Silane‐Crosslinked Asymmetric Polythiosemicarbazide Membranes for Organic Solvent Nanofiltration

Crosslinked polythiosemicarbazide (PTSC) membranes with a positively charged surface are fabricated via a reaction with (3‐glycidyloxypropyl)trimethoxysilane. The integrally asymmetric ultrafiltration membranes discussed here can be easily prepared by water‐induced phase separation using a PTSC solution in dimethylsulfoxide (DMSO). The crosslinked PTSC membranes are stable in DMSO, N,N‐dimethylformamide, and tetrahydrofuran and they reject molecules of molecular weights (MW) above 1300 g mol^?1. The influence of the crosslinking agent on the surface charge, membrane solvent resistance, and membrane performance is discussed. The crosslinked asymmetric PTSC membranes totally reject Direct Red dye (MW 1373 g mol^?1), while the pristine PTSC membrane does not show any rejection for this dye. This finding suggests that an inorganic‐type‐network is formed during the crosslinking reaction, which tunes the pore size of the prepared membranes.     

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     

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     

In situ chemically crosslinked chitosan membrane by adipic acid

Adipic acid, which is nontoxic, was used to dissolve chitosan. The chitosan/adipic acid solution was used to prepare chitosan membrane. After being heated at 80–100°C, the membrane was in situ chemically crosslinked by adipic acid, as verified by Fourier transform infrared and wide‐angle X‐ray diffractometer analysis. The crosslinked membrane did not collapse even without treatment in alkaline solution. In addition, the in situ crosslinking reaction was studied. The crosslinking degree (CLD) was quantitatively calculated based on the mass of water produced. The results showed that CLD was positively related to both heating temperature and time. Results of kinetic of crosslinking reaction suggested that the amidation was in agreement with the first‐order rate equation and that the temperature effect could be described with the Arrhenius equation. The results of weight loss of chitosan membrane in phosphate‐buffered solution (pH = 7.4) indicated that the best water resistance of chitosan membrane was obtained at 90°C. In brief, a straightforward, nontoxic, environment‐friendly, and economical chemically crosslinking approach has been developed for chitosan materials. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis of a new,yellow crosslinking polyvinylamine dye and its crosslinking/dyeing process through a crosslinker

A new, yellow crosslinking polyvinylamine dye was synthesized by the reaction of 2,4‐dinitrochlorobenzene with polyvinylamine prepared from Hofmann degradation of polyacrylamide. It was crosslinked and dyed to cotton and silk by a crosslinker synthesized from 1,3,5‐trichloro‐s‐triazine and sodium 2‐(p‐aminophenylsulfonyl)ethyl sulfate. The crosslinking/dyeing conditions of the yellow polyvinylamine dye, such as pH, cure temperature, and concentration of the crosslinker were investigated. The fixations of the polymeric dye by the crosslinker on cotton and silk were greater than 99%. The crosslinking covalent dye–fiber bond was proved indirectly by the comparison of IR spectra of the undyed fiber, the dyed fiber, and the crosslinked one, and also by the fact that no dye was stripped off from the crosslinked and dyed sample by extraction with DMF/water (1 : 1). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1568–1573, 2006     

Effect of gamma irradiation on the interpenetrating networks of gelatin and polyacrylonitrile: Aspect of crosslinking using microhardness and crosslink density measurements

The present article reports the effect of gamma irradiation on the hardness behavior of the interpenetrating polymer networks (IPNs) of gelatin and polyacrylonitrile (PAN). Various compositions of gluteraldehyde‐crosslinked gelatin and N, N′‐methylene bis acrylamide (MBA)‐crosslinked PAN were prepared and investigated for microhardness studies. The pre‐ and post‐irradiated IPNs were characterized for their crosslinking density, determined with swelling ratio measurements. It was found that the crosslinked IPNs get further hardened because of radiational hardening at specific doses in the range from 2 to 250 kGy. The role of acrylonitrile and crosslinker (MBA) in the IPNs, as a consequence of irradiation, has also been explained. A fair consistency has been observed between the microhardness results and crosslinking density measurements. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2581–2586, 2006     

Influence of crosslinking on crystallization,rheological, and mechanical behaviors of high density polyethylene/ethylene‐vinyl acetate copolymer blends

High density polyethylene (HDPE)/ethylene‐vinyl acetate copolymer (EVA) blends with selective crosslinking the EVA phase were prepared and the crystallization, rheological, and mechanical behaviors were studied. Selective crosslinking of EVA component could greatly improve both tensile and impact strengths of the HDPE‐rich blends and influence melting enthalpy at different annealing temperature in successive self‐nucleation and annealing procedure. Dynamic mechanical analysis reveals that glass transition temperatures of both the HDPE and EVA components are lowered upon blending and are raised upon crosslinking. The uncrosslinked HDPE/EVA blends are unstable in the melt and show increment in storage modulus (G′) and decay in loss tangent (tanδ) with annealing time associated with phase coarsening. However, morphology of selectively crosslinked blends in the melt state is highly unstable, characterized by a fast migration of uncrosslinked HDPE component out of the crosslinked EVA phase to the surface resulting in a rapid decay in G′ and an increment in tanδ at the early stage of annealing. POLYM. ENG. SCI., 54:2848–2858, 2014. © 2014 Society of Plastics Engineers     

Characterization,separation performance,and model analysis of STPP‐chitosan/PAN polyelectrolyte complex membranes

Polyelectrolyte complex membranes (PCMs) were prepared using sodium tripolyphosphate (STPP) solution surface‐crosslinking chitosan/polyacrylonitrile (PAN) composite membranes. Fourier transform infrared (FTIR) was used to characterize the surface‐crosslinking. The effects of different surface‐crosslinking time on morphologies, element distribution, and crystal structures were investigated by scanning electron microscopy (SEM), energy dispersion of X‐ray (EDX), and X‐ray diffraction (XRD). The effect of crosslinking ratio on swelling ratio was analyzed. The separation performances of PCMs in terms of permeation flux and separation factor were measured by dehydrating ethyl acetate aqueous solutions. A kinetic model of crosslinking reaction was proposed to investigate the effect of crosslinking agent concentration and surface‐crosslinking time on the crosslinking ratio of PCMs. It was found that the membrane possessed the excellent performance when surface crosslinked for 15 min. The permeation flux and separation factor were 336 g/(m² h) and 6270 in 97 wt % ethyl acetate aqueous solution at 313 K. The crosslinking ratio of PCM exponentially increased as time increased, while linearly increased as concentration and diffusion coefficient of crosslinking agent STPP solution increased. And the effect of crosslinking agent concentration on crosslinking ratio was inversely proportional to surface‐crosslinking time. The experimental results matched well with the kinetic model when STPP concentration was lower than 5 wt %. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

PTAM/PAN共混膜的抗静电性能研究

采用甲基丙烯酸氨基乙酯的均聚物(PTAM)与聚丙烯腈(PAN)共混,以硫氰酸钠溶液为凝固浴制备PTAM/PAN共混膜。探讨了PTAM含量、凝固时间以及凝固浴温度对共混膜抗静电性能的影响。结果表明:当共混膜中PTAM质量分数为7%、凝固时间为65 min、凝固浴温度为6℃时,PTAM/PAN共混膜体积电阻率降低到109Ω.cm。     

海藻酸钠/聚砜复合纳滤膜的制备与性能研究

以海藻酸钠(SA)水溶液为活性层铸膜液,分别以聚砜( PSF)、聚丙烯腈(PAN)为基膜,采用涂敷、热处理、交联剂交联的方法制备了荷负电复合纳滤膜,考察了海藻酸钠浓度、基膜、交联剂浓度等对膜性能的影响,制膜条件优化结果为,以聚砜超滤膜为基膜,海藻酸钠铸膜液质量分数为3％,交联剂为质量分数0.5％的硫酸和质量分数1％的戊...     

Phase morphologies of vulcanized chlorobutyl rubber/polyamide 12 blends: The breakup of pre‐crosslinked CIIR phase

Dynamic vulcanization to prepare blended thermoplastic vulcanizates (TPV) is a kind of complicated blending technology, where the breakup of the rubber phase happens accompanying with the crosslinking of rubber. In this study, we aim to investigate the effect of crosslinking on the breakup of chlorobutyl rubber (CIIR) phase in thermoplastic polyamide 12 (PA 12) matrix by purposely using pre‐crosslinked CIIR with different crosslink degrees and plasticizer contents. Besides, the effect of blending conditions on the breakup of crosslinked CIIR phase was studied. The results show that a low crosslink degree, a high content of plasticizer, a low blending temperature and a morderate rotor speed of 70 rpm facilitate the breakup of pre‐crosslinked CIIR in PA 12 matrix. This is ascribed to the decrease in the modulus of pre‐crosslinked CIIR phase because of either a low crosslink degree or a high content of plasticizer, the increase in the molten viscosity of thermoplastic matrix because of a low blending temperature and a moderate rotor speed. It is indicated that the breakup of pre‐crosslinked rubber is mainly dominated by the modulus of crosslinked rubber phase as well as the molten viscosity of thermoplastic matrix and shear stress. This study will provide guidance for the preparation of CIIR/PA TPV. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40765.     

Preparation and characterization of layered membranes constructed by sequential redox‐initiated grafting onto polyacrylonitrile ultrafiltration membranes

Layered membranes were prepared by sequential grafting—by means of redox initiators—of water‐soluble monomers, with oppositely charged ionic groups, onto ultrafiltration (UF) polyacrylonitrile (PAN) membranes at room temperature. Grafting of a single layer of 2‐hydroxyethylmethacrylate (HEMA) onto a PAN membrane gave a highly grafted membrane with a relatively high water flux. Bilayered membranes with various properties containing poly‐2‐(dimethylamino)ethyl methacrylate (p‐2DMAEMA) as the bottom layer and polymethacrylic acid or polystyrenesulfonic acid (p‐SSA) as the upper layer were prepared and compared—by means of infrared spectroscopy and electron microscopy—with single‐layered membranes of grafted polyhydroxyethylmethacrylate. Layered membranes exhibited a significant decline in water flux in comparison with the initial UF membranes. The flux could, however, be manipulated by controlling the concentration of monomers, the time of grafting, and the number of layers. When four layers of p‐2DMAEMA and p‐SSA were sequentially grafted onto a PAN membrane, pure water fluxes were stable over a wide range of pH values and did not change over long storage times. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 509–520, 2005     

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     

Preparation and characterization of membranes with positively charged main chain from polyethylenimine

A membrane, which has positively charged groups in the polymer main chain, was prepared from polyethylenimine by crosslinking and successive alkylation. Dibromoalkane was used as a crosslinking agent. The crosslinked membrane was alkylated using methyl iodide under several conditions. Elemental and ICP emission analyses were introduced to measure the rates of alkylation and quaternization. From the membrane potential measurement, the effective charge density was estimated. The highest value was about 1.0 M, which was obtained by a prolonged alkylation time. This value was larger than that of some commercial ion exchange membranes. The effective charge density, which was obtained by the last alkylation procedure, was 10 times larger than that of the former one, though the rate of quaternizing increased by less than a factor of two. This implies that the activity constant in the membrane increased when the charge density is increased. © 1993 John Wiley & Sons, Inc.     

Hexamethylene diisocyanate crosslinking 2‐hydroxypropyltrimethyl ammonium chloride chitosan/poly(acrylonitrile) composite nanofiltration membrane

The effects of membrane preparation conditions on membrane properties were studied in detail. The results suggested that composite nanofiltration (NF) membrane from 2.0 wt % 2‐hydroxypropyltrimethyl ammonium chloride chitosan (HACC) vaporized for 2.5 h at 50°C, and then crosslinked for 9 h at 50°C with hexamethylene diisocyanate (HDI)/ethanol (0.45/50 wt/wt) were found to have optimal performance. The resultant membrane was called HACC/PAN [poly(acrylonitrile)] NF membrane. The characteristics of this membrane such as pure water permeability, molecular weight cut‐off, rejection of salts, and swelling were investigated. And its cut‐off molecular weight (MWCO) was ～520 Da. At 25°C and 1.0 MPa, the permeability of water was 17.24 L/h m² MPa. Swelling in water decreased and rejection of salts increased with increasing HDI concentration, indicating pore contraction and increase in hydrophobicity as well as pore tortuosity due to crosslinking. The order of rejection to different salt solutes followed the decreasing of CaCl₂, MgCl₂, NaCl, KCl, and Na₂SO₄, suggesting that this membrane was positively charged. The rejections to MgCl₂ and CaCl₂ were more than 0.90; therefore, this membrane can be used for hardness removal in water treatment process. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007.     

Effect of the nature and degree of crosslinking on the Rose Bengal uptake by DVB‐, NNMBA‐, HDODA‐, and TTEGDA‐crosslinked aminopolyacrylamides

Polyacrylamides with 2–20 mol % divinyl benzene (DVB), N,N′‐methylene‐bisacrylamide (NNMBA), 1,6‐hexanediol diacrylate (HDODA), and tetraethyleneglycol diacrylate (TTEGDA) crosslinking and without crosslinking were prepared by free radical solution polymerization. Amino functions were incorporated into these polymers by transamidation with excess ethylenediamine. The dye uptake of nonprotonated and protonated aminopolyacrylamides was followed by batch equilibration method towards Rose Bengal (RB), Methyl Orange (MO), Methyl Red (MR), and Methylene Blue (MB). RB uptake by the polyacrylamide‐supported systems is higher than other dyes. Generally the dye uptake by the protonated systems is higher than the nonprotonated systems. To optimize the conditions of dye uptake, the effect of the concentration of RB solutions, temperature, and pH were followed. Kinetic studies showed that the uptake of RB by both nonprotonated and protonated crosslinked aminopolyacrylamides is a phase boundary process followed by three‐dimensional diffusion. The extent of RB uptake by the various systems depends on the nature and degree of crosslinking, and the relative rigidity/flexibility ofthe polyacrylamide support. Thus, the dye uptake followed the order: linear > NNMBA‐ > DVB‐ > TTEGDA‐ > HDODA‐crosslinked system. The dye uptake followed the same trend as the variation of amino capacity with degree of crosslinking in the respective crosslinked system. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

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.     

Crosslinking of polybenzimidazole membranes by divinylsulfone post‐treatment for high‐temperature proton exchange membrane fuel cell applications

Phosphoric acid‐doped polybenzimidazole (PBI) has been suggested as a promising electrolyte for proton exchange membrane fuel cells operating at temperatures up to 200 °C. This paper describes the development of a crosslinking procedure for PBI membranes by post‐treatment with divinylsulfone. The crosslinking chemistry was studied and optimized on a low‐molecular‐weight model system and the results were used to optimize the crosslinking conditions of PBI membranes. The crosslinked membranes were characterized with respect to chemical and physiochemical properties, showing improved mechanical strength and oxidative stability compared with their linear analogues. Fuel cell tests were further conducted in order to demonstrate the feasibility of the crosslinked membranes. Copyright © 2011 Society of Chemical Industry     

Surface characteristics of ionically crosslinked chitosan membranes

In this study, homogenous dense chitosan membranes were prepared by solution‐casting procedure. Then the membranes were ionically crosslinked by sulfuric acid. The surfaces of chitosan membranes before and after crosslinking were characterized by using FTIR‐ATR, X‐ray photoelectron spectroscopy (XPS), and atomic‐force microscopy (AFM) techniques. The XPS data suggest that the surface composition of crosslinked membrane does not change significantly with respect to uncrosslinked membrane and the most important evidence is a certain amount of sulfur, coming from the crosslinker. The result from FTIR‐ATR data shows the effectiveness of the crosslinking procedure by the shift in amide I and amide II bands. The investigation of membrane surfaces by AFM indicates that the crosslinking procedure modifies the surface morphology of chitosan. After crosslinking, the surface topography becomes more homogenous and relatively flat. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Preparation,morphologies, and properties of positively charged quaternized poly(phthalazinone ether sulfone ketone) nanofiltration membranes

Positively charged quaternized poly(phthalazinone ether sulfone ketone) (QAPPESK) nanofiltration (NF) membranes were prepared from chloromethylated poly(phthalazinone ether sulfone ketone) by the dye/wet phase inversion method with N‐methyl‐2‐pyrrolidone (NMP) and N,N‐dimethylacetamide (DMAc) as solvents. The effects of the ratio of NMP to DMAc, the evaporation time, the evaporation temperature, and the coagulation temperature on membrane performance were evaluated by the orthogonal design method. The results showed that the optimal preparation conditions were an NMP/DMAc ratio of 2/8, an evaporation time of 5 min at 70°C, and a coagulation temperature lower than 5°C. The effects of the additive type and concentration on the QAPPESK NF membrane cross‐section morphology and performance were investigated in detail. Furthermore, QAPPESK NF membranes exhibited good thermal stability with stable membrane performance for 120 h at 60°C. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009