SYNTHESIS AND PROPERTIES OF SULFONATED POLY(ARYLENE ETHER) CONTAINING TRIPHENYL METHANE MOIETIES FROM ISOCYNATE MASKED BISPHENOL

A novel sulfonated poly（arylene ether） containing triphenylmethane moieties was synthesized by the sulfonation of a designed parent polymer using chlorosulfonic acid as sulfonation agent. The sulfonation took place at the para position of the pendant phenyl rings because of the specially designed parent polymer. The position and degree of sulfonation were characterized by ^1H-NMR and elemental analysis. The sulfonated polymers are highly soluble in common organic solvents, such as dimethylsulfoxide, N,N＇-dimethylacetamide, dimethylformamide, ethylene glycol monomethyl ether, and can be readily cast into tough and smooth films from solutions. The films showed good thermal and hydrolysis stabilities. Moreover, Fenton＇s reagent test revealed that the films exhibited superior stability to oxidation. The proton conductivities of the films were comparable with Nation 117 under same conditions. The membrane electrode assembly （MEA） prepared with the asmade film （706 EW, 100 μm dry thickness） shows better cell performance than Nation 115-MEA in the whole current density range.

Highly stable side-chain-type cardo poly(aryl ether ketone)s membranes for vanadium flow battery

Vanadium flow batteries(VFBs)have drawn considerable attention as an emerging technology for largescale energy storage systems(ESSs).One of the pivotal challenges is the availability of eligible ion exchange membranes(ICMs)that provide high ion selectivity,proton conductivity,and stability under rigorous condition.Herein,a‘side-chain-type’strategy has been employed to fabricate highly stable phenolphthalein-based cardo poly(arylene ether ketone)s(PAEKs)membrane with low area resistance(0.058Ωcm^(2)),in which flexible alkyl spacers effectively alleviated inductive withdrawing effect from terminal ion exchange groups thus enabling a stable backbone.The assembled VFBs based on PAEKs bearing pendent alkyl chain terminated with quaternary ammonium(Q-PPhEK)demonstrated an energy efficiency above 80%over 700 cycles at 160 mA/cm^(2).Such a remarkable results revealed that the side-chain-type strategy contributed to enhancing the ICMs stability in strong oxidizing environment,meanwhile,more interesting backbones would be woken with this design engaging in stable ICMs for VFBs.

Anion Exchange Membranes Based on Chloromethylation of Fluorinated Poly（arylene ether）s

This report details the properties of fluorine-containing anion exchange membranes（AEMs） synthesized by chloromethylation and quaternization of fluorinated poly（arylene ether）s（FPAEs） based on decafluorobiphenyl and bisphenol A. Meanwhile, we compared their properties with those of their non-fluorinated counterparts, Udel-based AEMs. The reactivity of the chloromethylation of fluorinated poly（arylene ether）s was lowered by the strong elec- tron-withdrawing group, per-fluorinated biphenyl residue. Therefore higher temperature, more chloromethylation reagent, and longer reaction time were needed in the chloromethylation of FPAEs. Because of the hydrophobicity of fluorine, the swelling of FPAEs was depressed. In the FPAE-based AEMs, the water uptake of FPAE-1 membrane（F-1） was just 30%. There is a strong correlation between water uptake and conductivity for both Udel- and FPAE-based AEMs. Among all the membranes, the water uptake and the conductivity of FPAE-3 membrane（F-3） could reach up to 100% and 13.47 mS/cm respectively at 30 ℃. The mechanical properties of FPAE-based AEMs at room tempera- ture were worse than those of Udel-based ones because of the weak intermolecular interaction caused by the low po- larizability of fluorine. However, their high temperature mechanical properties are better, which can be explained in terms of low swelling.

磺化含芴聚醚醚酮酮的合成及与八苯胺基POSS的杂化

燃料电池作为一种绿色环保的清洁能源，具有启动速度快、工作温度低、比功率大及操作方便等优点，是最有希望替代石油等化石能源的未来能源之一．作为质子交换膜燃料电池（PEMFC）和直接甲醇燃料电池（DMFC）的核心部件，质子交换膜的研制备受关注．

3,3′-二苯甲酰基双酚-S及苯甲酰侧基聚芳醚腈的合成

利用双酚－Ｓ与苯甲酰氯形成的二元酚酯在ＡｌＣｌ３作用下进行Ｆｒｉｅｓ重排制备３，３′－二苯甲酰基双酚－Ｓ，以此与二氯苯甲腈进行缩聚反应合成了带苯甲酰基侧基的聚芳醚腈。

Properties of Multiblock Sulfonated Poly(arylene ether sulfone)s Synthesized by Precise Controllable Post-sulfonation for Proton Exchange Membranes

A series of multiblock sulfonated poly(arylene ether sulfone)s(SPAES)with various block lengths and predictable ion exchange capacity were synthesized from 4,4’-difluorodiphenyl sulfone,4,4’-dihydrodiphenyl sulfone and 4,4’-biphenol by one-pot and two-pot polymerization.;H-NMR and FTIR spectra confirmed the structure that sulfonic acid groups were introduced precisely on the poly(arylene ether sulfone)s by post-sulfonation which resulted in controllable sulfonation degree.The proton exchange membranes(PEMs)-based SPAES displayed excellent dimensional,thermal,antioxidant stability,proton conductivity and mechanical properties(maximum tensile stress>35 MPa).Thermogravimetric analysis indicated the prepared SPAES began to degrade above 310℃.The effects of polymerization processes,those were,one-pot hydrophobic segment process,one-pot hydrophilic segment process and two-pot process,on the properties of polymers were investigated.The proton conductivity and microphase separation of SPAES PEMs increased in order of those prepared by one-pot hydrophobic segment process,two-pot process and one-pot hydrophilic segment process.The highest conductivities of SPAES synthesized by the above processes under 80℃ and 100%relative humidity were 213(MS4),297(MB3)and 360 mS·cm^(-1)(MQ2),respectively.

New applications of poly(arylene ether)s in organic light-emitting diodes

Compared with conventional π-conjugated polymers,poly（arylene ether）s（PAEs） may take advantages of excellent thermal properties,well-defined effective conjugated length and no catalyst contamination.Recently,their applications have been extended from engineering plastics to optoelectronic materials.In this review,various kinds of functional PAEs used as fluorescent polymers,host polymers and phosphorescent polymers in organic light-emitting diodes（OLEDs） are outlined,and their molecular design,synthesis and device performance are overviewed.

磷酸掺杂磺化聚(氟化亚芳基醚)-聚(环氧乙烷)共混膜的制备研究

为提高聚合物电解质膜燃料电池(PEMFC)的高温性能(150℃以上),采用磺化的聚芳基醚(SDF-F)和聚环氧乙烷(PEO)合成了新的共混膜,并使用磷酸掺杂;对新的共混膜进行了表征,并通过测量拉伸强度确定了酸掺杂共混膜的机械强度。结果表明,SDF-F和PEO成功共聚成共混膜且2种聚合物均匀混合,共混膜的磷酸掺杂水平随着PEO含量的增加而增加,当PEO的质量分数为60%时,掺杂的磷酸质量分数可达784%;共混膜的机械强度随着PEO含量的增加而下降,但即便PEO的质量分数为60%时,共混膜的拉伸强度仍有17 MPa。新共混膜能够完全满足高温聚合物电解质膜燃料电池的要求。

含铂芳香炔聚芳醚合成及性能研究

基于实现铂乙炔化合物光限幅材料的固态化和实用化的目的,通过分子设计合成了一种新型的含氟端基的铂芳香炔单体,并通过亲核反应的方式将其引入到聚芳醚主链中,制备出了溶解性优异的含铂乙炔基团的聚芳醚共聚物,最后通过流延法制备了固态光限幅膜材料。对单体和聚合物进行了结构、热性能、力学性能以及光物理表征,并对聚合物溶液和固态膜材料的非线性光学性能进行了研究。结果表明,该共聚物制成的固态膜材料具有较好的光限幅能力,同时也兼具了聚芳醚优异的热力学性能和机械性能。该研究结果为激光防护材料的固态化、实用化发展提供了新思路。

新型含氟聚芳醚酮的合成与表征

A kind of highly fluorinated bisphenol monomer was synthesized. It was characterized by FTIR, 1H NMR and MS. 6F PEEK and 6F PEEKK were prepared via aromatic nucleophilic substitution, based on [3,5 di(trifluoromethyl)] phenylhydroquinone and difluoro monomers. The T gs of 6F PEEK and 6F PEEKK are 423 and 436 K, respectively. The 6F polymers exhibit a high thermal stability and good solubility. The flexible, creasable and transparent thin films were easily obtained by compression moulding and solution casting.

磺化聚苯并咪唑/磺化聚醚砜酸碱复合质子交换膜的制备与表征

为提高膜的尺寸稳定性和阻醇性能,以磺化聚苯并咪唑(S-PBI)与高磺化度聚醚砜(ABPS)两种聚合物为原料,采用溶液共混的方法,制备了系列酸碱复合质子交换膜。研究了复合膜的甲醇溶胀性、吸水率、甲醇渗透系数、质子传导率随S-PBI含量的变化规律。研究表明,随着S-PBI含量的增加,膜的阻醇性能和尺寸稳定性明显提高;同时,复合膜具有较好的质子传导率,有望应用于直接甲醇燃料电池。

侧基磺酸型含氟聚芳醚的合成

Six highly fluorinated poly(arylene ether)s were prepared by using a nucleophilic polycondensationreaction and their sulfonation selectivity was investigated.Single site of each repeated unit on pendant phenylgroup could be obtainedviathe postsulfonation approach under mild reaction conditions.Phenylated fluorina-ted poly(arylene ether)(Ph-FPAE) showed more excellent controllability over substituted sites and sulfonationdegree when chlorosulfonic acid was used as sulfonation reagent.The resulting sulfonated Ph-FPAE(Ph-SF-PAE) exhibited good thermal stability,solubility and hot-water dimensional stability,and also had a protonconductivity of 0.10 S/cm at 100℃.The results showed that Ph-SFPAE might be a candidate material forproton exchange membrane in fuel cell applications.

含芴可交联聚芳醚酮的合成

以4,4′-二氟二苯甲酮、双酚芴和二烯丙基双酚A为单体,调整双酚芴和二烯丙基双酚A的摩尔比,通过亲核取代逐步加成反应合成了一系列含芴可交联的聚芳醚酮(PAEK);用红外光谱仪、核磁共振波谱仪、差示扫描量热仪、热重分析仪对所制备的含芴可交联PAEK的结构、热交联行为、热稳定性等进行了表征。结果表明,所制备的聚合物可通过热引发交联,交联后的聚合物具有优良的耐热性能,交联后聚合物的耐溶剂性能得到提高,最高凝胶含量达到97.5%。

含氰基侧基聚芳醚砜的合成与表征

以２，６－二卤苯甲腈、４，４′－二氯二苯砜、４，４′－二羟基二苯砜、间苯二酚、对苯二酚、酚酞及双酚Ａ为主要原料，合成了含不同结构单元和不同氰基含量的含氰基侧基的聚芳醚砜，并采用ＩＲ，１３ＣＮＭＲ等分析手段对其结构进行了表征。同时研究了结构单元和氰基含量对聚芳醚砜性能的影响。

酚酞型聚芳醚腈砜的合成与性能研究

以酚酞、２，６二卤苯甲腈、４，４’，二氯二苯砜和４，４’，二羟基二苯砜为主要原料进行共缩聚反应，合成了酚酞型聚芳醚腈砜（ＰＰ－ＰＥＮＳ）。采用红外光谱、热分析等方法对共聚物的结构、热氧稳定性和玻璃化转变温度进行了表征。

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。

主链含苯基均三嗪联苯型聚芳醚的热稳定性

利用热重分析(TG、DTG)研究了主链含苯基均三嗪联苯型聚芳醚在不同气氛和升温速率时的热降解动力学。比较了升温速率和气体气氛对热降解行为的影响,结果表明,该聚合物具有优异的耐热性和耐热氧化稳定性。用Flynn-Wall-Ozawa,Freeman-carroll等方法进行了动力学处理,计算得热降解反应活化能分别为291.19kJ/mol,286.83kJ/mol,与Kissinger法计算活化能值283.25kJ/mol非常接近。结合Coats-Redfern方法,推测出聚合物在氮气气氛中的热分解机理为F2机理,其机理函数积分式为g(α)=1/(1-α)。

含氟磺化聚芳醚酮质子交换膜的制备与性能研究

以六氟双酚A（6FBPA）,4,4′-二氟二苯酮（DFBP）和3,3′-二磺酸钠基-4,4′-二氟二苯酮（SDFBP）为单体,调整单体DFBP与SDFBP的摩尔投料比,通过缩合共聚反应合成了一系列离子交换容量不同的含氟磺化聚芳醚酮共聚物（SPEK-6Fs）。采用红外（FT-IR）、核磁共振氢谱（1H-NMR）对共聚物的结构进行了表征,同时对所制备的质子交换膜的吸水率、尺寸稳定性、甲醇透过率、质子电导率及抗氧化性能等进行了一个综合的评价。结果表明：所合成的聚合物具有较高的分子量,可通过溶液浇铸成膜法制备成柔韧、透明的膜,所制备的膜具有良好的尺寸稳定性,在同等测试条件下,具有与杜邦公司Nafion 117膜相当的质子电导率,同时,其甲醇渗透率比Nafion 117膜低1~2个数量级。

聚芳醚腈砜的研究进展

介绍了聚芳醚腈砜的合成方法,并对其结构和性能进行了评述。

新型含磷和氟聚芳醚的制备、表征及性能

通过分子设计合成了一种含有三苯基膦结构的二氟单体——4,4'-二氟二苯苯磷氧(BFPPO).在碱催化条件下,BFPPO与2-双-(4-羟苯基)六氟丙烷(六氟双酚A)缩聚得到一种新型含三苯基膦结构的聚芳醚材料(6F-PAEPO).用FTIR,1H,31P和16F NMR等表征手段确定了聚合物的结构.结果表明,聚合物表现出良好的热稳定性、有机溶剂可溶性、机械性能和光透过性能,其中聚合物的玻璃化转变温度高达211℃,在空气和氮气气氛下5%热失重温度分别为512和523℃,聚合物薄膜的最大光透过率超过80%.尤其是聚合物由于主链中三苯基磷氧结构的存在,表现出了优异的阻燃性能,有限氧指数(LOI)达到39.9%.