed as a result of physical and chemical crosslinking. In this study, ¹H‐NMR and FTIR have been used to confirm the chemical structures of the copolymers. Mechanical and thermal properties, swelling and proton conductivity are affected by the crosslinker (PEG) content in the copolymers. Compared to the noncrosslinked C‐SPAEK membrane, the crosslinked membranes become more flexible and greatly reduced water uptake and swelling ratio with only slight sacrifice in proton conductivities. And the crosslinked membranes keep higher proton conductivities without a sharply decrease at higher temperature. These results show that the crosslinked membranes have potential applications as proton exchange membranes for fuel cell. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and characterization of alginate hydrogel membranes crosslinked using a water‐soluble carbodiimide

The preparation of alginate hydrogel membranes by the film immersion method was optimized for maximum crosslinking using swelling measurements as an indicator of the degree of crosslinking. The variables investigated were the concentration of the nonsolvent (ethanol) for sodium alginate, water‐soluble carbodiimide (WSC) concentration, and pH of the crosslinking medium. Optimum conditions resulted when the crosslinking medium contained 60 vol % ethanol and 100 mM WSC at pH 4. Membranes prepared using different ethanol concentrations (100 mM WSC, pH 4) and different WSC concentrations (60 vol % ethanol, pH 4) were investigated using infrared spectroscopy. The spectra showed the characteristic ester linkage (crosslinking) band at 1698 cm^?1 in cases where swelling measurements indicated that crosslinking had occurred. Differential scanning calorimetry of noncrosslinked and crosslinked membranes indicated that crosslinking increased the crystallinity of the membrane. Durability trials showed that membranes crosslinked using the optimum conditions determined in this work retained all weight when immersed in water for 32 days. Membranes prepared using these conditions possessed the characteristics required for use in the pervaporation separation of ethanol–water mixtures. These membranes also have potential as protective coatings for hydrophobic, microporous membranes in the membrane distillation and osmotic distillation concentration of feeds containing surface active components. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 747–753, 2003     

Potential of DMSO as greener solvent for PES ultra‐ and nanofiltration membrane preparation

In this article, the performance of polyethersulfone (PES) ultra‐ and nanofiltration membranes, prepared with the non‐toxic solvent dimethyl sulfoxide (DMSO), was investigated. The membranes were prepared by immersion precipitation via phase inversion. Experimental results proved that DMSO is a better alternative to N‐methyl‐2‐pyrrolidone (NMP) as solvent for PES ultrafiltration membranes as the membranes had a higher permeability and rejection of bovine serum albumin (BSA). An explanation was found based on experimental cloud point data and scanning electron microscopy images showing the morphology. The rejection of BSA and rose Bengal (RB) was proportional to the polymer concentration. On the contrary, the permeability decreased with increasing polymer concentration. For a casting thickness of 250 µm, an optimal balance between permeability and rejection of macromolecules for ultrafiltration was found at 24 wt % PES. The permeability was inversely proportional to the casting thickness, but a small decrease in rejection was observed when lowering the thickness. A good balance between permeability and rejection of RB was found, using a reference nanofiltration membrane of 28.5 wt % PES with 150 µm casting thickness. This membrane achieved a RB rejection of 95.3% and a pure water flux of 2.03 L m^?2 h^?1 bar^?1. The membrane thickness and polymer concentration did not have a clear influence on the hydrophilicity of the membranes. It can be concluded that DMSO is a benign alternative as compared to traditional solvents such as NMP and also results in better PES membrane performances. DMSO is a perfectly suitable solvent for ultrafiltration applications and has potential to be used for nanofiltration applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46494.     

Preparation of a crosslinked polyelectrolyte membrane for fuel cells with an allyl methacrylate based two‐step reaction

In this study, a proton‐exchange membrane for fuel cells was prepared via a two‐step reaction with an allyl methacrylate (AMA) as an asymmetric crosslinking agent. First, a linear‐chain polymer was synthesized, consisting of hydrophilic 2‐acrylamido‐2‐methylpropanesulfonic acid (AMPS), hydrophobic 2,2,2‐trifluoroethyl methacrylate (TFEMA), and AMA. Subsequently, we crosslinked the linear‐chain polymer by reacting the remaining allyl group during dry heating. The proton conductivity of the prepared membrane was 7 × 10^?2 S/cm at room temperature. The membrane was characterized by Fourier transform infrared spectroscopy, differential scanning calorimetry, and atomic force microscopy. The polymer electrolyte membrane fuel cell (PEMFC) performance was evaluated for a membrane electrode assembly composed of the crosslinked AMPS–TFEMA–AMA/ fluoroalkyl graft polymer (FGP) membrane. As a result of a power‐generation test, a maximum power density of 174 mW/cm² at a current density of 400 mA/cm² was observed for a PEMFC single cell. Consequently, it was confirmed that the AMPS–TFEMA–AMA/FGP membrane for PEMFC could easily be prepared via a two‐step reaction at a low cost and that PEMFC exhibited a cell performance and that of cells with the Nafion membrane. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Crosslinked monosulfonated poly(arylene ether) using cyclodimerization of trifluorovinyl ether groups for fuel cell applications

A crosslinker and crosslinkable sulfonated poly(arylene ether)s with trifluorovinyl ether groups were synthesized via reaction of 4‐trifluorovinyloxyphenol for application in fuel cells. Crosslinked poly(arylene ether) membranes were prepared by thermal irradiation, and the cyclodimerization of the trifluorovinyl ether groups in the polymers as well as the crosslinker was confirmed using differential scanning calorimetry and infrared measurements. These crosslinked membranes showed a low swelling ratio, comparable to that of Nafion 112. The proton conductivity of the crosslinked membranes was 0.17 and 0.3 S cm^?1 at 30 and 80 °C, respectively, much higher than that of Nafion 112 under the same conditions. The excellent dimensional stability and high conductivity of the crosslinked membranes can be attributed to this new type of crosslinking system (end‐group crosslinking) as well as the chemical structure of crosslinked (multi‐block) polymers. Copyright © 2011 Society of Chemical Industry     

Preparation of water‐swollen hydrogel membranes for gas separation

Water‐swollen hydrogel (WSH) membranes for gas separation were prepared by the dip‐coating of asymmetric porous polyetherimide (PEI) membrane supports with poly(vinyl alcohol) (PVA)–glutaraldehyde (GA), followed by the crosslinking of the active layer by a solution method. Crosslinked PVA/GA film of different blend compositions (PVA/GA = 1/0.04, 0.06, 0.08, 0.10, 0.12 mol %) were characterized by differential scanning calorimetry (DSC) and their water‐swelling ratio. The swelling behavior of PVA/GA films of different blend compositions was dependent on the crosslinking density and chemical functional groups created by the reaction between PVA and GA, such as the acetal group, ether linkage, and unreacted pendent aldehydes in PVA. The permeation performances of the membranes swollen by the water vapor contained in a feed gas were investigated. The behavior of gas permeation through a WSH membrane was parallel to the swelling behavior of the PVA/GA film in water. The permeation rate of carbon dioxide through the WSH membranes was 10⁵ (cm³ cm^?2 s^?1 cmHg) and a CO₂/N₂ separation factor was about 80 at room temperature. The effect of the additive (potassium bicarbonate, KHCO₃) and catalyst (sodium arsenite, NaASO₂) on the permeation of gases through these WSH membranes was also studied. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1785–1791, 2001     

Preparation and Characterisation of Proton Exchange Membranes Based on Crosslinked Polybenzimidazole and Phosphoric Acid

Crosslinked polybenzimidazole (PBI) was synthesised via free radical polymerisation between N‐vinylimidazole and vinylbenzyl substituted PBI. The degree of crosslinking increases with increasing content of the crosslinker. The phosphoric acid doping behaviour, mechanical properties, proton conductivity and acid migration stability of crosslinked PBI and linear PBI are discussed. The results show that the acid doping ability decreases with increasing degree of crosslinking of PBI. The introduction of N‐vinylimidazole in PBI is beneficial to its oxidation stability. The mechanical stability of crosslinked PBI/H₃PO₄ membrane is better than that of linear PBI/H₃PO₄ membrane. The proton conductivity of the acid doped membranes can reach ∼10^–4 S cm^–1 for crosslinked PBI/H₃PO₄ composite membranes at 150 °C. The temperature dependence of proton conductivity of the acid doped membranes can be modelled by an Arrhenius relation. The proton conductivity of crosslinked PBI/H₃PO₄ composite membranes is a little lower than that of linear PBI/H₃PO₄ membranes with the same acid content. However, the migration stability of H₃PO₄ in crosslinked PBI/H₃PO₄ membranes is improved compared with that of linear PBI/H₃PO₄ membranes.     

Synthesis,properties and pyrolysis of siloxane‐ and imide‐modified epoxy resin cured with siloxane‐containing dianhydride

Hydrosilylation of nadic anhydride with tetramethyl disiloxane yielded 5,5′‐(1,1,3,3‐tetramethyl disiloxane‐1,3‐diyl)‐bis‐norborane‐2,3‐dicarboxylic anhydride (I), which further reacted with 4‐aminophenol to give N,N′‐bis(4‐hydroxyphenyl)‐5,5′‐bis‐(1,1,3,3‐tetramethyl disiloxane‐1,3‐diyl)‐bis‐norborane‐2,3‐dicarboximide (II). Epoxidation of II with excess epichlorohydrin formed a siloxane‐ and imide‐modified epoxy oligomer (ie diglycidyl ether of N,N′‐bis(4‐hydroxyphenyl)‐5,5′‐bis(1,1,3,3‐tetramethyl disiloxane‐1,3‐diyl)‐bis‐norborane‐2,3‐dicarboximide) (III). Equivalent ratios of III/I of 1/1 and 1/0.8 were prepared and cured to produce crosslinked materials. Thermal mechanical and dynamic mechanical properties were investigated by TMA and DMA, respectively. It was noted that each of these two materials showed a glass transition temperature (T_g) higher than 160 °C with moderate moduli. The thermal degradation kinetics was studied with dynamic thermogravimetric analysis (TGA) and the estimated apparent activation energies were 111.4 kJ mol^?1 (in N₂), 117.1 kJ mol^?1 (in air) for III/I = 1/0.8, and 149.2 kJ mol^?1 (in N₂), 147.6 kJ mol^?1 (in air) for III/I = 1/1. The white flaky residue of the TGA char was confirmed to be silicon dioxide, which formed a barrier at the surface of the polymer matrix and, in part, accounted for the unique heat resistance of this material. Copyright © 2005 Society of Chemical Industry     

Pervaporation separation of water/isopropanol mixtures through crosslinked carboxymethyl chitosan/polysulfone hollow‐fiber composite membranes

Carboxymethyl chitosan (CMCS)/polysulfone (PS) hollow‐fiber composite membranes were prepared through glutaraldehyde (GA) as the crosslinking agent and PS hollow‐fiber ultrafiltration membrane as the support. The permeation and separation characteristics for dehydration of isopropanol were investigated by the pervaporation method. Pure chitosan, carboxymethyl chitosan, and crosslinked carboxymethyl chitosan membranes were characterized by Fourier transform infrared (FT‐IR) spectroscopy and X‐ray diffraction (XRD) to study the crosslinking reaction mechanism and degree of crystallinity, respectively. The effects of feed composition, crosslinking agent, membrane thickness, and feed temperature on membrane performance were investigated. The results show that the crosslinked CMCS/PS hollow‐fiber composite membranes possess high selectivity and promising permeability. The permeation flux and separation factor for isopropanol/water is 38.6 g/m²h and 3238.5, using 87.5 wt % isopropanol concentration at 45°C, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1959–1965, 2007     

In situ crosslinking of hyperbranched polyglycerol in casting solutions and its effect on the structure and properties of porous PVDF membranes

Porous membranes were prepared via phase inversion process from casting solutions composed of poly(vinylidene fluoride), hyperbranched polyglycerol (HPG), and N,N‐dimethylacetamide. To seek a stable presence of HPG in the resulting membranes, it was crosslinked in the casting solutions using 4,4′‐oxydiphthalic anhydride as the crosslinking agent. The membranes were characterized in terms of morphology, surface and bulk chemical compositions, water contact angle, porosity, water flux, and bovine serum albumin (BSA) adsorption experiments. The effects of HPG content and crosslinking degree on the membrane structure and properties were investigated. The increasing of crosslinking degree resulted in a significant improvement in HPG stability in the membrane matrix, and a remarkable enrichment of the crosslinked HPG at the separation surface was observed when the membrane was shaken in water at a relatively high temperature (60°C). This enrichment led to a decrease in the value of water contact angle and an improvement in fouling‐resistance. To optimize the membrane performance, a small amount of poly(vinylpyrrolidone) (PVP) was used as an additive, and it was found that the addition of PVP led to a considerable increase in water flux. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010