Sulfone Copolymers Research Articles

Preparation and characterization of a low viscosity spray dust suppressant based on xanthan gum grafted sodium α-olefin sulfonate copolymer with proactive coal-adhesive and surface-active properties

To address the problem of the high viscosity of current composite dust suppressants, which results in spray droplet sizes that are not optimal for capturing respirable dust, a low viscosity, proactive coal-adhesive, long-lasting spray dust suppressant, XG-AOS/Tre, has been developed. The suppressant utilizes xanthan gum (XG) from microbial fermentation, with α-olefin sulfonate grafted onto its hydroxyl groups to form a copolymer (XG-AOS), reducing its viscosity while maintaining the surface activity of the hydrocarbon chain and its affinity for coal dust. It has a weighted average molecular weight of 398341, a surface tension of 26.1 mN/m, a viscosity of 1.59 mPa·s, and a contact angle of 48° with coal cake. The suppressant achieves a total dust suppression rate of 85.7 % and a respirable dust suppression rate of 85.9 %. Because of its surface activity and high molecular weight, it efficiently wets and settles coal dust. It retains 47.3 % of the water in its solution 24 h after being sprayed and forms an adhesive film upon complete evaporation, providing the coal dust with resistance to wind erosion. The dust suppressant improves the dust suppression rate for dust control in coal mining. Its properties contribute to the sustainable development and environmental protection of the coal industry.

Contribution of Adsorption and Hematocrit Levels to Ganciclovir Clearance in an in Vitro Continuous Hemodiafiltration Model.

Estimation of the continuous hemodiafiltration (CHDF) clearance (CLCHDF) of ganciclovir (GCV) is crucial for achieving efficient treatment outcomes. Here, we aimed to clarify the contribution of diafiltration, adsorption, and hematocrit level to the CLCHDF of GCV in an in vitro CHDF model using three membranes: polyacrylonitrile and sodium methallyl sulfonate copolymer coated with polyethylenimine (AN69ST); polymethylmethacrylate (PMMA); and polysulfone (PS). In vitro CHDF was performed with effluent flow rates (Qe) of 800, 1500, and 3000 mL/h. The initial GCV concentration was 10 µg/mL while that of human serum albumin (HSA) was 0 or 5 g/dL. The CLCHDF, diafiltration rates, and adsorption rates were calculated. The whole blood-to-plasma ratio (R) of GCV for a hematocrit of 0.1 to 0.5 was determined using blood samples with 0.5 to 100 µg/mL of GCV. The in vitro CHDF experiment using AN69ST, PMMA, and PS membranes showed that the total CLCHDF values were almost the same as the Qe and not influenced by the HSA concentration. The diafiltration rate exceeded 88.1 ± 2.8% while the adsorption rate was lower than 9.4 ± 9.4% in all conditions. The R value was 1.89 ± 0.11 and was similar at all hematocrit levels and GCV concentrations. In conclusion, diafiltration mainly contributes to the CLCHDF of GCV, rather than adsorption. Hematocrit levels might not affect the relationship between the plasma and blood CLCHDF of GCV, and the CLCHDF of GCV can be estimated from the Qe and R, at least in vitro.

Sulfonated Pentablock Copolymer (NexarTM) for Water Remediation and Other Applications.

This review focuses on the use of a sulfonated pentablock copolymer commercialized as NexarTM in water purification applications. The properties and the use of sulfonated copolymers, in general, and of NexarTM, in particular, are described within a brief reference focusing on the problem of different water contaminants, purification technologies, and the use of nanomaterials and nanocomposites for water treatment. In addition to desalination and pervaporation processes, adsorption and photocatalytic processes are also considered here. The reported results confirm the possibility of using NexarTM as a matrix for embedded nanoparticles, exploiting their performance in adsorption and photocatalytic processes and preventing their dispersion in the environment. Furthermore, the reported antimicrobial and antibiofouling properties of NexarTM make it a promising material for achieving active coatings that are able to enhance commercial filter lifetime and performance. The coated filters show selective and efficient removal of cationic contaminants in filtration processes, which is not observed with a bare commercial filter. The UV surface treatment and/or the addition of nanostructures such as graphene oxide (GO) flakes confer NexarTM with coating additional functionalities and activity. Finally, other application fields of this polymer are reported, i.e., energy and/or gas separation, suggesting its possible use as an efficient and economical alternative to the more well-known Nafion polymer.

Conjugated Polymer/Recombinant Escherichia coli Biohybrid Systems for Photobiocatalytic Hydrogen Production.

Biohybrid photocatalysts are composite materials that combine the efficient light-absorbing properties of synthetic materials with the highly evolved metabolic pathways and self-repair mechanisms of biological systems. Here, we show the potential of conjugated polymers as photosensitizers in biohybrid systems by combining a series of polymer nanoparticles with engineered Escherichia coli cells. Under simulated solar light irradiation, the biohybrid system consisting of fluorene/dibenzo [b,d]thiophene sulfone copolymer (LP41) and recombinant E. coli (i.e., a LP41/HydA BL21 biohybrid) shows a sacrificial hydrogen evolution rate of 3.442 mmol g-1 h-1 (normalized to polymer amount). It is over 30 times higher than the polymer photocatalyst alone (0.105 mmol g-1 h-1), while no detectable hydrogen was generated from the E. coli cells alone, demonstrating the strong synergy between the polymer nanoparticles and bacterial cells. The differences in the physical interactions between synthetic materials and microorganisms, as well as redox energy level alignment, elucidate the trends in photochemical activity. Our results suggest that organic semiconductors may offer advantages, such as solution processability, low toxicity, and more tunable surface interactions with the biological components over inorganic materials.

In English

The main idea of this work is the investigation of structural and morphological characteristics of microcrystalline cellulose with switchgrass (Panicum virgatum L.) by the method of organo-solvent cooking with the addition of various brands of ion-exchange resins instead of sulfuric acid. A sulfonated copolymer of styrene and divinyl benzene with two functional groups per ring - Purolite CT-275 and a sulfonated copolymer based on tetrafluoroethylene - Nafion NR-50 were chosen as initial ion exchange resins. Air-dry switchgrass (Panicum virgatum L.), a technical culture, was used for the research. Microcrystalline cellulose (MCC) was obtained from it by the method of organo-solvent cooking with the addition of a solid catalyst. Using the methods of XRD, FTIR-ATR, AFM, TGA and DSC, the structure and morphology of MCC were studied. It is found that the use of ion-exchange resins in the organo-solvent method of obtaining MCC in a batch reactor requires the use of protective covers for the catalyst to avoid its mechanical damage. It has been found that only sulfonated copolymers based on tetrafluoroethylene are stable in the cooking solution, in contrast to sulfonated copolymers of styrene and divinylbenzene, and allow obtaining MCC from millet with a yield of 53 % versus 40 % for the classical method and a degree of polymerization of 440 versus 578, respectively. Due to the destruction of amorphous binders in the MCC’s from switchgrass (Panicum virgatum L.), regardless of the conditions of its production, we observe further ordering of the structure of the obtained MCC which is expressed in narrower and more intense peaks in the range 2θ = 22–23°. The FTIR-ATR method showed that the obtained MCC has functional groups similar to commercial M-1021. The AFM method showed that MCC has a globular and wavy relief. Surface roughness with globular relief is 12.6 nm.

Positional isomerism engineering toward minimizing exciton binding energy in sulfone copolymers for enhanced uranyl photoreduction

Conjugated microporous polymers (CMPs) have emerged as promising platforms for photocatalytic separation and enrichment of radionuclides. However, the development of CMPs with efficient exciton dissociation and free charge generation is still highly hindered by their high exciton binding energy (Eb). Herein, for the first time, three sulfone-containing CMPs are fabricated to regulate Eb by position isomerism of altering linkage sites. Temperature-dependent photoluminescence spectra reveals that ECUT-3,7-SO with 3,7-site linkage achieves a diminished Eb of 40.1 meV. DFT calculation complementally demonstrate that the Eb is related to its strongly polarized electric field and large conjugation degree, which can be easily regulated via position isomerism of its building blocks. Among the three, ECUT-3,7-SO exhibits a completely conjugated structure and a large molecular dipole moment, thus significantly reducing the Eb. As a result, ECUT-3,7-SO exhibits the highest photoreduction uranium rate constant (k, T = 298.15 K) of 0.081 min−1, and the maximum uranium extraction capacity of 918.0 mg g−1 under visible-light irradiation. This work highlights the importance of positional isomerization to the development of low exciton binding energy photocatalyst for uranium resource field.

Evaluation of the Antiviral Activity of Drugs from the Group of Polymer Electrolyte Derivatives against a Wide Range of Viruses

Background. The modern healthcare system is constantly improving and introducing new measures to protect the population from viral diseases, but the experience of the COVID-19 pandemic has shown that infections cannot always be controlled on global scale. In this regard, the development of new broad-spectrum antiviral drugs is more relevant than ever.The aim of the study was to investigate the antiviral activity and cytotoxicity of copolymers of sodium styrene sulfonate and vinyl monomers of various chemical structures, as well as to identify promising polymers for the development of new antiviral agents.Materials and methods. 14 copolymers of sodium styrene sulfonate (NaSS) with various functional comonomers were synthesized. Three viruses with different reproduction strategies and transmission methods — respiratory syncytial virus, influenza virus, and herpes virus — were selected for the assessment of antiviral activity.Results. The screening identified copolymers that showed high activity against all three viruses. It was found that the introduction of various functional groups into the structure of NaSS did not decrease antiviral activity, but significantly reduced cytotoxicity. The molecular weight has also shown a noticeable effect on the activity. Different sensitivity of viruses and cells to the studied polymers was revealed, likely due to the structural features of the virus shell and cell wall.Conclusions. The results demonstrate the potential of sodium styrene sulfonate copolymers as a model for developing a broad-spectrum antiviral drug.

Development of Novel Star-Like Branched-Chain Acrylamide (AM)-Sodium Styrene Sulfonate (SSS) Copolymers for Heavy Oil Emulsion Viscosity Reduction and Its Potential Application in Enhanced Oil Recovery.

Injecting water with chemicals to generate emulsions in the reservoir is a promising method for enhancing heavy oil recovery because oil-in-water (O/W) emulsions significantly reduce oil viscosity. To enhance heavy oil recovery efficiency, we developed new star-like branched AM-SSS copolymers (SB-PAMs) with reduction in the viscosity of the heavy oil emulsion, which was synthesized by reversible addition-fragmentation chain transfer (RAFT) controlled radical polymerization. The core structure of the branched polymer was RAFT polymerization of acrylamide (AM) and N,N'-methylene bis-acrylamide (BisAM), in the presence of 3-(((benzylthio)carbonothioyl)thio)propanoic acid as a chain transfer agent, followed by chain extension with AM and SSS. The core structures were achieved by incorporation of total monomer ratios [BisAM]/[AM] of 1:11. The expansion of the core structures by copolymerization of AM and SSS resulted in star-like branched polymer SB-PAM-co-SSS with apparent molecular weights ranging from 240 to 2381 kDa. 1H-nuclear magnetic resonance (1H NMR) and Fourier transform infrared (FTIR) confirmed the synthesized polymer structure. The molecular weight was determined by gel permeation chromatography (GPC). The polydispersity coefficient was between 1 and 7, which has a broad molecular weight distribution. The polymer dissolves only 0.75 h in deionized water, faster than conventional polyacrylamide. At 50 °C, the viscosity of the 1000 mg/L SB-polymer solution can reach up to 45 mPa·s. First, heavy oil viscosity reduction by 800 mg/L SB polymer can reach 91.7%, at a water dehydration rate of 90.4%; second, with 0.6 PV injection, 800 mg/L SB polymer improved oil recovery up to 23.66% after water flooding; and third, SB-polymer-assisted hot water flooding shows that heavy oil recovery improved by 19.46% at 110 °C with 0.6 pore volume (PV) SB-polymer injection. This novel branched chain polymer with heavy oil emulsion capability will shed light on high-temperature polymer flooding and the development of a new candidate structure for heavy oil viscosity reduction.

The influence of continuous renal replacement therapy on 1,3-β-d-glucan levels in critically ill patients: a single-center retrospective propensity score study

1,3-β-d-Glucan (BDG) is commonly used for diagnosing invasive fungal infections (IFIs). While exposure to cellulose-based hemodialyzers is known to cause false-positive BDG results, the impact of modern hemofilters used in continuous renal replacement therapy (CRRT) remains unclear. This retrospective, single-center cohort study aimed to evaluate the effect of CRRT on BDG levels in critically ill patients. We included adult intensive care unit (ICU) patients with ≥1 BDG measurement between December 2019 and December 2020. The primary outcome was the rate of false-positive BDG results in patients exposed to CRRT compared to unexposed patients. Propensity score analysis was performed to control for confounding factors. A total of 103 ICU patients with ≥1 BDG level were identified. Most (72.8%) were medical ICU patients. Forty patients underwent CRRT using hemofilter membranes composed of sodium methallyl sulfonate copolymer (AN 69 HF) (82.5%) and of polyarylethersulfone (PAES) (17.5%). Among the 91 patients without proven IFI, 31 (34.1%) had false-positive BDG results. Univariable analysis showed an association between CRRT exposure and false-positive BDG results. However, the association between CRRT exposure and false-positive BDG results was no longer significant across three propensity score models employed: 1:1 match (n = 32) (odds ratio (OR) 1.65, p = .48), model-adjusted (n = 91) (OR 1.75, p = .38), quintile-adjusted (n = 91) (OR 1.78, p = .36). In this single-center retrospective analysis, exposure to synthetic CRRT membranes did not independently increase the risk of false-positive BDG results. Larger prospective studies are needed to further evaluate the association between CRRT exposure and false-positive BDG results in critically ill patients with suspected IFI.

Novel Modified Styrene-Based Microspheres for Enhancing the Performance of Drilling Fluids at High Temperatures.

Ensuring wellbore stability is of utmost importance for safety when drilling in deep formations. However, high temperatures severely disrupt the drilling fluid gel system, leading to severe stability issues within ultra-deep formations containing micropores. This study focused on the development of a polymer-based plugging material capable of withstanding high temperatures up to 200 °C. A kind of microsphere, referred to as SST (styrene-sodium styrene sulfonate copolymer), was synthesized with a particle size of 322 nm. Compared to polystyrene, the thermal stability of SST is greatly improved, with a thermal decomposition temperature of 362 °C. Even after subjecting SST to hot rolling at 200 °C for 16 h, the particle size, elemental composition, and zeta potential remained stable within an aqueous dispersion system. The results of core displacement and NMR tests demonstrate that SST considerably reduces the pore diameter with a remarkable plugging efficiency of 78.9%. Additionally, when drilling fluids reach 200 °C, SST still enhances drilling fluid suspension and dispersion, and reduces fluid loss by over 36% by facilitating the dispersion of clay particles, improving the gel structure of the drilling fluid, resisting clay dehydration, and promoting plugging. The development of SST provides valuable insights into the preparation of high-temperature-resistant microspheres and the formulation of effective plugging agents for deep-well drilling fluids.

In vitro analysis of factors affecting the continuous hemodiafiltration clearance of teicoplanin.

In the treatment of sepsis, continuous hemodiafiltration (CHDF) and the administration of antibiotics such as teicoplanin (TEIC) are frequently performed in parallel. We aimed to clarify the factors influencing the CHDF clearance (CLCHDF ) of TEIC using a polymethylmethacrylate (PMMA) membrane or a polyacrylonitrile and sodium methallyl sulfonate copolymer membrane coated with polyethylenimine (AN69ST). We also investigated whether the adsorption of TEIC onto the hemofilters inhibits the adsorption of interleukin (IL)-6 onto the membranes. TEIC, human serum albumin (HSA), and IL-6 were incubated with pieces of hemofilter membranes and adsorption rates were calculated. The CLCHDF , diafiltration rate, and adsorption rate of TEIC were calculated using an in vitro CHDF circuit model. The adsorption rates of TEIC onto the pieces of PMMA and AN69ST membranes ranged from 15.0% to 100% and from -10% to 5%, respectively. The adsorption rate of IL-6 was similar with or without TEIC. The CLCHDF and adsorption rate of TEIC under PMMA-CHDF depended on HSA, but not on effluent flow rate (Qe). The CLCHDF under AN69ST-CHDF depended on HSA and Qe. The observed CLCHDF under AN69ST-CHDF was similar to the predicted value (the product of Qe and the plasma unbound fraction). The observed CLCHDF under PMMA-CHDF was 2.0-7.8 times greater than the predicted value. Adsorption mainly contributes to the CLCHDF of TEIC using PMMA membranes, whereas diafiltration mainly contributes to the CLCHDF of TEIC using AN69ST membranes. TEIC adsorption might not affect the adsorption of IL-6 onto PMMA membrane.

Semi-fluorinated Poly(aryl ether sulfone)s via step-growth polymerization of perfluorocyclohexene with bisphenols

Perfluorocyclohexene (PFCH) undergoes step-growth polymerization and copolymerization with variable sulfone and polyaromatic containing bisphenols in the presence of triethyl amine under mild conditions affording a new class of semi-fluorinated poly(aryl ether sulfone)s. The apparent vinyl addition/elimination mechanism provides regio-selective vinyl versus allylic substituted polymers with reactive 1,2-diaryloxyvinylene linkages in the main chain. Moderate to high molecular weight (ca. 50 kDa) polymers gave tough, creaseable films from solution with excellent transparency, and variable refractive indices ranging from 1.61 to 1.65 (at 589.2 nm). The amorphous sulfone copolymers exhibited glass transition temperatures (T g ) ranging from 122 to 225 °C and thermal stabilities with decomposition temperatures (T d at 5% wt. loss) ranging from 336 to 404 °C in N 2 . Enchained PFCH vinylene ether groups provide competing but controllable branch sites during later stages of polymerization and further serve as effective targets for post-polymerization functionalization or simple thermally induced crosslinking. Semi-fluorinated poly(aryl ether sulfone) thermoplastics and tailored networks are pursued for optical, electronic, and gas separation applications. • Poly(aryl ether sulfone)s via base mediated polymerization of decafluorocyclohexene and commercial bisphenols. • Tough flexible films provide high thermal stability, excellent optical transparency, and variable refractive index. • Step-growth addition/elimination affords reactive vinylene ether enchainment available for post reactions or crosslinking.

Preparation and Mechanism of Stability for High-Temperature and High-Salinity Gels

Summary By using an acrylamide (AM)-acrylamide propyl sulfonate (AMPS) copolymer crosslinked with hydroquinone (HQ) and hexamethylenetetramine (HMTA), a stable gel was prepared at 150℃ in simulated brine with a salinity of 25×104 mg/L. The gelation time, strength, and thermal stability of gel were investigated, and the results indicated that the dosage of the crosslinker was the key factor controlling the stability and gelation time of gel. When the polymer concentration was more than 0.7 wt% and the concentrations of HQ and HMTA were more than 0.2 wt%, respectively, a gel aged under high temperature and high salinity for 180 days could be obtained, but its gelation time was short and could be extended by adding lauramidopropyl hydroxy sulfobetaine (LHSB). When the crosslinker concentration was low, the gel would exhibit syneresis problems after aging at 150℃. Cryo-scanning electron microscopy (cryo-SEM), 13C nuclear magnetic resonance (13C-NMR), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared spectroscopy (FT-IR) analyses showed that the presence of AMPS in the crosslinked polymer controlled the gel resistance to high temperature and high salinity. Using AM-AMPS copolymer with high AMPS content and regulating the crosslinker concentration can effectively inhibit the intramolecular catalytic hydrolysis of AMPS and enhance the stability of gel. The research results could guide the design and development of gels for conformance control in high-temperature and high-salinity reservoirs.

Luminescence of Terbium Ions in Aqueous Solutions of Sodium Styrene Sulfonate Copolymers with 4-Methacrylamidosalicylic Acid

Water-soluble copolymers of sodium styrene sulfonate and 4-methacrylamidosalicylic acid of 93.7 mol % composition have been synthesized, and their interaction with terbium and gadolinium ions has been investigated to fabricate luminescent probes promising for their visualization in biomedical research. It has been shown that, in aqueous solutions in the copolymer concentration range 0.15–1.7 mg mL–1 and at the ratio [Tb3+]/[COO–] = 1, water-soluble luminescent metal polymer complexes with a luminescence lifetime of 823 µs are formed. When Tb3+ ions are partially replaced in the complex by Gd3+ ions, bimetallic complexes with intense luminescence are formed.

Introduction of a crystalline block as a strategy to increase swelling resistance and dimensional stability of sulfonated copolyimide

AbstractThe introduction of blocks inclined to form areas of high crystallinity into the sulfonated block co‐polyimide is investigated as a prospective strategy to increase swelling resistance and dimensional stability of the polymer in application to the proton exchange membranes development. The novel copolymer with the highly crystalline block was obtained and characterized by the means of static and dynamic light scattering, IR spectroscopy, thermal gravimetric analysis and differential scanning calorimetry. The structural and morphological features of the obtained copolymer were investigated with X‐ray diffraction analysis and atomic force microscopy. Transport properties of the co‐polyimide are evaluated in terms of pervaporation, proton conductivity measurements and dielectric spectroscopy experiments. The article aims at the evaluation of the influence of the high‐crystalline block introduction on morphological, transport and physical properties of the sulfonated copolymer. The properties of the obtained crystalline sulfonated copolymer are compared to the ones of the similar amorphous polyimide. The studied crystalline copolymer showed constancy of the proton conductivity values in the broad range of temperatures (20–120°C, RMSD of 0.23%) and relative humidity values.

Contribution of diafiltration and adsorption to vancomycin clearance in a continuous hemodiafiltration circuit model in vitro.

Vancomycin (VCM) is eliminated mainly by diafiltration under continuous hemodiafiltration (CHDF), but the contribution of adsorption to CHDF clearance (CLCHDF ) of VCM using a polyacrylonitrile and sodium methallyl sulfonate copolymer membrane coated with polyethylenimine (AN69ST) or a polymethylmethacrylate (PMMA) membrane is unknown. This study sought to investigate the contribution of diafiltration and adsorption to the CLCHDF of VCM using AN69ST and PMMA membranes in vitro. An in vitro CHDF circuit model was developed. The initial concentration of VCM was 50μg/mL and human serum albumin (HSA) was prepared at a concentration of 0, 2.5, or 5.0g/dL. The effluent flow rate (Qe) was set at 800, 1500, or 3000mL/h. The CLCHDF , diafiltration rate, and adsorption rate of VCM were calculated. Total CLCHDF of VCM using the AN69ST membrane increased and decreased with increasing Qe and HSA concentration, respectively. Diafiltration and adsorption rates were 82.1±9.8% and 12.1±6.1% under all conditions, respectively. Total CLCHDF using the PMMA membrane increased with increasing Qe. Diafiltration and adsorption rates were 89.2±20.4% and 4.6±17.0% under all conditions, respectively. The observed CLCHDF values significantly correlated with the predicted CLCHDF , calculated according to a previous study as the product of Qe and the plasma unbound fraction. Diafiltration predominantly contributed to CLCHDF of VCM using AN69ST and PMMA membranes. When diafiltration rather than adsorption mainly contributes to the CLCHDF of VCM, the CLCHDF could be predicted from the Qe and HSA concentration, at least in vitro.

Design synthesis and performance of anti-collapse drilling polymer mud with higher stability

PurposeThe purpose of this paper is to study the influence of different factors on mud performance, find the best conditions and synthesize a new type of anti-collapse drilling polymer mud with higher stability. The anti-collapse mechanism of drilling polymer mud was also suggested.Design/methodology/approachExploring the influence of different molecular weight thickeners, filtrate reducers, soda ash addition and film-forming components on the mud performance, so as to obtain the best ratio of anti-collapse drilling polymer mud.FindingsThe results show that the use of vegetable glue, sulfonate copolymer and vegetable fiber powder can synthesize a high-viscosity, high-stability, collapse-resistant mud. When the mass ratio of vegetable fiber powder: vegetable glue: sulfonate copolymer is 40:1:2, the mud viscosity is 21.2 s, the fluid loss in 30 min is only 12.5 mL, and the mud film thickness is 1.5 mm, which is one ideal anti-collapse polymer mud.Originality/valueCompared with ordinary polymer mud and bentonite mud, this anti-collapse polymer mud not only uses vegetable glue instead of traditional tackifiers but also effectively uses vegetable fiber powder produced from waste wood, which is environmentally friendly and highly stable specialty. It can effectively improve the safety and quality of construction during drilling in water-sensitive geology.

Asymmetric Conjugate Addition to Nitrostyrenes Catalyzed by Ni on a Diamine–Sulfonate Copolymer

Key words nickel catalysis - chiral diamines - polysulfonates - conjugate addition

Selective removal of toxic organic dyes using Trӧger base-containing sulfone copolymers made from a metal-free thiol-yne click reaction followed by oxidation.

Three copolymers TCP1–3 bearing Trӧger's base (TB) units intercalated with various thioether groups were synthesized using a catalyst-free thiol-yne click reaction. TCP1–3 display excellent solubility in common organic solvents allowing for their structural, and photophysical characterization. The thioether groups in TCP1–3 were selectively oxidized into their respective sulfone derivatives under mild oxidation reaction conditions affording the postmodified copolymers TCP4–6. Investigation of organic dye uptake from water by TCP1–6 proved their efficiency as selective adsorbents removing up to 100% of the cationic dye methylene blue (MEB) when compared to anionic dyes, such as Congo red (CR), methyl orange (MO) and methyl blue (MB). The sulfone-containing copolymers TCP4–6 display superior and faster MEB removal efficiencies with respect to their corresponding synthons TCP1–3.

Structure and properties of sulfonated poly(arylene ether)s with densely sulfonated segments containing mono-, di- and tri-tetraphenylmethane as proton exchange membrane

Multiple factors affecting the sulfonated poly (arylene ether) proton exchange membrane materials are worthy of being systematically explored. In order to investigate the variation of membrane materials based on ion exchange capacity (IEC) and hydrophilic segment length, three series of dense sulfonated poly (arylene ether)s (mt-SPAE-y, dt-SPAE-y and tt-SPAE-y) containing mono-, di- and tri-sulfonated tetraphenylmethane structural units were synthesized. Each series contains three sulfonated copolymers with different IEC values. Small angle X-ray scattering and transmission electron microscopy results show that increasing the IEC value is conducive to the aggregation of hydrophilic ion clusters, while the growth of hydrophilic segment length helps to the formation of larger hydrophilic ion clusters. Both variations favor the construction of connected hydrophilic ion channels. Based on the highest IEC value and the longest hydrophilic segment length, the tt-SPAE-1.94 membrane forms a connected hydrophilic channel that allows it to exhibit the highest proton conductivity and lowest activation energy of the proton conductivity. Good thermal properties, mechanical properties and oxidation resistance lay the foundation for the durability of the membrane in fuel cells. Finally, the tt-SPAE-1.94 membrane was used for membrane electrode assembly at 80 °C and 95% relative humidity, exhibiting a power density of 418 mW cm−2 in H2/air fuel cell test. In summary, both the increase in the IEC value and the length of the hydrophilic segment contribute to the formation of good hydrophilic-hydrophobic phase morphology, thereby enhancing the macroscopic properties of the sulfonated poly (arylene ether) proton exchange membrane material. The results prove that these three series of membranes show outstanding prospects in actual fuel cell operation and have considerable research value.