New sulfonated engineering polymers via the metalation route. II. Sulfinated/sulfonated poly(ether sulfone) PSU Udel and its crosslinking

New mixed sulfinated/sulfonated polysulfone PSU Udel has been produced by partial oxidation of sulfinated PSU with NaOCl. From the mixed sulfinated/sulfonated PSU, thin crosslinked polymer films have been produced by S-alkylation of the residual sulfinate groups with α,ω-diiodoalkanes having 4–10  (CH₂) units. The advantages of the partial oxidation process using NaOCl are as follows: (1) The desired oxidation degree can be adjusted finely. (2) No side reactions take place during oxidation. (3) The partially oxidized polymers is stable at ambient temperature. By variation of the oxidation degree of the sulfinated/sulfonated prepolymer and by variation of the chain length of the diiodo crosslinker, crosslinked membranes with a large range of properties in terms of ionic conductivity, swelling, and permselectivity have been produced. The partially oxidized polymers have been characterized by redox titration, ¹H-NMR, and FTIR. The crosslinked membranes have been characterized in terms of ionic conductivity (resistance), permselectivity, and swelling in dependence on ion-exchange capacity and oxidation degree of the prepolymers. In addition, the thermal stabilities of the membranes have been determined by TGA, and FTIR spectra have been recorded on the crosslinked films. Selected membranes show low ionic resistances, low swelling, and good temperature stability which makes them promising candidates for application in (electro)membrane processes. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1441–1448, 1998     

Development of ionomer membranes for fuel cells

In this contribution an overview is given about the state-of-the-art at the membrane development for proton-conductive polymer (composite) membranes for the application membrane fuel cells, focusing on the membrane developments in this field performed at ICVT.For preparation of the polymers, processes have been developed for sulfonated arylene main-chain polymers as well as for arylene main-chain polymers containing basic N-containing groups, including a lithiation step. Covalently cross-linked polymer membranes have been prepared by alkylation of the sulfinate groups of sulfinate group-containing polymers with α,ω-dihalogenoalkanes. The advantage of the covalently cross-linked ionomer membranes was their dimensional stability even at temperatures of 80–90°C, their main disadvantage their brittleness when drying out, caused by the inflexible covalent network. Sulfonated and basic N-containing polymers (commercial polymers as well as self-developed ones) have been combined to acid–base blends containing ionic cross-links. The main advantage of these membrane type was its flexibility even when dried-out, its good to excellent thermal stability, and the numerous possibilities to combine acidic and basic polymers to blend membranes having fine-tuned properties. The main disadvantage of this membrane type was the insufficient dimension stability at T>70–90°C, caused by breakage of the ionic cross-links, where the ionic cross-links broke as easier as lower the basicity of the polymeric base was. Some of the acid–base blend membranes were applied to H₂ membrane fuel cells and to direct methanol fuel cells up to 100°C, yielding the result that these membranes show very good perspectives in the membrane fuel cell application.     

Preparation and Characterization of Chitosan Composite Membranes Crosslinked by Carboxyl-capped Poly（ethylene glycol）

In this study a series of chemically crosslinked chitosan/poly（ethylene glycol） （CS/PEG） composite membranes were prepared with PEG as a crosslinking reagent other than an additional blend. First, carboxyl-eapped poly（ethylene glycol） （HOOC-PEG-COOH） was synthesized. Dense CS/PEG composite membranes were then prepared by casting/evaporation of CS and HOOC-PEG-COOH mixture in acetic acid solution. Chitosan was chemically crosslinked due to the amidation between the carboxyl in HOOC-PEG-COOH and the amino in chitosan under heating, as confirmed by FTIR analysis. The hydrophilicity, water-resistance and mechanical properties of pure and crosslinked chitosan membranes were characterized, respectively. The results of water contact angle and water absorption showed that the hydrophilicity of chitosan membranes could be significantly improved, while no significant difference of weight loss between pure chitosan membranes and crosslinked ones was detected, indicating that composite membranes with amidation crosslinking possess excellent water resistanance ability. Moreover, the tensile strength of chitosan membranes could be significantly enhanced with the addition of certain amount of HOOC-PEG-COOH crosslinker, while the elongation at break didn＇t degrade at the same time. Additionally, the results of swelling behaviors in water at different pH suggested that the composite membranes were pH sensitive.     

Sulfonated and crosslinked polyphosphazene-based proton-exchange membranes

Proton-exchange membranes, for possible use in H₂/O₂ and direct methanol fuel cells have been fabricated from poly[bis(3-methylphenoxy)phosphazene] by first sulfonating the base polymer with SO₃ and then solution-casting thin films. The ion-exchange capacity of the membrane was 1.4 mmol/g. Polymer crosslinking was carried out by dissolving benzophenone photoinitiator in the membrane casting solution and then exposing the resulting films after solvent evaporation to UV light. The crosslinked membranes look particularly promising for possible proton exchange membrane (PEM) fuel cell applications. A sulfonated and crosslinked polyphosphazene membrane swelled less than Nafion 117 in both water and methanol. Proton conductivities in crosslinked and non-crosslinked 200 μm thick water-equilibrated polyphosphazene films at temperatures between 25°C and 65°C were essentially the same and only 30% lower than those for Nafion 117. Additionally, water and methanol diffusivities in the crosslinked polyphosphazene membrane were very low (≤1.2×10⁻⁷ cm²/s). Sulfonated/crosslinked polyphosphazene films showed no signs of mechanical failure (softening) up to 173°C and a pressure of 800 kPa and did not degrade chemically when soaked in a hot hydrogen peroxide/ferrous ion solution.     

Comparative investigations of ion-exchange membranes

The equilibrium and transport properties (conductivity, transport number, diffusion) of crosslinked ionomer membranes based on sulfinated and sulfonated PSU in aqueous solutions of HCl, NaCl and KCl have been investigated and compared with a Nafion 117 membrane. It has been found that these membranes are more compact and their conducting paths are of smaller dimension than that of the Nafion 117. The influence of length of crosslinking chain, changing from –(CH₂)₄– to –(CH₂)₁₂–, is particularly indicated by the diffusion coefficients; the conductivity and transport numbers of counterions are influenced only slightly. Practically no dependence of this effect on the transport number of H⁺ has been found.     

Pervaporation separation of aromatic/aliphatic hydrocarbons by crosslinked poly(methyl acrylate-co-acrylic acid) membranes

Copolymers of methyl acrylate and acrylic acid were synthesized to fabricate membranes ionically crosslinked using aluminum acetylacetonate for the separation of toluene/i-octane mixtures by pervaporation at high temperatures. The formation of the ionic crosslinking via bare aluminum cations was characterized by UV–VIS spectroscopy and solubility tests. Reproducibility and the reliability of the methodology for membrane formation and crosslinking were confirmed. The effects of acrylic acid content, crosslinking conditions, pervaporation temperature, and feed composition on the normalized flux and the selectivity for toluene/i-octane mixtures were determined. A typical crosslinked membrane showed a normalized flux of 26 kg μm m⁻² h⁻¹ and a selectivity of 13 for a 50/50 wt.% feed mixture at 100°C. The pervaporation properties including solubility selectivity and diffusivity selectivity are discussed in terms of swelling behavior. The performance of the current membranes were benchmarked against other membrane materials reported in the literature.     

Pervaporation separation of water-acetic acid mixtures through poly(vinyl alcohol) membranes crosslinked with glutaraldehyde

Poly(vinyl alcohol) (PVA) membranes crosslinked with glutaraldehyde (GA) were prepared by a solution method for the pervaporation separation of acetic acid-water mixtures. In the solution method, dry PVA films were crosslinked by immersion for 2 days at 40°C in reaction solutions which contained different contents of GA, acetone and a catalyst, HCl. In order to fabricate the crosslinked PVA membranes which were stable in aqueous solutions, acetone was used as reaction medium in stead of aqueous inorganic salt solutions which have been commonly used in reaction solution for PVA crosslinking reaction. The crosslinking reaction between the hydroxyl group of PVA and the aldehyde group of GA was characterized by IR spectroscopy. Swelling measurements were carried out in both water and acetic acid to investigate the swelling behavior of the membranes. The swelling behaviour of a membrane fabricated at different GA content in a reaction solution was dependent on crosslinking density and chemical functional groups created as a result of the reaction between PVA and GA, such as the acetal group, ether linkage and unreacted pendent aldehydes in PVA. The pervaporation separation of acetic acid-water mixtures was performed over a range of 70–90 wt% acetic acid in the feed at temperatures varying from 35 to 50°C to examine the separation performances of the PVA membranes. Permeation behaviour through the membranes was analyzed by using pervaporation activation energies which had been calculated from the Arrhenius plots of permeation rates.     

Preparation and pervaporation properties of crosslinked hyperbranched poly(amine-ester) membranes

Crosslinked hyperbranched poly(amine-ester) (HPAE) membranes were prepared by crosslinking its terminal hydroxyl groups with glutaraldehyde (GA). The crosslinked HPAE membranes showed high reactivity and good hydrophilicity. The crosslinking degree was investigated by Fourier transformation infrared spectra (FT-IR). Atom force microscope (AFM) and scanning electron microscope (SEM) reveals that the crosslinked HPAE films have smooth surfaces, dense and homogenous matrices. The swelling degree of the membrane was higher in water than that in isopropanol. From the permeation of pure water through the HPAE membrane, the effect of hydroxyl/aldehyde group ratio on the permeation flux and separation factor was investigated. The results indicated that the permeation flux increase was accompanied with the separation factor decrease if the water concentration increased in the feed solution.     

Pervaporation dehydration of ethylene glycol with chitosan–poly(vinyl alcohol) blend membranes: Effect of CS–PVA blending ratios

Chitosan–poly(vinyl alcohol), CS–PVA, blended membranes were prepared by solution casting of varying proportions of CS and PVA. The blend membranes were then crosslinked interfacially with trimesoyl chloride (TMC)/hexane. The physiochemical properties of the blend membranes were determined using Attenuated Total Reflection-Fourier Transform Infrared Spectroscopy (ATR-FTIR), X-ray diffraction (XRD), differential scanning calorimetry (DSC), tensile test and contact angle measurements. Results from ATR-FTIR show that TMC has crosslinked the blend membranes successfully, and results of XRD and DSC show a corresponding decrease in crystallinity and increase in melting point, respectively. The crosslinked CS–PVA blend membranes also show improved mechanical strength but lower flexibility in tensile testing as compared to uncrosslinked membranes. Contact angle results show that crosslinking has decreased the surface hydrophilicity of the blend membranes. The blend membrane properties, including contact angle, melting point and tensile strength, change with a variation in the blending ratio. They appear to reach a maximum when the CS content is at 75 wt%. In general, the crosslinked blend membranes show excellent stability during the pervaporation (PV) dehydration of ethylene glycol–water mixtures (10–90 wt% EG) at different temperatures (25–70 °C). At 70 °C, for 90 wt% EG in the feed mixture, the crosslinked blend membrane with 75 wt% CS shows the highest total flux of 0.46 kg/(m² h) and best selectivity of 986. The blending ratio of 75 wt% CS is recommended as the optimized ratio in the preparation of CS–PVA blend membranes for pervaporation dehydration of ethylene glycol.     

不同交联剂含量对戊二醛交联壳聚糖膜结构与性 能影响的研究

仔细研究壳聚糖膜的结晶度、溶胀度及其对二价铜离子的吸附量与交联剂戊二醛含量(特别是在戊二醛含量较低时)的关系。结果发现膜的结晶度、溶胀度以及对铜离子的吸附量均在戊二醛摩尔分数为0.25%时达到极大值。结晶度的增大可归结于轻度交联能使壳聚糖分子链在成膜时排列更为有序;而溶胀度和对铜离子吸附量的增加则可认为是交联能使壳聚糖中原先被氢键作用所束缚的氨基获得了自由。     

Highly conductive and stable anion-exchange membranes based on crosslinked poly(arylene ether sulfone)-block-poly(phenylene oxide) Networks

In the field of the developments of next-generation polymer electrolyte membranes, high conductivity is often regarded as the first important performance requirement. There is still a huge challenge to face, which is hard to achieve the balance between high ion conductivity (mainly related to ion-exchange capacity [IEC]) and good mechanical-dimensional stability (represented by swelling ratio [SR]). Here, a family of crosslinked block polyelectrolytes consisting of hydrophobic rigid poly(arylene ether sulfone) segments to ensure enough dimensional stability and hydrophilic poly(phenylene oxide) segments bearing long-flexible chains with high-density multications to serve as crosslinker and carrier for ion transport are prepared. The polyelectrolyte with an IEC of 3.04 mmol g⁻¹ exhibits a high hydroxide conductivity of 126 mS cm⁻¹ and a low SR of 8.6% at 80 °C. No obvious degradation below 200 °C is observed, and maximum tensile strength reaches 28.4 MPa. As a conclusion, these crosslinked membranes based on well-designed block polyelectrolytes exhibit an excellent combination of high ion conductivity and good mechanical-dimensional stability to meet the performance requirements for the application of anion-exchange membranes. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 391–401     

Synthesis and characterization of grafted/crosslinked proton conducting membranes based on amphiphilic PVDF copolymer

A novel graft copolymer consisting of a poly(vinylidene fluoride‐co‐chlorotrifluoroethylene) backbone and poly(glycidyl methacrylate) side chains, that is, P(VDF‐co‐CTFE)‐g‐PGMA, was synthesized through atom transfer radical polymerization (ATRP) using CTFE units as a macroinitiator. Successful synthesis and microphase‐separated structure of the polymer were confirmed by ¹H NMR, FTIR spectroscopy, and TEM. As‐synthesized P(VDF‐co‐CTFE)‐g‐PGMA copolymer was sulfonated by sodium bisulfite, followed by thermal crosslinking with sulfosuccinic acid (SA) via the esterification to produce grafted/crosslinked polymer electrolyte membranes. The IEC values continuously increased with increasing SA content but water uptake increased with SA content up to 10 wt %, above which it decreased again as a result of competitive effect between crosslinking and hydrophilicity of membranes. At 20 wt % of SA content, the proton conductivity reached 0.057 and 0.11 S/cm at 20 and 80 °C, respectively. The grafted/crosslinked P(VDF‐co‐CTFE)‐g‐PGMA/SA membranes exhibited good mechanical properties (>400 MPa of Young's modulus) and high thermal stability (up to 300 °C), as determined by a universal testing machine (UTM) and TGA, respectively. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1110–1117, 2010     

Polysulfone — sulfonated poly(ether ether) ketone blend membranes: systematic synthesis and characterisation

The effect of sulfonated poly(ether ether ketone) (SPEEK) in membrane formation and separation properties has been investigated in polysulfone(PSU)/SPEEK/N-methyl-2-pyrrolidinone (NMP) systems. Charged ultrafiltration/nanofiltration membranes were obtained reliably in the range of 0.5–5 wt.% SPEEK in the polymer blend. All PSU/SPEEK blend membranes had substantially higher water flux, salt rejection, porosity and greatly reduced particle adhesion compared to the PSU base membrane. Further, all of these properties varied systematically with variation of SPEEK content. Reproducibility and stability of the membrane properties was excellent. Pore sizes determined from dextran retention data and AFM measurements showed reasonable agreement. Membranes with 5 wt.% SPEEK demonstrated excellent overall properties. Such membranes had very high permeability, 22.6±1.6×10⁻¹¹ m³ s⁻¹ N⁻¹, 0.999 fractional rejection of 4000 Da dextran, 0.65 rejection of 0.001 M NaCl, and only 0.75 mN m⁻¹ adhesion of a 4 μm silica particle. Such membranes are very promising for scale-up of production and testing on real process streams.     

Transport and thermal properties of poly(ether imide)/acetylene-terminated monomer blends

Blends of an acetylene-terminated monomer (ATM) with a commercially available poly(etherimide) (PEI, Ultem™) were prepared, crosslinked, and characterized. Varying degrees of crosslinking were achieved through thermal treatment at 150–270°C. Incorporation of the uncrosslinked additive into the PEI resulted in reductions in the glass transition temperature, gas permeabilities and selectivities, and thermal stability. These behavior are consistent with antiplasticization of the polymer host by the ATM additive. Crosslinking of the actylene-terminated additive led to increases in thermal and chemical stability and improved gas selectivities as compared to the uncrosslinked blend. Gas transport properties are reported as a function of temperature. For the blend composition considered (9 wt% ATM in PEI), the fully crosslinked blend had transport properties which were essentially equivalent to the virgin PEI. Further, processing of the blend could be achieved in the same manner as for the virgin PEI. The resistance of the crosslinked blend to chemical dissolution or swelling was markedly improved as compared to PEI.     

High-resolution NMR of crosslinked polymers: Effects of crosslinked density and solvent interaction

Measurements have been made of the dependence of nuclear magnetic resonance bandwidths of polymers on the degree of crosslinking. Poly(methyl methacrylates) and poly(hexadecyl acrylates) were studied. Three regions of behavior are apparent: (1) in lightly crosslinked materials, bandwidths are quite insensitive to the degree of crosslinking, and the networks behave almost as linear polymers in solution; (2) in moderately crosslinked material, bandwidths are significantly affected by the degree of crosslinking; and (3) in highly crosslinked materials, bandwidths are extremely sensitive to crosslink density, and the polymer peaks become so broad that they disappear almost completely. These results indicate that segmental motion of a polymer in solution is not a function solely of its molecular weight, and that a certain degree of crosslinking is required to restrict polymer motion at the segmental level. The solvent (benzene) peak is always a singlet in swollen poly(methyl methacrylate) systems with swelling ratios up to 6.4 (regions 1 and 2, above) but as the swelling ratio further decreases to 3.5 (region 3), the solvent peak splits into a doublet; this phenomenon may indicate the existence of two different arrangements of solvent molecules in the swollen network, for which interchange is not sufficiently rapid to produce a single line.     

Anhydrous proton conducting membranes based on crosslinked graft copolymer electrolytes

A comb-like copolymer consisting of a poly(vinylidene fluoride-co-chlorotrifluoroethylene) backbone and poly(hydroxy ethyl acrylate) side chains, i.e. P(VDF-co-CTFE)-g-PHEA, was synthesized through atom transfer radical polymerization (ATRP) using CTFE units as a macroinitiator. Successful synthesis and a microphase-separated structure of the copolymer were confirmed by proton nuclear magnetic resonance (¹H NMR), FT-IR spectroscopy, and transmission electron microscopy (TEM). This comb-like polymer was crosslinked with 4,5-imidazole dicarboxylic acid (IDA) via the esterification of the –OH groups of PHEA and the –COOH groups of IDA. Upon doping with phosphoric acid (H₃PO₄) to form imidazole–H₃PO₄ complexes, the proton conductivity of the membranes continuously increased with increasing H₃PO₄ content. A maximum proton conductivity of 0.015 S/cm was achieved at 120 °C under anhydrous conditions. In addition, these P(VDF-co-CTFE)-g-PHEA/IDA/H₃PO₄ membranes exhibited good mechanical properties (765 MPa of Young's modulus), and high thermal stability up to 250 °C, as determined by a universal testing machine (UTM) and thermal gravimetric analysis (TGA), respectively.     

Utilizing thiol–ene chemistry for crosslinked nickel cation‐based anion exchange membranes

Metal cation‐based anion exchange membranes (AEMs) are a unique class of materials that have shown potential to be highly stable AEMs with competitive conductivities. Here, we expand upon previous work to report the synthesis of crosslinked nickel cation‐based AEMs formed using the thiol–ene reaction. These thiol–ene‐based samples were first characterized for their morphology, both with and without nickel cations, where the nickel‐containing membranes demonstrated a disordered scattering peak characteristic of ionic clusters. The samples were then characterized for their water uptake, chemical and mechanical stability, and conductivity. They showed a combination of high water content and extreme brittleness, which also resulted in fairly low conductivity. The brittleness resulted from large water swelling as well as the need for each nickel cation to act as a crosslinker, necessary with the current nickel‐coordination chemistry. Therefore, increasing the ion exchange capacity (IEC) for these types of AEMs, important for enhancing conductivity, also increased the crosslink density. The low conductivity and brittleness seen in this work demonstrated the need to develop non‐crosslinking metal‐complexes. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 328–339     

Improving anion exchange membranes for DMAFCs by inter-crosslinking CPPO/BPPO blends

New anion exchange membranes are prepared by heat-treating the blend base membranes of chloroacetylated poly(2,6-dimethyl-1,4-phenyleneoxide)(CPPO)/bromomethylated poly(2,6-dimethyl-1,4-phenylene oxide) (BPPO). A partially inter-crosslinked structure can be formed therein via a Friedel–Crafts reaction without adding any crosslinking reagent or catalyst. FT-IR and NMR analyses are used to confirm this inter-crosslinking structure and quantify the crosslinking distribution. Physical properties, such as toughness and thermal stability, are enhanced remarkably due to this heat treatment. Furthermore, the final membranes exhibit a high hydroxyl conductivity (up to 0.032 S cm⁻¹ at 25 °C) and extremely low methanol permeability (1.26–1.04 × 10⁻⁷ cm² s⁻¹), which match the requirements for application in low temperature direct methanol alkaline fuel cells (DMAFCs).     

Metal complexation of crosslinked polyacrylamide-supported dithiocarbamates: Effect of the molecular character and extent of crosslinking on complexation

Dithiocarbamate functions were incorporated into different polyacrylamide matrices crosslinked with a flexible and hydrophilic crosslinking agent, tetraethyleneglycol diacrylate (TEGDA), and their complexation behaviours were investigated. Crosslinked polyacrylamides with varying extents of the tetrafunctional TEGDA crosslinks were prepared by free radical solution polymerization at 60°C using potassium persulphate as initiator in ethanol. The dithiocarbamate functionality was incorporated into these polyacrylamides by a two-step polymer-analogous reaction involving (i)trans-amidation with ethylenediamine and (ii) dithiocarbamylation of the aminopolyacrylamide with carbon disulphide and alkali. The complexations of dithiocarbamate with Cu(II), Ni(II), Zn(II), Co(II) and Hg(II) ions were followed under different conditions. The metal ion intake varied with the extent of the crosslinking agent and the observed trend in complexation is Hg(II) > Cu(II)> Zn(II)> Co(II)> Ni (II). The time-course of complexation, the possibility of recycling, swelling characteristics, and spectral and thermal analyses were carried out. The thermal stability increases upon complexation with metal ions.     

Crosslinking and stabilization of nanoparticle filled PMP nanocomposite membranes for gas separations

Poly(4-methyl-2-pentyne) (PMP) has been crosslinked using 4,4′-(hexafluoroisopropylidene) diphenyl azide (HFBAA) to improve its chemical and physical stability over time. Crosslinking PMP renders it insoluble in good solvents for the uncrosslinked polymer. Gas permeability and fractional free volume (FFV) decreased as crosslinker content increased, while gas sorption was unaffected by crosslinking. Therefore, the reduction in permeability upon crosslinking PMP was due to decrease in diffusion coefficient. Compared to the pure PMP membrane, the permeability of the crosslinked membrane is initially reduced for all gases tested due to the crosslinking. By adding nanoparticles (FS, TiO₂), the permeability is again increased; permeability reductions due to crosslinking could be offset by adding nanoparticles to the membranes. Increased selectivity is documented for the gas pairs O₂/N₂, H₂/N₂, CO₂/N₂, CO₂/CH₄ and H₂/CH₄ using crosslinking and addition of nanoparticles. Crosslinking is successful in maintaining the permeability and selectivity of PMP membranes and PMP/filler nanocomposites over time.