Preparation and properties of covalently cross-linked sulfonated copolyimide membranes containing benzimidazole groups

A series of sulfonated copolyimides containing benzimidazole groups (SPIs) were synthesized by random copolymerization of 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTDA), 2-(4-aminophenyl)-5-aminobenzimidazole (APABI), 4,4′-diaminodiphenyl ether-2,2′-disulfonic acid (ODADS) and 9,9-bis(4-aminophenyl)fluorene (BAPF) in m-cresol in the presence of benzoic acid and triethylamine at 180 °C for 20 h. Membranes with good mechanical properties were prepared by solution cast method. Proton exchange treatment resulted in ionic cross-linking and the membranes were further covalently cross-linked by treating them in polyphosphoric acid (PPA) at 180 °C for 6 h. The covalently cross-linked membranes displayed slightly lower ion exchange capacities (IECs) and proton conductivities than the corresponding covalently uncross-linked ones because small part of the sulfonic acid groups had been consumed during the cross-linking process. Fenton’s test (3% H₂O₂ + 3 ppm FeSO₄, 80 °C) revealed that benzimidazole groups played an important role in the radical oxidative stability of the membranes, while the cooperative effect of benzimidazole groups and covalent cross-linking led to much more significant enhancements in the radical oxidative stability of the membranes than each alone. The membrane 4 (ODADS/APABI/BAPF = 2/1/1, by mol), for example, after covalent cross-linking could maintain membrane form within 8 h measurement, which was much longer than that (3 h) before covalent cross-linking under the same conditions. The membrane 5 (ODADS/BAPF = 3/1, by mol) without benzimidazole groups, however, after covalent cross-linking started to break into pieces after 85 min measurement, which was only slightly longer than that (60 min) before cross-linking under the same conditions.     

Novel organotin‐containing shell‐cross‐linked knedel and core‐cross‐linked knedel: Synthesis and application in catalysis

A series of novel organotin‐containing core‐cross‐linked knedels and shell‐cross‐linked knedels were first synthesized facilely from poly(styrene)‐b‐poly(acrylate acid) nanoparticles in different selective solvents [Tetrahydrofuran (THF)/H₂O or THF/n‐octane] by using organotin compound 1,3‐dichloro‐tetra‐n‐butyl‐distannoxane as a new cross‐linker. The formation of the 1‐chloro‐3‐carboxylato‐tetra‐n‐butyl‐distannoxane layer in our cross‐linking reaction was supported by Fourier transform infrared (FT‐IR) and inductive coupled plasma emission spectrometer (ICP) analysis of the resulting shell‐cross‐linked knedels and core‐cross‐linked knedels. Transmission electron microscopy (TEM) study showed the spherical morphology and the size of the core‐cross‐linked knedels and shell‐cross‐linked knedel. Especially, the layer structure of the core‐cross‐linked knedels was clearly displayed in TEM image. The increase of extent of cross‐linking lead to the increasing of diameter for the shell‐cross‐linked knedels, whereas there was no significant effect on the core‐cross‐linked knedels. Dynamic light scattering (DLS) measurements gave hydrodynamic diameters of the core‐cross‐linked knedels that were in agreement with the TEM diameters. Moreover, the wall thickness of the shell layer of the core‐cross‐linked knedels could be easily modified by varying the block copolymer composition. Notably, the organotin‐containing core‐cross‐linked knedel exhibited highly efficient catalytic activity for the aqueous esterification reaction under nearly neutral conditions. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Synthesis and properties of novel sulfonated (co)polyimides bearing sulfonated aromatic pendant groups for PEFC applications

Novel sulfonated diamines bearing aromatic pendant groups, namely, 3,5‐diamino‐3′‐sulfo‐4′‐(4‐sulfophenoxy) benzophenone (DASSPB) and 3,5‐diamino‐3′‐sulfo‐4′‐(2,4‐disulfophenoxy) benzophenone (DASDSPB), were successfully synthesized. Novel side‐chain‐type sulfonated (co)polyimides (SPIs) were synthesized from these two diamines, 1,4,5,8‐naphthalene tetracarboxylic dianhydride (NTDA) and nonsulfonated diamines such as 4,4′‐bis(3‐aminophenoxy) phenyl sulfone (BAPPS). Tough and transparent membranes of SPIs with ion exchange capacity of 1.5–2.9 meq g^?1 were prepared. They showed good solubility and high thermal stability up to 300 °C. They showed isotropic membrane swelling in water, which was different from the main‐chain‐type and sulfoalkoxy‐based side‐chain‐type SPIs. The relative humidity (RH) and temperature dependence of proton conductivity were examined. At low RH, the novel SPI membranes showed much higher conductivity than the sulfoalkoxy‐based SPIs. They showed comparable or even higher proton conductivity than Nafion 112 in water at 60 °C (>0.10 S cm^?1). The membrane of NTDA‐DASDSPB/BAPPS (1/1)‐s displayed reasonably high proton conductivities of 0.05 and 0.30 S cm^?1 at 50 and 100% RH, respectively, at 120 °C. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2862–2872, 2006     

Synthesis and properties of novel sulfonated polyimides containing binaphthyl groups as proton‐exchange membranes for fuel cells

A novel sulfonated diamine monomer, 2,2′‐bis(p‐aminophenoxy)‐1,1′‐binaphthyl‐6,6′‐disulfonic acid (BNDADS), was synthesized. A series of sulfonated polyimide copolymers containing 30–80 mol % BNDADS as a hydrophilic component were prepared. The copolymers showed excellent solubility and good film‐forming capability. Atomic force microscopy phase images clearly showed hydrophilic/hydrophobic microphase separation. The relationship between the proton conductivity and degree of sulfonation was examined. The sulfonated polyimide copolymer with 60 mol % BNDADS showed higher proton conductivity (0.0945–0.161 S/cm) at 20–80 °C in liquid water. The membranes exhibited methanol permeability from 9 × 10^?8 to 5 × 10^?7 cm²/s at 20 °C, which was much lower than that of Nafion (2 × 10^?6cm²/s). The copolymers were thermally stable up to 300 °C. The sulfonated polyimide copolymers with 30–60 mol % BNDADS showed reasonable mechanical strength; for example, the maximum tensile strength at break of the sulfonated polyimide copolymer with 40 mol % BNDADS was 80.6 MPa under high moisture conditions. The optimum concentration of BNDADS was found to be 60 mol % from the viewpoint of proton conductivity, methanol permeability, and membrane stability. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 222–231, 2007     

Cross‐linked polybenzimidazole membranes for high temperature proton exchange membrane fuel cells with dichloromethyl phosphinic acid as a cross‐linker

Phosphoric acid doped polybenzimidazole (PBI) membranes have been covalently cross‐linked with dichloromethyl phosphinic acid (DCMP). FT‐IR measurements showed new bands originating from bonds between the hydrogen bearing nitrogen in the imidazole group of PBI and the CH₂ group in DCMP. The produced cross‐linked membranes show increased mechanical strength, making it possible to achieve higher phosphoric acid doping levels and therefore higher proton conductivity. Oxidative stability is significantly improved and thermal stability is sufficient in a temperature range of up to 250°C, i.e. within the temperature range of operation of PBI‐based fuel cells. Copyright © 2008 John Wiley & Sons, Ltd.     

Preparation and properties of ionically cross‐linked chitosan nanoparticles

Chitosan nanoparticles were fabricated by a method of tripolyphosphate (TPP) cross‐linking. The influence of fabrication conditions on the physical properties and drug loading and release properties was investigated by transmission electron microscopy (TEM), dynamic light scattering (DLS), and UV–vis spectroscopy. The nanoparticles could be prepared only within a zone of appropriate chitosan and TPP concentrations. The particle size and surface zeta potential can be manipulated by variation of the fabrication conditions such as chitosan/TPP ratio and concentration, solution pH and salt addition. TEM observation revealed a core–shell structure for the as‐prepared nanoparticles, but a filled structure for the ciprofloxacin (CH) loaded particles. Results show that the chitosan nanoparticles were rather stable and no cytotoxicity of the chitosan nanoparticles was found in an in vitro cell culture experiment. Loading and release of CH can be modulated by the environmental factors such as solution pH and medium quality. Copyright © 2008 John Wiley & Sons, Ltd.     

Size and morphology controllable core cross‐linked self‐aggregates from poly(ethylene glycol‐b‐succinimide) copolymers

We developed a simple route to prepare stabilized micelles and nanovesicles in aqueous solutions. A hydrophobic poly(succinimide) (PSI) was conjugated with the hydrophilic poly(ethylene glycol) (PEG) as a new type of cross‐linkable unit. Spherical aggregates were formed when dissolving the amphiphilic PEG₆₈₂‐b‐PSI₁₃₀ copolymer in aqueous solutions directly, and polymer nanovesicles were prepared by a precipitation‐dialysis method using PEG₄₅₅‐b‐PSI₁₃₀ copolymer. Bifunctional primary amine was added to the micelle or nanovesicle solutions to prepare cross‐linked structures via aminolysis reaction of the succinimide units. The degree of cross‐linking was controlled by adjusting the molar ratio of the cross‐linker to the succinimide units. Increasing the degree of cross‐linking leads to the compaction of the micelle core thus reduced diameter. The cross‐linked polymer micelles or nanovesicles maintained their morphology in extremely diluted solutions because of their structural stability. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Wet 3‐D printing of epoxy cross‐linked chitosan/carbon microtube composite

Over the last decays, the use of conductive biopolymer composites has been growing in areas such as biosensors, soft robotics, and wound dressing applications. They are generally soft hydrophilic materials with good elastic recovery and compatible with biological environments. However, their application and removal from the host are still challenging mainly due to poor mechanical strength. This work displays a technique for the fabrication of complex‐shaped conductive structures with improved mechanical strength by wet three‐dimensional (3‐D) printing, which uses a coagulation bath to quickly solidify an epoxy cross‐linked chitosan/carbon microtube composite ink. The fabricated conductive structure demonstrated higher elongation strength and improved elastic stability upon the introducing of polypropylene glycol diglycidyl ether (PPGDGE) as the epoxy cross‐linker, which can be due to the formation of networks between oxiran groups of PPGDGE and chitosan amino groups.     

Synthesis and characterization of ionic conducting sulfonated polybenzimidazoles

By copolymerization of the disodium‐2,2′‐disulfonate‐4,4′‐oxydibenzoic acid (SODBA), the 4,4′‐oxybis(benzoic acid) (OBBA) with the bis 3,4‐(diaminophenyl)sulfone (BDAPS), a series of high molecular weight sulfonated polybenzimidazoles (sPBI) were prepared by varying the ratio of monomers SODBA/OBBA. Polymers with ion exchange capacity (IEC) ranging from 0 to 3.2 meqH⁺/g were obtained. The chemical structure of the sPBI was confirmed by NMR, Fourier‐transform infra‐red (FTIR). Although the sPBI display a very poor solubility in organic solvents, they are, in the ammonium salt form, soluble in polar aprotic solvents such as DMF, NMP, or DMSO. Tough and ductile membranes from solution casting method were prepared. The water uptake and the ionic conductivity were determined at 30 and 90 °C. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1732–1742, 2010     

Narrow‐disperse,cross‐linked polymer microspheres by one‐step dispersion polymerization with a chain transfer agent

The increasing demand for monodispersed cross‐linked polymers in high‐quality applications requires continuous improvement in their preparation process. In this study, an appropriate amount of a chain transfer agent was added to a traditional cross‐linking system, resulting in the preparation by one‐step dispersion polymerization of cross‐linked polystyrene (PS) microspheres with a particle size of 3.867 μm and a diameter coefficient of variation of 0.011. The particles were characterized using scanning electron microscopy (SEM) and an Ubbelohde viscometer. The results show that the tertiary dodecyl mercaptan (TDDM) chain transfer during nucleation increases the oligomer concentration, promotes the aggregation of the oligomers, increases the primary particle size, and reduces the cross‐linking effect. This controls the volume of cross‐linked chains in the primary particles, thus avoiding the problem of poor dispersion of the polymer microspheres due to the introduction of divinylbenzene (DVB). This study produces a preparation method for cross‐linked microspheres.     

Fully aromatic macrocycle‐terminated polyimide: synthesis and cross‐linking

This study reported a method to prepare fully aromatic macrocycle‐terminated polyimides (MC‐PI). The macrocycle of aryl ether ketones was prepared from (4‐amino)phenylhydroquinone and a di‐fluoro monomer under pseudo high dilution condition. Novel aromatic fully MC‐PI oligomers were successfully prepared by the reaction of 2,3,3′,4′‐biphenyltetracarboxylic diandhydride with 2,5‐bis(4′‐aminophenoxy)‐biphenyl and sulfur‐containing macrocycle of aryl ether ketone. The MC‐PI oligomers were cross‐linkable in the heating, and the glass transition temperatures of the polyimides increased after thermally cured. The cross‐linking reaction of MC‐PI could form fully aromatic thermosetting polyimide by ring‐opening reaction. After cross‐linking, these polyimides showed higher glass transition temperatures and excellent thermal stability. Copyright © 2013 John Wiley & Sons, Ltd.     

Synthesis and characterization of sulfonated homo‐ and co‐polyimides based on 2,4 and 2,5‐diaminobenzenesulfonic acid for proton exchange membranes

A series of sulfonated homo‐ and random co‐polyimides (co‐SPI) based on 2,4‐diaminobenzenesulfonic acid (2,4‐DABS) and 2,5‐diaminobenzenesulfonic acid (2,5‐DABS) has been synthesized via conventional two‐step polyimidization method. 2,4‐DABS and 2,5‐DABS were used as sulfonated diamine compounds, 4,4′‐oxydianiline (ODA) and 4,4′‐diaminodiphenyl sulfone (DDS) were used as non‐sulfonated diamine compounds. Mixtures of sulfonated and non‐sulfonated diamine compounds were reacted with benzophenonetetracarboxylic dianhydride (BTDA) to obtain co‐SPI membranes. Molar ratios of sulfonated to non‐sulfonated diamine were systematically varied to produce copolymers of controlled compositions. The co‐SPIs were evaluated for thermal oxidative stability, ion exchange capacity (IEC), water uptake, proton conductivity, solubility, and hydrolytic stability. Proton conductivity and hydrolytic stability of the co‐SPIs were compared with the fully aromatic polyimide, homo‐SPIs (BTDA/2,4‐DABS and BTDA/2,5‐DABS). Regarding thermogravimetric analysis (TGA) analysis, it is concluded that desulfonation temperature in the range of 200–350°C suggests high stability of sulfonic acid groups. co‐SPIs with 40 mol% of 2,4‐DABS showed similar or higher proton conductivity than Nafion® 117 in water. Proton conductivity values of the co‐SPIs were mainly a function of IEC and water uptake. Consequently, the optimum concentration of 2,4‐DABS was found to be in the range of 30–40 mol% from the viewpoint of proton conductivity, IEC, and hydrolytic stability. Copyright © 2008 John Wiley & Sons, Ltd.     

Nanofiltration membrane cross‐linked by m‐phenylenediamine for dye removal from textile wastewater

In this work, m‐phenylenediamine (MPD) is used to prepare cross‐linked polyetherimide (PEI)‐based nanofiltration (NF) membrane for treatment of dye containing wastewater. The effects of dope solution composition, cross‐linking time, and dye concentration on membrane performance are investigated. Results indicate that the rejection of dye is increased with the increase of acetone concentration in the dope solution, cross‐linking time, and dye concentration. Meanwhile, membrane flux showed the opposite trend. With the aid of SEM and FTIR analysis, the cross‐linking between MPD and PEI is confirmed. The cross‐linked membrane has thicker and dense selective layer compared to the unmodified membrane. The cross‐linked NF membrane (PEI: 15 wt%; acetone: 20 wt%; cross‐linking time: 10 minutes) showed good performance in filtration of synthetic dye wastewater (Reactive Red 120, 1500 ppm) with 98% dye rejection and 0.013 L m^?2 hour^?1 of flux at relatively low operating pressure (60 psi).     

燃料电池用磺化聚酰亚胺质子交换膜材料的制备与性质

以联萘二酐、磺化二胺和含咪唑基团的非磺化二胺单体为原料,制备了一系列高相对分子质量的磺化聚酰亚胺,该类聚合物具有优异的溶解性和良好的成膜性.得到的质子交换膜具有优异的水解稳定性.苯并咪唑碱性基团的存在提高了磺化聚酰亚胺质子交换膜膜的溶胀稳定性和热稳定性、降低了膜的甲醇透过率.质子导电率测试结果表明,IEC值为2.55mequiv·g-1的膜室温条件下的质子导电率为0.121 S·cm-1,高于在相同测试条件下Nafion 117膜的质子导电率(0.09 S·cm-1).     

Chemically modified proton‐conducting membranes based on sulfonated polyimides: Improved water stability and fuel‐cell performance

A series of branched/crosslinked sulfonated polyimide (B/C‐SPI) membranes were prepared and evaluated as proton‐conducting ionomers based on the new concept of in situ crosslinking from sulfonated polyimide (SPI) oligomers and triamine monomers. Chemical branching and crosslinking in SPI oligomers with 1,3,5‐tris(4‐aminophenoxy)benzene as a crosslinker gave the polymer membranes very good water stability and mechanical properties under an accelerated aging treatment in water at 130 °C, despite their high ion‐exchange capacity (2.2–2.6 mequiv g^?1). The resulting polymer electrolytes displayed high proton conductivities of 0.2–0.3 S cm^?1 at 120 °C in water and reasonably high conductivities of 0.02–0.03 S cm^?1 at 50% relative humidity. In a single H₂/O₂ fuel‐cell system at 90 °C, they exhibited high fuel‐cell performances comparable to those of Nafion 112. The B/C‐SPI membranes also displayed good performances in a direct methanol fuel cell with methanol concentrations as high as 50 wt % that were superior to those of Nafion 112. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3751–3762, 2006     

Stable poly (ionic liquids) with unique cross‐linked mesoporous‐macroporous structure as efficient catalyst for alkylation of o‐xylene and styrene

In this work, using divinylbenzene (D), 1‐vinylimidazole (V) and 1‐vinyl‐3‐butylimidazolium bromide ([VBIM][Br]) as monomers, the binary‐monomer poly (ionic liquids) (PILs) and ternary‐monomer PILs were successfully synthesized, via hydrothermal polymerization and anion exchange, sequentially. Compared with each other, the ternary polymeric acidic IL catalyst has a clear spongy porous structure, while having a more stable macroporous structure, a larger specific surface area, more acidic groups and more active sites. Catalytic performance of catalyst was investigated through the alkylation of o‐xylene and styrene. The effect of the amount of IL added and the length of the cation chain on the ternary polymerization of acidic IL was systematically investigated. Under optimal reaction conditions (molar ratio of monomers was D:V:[VBIM][Br] = 2:1:1, the most suitable cation chain length was C₄), the synthesized MPD‐[C₄V]‐[VBIM][SO₃CF₃] has a larger specific surface area (89.47 m²/g), large pore volume (0.29 cm³/g), and abundant mesopores and macropores, which help to improve the contact between the active site and reactants. Moreover, the catalyst could maintain a relatively high conversion of styrene (99.0%), 1,2‐diphenylethane yield (98.7%) and high thermostability under reaction and be easily be divided from the solution, which is critical for heterogeneous solid catalysts.     

Synthesis and characterization of polymer electrolytes based on cross‐linked phenoxy‐containing polyphosphazenes

A new method to prepare the polymer electrolytes for lithium‐ion batteries is proposed. The polymer electrolytes were prepared by reacting poly(phosphazene)s (MEEPP) having 2‐(2‐methoxyethoxy)ethoxy and 2‐(phenoxy)ethoxy units with 2,4,6‐tris[bis(methoxymethyl)amino]‐1,3,5‐triazine (CYMEL) as a cross‐linking agent. This method is simple and reliable for controlling the cross‐linking extent, thereby providing a straightforward way to produce a flexible polymer electrolyte membrane. The 6 mol % cross‐linked polymer electrolyte (ethylene oxide unit (EO)/Li = 24:1) exhibited a maximum ionic conductivity of 5.36 × 10^?5 S cm^?1 at 100 °C. The ⁷Li linewidths of solid‐state static NMR showed that the ionic conductivity was strongly related to polymer segment motion. Moreover, the electrochemical stability of the MEEPP polymer electrolytes increased with an increasing extent of cross‐linking, the highest oxidation voltage of which reached as high as 7.0 V. Moreover, phenoxy‐containing polyphosphazenes are very useful model polymers to study the relationship between the polymer flexibility; that is, the cross‐linking extent and the mobility of metal ions. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 352–358     

Chemical cross‐linking with a diazirine photoactivatable cross‐linker investigated by MALDI‐ and ESI‐MS/MS

Crystallography and nuclear magnetic resonance are well‐established methods to study protein tertiary structure and interactions. Despite their usefulness, such methods are not applicable to many protein systems. Chemical cross‐linking of proteins coupled with mass spectrometry allows low‐resolution characterization of proteins and protein complexes based on measuring distance constraints from cross‐links. In this work, we have investigated cross‐linking by means of a heterobifunctional cross‐linker containing a traditional N‐hydroxysuccinimide (NHS) ester and a UV photoactivatable diazirine group. Activation of the diazirine group yields a highly reactive carbene species, with potential to increase the number of cross‐links compared with homobifunctional, NHS‐based cross‐linkers. Cross‐linking reactions were performed on model systems such as synthetic peptides and equine myoglobin. After reduction of the disulfide bond, the formation of intra‐ and intermolecular cross‐links was identified and the peptides modified with both NHS and diazirine moieties characterized. Fragmentation of these modified peptides reveals the presence of a marker ion for intramolecular cross‐links, which facilitates identification. Copyright © 2010 John Wiley & Sons, Ltd.     

Molecular modification of slightly cross‐linked HDPE: comparison of electron beam irradiation and peroxide treatments

The aim of this study is to investigate the changes in molecular structure of high density polyethylene after slightly cross‐linking with either electron beam irradiation or chemically with the peroxide method, by examining both the gel and sol parts of the polymer. Melt flow index and dynamic mechanical thermal analysis tests verify the cross‐linking process after each treatment method. Differential scanning calorimetry and Fourier transformed infrared tests, together with rheology and viscometry tests, show that the cross‐linking process has resulted in not only cross‐linking long chains but also chain scission of short chains, thus broadening the molecular weight distribution. Because these created short chains act like lubricants, cross‐linked chains flow easier. Therefore, the polymer remains processable according to the melt flow index test, and this will make the usage of slightly cross‐linked high density polyethylene in injection molding processes possible. Copyright © 2016 John Wiley & Sons, Ltd.     

Quality testing of human albumin by capillary electrophoresis using thermally cross‐linked poly(vinyl pyrrolidone)‐coated fused‐silica capillary

To detect the quality of medicinal human albumin by capillary electrophoresis, we produced a fused‐silica capillary coated with thermally cross‐linked poly(vinyl pyrrolidone) to prohibit protein adsorption. This type of capillary was easily obtained by injecting an aqueous poly(vinyl pyrrolidone) solution into a fused‐silica capillary and thermally annealing it at 200°C. Notably, stable and low electro‐osmotic flow was obtained in the poly(vinyl pyrrolidone)‐coated capillary at pH 2.20–9.00, and the separation of a mixture of four basic proteins indicated that the poly(vinyl pyrrolidone)‐coated capillary exhibits excellent repeatability and separation efficiency; moreover, the separation of these four basic proteins could even be achieved at pH 7.00. The protein recovery percentage of human serum albumin in a single‐protein solution and a mixed blood proteins solution was determined to be 97.03 and 95.40% in the poly(vinyl pyrrolidone)_50–3 (representing the concentration of the capillary‐injected poly(vinyl pyrrolidone) aqueous solution, 50 mg/mL, and thermal annealing time, 3 h) capillary, respectively. Based on these results, we used the poly(vinyl pyrrolidone)_50–3‐coated capillary to quantify the protein content of human albumin, and the results obtained from run to run, day to day and capillary to capillary demonstrated that the coated capillary could be used for quality testing commercially available human albumin.