磺化聚醚醚酮/蒙脱土复合型质子交换膜制备与性能

以磺化聚醚醚酮(SPEEK)为基体,以有机改性的蒙脱土(OMMT)为无机相,采用溶液插层法成功制备出了可望应用于直接甲醇燃料电池的SPEEK/OMMT复合型质子交换膜.通过X射线衍射(XRD)表征了复合膜的微观结构,并采用交流阻抗和隔膜扩散方法分别考察了复合膜的质子传导性能和阻醇性能.结果表明,蒙脱土的片层间距超过4.4 nm,SPEEK高分子链已插层到蒙脱土片层之间.与纯SPEEK膜相比,SPEEK/OMMT复合膜的质子传导率有所降低,但在90℃也达到了1.2×10-2S/cm的水平,而且蒙脱土的加入明显地降低了SPEEK膜的甲醇渗透率.     

磷钨酸/磺化聚芳醚酮砜复合型高温燃料电池用质子交换膜

为了满足高温质子交换膜燃料电池使用要求,采用溶液铺膜法制备了磺化聚芳醚酮砜(SPAEEKS)与磷钨酸(HPA)复合型质子交换膜。红外光谱证明磷钨酸中的桥氧原子和端氧原子与磺酸基团形成了强烈的相互作用。扫描电镜照片显示磷钨酸粒子能够均匀地分散在聚合物的基体中。磷钨酸的引入提高了复合膜的热稳定性 ,含有 30wt%HPA、SPAEEKS磺化度为0.8的复合膜(HPA30/SPAEEKS-0.8)的玻璃化转变温度达到236℃,质量损失5%时的热分解温度达到了299℃。在相同测试条件下,HPA30/ SPAEEKS-1. 0在80℃时质子传导率高于Nafion 117,而且在120℃ 达到了0.098S/cm。结果表明,HPA30/SPAEEKS-1. 0 有望在高温质子交换膜燃料电池中得到应用。     

磺化聚芳醚砜与可溶性聚酰亚胺共混材料制备气体除湿膜

在不同反应条件下制备了一系列磺化聚芳醚砜（ＳＰＥＳ－Ｃ）样品，采用磺化程度较高的产物与可溶性聚酰亚胺（ＰＩ）进行共混并纺制成中空纤维膜，研究了磺化条件对材料磺化程度、共混相容性及成膜性能的影响，通过测试膜对空气中水蒸汽的脱除效果得到了一些规律性的结论。     

磺化聚醚砜上浆剂对碳纤维/聚醚砜复合材料界面性能的影响

为了提高碳纤维(CFs)增强热塑性树脂聚醚砜(PES)复合材料的界面结合力,对PES进行磺化改性,得到磺酸基聚醚砜(SPES)制备的CFs上浆剂,研究了SPES上浆剂对CFs/PES复合材料界面性能的影响和上浆剂质量分数对CFs/PES复合材料的作用效果。结果表明:经过SPES上浆的纤维毛丝量降低、耐磨性提高。同时FTIR和XPS分析表明:SPES中的—SO3H基团与CFs表面微量的活性官能团发生了化学反应,提高了增强体CFs与基体树脂PES间的黏连。当上浆剂含量为1wt%时,CFs/PES复合材料的层间剪切强度(ILSS)提高最显著,比未上浆改性的CFs/PES复合材料的提高了24%。SEM照片证实在此浓度下CFs与PES结合更加紧密。动态力学热分析(DMTA)结果亦证明1wt%的SPES上浆剂提高了CFs/PES复合材料的玻璃化转变温度。     

具柔性链段磺化聚芳醚酮质子交换膜的制备与性能研究

以二氟二苯甲酮(DFBP),磺化二氟二苯甲酮(SDFBP),4,4’-二羟基二苯醚(DOPE)和双酚芴(BHF)为单体,通过亲核缩聚反应合成了分子链磺酸含量不同具柔性链段的磺化聚芳醚酮.研究结果表明:所合成的聚合物具有较高的分子量,可通过流延成膜的方法制备出柔韧、透明的膜.所制备的膜具有较高的吸水率与尺寸稳定性及抗氧化性,在同等测试条件下,具有与Nafion 117膜相当的质子传导率,且甲醇透过率比Nafion 117膜低1、2个数量级.     

Hydrophilic and hydrophobic interactions in cross-linked chitosan membranes

Chitosan membranes with different cross-linking density were prepared by modifying cross-linking time. Sodium tripolyphosphate was the cross-linking agent. A pulsed nuclear magnetic resonance study was performed on uncross-linked and cross-linked membranes. Different fraction of water molecules were identified in different zones within the membranes. The ratio of water molecules per chitosan repeating unit were calculated. A maximum of twelve water molecules were tightly coordinated to the chitosan repeating unit. Also, a very small water molecule fraction was identified but it was mobile enough as not to contribute to the dipolar interactions. The cross-linking reaction could lead to the formation of hydrophilic and hydrophobic interactions. These two types of interactions could result in the coexistence of a network formed by hydrophilic and hydrophobic micropores. This knowledge could be useful for the interpretation of results of hydrophobic drugs permeation across hydrophilic membranes. For example, the increment of estradiol fluxes across chitosan membranes with an increase in cross-linking density.     

磺化酚酞型聚醚砜/蒙脱土质子导电复合膜的表征与性能

采用浓硫酸为磺化剂,制备了磺化度为70.26%的磺化酚酞型聚醚砜,并通过添加有机蒙脱土制备了复合质子交换膜.研究了不同含量有机蒙脱土的复合质子交换膜的外观形貌,含水量,热稳定性和质子电导率,发现有机蒙脱土已经很好地分散在聚合物溶液中,复合膜的质子电导率在多种条件下均随着OMMT的添加量的增加而增加,其中SPES-C/OMMT10在80℃下经质子化处理后质子电导率达到8.53×10-4S/cm.     

改性SiO2／磺化聚醚醚酮复合质子交换膜的形貌与性能研究

用球磨法对SiO2进行了改性并制备改性SiO2/磺化聚醚醚酮(SPEEK)复合膜,用扫描电镜分析了膜的形貌,并测定了其热稳定性、拉伸强度、电导率等性能.SEM分析结果表明,当SiO2含量为10%时,KH560改性SiO2(简记为:SiO2-KH560)在复合膜中的分布更均匀,并基本呈纳米尺度分布;膜的性能测定结果表明,复合膜的热稳定性都较均质膜有较大的提高;当SPEEK离子交换容量相同时,与均质膜相比,复合膜的电导率以及抗拉强度有增大趋势.     

磺化聚醚砜复合反渗透膜的制备与性能研究

通过亲核取代反应制备了酚酞型聚醚砜(PES),利用浓硫酸对其磺化后得到了磺化聚醚砜(SPES),并通过核磁光谱对其结构进行了表征.将SPES与一定量的PVA溶解混合后,以聚砜超滤膜为支撑层,采用刷涂法制备了复合反渗透膜(SPES-PVA).扫描电镜照片显示该方法制备的反渗透膜表面平整,而且无缺陷.PVA的加入提高了膜的截盐率以及耐氯性.采用该方法得到的复合反渗透膜具有良好的截盐率和水通量.其中,当PVA的加入量为0.1%时,SPES-PVA-0.1复合反渗透膜对氯化钠的截盐率达到了97.8%,水通量为12.3L/(m2·h).     

一种新型的磺化聚芳醚酮质子交换膜材料

利用先聚合后磺化的方法合成了一种新型磺化聚芳醚酮,FTIR和HNMR结构表征表明,其磺酸基只连在悬挂侧链上.利用浇铸法将该材料制备成膜,对膜的离子交换容量(IEC)、平均当量重量(EW)、磺化度(SD)、吸水性、线性膨胀率及其电导率进行了表征,结果表明这种膜材料具有良好的吸水性和较低的线性溶胀率,所制得的膜在100℃、100%相对湿度时的质子电导率与Nafion-117~(R)膜相近,有望作为质子交换膜使用.     

聚乙二醇/磺化聚苯醚质子交换膜的制备与性能研究

采用溶液共混浇铸法制备了一系列的聚乙二醇/磺化聚苯醚(PEG/SPPO)共混膜SPPO的红外光谱图显示了磺酸基团的成功引入;X-射线衍射图表明,加入柔性的聚乙二醇,SPPO的有序程度降低;膜的离子交换容量(IEC值)、质子传导率和吸水率等理化性能结果表明:PEG/SPPO共混膜的质子传导率和离子交换容量虽然较纯SPPO膜有所下降,但是最大也分别达到了1.80mequiv.g-1和0.061S/cm(PEG/SPPO=10/90,90℃),仍然可以满足质子交换膜的使用要求,而复合膜的吸水率和溶胀率较SPPO膜大幅降低。整体来说,复合膜的各项综合性质良好,有望应用于直接甲醇燃料电池。     

9,10-Diphenylanthracene-containing poly(arylene ether sulfone)s with improved glass transition temperature and photocrosslinking properties

In this study, novel poly(arylene ether sulfone)s containing 9,10-diphenylanthracene units were synthesized and their thermal and optical properties were investigated. This new bisphenol monomer, 9,10-bis(4-hydroxyphenyl)anthracene, was facially synthesized in two steps and showed similar reactivity for SNAr reactions as other bisphenol monomers, such as bisphenol A. The introduction of an anthracene unit to poly(arylene ether sulfone)s can obviously improve glass transition temperature and retain good solubility and high decomposition temperatures. The glass transition temperature of poly(arylene ether sulfone) reached up to 265 °C when the bisphenol A was entirely substituted by bis(4-hydroxyphenol)anthracene. These polymers are soluble in chloroform, N,N-dimethylformamide and N-methyl-2-pyrrolodone and can be film-formed through spin-coating. Interestingly, anthracene units endowed these polymers with photocrosslinkable properties and further improved their thermal stability.     

聚醚砜酮合金超滤膜的制备及表征

采用含二氮杂萘酮结构的磺化聚醚砜酮与聚醚砜酮共混的方法制备了一种新型荷电超滤膜.通过孔隙率、表面接触角、离子交换容量以及对达旦黄水溶液、聚乙二醇(PEG)6000水溶液分离性能的测试和扫描电镜对膜孔结构的观察,研究了合金膜中磺化聚醚砜酮含量对膜性能的影响规律.结果表明:当铸膜液中磺化聚醚砜酮含量从0增加到3%时,合金超滤膜水通量增大到491 L/(m2.h),对PEG6000的截留率可达86%.合金超滤膜具有高水通量、高截留率、亲水性好等特点.     

质子交换膜用部分含氟磺化聚芳醚的合成与性能研究

通过直接磺化的方法,合成了一种部分含氟的磺化聚芳醚.由于特殊单体结构的设计,在聚合物主链上引入甲基取代基,对聚合物主链进行保护.用氯磺酸直接磺化方法在聚芳醚侧基上引入磺酸功能基,实现了聚合物磺化结构的可控定位合成,得到了稳定性较好的磺化聚芳醚.用溶液浇膜法制备了质子交换膜,研究了膜的各种性能.这种膜具有较高的导电性、吸水性和好的抗水解性、热稳定性.由于特殊结构的设计和部分氟的引入,这种膜的抗氧化性有显著的提高.     

Preparation and characterization of a novel hyperbranched polyphosphate ester

Polyphosphate esters have received a great deal of attention due to their important application in biomaterials field. Hyperbranched structure of polymers may support unique properties, including low viscosity and perfect intrinsic property. We report here three generations of hyperbranched polyphosphate esters (HPPE-1, HPPE-2 and HPPE-3) synthesized from a dehydrochlorination reaction between 1,3,5-tris(2-hydroxyethyl)cyanuric acid (THEIC) and phosphorus oxychloride (POCl₃), and characterize their chemical structures by FT-IR, ¹H NMR, ¹³C NMR, ³¹P NMR and 2D NMR (¹H,¹H-COSY and ¹³C, ¹H-HSQC) techniques. Degrees of branching of HPPE-1, HPPE-2 and HPPE-3 are 0.90, 0.91 and 0.87 respectively from the calculation of their ¹³C NMR spectra. Molecular weights of HPPE-1, HPPE-2 and HPPE-3 are m/z 1530, 1768 and 2750 from their MALDI-TOF-MS spectra. Study on thermal degradation mechanism of the HPPE-2 by a 3D FT-IR/TG technology shows that there are two cracking processes of its molecular chains, including the thermal degradation of hydroxylethyl-ended groups, nitrogen heterocycle and –CH₂CH₂– groups of HPPE-2.     

磺化含侧苯基杂萘联苯聚醚砜质子交换膜材料的合成与性能

以4-(3-苯基-4-羟基苯基)-2,3-二氮杂萘-1-酮、4-(4-羟基苯基)-2,3-二氮杂萘-1-酮和4,4’-二氯二苯砜为单体,合成了一系列含侧苯基杂萘联苯聚醚砜,然后以浓硫酸为磺化剂,制备磺化含侧苯基杂萘联苯聚醚砜(SPPES-P)。采用FT-IR、1 H NMR对聚合物的结构进行了表征,表明磺酸基被成功地引入到聚合物侧链苯基上。采用溶液法制备了SPPES-P质子交换膜。考察了SPPES-P膜的吸水率、溶胀率、质子传导率,以及甲醇渗透性能和耐氧化性能,SPPES-P膜具有较好的阻醇性和耐氧化性能。     

聚醚砜微孔膜制备中非溶剂添加剂作用研究

以聚醚砜（ＰＥＳ）为膜材料，ＤＭＡｃ为溶剂，研究了３种非溶剂加剂（ＮＳＡ）－ＥｇＯＨ，ＤｅＯＨ和ＢｕＯＨ在水和ＮＳＡ中凝胶对于板微孔膜性能的影响，利用浊点法得到ＰＥＳ／ＤＭＡｃ／ＮＳＡ和ＰＥＳ／ＤＭＣｓ／ＮＳＡ／Ｈ２Ｏ体系２５℃的相图，并以邻近比α值来表征膜溶液组成点靠近相分离的程度，添加了ＮＳＡ的铸膜液在水中凝胶制备微孔膜，以ＥｇＯＨ为非溶剂添加物，在相同聚合物浓度，相同凝胶条件下，仅仅改变铸膜     

New fluorinated poly(ether sulfone imide)s with high thermal stability and low dielectric constant

A new aromatic diamine monomer with four pendant trifluoromethyl groups, 2,2′-bis{3-[3,5-di(trifluoromethyl)phenyl]-4-[4-amino-phenoxy]phenyl}sulfone (3), was successfully synthesized through free-radical substitution, Suzuki coupling and nucleophilic substitution reactions using bis(4-fluorophenyl)sulfone and N-bromosuccinimide as starting materials. Then it was employed to prepare a series of fluorinated poly(ether sulfone imide)s (PESIs 5a–c) with various commercial aromatic dianhydrides via a one-step high-temperature polycondensation. These polymers could be easily dissolved in some strong polar organic solvents, such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide, chloroform, dichloromethane and tetrahydrofuran at room temperature. Flexible and transparent films can be obtained easily by solution casting. They had high thermal stability and didn't show significant weight loss up to temperature of approximately 530 °C in nitrogen and air atmospheres. They also revealed low dielectric constants with the values in the range of 2.74–2.90 at 1 MHz measured for their capacitance.     

Fluorinated poly(ether sulfone) ionomers with disulfonated naphthyl pendants for proton exchange membrane applications

Proton exchange membranes based on fluorinated poly(ether sulfone)s with disulfonated naphthyl pendants (sSPFES) have been successfully prepared by post functionalization through polymeric S_NAr reaction. Copolymer structure was confirmed by H-nuclear magnetic resonance spectroscopy and Fourier transform infrared spectroscopy, the physico-chemical properties of the sSPFES membranes were evaluated by thermogravimetric analysis, gel permeation chromatography, electro-chemical impedance spectroscopy, atomic force microscopy, Fenton, water-swelling and fuel cell test. The pendant grafting degree was controlled by varying the feeding amount of the disulfonaphthols, resulting in the ion exchange capacity about 1.28-1.73 mmol/g. The obtained sSPFES membranes were thermal stable, mechanical ductile, and exhibited dimensional change less than 17%, water uptake below 70%, and proton conductivity as high as 0.17-0.28 S/cm at 90°C in water. In a single H₂/O₂ fuel cell test at 80°C, the sSPFES-B-3.2 membrane (1.61 mmol/g) showed the maximum power output of 593–658 mW/cm² at 60%-80% relative humidity, indicating their rather promising potential for fuel cell applications.