Synthesis and characterization of sulfonated poly(arylene ether ketone ketone sulfone) membranes for application in proton exchange membrane fuel cells

A series of sulfonated poly(arylene ether ketone ketone sulfone) (SPAEKKS) copolymers were synthesized by nucleophilic polycondensation. The copolymers exhibit good thermal and oxidative stabilities, all the SPAEKKS copolymers can be cast into tough membranes. Ionic exchange capacities (IEC), water uptake properties, thermal stabilities, methanol diffusion coefficients and proton conductivities were thoroughly studied. Also the microstructures of the membranes were investigated by TEM. The proton conductivity of the SPAEKKS-4 membrane is close to that of Nafion-117 at 80 °C. The methanol diffusion coefficient of the membrane is much lower than that of Nafion-117 under the same testing conditions. The SPAEKKS membranes are promising in proton exchange membranes fuel cell (PEMFC) application.     

双酚S型聚酰亚胺二胺单体的合成与表征

以对氯硝基苯和双酚S为原料经缩合和铁粉还原合成了聚酰亚胺二胺单体4,4’-双(4-氨基苯氧基)二苯基砜(P-BAPS);考查了工艺条件对产物收率的影响,并利用红外光谱(IR)、差式扫描量热仪(DSC)对其及聚合物进行表征.结果表明:当n(硝基物)∶n(铁粉)=1∶6.75,80℃下反应6h,产物收率可达87.70％;相...     

Synthesis and characterization of partially fluorinated hydrophobic–hydrophilic multiblock copolymers containing sulfonate groups for proton exchange membrane

A new hydrophobic–hydrophilic multiblock copolymer has been successfully synthesized based on the careful coupling of a fluorine terminated poly(arylene ether ketone) (6FK) hydrophobic oligomer and a phenoxide terminated disulfonated poly(arylene ether sulfone) (BPSH) hydrophilic oligomer. ¹⁹F and ¹H NMR spectra were used to characterize the oligomers’ molecular weights and multiblock copolymer's structure. The comparison of the multiblock copolymer ¹³C NMR spectrum with that of the random copolymer showed that the transetherification side reaction was minimized in this synthesis. The morphologies of membranes were investigated by tapping mode atomic force microscopy (AFM), which showed that the multiblock membrane acidified by the high temperature method has sharp phase separation. Membrane properties like protonic conductivity, water uptake, and self-diffusion coefficient of water as a function of temperature and relative humidity (RH) were characterized for the multiblock copolymer and compared with ketone type random copolymers at similar ion exchange capacity value and Nafion^® controls. The multiblock copolymers are promising candidates for proton exchange membranes especially for applications at high temperatures and low relative humidity.     

Study on Polymerization Conditions and Structure of Poly(phenylene Sulfide Sulfone)

High molecular weight linear poly(phenylene sulfide sulfone)s (PPSS) were prepared by aromatic nucleophilic substitution reaction at atmospheric pressure. Influences of various polymerization conditions, such as solvent, catalyst, molar ratio, reaction temperature and time, on the molecular weight of PPSS were examined. The intrinsic viscosity of PPSS obtained under optimum synthesis conditions according to orthogonal experiments was 0.55 dl/g. The results of FT-IR, ¹H-NMR, UV spectrum and Raman spectrum confirmed the linear chain nature of product. The maximum UV absorption of PPSS increased with the increase of its intrinsic viscosity. X-ray diffraction and SALS studies indicated that some local ordered structures formed in the samples annealed between 220 ^○C∼240 ^○C for 4 h. The improvement in thermal performance of PPSS of high molecular weight was confirmed by DSC and TGA experiments.     

Supertoughness in Polysulfone/Poly(ethylene‐octene) Blends

Summary: Poly(sulfone of Bisphenol A) (PSU) based blends were obtained by melt blending PSU with up to 15 wt.‐% poly(ethylene‐octene) either modified with maleic anhydride (mPEO) or not (PEO). The dispersed particle size was small and similar in blends with PEO or mPEO. These facts indicated respectively that the interfacial tension was low and the lack of compatibilizing effect of mPEO. Some preferential presence of PEO in the outer surface of the specimens was observed, and was attributed to the large viscosity difference between the two components of the blends. This had no effect on the modulus of elasticity, but speeded up both the yield stress and ductility decreases at rubber contents above 3.25 wt.‐%. However, despite the immiscibility of the components, and thanks to the small particle size of the blends, super‐toughness was attained in the unmodified PSU/PEO blends. This was at PEO contents (3.25 wt.‐%) at which the modulus, yield stress and ductility of the blends were almost as good as those of pure PSU. It appeared that a change of the chemical nature of the rubber did not influence by itself super‐toughness, unless it was accompanied by either a morphological or adhesion change.

Impact strength of PSU‐based blends vs. PEO (○) or mPEO (?) content.     

高温二级膜法处理高含盐量高COD工业废水研究

采用相转化法制得杂萘联苯聚芳醚砜酮超滤基膜,采用界面聚合法制成聚酰胺表层反渗透复合膜,对高含盐、高COD含量的工业废水进行处理实验。考察温度、压力等操作条件对二级反渗透废水处理系统眭能的影响。结果表明,60℃下,经过二级反渗透处理后,对总盐度的脱除率（以电导率计）达到93.9％,对COD的脱除率达到98.3％,在为期10d的处理实验中COD截留率变化幅度在1.2％以下,体现出良好的长期热稳定性能。     

The study on poly(ether sulfone) modified cyanate ester resin and epoxy resin cocuring blends

Poly(ether sulfone) terminated with phenolic hydroxyl groups modified cyanate ester resin and epoxy resin cocuring blends were investigated by differential scanning calorimetry, Fourier transform infrared spectroscopy, scanning electron microscopy, rheometry, and mechanical properties measurement. The results suggested that poly (ether sulfone) (PES) could accelerate the polycyclotrimerization reaction of cyanate ester and cocuring processes between cyanate ester and epoxy of modified blends because of the presence of phenolic hydroxyl groups at the end of the PES molecules. It was found that the evolution of the morphologies and complex viscosities of the modified blends sensitive to molecular weight and content of PES, the tensile strength and elongation at break of the modified blends were correlated with the morphologies of modified blends. Moreover, the evolution of complex viscosities of the modified blends also showed an exponential growth at the early stage of phase separation, which demonstrated experimentally that the coarsening processes of droplets of bisphenol‐A dicyanate and diglycidyl ether of bisphenol A and the final morphologies obtained in the blends modified with PES were affected by viscoelastic behavior. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Quaternary ammonium-functionalized poly(ether sulfone ketone) anion exchange membranes: The effect of block ratios

Anion exchange membranes based on quaternary ammonium-functionalized poly(ether sulfone ketone) block copolymers (QA-PESK) with various hydrophilic–hydrophobic oligomer block ratios (10:7, 10:18, and 10:26) were synthesized, and the block length effect on the membranes' physicochemical and electrical properties were systematically investigated. The QA-PESK-10-18 membrane, prepared using a hydrophilic and hydrophobic block ratio of 10:18, displayed well-balanced hydrophilic/hydrophobic phase separation, the highest conductivity of 23.19 mS cm⁻¹ at 20 °C and 57.84 mS cm⁻¹ at 80 °C, and the highest alkaline stability among the three block ratios tested, indicating that the membranes' properties were closely related to their morphologies, which were determined by the hydrophilic/hydrophobic ratio of the block copolymer. The H₂/O₂ single cell performance using the QA-PESK-10-18 revealed a maximum power density of 235 mW cm⁻².     

高疏水氟化SiO2/聚醚砜复合膜的制备与表征

以正硅酸乙酯（TEOS）和全氟癸基三乙氧基硅烷（PFDTES）为混合Si源,以聚醚砜（PES）为基膜材料,通过真空过滤和热处理工艺制备单侧高疏水氟化SiO₂/PES（fSiO₂/PES）复合膜。通过ATR-FTIR、XPS、TEM和FESEM等对单侧高疏水fSiO₂/PES复合膜进行表征,考察PFDTES修饰量和热处理条件对膜疏水性能的影响,并评价fSiO₂/PES复合膜的疏水稳定性能。结果表明,当PFDTES:TEOS的质量比为3时,高疏水fSiO₂/PES复合膜的疏水性能较好（接触角为131.5°）;当热处理温度为100℃,热处理时间为4 h时,高疏水fSiO₂/PES复合膜表面的接触角为138.9°,且其对不同pH值的溶液都有良好的疏水性能。      

Hydrophobizing polyether sulfone membrane by sol-gel for water desalination using air gap membrane distillation

ABSTRACT

The hydrophobic polyether sulfone membranes were prepared by the sol-gel method to be applied in an air gap membrane distillation setup for desalination. The surface modifications were carried out using Trimethylsilyl chloride (TMSCl) and Methyltrimethoxysilane (MTMS) solutions. The membranes were characterized using Attenuated Total Reflection Infrared (ATR-IR) spectroscopy, Scanning Electron Microscopy (SEM), and Optical Contact Angle (OCA) methods. The effects of membrane preparation as well as operating conditions such as temperature difference, salt concentration, feed rotation speed, and cold-side temperature on membrane performance were investigated using central composite design method. It was found that feed temperature has the largest effect among the parameters on the permeation flux. The flow rate and salt rejection of the membrane in the optimum conditions were 4.47 Kg m^?2 h^?1 and 99.37%, respectively.