Electrochemical and structural characterization of sulfonated polysulfone

We describe the synthesis, as well as the electrochemical and structural characterization, of sulfonated polysulfone intended for use in PEM fuel cells. Starting from a commercial polysulfone, we assessed the performance of these prepared ionomers using synthesis protocols compatible with industrial production. The efficiency of the trimethylsilyl chlorosulfonate and chlorosulfonic acid reagents in the sulfonation process was confirmed by ¹H NMR, FTIR, elemental analysis, chemical titration and thermal analysis (DSC and TGA). Chlorosulfonic acid was the most effective sulfonation reagent. However, based on SEC-MALLS, this reagent induced degradation of the backbone that is detrimental to the thermomechanical stability and lifespan of the membranes. The electrical characterization of the membranes was undertaken using impedance spectroscopy in contact with different HCl aqueous solutions at various temperatures. The activation energies, which ranged from 8.2 to 11 kJ/mol, were in agreement with the prevailing proton vehicular mechanism.     

Modification of polysulfone membranes with polyethylene glycol and lignosulfate: electrical characterization by impedance spectroscopy measurements

Two sets of composite membranes having an asymmetric sulfonated polysulfone membrane as support layer have been obtained and electrically characterized (membranes SPS-PEG and PA-LIGS). The skin layer of the membrane SPS-PEG contains different percentages of polyethylene glycol in the casting solution (5, 25, 40, and 60 wt%), while lignosulfonate was used for manufacturing PA-LIGS membranes (5, 10, 20, and 40 wt%). Membrane electrical characterization was done by means of impedance spectroscopy (IS) measurements, which were carried out with the membranes in contact with NaCl solutions at different concentrations (10(-3) < or = c(M) < or = 5x10(-2)). Electrical resistance and equivalent capacitance of the different membrane samples were determined from IS plots by using equivalent circuits as models. Results show a clear decrease in the membrane electrical resistance as a result of both polysulfone sulfonation and the increase of the concentration of modifying substances, although a kind of limit concentration was obtained for both polyethylene glycol and lignosulfonate (40 and 20%, respectively). Results also show a decrease of around 90% in electrical resistance due to polysulfone sulfonation, while the value of the dielectric constant (hydrated state) clearly increases.     

Pervaporation separation of water/ethanol mixture by sulfonated polysulfone membrane

For dehydrating a water/ethanol mixture by pervaporation, a sulfonated polysulfone membrane was prepared. The separation performance of water and ethanol are shown to strongly depend on the degree of substitution of polysulfone membrane. The degree of substitution increased with increasing chlorosulfonic acid in the casting solution, and the substitution reaction was achieved within 2 h. The water permeation rate and separation factor increased with increasing substitution of polysulfone membrane up to a substitution of 2.0. The effect of sulfonation on separation performance was due to the improvement of hydrophilicity of sulfonated membrane. It was found that the solubility of water/ethanol in the membrane was not the dominant factor for separation but it was rather the diffusion difference in the membrane. The diffusion difference between permeate through sulfonated membrane was the dominant factor for separating the water/ethanol mixture. The high performance of pervaporation membrane can be prepared by sulfonated polysulfone.     

Immobilizing sulfotransferase 1A1 on magnetic microparticles and their evaluation using capillary electrophoresis

Sulfotransferases are categorized as phase II metabolic enzymes. Human sulfotransferase 1A1 (SULT1A1) is involved in the sulfonation of xenobiotics with aid from the cofactor 3'‐phosphoadenosine‐5'‐phosphosulfate that acts as a sulfonate donor. In this study, we have attempted to immobilize SULT1A1 on magnetic microparticles (MMs). Different functionalized MMs were used to immobilize SULT1A1 and their enzyme activity was compared to the control (enzyme in solution). Paracetamol was used as model substrate. Separation of paracetamol and paracetamol sulfate by CE‐UV was optimized and validated. MMs with epoxy based immobilization of SULT1A1 showed better enzyme activity. Hence, they were tested for repeated usage to allow their implementation for the development of a CE immobilized micro enzyme reactor.     

表面处理剂对聚酯薄膜与紫外光固化光油之间附着力的影响

聚酯薄膜与紫外光(UV)固化光油之间的附着力极差,用胶带拉脱时完全脱落.为此,分别采用AF-201磺化聚酯、YF-40聚丙烯酸树脂、PR-32聚氨酯、EX-40F丙烯酸改性聚氨酯和PX-1010丙烯酸改性聚酯等表面处理剂对聚酯薄膜表面进行涂覆处理,以改善聚酯薄膜的表面性能,提高其与UV光油之间的附着力.附着力测定结果表明,PX-1010丙烯酸改性聚酯可明显提高聚酯薄膜与UV光油的附着力.     

Modified polyaniline through simultaneous electrochemical polymerization of aniline and metanilic acid

Simultaneous electropolymerization of aniline and metanilic acid in aqueous HClO₄ leads to a copolymer similar to that obtained by direct sulfonation of polyaniline. Characterization by electrochemical and spectroscopic methods (UV -visible, Fourier transform IR and proton NMR) indicated the presence of polyaniline linear chains in which metanilic acid units were inserted as spacers. Elemental analysis showed that the copolymer was 40% doped by the sulfonate side-groups intramolecularly (self-doping) and 20% doped by ClO₄⁻ intermolecularly. The presence of sulfonate functional groups decreased electronic conductivity and increased solubility in alkaline solvents, but the electtrochemical properties remained principally that of polyaniline.     

Preparation of an efficient nanofiltration membrane based on blending of polysulfone and polysulfone-g-butylacrylate prepared by ATRP

Polysulfone is one of the most common used polymers for preparation of nanofiltration membranes. These membranes are highly susceptible to fouling problems because of their surface hydrophobic nature. In this paper a new approach for modification of polysulfone to overcome the fouling problems was introduced. The modification was carried out via blending of polysulfone with a modified grafted polysulfone using atom transfer radical polymerization (ATRP) method. The modified grafted polysulfone was synthesized via ATRP grafting of n-butylacrylate from chloromethylated polysulfone. The graft copolymers were characterized by FT-IR, NMR, DSG and TGA techniques. Furthermore, surface morphology and performance of the corresponding membrane were studied in detail using SEM and pure water flux and salt rejection experiments, respectively. The results indicated that the prepared modified polysulfone membranes have high surface hydrophilicity and therefore better fouling resistance and very good water permeability.     

Sulfobutylated Lignosulfonate with Ultrahigh Sulfonation Degree and Its Dispersion Property in Low-Rank Coal-Water Slurry

Using a simple method, we developed a new family of alkyl sulfonic acid modified lignosulfonate (ASLSs) with simultaneously improved sulfonation degrees and molecular weights via one step. Direct sulfonation occurred on both phenolic and alcoholic hydroxyl groups of alkali lignin raw material with 1,4-butylenesulfone used as sulfonation agent. A sulfonation degree of 3.86 mmol/g had been achieved which presents as one of the highest sulfonation degrees among those of reported LSs, to date. ¹H-NMR and Fourier transform infrared spectroscopy measurements confirmed the efficient sulfonation. Furthermore, the dispersion properties were investigated in low-rank coal-water slurry (CWS). ASLS3 showed better viscosity-reduction effect than naphthalene sulfonate formaldehyde condensate (FDN) in CWS with dosages from 0.6% to 1.0 wt%. ASLS3 had the similar sulfonation degree with FDN; however, the large steric hindrance, soft long alkyl chain-C₄H₈-SO₃H, and their efficient anchoring effect of ASLSs contributed to their improved dispersion properties.     

Effect of age and chemical treatments on characteristic parameters for active and porous sublayers of polymeric composite membranes

Changes in the transport parameters and the chemical nature of the surface of composite polyamide/polysulfone membranes due to both aging and treatment with chemical products (HCl, H(3)NO, and NaOH) have been considered. Hydraulic and salt permeability were obtained from water flow and salt diffusion measurements, respectively, and their values seem to indicate a modification in the structural parameters (porosity/thickness) of aging samples, while HCl and HNO(3) treatments will act in the opposite way. Chemical modifications in the membrane surfaces were studied by X-ray photoelectron spectroscopy (XPS), which mainly show the effect of H(3)NO and HCl on the polyamide active layer of the membranes (polyamide oxidation), but no chemical damage for that sublayer. Electrical characterization of both sublayers of the composite membranes were determined from impedance spectroscopy (IS) measurements using equivalent circuits as models, and these results indicate: (i) a strong increase of the membrane electrical resistance as a consequence of aging, mainly that associated with the active sublayer (30 times higher for an old sample than for a fresh one) and treatment with NaOH; (ii) the reduction of this effect when the samples were treated with HCl and HNO(3) solutions. Changes in the values of the electrical resistance of the composite membranes are in agreement with those obtained for permeabilities, but the electrical parameter also allows the determination of the contribution of each sublayer.     

不同磺化及碱处理聚醚醚酮的表面化学组成及体外生物活性评价

提出一种酸碱结合改性聚醚醚酮（PEEK）方法,并评价其对PEEK表面类骨磷灰石形成的影响.结果表明,通过磺化处理引入-SO₃H,显著改善了样品的亲水性,且磺化程度与H₂SO₄浓度和磺化反应时间成正比,并影响样品的表面形貌.质量分数为85% H₂SO₄处理30 min的PEEK-S具有较好的改性效果.将PEEK-S进一步用NaOH处理,可继续引入Na元素并提高样品的亲水性,但会受处理时间的影响.模拟体液（SBF）浸泡的生物活性评价结果表明,磺化后碱处理24 h的PEEK-Na具有快速的类骨磷灰石沉积能力,浸泡3 d的样品表面即可完全被沉积的类骨磷灰石覆盖,表现出较佳的生物活性.此酸碱双重改性方法操作简单,可大幅度提升PEEK的生物活性,具有较好的应用前景.     

Biofouling potentials of microporous polysulfone membranes containing a sulfonated polyether-ethersulfone/polyethersulfone block copolymer: correlation of membrane surface properties with bacterial attachment

Multivariate methods were used to identify relationships between bacterial attachment (biofouling potential), water transport, and the surface properties of nine modified polysulfone (MPS) membranes comprising blends of polysulfone (PS) with a sulfonated polyether-ethersulfone/polyethersulfone block copolymer. The topology of the microporous MPS membranes, including surface roughness, surface height, pore size and pore geometry were determined by atomic force microscopy (AFM) and digital image analysis. Other measurements included relative surface hydrophobicity by captive bubble contact angle, surface charge (i.e., degree of sulfonation) by uranyl cation binding, wt% solids, porosity, membrane thickness, water flux, and the affinity of membranes for a hydrophilic Flavobacterium and hydrophobic Mycobacterium species. The mycobacteria attached best to the MPS membranes, but the attachment of both organisms was inversely correlated with the mean aspect ratio of pores, suggesting that irregular or elliptic pores discouraged attachment. Multivariate regression analyses identified the pore mean aspect ratio, mean surface height, PS content, and the n-methylpyrrolidone+propionic acid (NMP–PA) solvent concentration as influential factors in Mycobacterium attachment, whereas membrane thickness, surface roughness, pore mean aspect ratio, porosity, and the mean pore area/image area ratio influenced Flavobacterium attachment. Cluster analyses revealed that Mycobacterium attachment was associated with hydrophobic determinants of the MPS membranes, including PS content, wt% solids, and air bubble contact angle. In contrast, Flavobacterium attachment was primarily associated with membrane thickness and charge (i.e., uranyl cation binding or degree of sulfonation). Membrane flux was inversely correlated with surface hydrophobicity and PS content, but (in contrast to cell attachment) positively correlated with most pore geometry parameters including the mean aspect ratio, suggesting that pore geometry can be optimized to minimize cell attachment and maximize water transport. Other variables influencing water flux included the NMP–PA solvent concentration and membrane roughness. The results should facilitate the design of novel microporous PS membranes having reduced biofouling potentials and greater water fluxes.     

Effect of reactive oxygen species generated with ultraviolet lamp and plasma on polyimide surface modification

Understanding the effect of reactive oxygen species (ROS), such as singlet oxygen molecule and atomic oxygen, on polyimide (PI) film properties, such as wettability, morphology, and chemical bonding state, is essential for further development of PI‐based surfaces. We investigated the effect of different ROS generated during ultraviolet (UV) and plasma treatment in oxygen gas on surface modification of Kapton PI. Different surface modification techniques, UV and plasma treatment, are known to generate different ROS. In this work, we demonstrate the effect of different ROS on PI surface modification. From the diagnostics of ROS by means of electron spin resonance and optical emission spectroscopy, we confirmed that during UV treatment, excited singlet oxygen molecules are the main ROS, while plasma treatment mainly generated atomic oxygen. The wettability of PI surface treated by UV and plasma resulted in hydrophilic PI surfaces. XPS results show that the wettability of PI samples is mainly determined by their surface O/C ratio. However, chemical bonding states were different: while UV treatment tended to generate C=O bonds, while plasma treatment tended to generate both C―O and C=O bonds. Singlet oxygen molecules are concluded to be the main oxidant during UV treatment, and their main reaction with PI was concluded to be of the addition type, leading to an increase of C=O groups on the surface of PI film. Meanwhile, atomic oxygen species were the main oxidant during plasma treatment, reacting with the PI surface through both etching and addition reaction, resulting in a wider variety of bonds, including both C―O and C=O groups.     

Preparation and characterizations of asymmetric sulfonated polysulfone membranes by wet phase inversion method

This paper presents an original approach to prepare the asymmetric sulfonated polysulfone membranes by using wet phase inversion method and their applications for dehydrating a water/ethanol mixture by pervaporation. The separation performances of sulfonated membranes were strongly affected by the degree of sulfonation and the degree of swelling of membranes. The substitution degree of sulfonic group enhanced the permselectivity of sulfonated polysulfone membranes by increasing the hydrophilicity of polymer backbone. Based on the observations of membrane morphology and light transmittance measurements, the degree of sulfonation of polysulfone presented less influence on the membrane formation pathway and the final structure of membrane in wet phase inversion process. It was also found that the sulfonated membranes showed well hydrophilic properties and facilitated water adsorption in the membranes. The sorption and permeation properties also showed that the permselectivity of asymmetric membrane was dominated by the permeate diffusion rather than the permeate sorption in the skin layer. The high separation performance of pervaporation membrane can be achieved by phase inverse method with sulfonated polysulfone.     

Fabrication of multi-layer composite hollow fiber membranes for gas separation

Using multilayer composite hollow fiber membranes consisting of a sealing layer (silicone rubber), a selective layer (poly(4-vinylpyridine)), and a support substrate (polysulfone), we have determined the key parameters for fabricating high-performance multilayer hollow fiber composite membranes for gas separation. Surface roughness and surface porosity of the support substrate play two crucial roles in successful membrane fabrication. Substrates with smooth surfaces tend to reduce defects in the selective layer to yield composite membranes of better separation performance. Substrates with a high surface porosity can enhance the permeance of composite membranes. However, SEM micrographs show that, when preparing an asymmetric microporous membrane substrate using a phase-inversion process, the higher the surface porosity, the greater the surface roughness. How to optimize and compromise the effect of both factors with respect to permselectivity is a critical issue for the selection of support substrates to fabricate high-performance multilayer composite membranes. For a highly permeable support substrate, pre-wetting shows no significant improvement in membrane performance. Composite hollow fiber membranes made from a composition of silicone rubber/0.1–0.5 wt% poly(4-vinylpyridine)/25 wt% polysulfone show impressive separation performance. Gas permeances of around 100 GPU for H₂, 40 GPU for CO₂, and 8 GPU for O₂ with selectivities of around 100 for H₂/N₂, 50 for CO₂/CH₄, and 7 for O₂/N₂ were obtained.     

Study on the synthesis and properties of an environmentally friendly water treatment agent

The long-term application of phosphorus-containing or nitrogen-containing water treatment agents can easily lead to the eutrophication of water bodies. Here, a random copolymer IA/SMAS was synthesized by itaconic acid (IA) and sodium methacrylate sulfonate (SMAS) monomer by the aqueous polymerization method. The optimal synthesis conditions were as follows: a raw material mass ratio (IA:SMAS) of 2:1, a temperature of 95 °C and a reaction time of 6 h. In addition, ammonium persulfate and isopropanol were both added at 5 % of the total raw material mass. The copolymer IA/SMAS was characterized by infrared spectroscopy (IR), elemental analysis, nuclear magnetic resonance (NMR), field emission scanning electron microscopy (FESEM), and EDS. Its molecular weight and distribution were analyzed by gel chromatography (GPC). Static methods were used to evaluate copolymers and their performance in synergy with electrostatic fields. The scale inhibition mechanism of the copolymer and its synergistic effect with electrostatic field were also studied by a scanning electron microscope (SEM) and X-ray diffraction (XRD). The results show that the copolymer had excellent scale inhibition performance for calcium carbonate and good dispersion effect on iron oxide. The addition of the electrostatic field improved the scale inhibition performance of IA/SMAS copolymer by 16 %. Thus, the copolymer is a phosphorus-free and nitrogen-free water treatment agent that achieves excellent performance and can significantly disrupt the surface morphology and crystalline structures of crystals.     

Li-SGO掺杂半互穿网络型多孔单离子传导聚合物复合电解质的制备

本文成功制备了磺酸锂功能化石墨烯,通过原位聚合方式成功将其添加到单离子传导聚合物电解质中制备出磺酸锂功能化石墨烯改性半互穿网络型多孔单离子传导聚合物复合电解质.与未掺杂磺酸锂功能化石墨烯半互穿网络型多孔单离子传导聚合物电解质相比,该电解质具有更高的孔隙率、吸液率、机械拉伸强度和离子电导率.电化学测试结果表明,掺杂磺酸锂...     

Chemical Functionalisation of Vinyl Polymers to Obtain Heparin-Like Materials

Vinyl polymers such as poly(ethylene-co-vinyl alcohol) (EVAL) and polyallylamine (PALA) both commercially available were chemically modified by introduction of carboxylic and sulfonate groups to obtain polymeric materials with improved haemocompatibility. The introduction of carboxyl groups was carried out by reaction of EVAL's hydroxy groups with acrylonitrile followed by basic hydrolysis of  CN groups. Amino groups of PALA were transformed into sulfonate groups by reaction with pyridine-SO₃ complex. Influence of reagents molar ratio, temperature and reaction time on the carboxylation degree was evaluated. In particular, yields of 86% (EVAL-CN 0.52) and 30% (EVALCOOH 0.16) were obtained for the cyanoethylation and the hydrolysis reaction of the  CN groups, respectively, whereas a sulfonation of 24% of the PALA amino groups was found. The functionalised polymers were characterized by physicochemical measurements. Preliminary biological tests proved the importance of strong acidic groups on the anticoagulant properties of the polymeric materials.     

Preparation and characterization of polyaniline/polysulfone nanocomposite ultrafiltration membrane

Novel nanocomposite membrane was prepared through the filtration of polyaniline (PANI) nanofiber aqueous dispersion with polysulfone (PS) ultrafiltration (UF) membrane. Scanning electron microscope (SEM) images showed that PANI nanofiber layer was formed on the PS membrane surface. Atomic force microscopy (AFM) analysis indicated that the nanocomposite membrane had rougher surface than the PS substrate membrane. Compared with the PS substrate membrane, the nanocomposite membrane had much better permeability for the good hydrophilicity of PANI nanofiber layer, and had almost the same rejection performance. In addition, the nanocomposite membrane had positive surface potential under acidic condition because PANI could be protonated easily by acid. During the filtration of BSA solution, the nanocomposite membrane showed much better antifouling performance than the substrate membrane for the hydrophilicity and steric hindrance effect of its nanofiber layer. Moreover, under acidic solution condition, strong electrostatic repulsion between PANI nanofibers and BSA existed and improved membrane antifouling performance further.     

Sulfonation of metallocene‐based polyolefinic elastomers and its influence on physicomechanical properties: Effect of reaction parameters,styrene grafting,and pendant chain length

Direct sulfonation and styrene‐mediated sulfonation were carried out onto metallocene‐based poly(ethylene‐co‐octene) (POE) and poly(ethylene‐co‐butene) (PBE) elastomers to impart polarity on the completely nonpolar rubbery matrices and to prepare a new class of elastomer. The influence of styrene‐grafting and pendant chain length on the degree of sulfonation was also studied. The effects of sulfonation, styrene grafting and styrene‐mediated sulfonation at their optimized levels on various physicomechanical properties were thoroughly investigated, and the resultant properties were correlated with structures of the modified elastomers. Higher extent of sulfonic acid groups were introduced through direct sulfonation in comparison with the styrene‐mediated sulfonation, whereas better thermal and mechanical properties were obtained through styrene‐mediated sulfonation in comparison with the direct sulfonation process. PBE had shown higher degree of sulfonation and percentage grafting than POE. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 8023–8040, 2008     

Modification of active and porous sublayers of aged polyamide/polysulfone composite membranes due to HNO3 treatment: effect of treatment time

Changes in electrical and transport parameters for aged composite polyamide/polysulfone membrane samples (PAC) and their porous support layers (PSU) as a result of chemical treatment (immersion in 1 M HNO3 solution) at four different times (12 h < or = t < or = 72 h) have been obtained. Salt permeability, ion transport number, and membrane electrical resistance for the treated samples were determined from salt diffusion, membrane potential, and impedance spectroscopy measurements, which were carried out with the membranes in contact with NaCl solutions at different concentrations and compared with those determined for fresh and aged nontreated samples. Results show the strong effect of aging on membrane parameters, particularly the decrease in salt permeability (P(s)) and the increase in membrane electrical resistance (R(m)), while ion transport number is hardly affected by aging, chemical treatment, or treatment time. Results show how the compaction of the porous structure causes by aging (dried membrane matrix structure) can be partially reduced by HNO3 treatment, and they also allow the estimation of 24-h treatment as the optimum time (higher salt permeability and lower membrane electrical resistance), mainly for the polysulfone support layer. The use of equivalent circuits in the analysis of impedance spectroscopy data allows separate estimation of the electrical resistance associated with each sublayer of the composite PAC membrane samples. On the other hand, chemical changes in the active top layer of the PAC membrane (polyamide active layer) were obtained from XPS analysis, which show some modifications in the atomic concentration percentages of the polyamide characteristic elements as a result of acidic treatment time, which are more significant after 72-h acidic immersion.