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.

Synthesis and properties of soluble poly（aryl ether sulfone ether ketone）s copolymers containing pendant methyl groups

A series of Poly（arly ether sulfone ether ketone）s containing pendant methyl groups were synthesized by the reaction of 4,4＇-[sulfonylbis （1,4-phenylene）dioxy] dibenzoyl chloride （SODBC） with 4,4＇- diphenoxy diphenylsulfone （DPODPS）, 4,4＇- di（2-methylphenoxy） diphenylsulfone （o-Me-DPODPS）, 4,4＇- di（3-methylphenoxy） diphenylsulfone （m-Me-DPODPS）, 4,4＇- di （2,6-bimethylphenoxy） biphenylsulfone（o-Me2-DPODPS） respectively, in a mixture of 1,2-dichloroethane （DCE） and N-methylpyrrolidone （NMP）. These reactions were catalyzed by anhydrous aluminum chloride （AlCl）. The characteristic of copolymers were studied by means of advanced analytical techniques such as FT-IR,1H-NMR, DSC, TGA and WAXD. The results show glass transition temperature （Tg） in the range of 193-206℃, thermally stable in excess of 434℃ and excellent solubility in polar solvents. Methyl-substituted Poly（aryl ether sulfone ketone）s had higher glass transition temperatures, lower initial decomposition temperatures than the unsubstituted ones.

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.

Sulfonated poly(aryl ether ketone sulfone)modified by polyoxometalates LaW_(10) clusters for proton exchange membranes with high proton conduction performance

Polyoxometalates(POMs)are classified as solid superacids which can exhibit notable proton conductivity,making them a promising functional inorganic filler for enhancing the proton conductivity of proton exchange membranes(PEMs).In this study,a series of hybrid membranes were obtained by molecular-level hybridization of Weakley-type POM Na_(7)H_(2)LaW_(10)O_(36)(LaW_(10))clusters into sulfonated poly(aryl ether ketone sulfone)(SPAEKS).All hybrid membranes exhibited greater proton conductivity than the pristine membrane in the 30–80℃temperature range.When the doping amount of LaW 10 reached 7 wt.%,the proton conductivity of M-LaW 10^(-7)achieved 64 mS·cm^(−1)at 80℃.Lanthanide ions'high coordination number property and variable coordination environment can aid to attract more water molecules from the environment.LaW 10 and these bound water can construct denser hydrogen bonds with–SO_(3)H of SPAEKS.These intensive hydrogen bonds will facilitate the constitution of more continuous proton transport channels,and improve the proton conductivity of the hybrid membrane.This work off ers a fresh approach to using POMs containing rare-earth components in PEMs.

PES-COOH/3D-TFC纳滤膜的制备及性能研究

采用分子设计手段,将不同含量羧基基团引入亲水性羧化聚芳醚砜材料(PES-COOH)活性分离层以改善其亲水性,同时结合3D打印技术制备了具有低曲折度、微通孔结构且孔隙率可调的支撑层,开发出渗透、截留、抗污染性能均得到提升的PES-COOH/3D-TFC纳滤膜.通过红外光谱、扫描电镜、生物显微镜、水接触角测试和Zeta电位测试等方法测试了其物理化学性能,并探究了分离层羧基基团含量和支撑层微观结构对复合膜性能的影响.结果表明:当分离层羧基含量为60%、支撑层孔隙率为70%时,复合纳滤膜的水通量为4.4 L/(m^(2)·h)、硫酸钠截留率为78.1%,抗污染测试中通量衰减率和通量恢复率分别为23.8%和96.2%.

Comb-shaped 2-Methylimidazolium Poly(arylene ether sulfone) Anion Exchange Membranes with High Alkaline Stability

A series of comb-shaped poly(arylene ether sulfone)s containing pendant 2-methyl-3-alkylimidazolitun group(ImPAES-Cx,x=1,6,10)was prepared and characterized as novel anion exchange membranes.These Im-PAES-Cx membranes were obtained by benzylic bromination and imidazolium functionalization.The characteristic nano-phase separation structure was formed in membranes with longer alkyl side chains,as confmned by small-angle X-ray scattering.The nano-phase separation structures endowed ImPAES-Cx membranes with improved ionic conductivity,dimensional stability(at least 60% decrease water uptake and swelling ratio at 60℃)and mechanical properties,together with excellent alkaline stability.Especially,ImPAES-C6 membranes possessed enhanced hydroxide conductivity and chemical stability simultaneously.These results suggest that it is a feasible strategy to introduce appropriate length of alkyl side chains into anion exchange membranes(AEMs)to improve the performance.

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.

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．

镀镍碳纳米管/PPESK复合材料的制备及微波吸收性能

采用化学镀工艺在多壁碳纳米管表面包覆镍-磷合金,并将其与杂萘联苯聚醚砜酮(PPESK)混合制备吸波复合材料。通过扫描电镜、能量散射光谱对镀镍碳管的形貌和成分进行分析,反射率测试系统对复合材料在8 GHz^18 GHz频段的微波吸收特性进行表征。结果表明,在镀镍过程中使用超声振荡有利于得到均匀的镀层。当吸波样品平均厚度为0.97 mm,碳管含量为5 phr时,镀镍碳管/PPESK复合材料的最大吸收峰在10.9 GHz(RL=-27.5 dB),RL<-10 dB的频宽为4.0 GHz。随着填料含量增加,吸收峰往低频方向移动。

聚芳醚腈砜(PENS)的热分解动力学

研究了惰性气氛下ＰＥＮＳ的热分解反应，发现该过程为一级反应。以Ｋｉｓｓｉｎｇｅｒ最大失重速率法求得热分解反应的表观活化能为２２１．７ｋＪ／ｍｏｌ。由Ｏｚａｗａ等失重百分率法求得０～３０％失重百分率下反应的活化能在２２８．４～２３７．２ｋＪ／ｍｏｌ之间，频率因子Ａ值在２．３０４×１０１４～４．６１６×１０１４ｍｉｎ－１之间。随着失重百分率的增大，热分解反应活化能增大。结果表明，ＰＥＮＳ具有较高的热稳定性，预测氮气中２５３℃失重５％的热老化寿命为１０ａ。

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。

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.

溶液喷射纺丝制备PES-C/PES-CB复合纳米纤维膜

通过在酚酞聚醚砜(PES-C)纺丝液中添加不同含量的两性离子改性的酚酞聚醚砜(PES-CB),然后利用溶液喷射纺丝法制备PES-CB/PES-C复合纳米纤维膜,并通过扫描电子显微镜、红外、差示扫描量热仪、热重分析、接触角等对复合纳米纤维膜进行了测试表征,最后将复合纳米纤维膜进行淀粉溶液过滤测试。结果表明,随着PES-CB含量的增加,纳米纤维的直径不断减小,当PES-CB添加量达到30%时,复合纳米纤维膜的平均直径减小到300nm左右。同时由于两性离子支链的存在,纤维膜的亲水性也得到提高,但其耐热性降低。过滤测试结果表明,随着PES-CB含量的增加,膜的抗污染能力得到明显提高,当PES-CB添加量达到30%时,过滤淀粉溶液的水通量恢复率(FRR%)达到83%左右。结合纺丝过程及过滤性能测试来看,PES-CB添加量在30%左右制备的复合纳米纤维膜综合性能最佳。

Synthesis, Curing and Properties of Poly(phthalazione ether sulfone ketone) Copolymers Crosslinked by Click Chemistry

Functionalized poly（phthalazinone ether sulfone ketone） was synthesized by successive chloromethylation and azidation, followed by curing reaction with the propargyl end-groups of various molecular weight crosslinking agents in the presence of Cu（I） catalyst via the azide-alkyne click reaction. The influences of the chain length of crosslinking agents on the poly（phthalazinone ether sulfone ketone） system were studied. FTIR and DSC tests demonstrated certain crosslinking by azide-alkyne reaction with the formation of triazole ring. DSC results showed that curing temperature shifted to lower temperatures considerably in the presence of Cu（I） catalyst. TGA showed cured polymers were of much higher thermal stability, including higher thermal decomposition temperatures and higher char-yielding properties. After being cured, the polymers became insoluble in organic solvents and the gel fraction of the cured polymers exceeded 71%. Wide-angle X-ray diffraction results indicated there was a short distance order in the poly（ether sulfone） （PES） main chain except for the azido methyl poly（phthalazinone ether sulfone ketone） and 4,4＇-bis（2-propynyloxy） biphenyl （AMPPESK-BP） system.

A Janus separator towards dendrite-free and stable zinc anodes for long-duration aqueous zinc ion batteries

Critical issues of Zn anodes including undesirable dendrites formation and parasitic reactions severely limit the reversibility and cyclability of Zn anodes.To address these issues,a functional Janus separator with the structure of a mechanically strong sulfonated poly(arylene ether sulfone)(SPAES)dense layer composited on a porous glass fiber(GF)substrate is designed.The SPAES dense layer that faces the Zn anode containing abundant sulfonic acid groups effectively promotes the desolvation process of hydrated Zn ions,guides uniform Zn ion transfer,and blocks anions and water,contributing to dendrite-free and highly reversible Zn plating/stripping cycles,while the porous GF substrate retains high electrolyte uptake.As a result,the Zn symmetric cell with the Janus separator demonstrates an ultralong cycling lifespan of over 2000 h at the areal capacity of 1 m A h cm^(-2),which is 23-fold superior to that with a pristine glass fiber separator(<90 h).More impressively,the as-prepared Janus separator enables outstanding rate performance and excellent cycling stability of full Zn ion batteries with diverse cathode materials.For instance,when paired with the V_2O_(5)cathode,the full battery with a Janus separator attains an ultrahigh initial specific capacity of 416.3 m A h g^(-1)and capacity retention of 60%over 450 cycles at 1 A g^(-1),exceeding that with a glass fiber separator.Hence,this work provides a facile yet effective approach to mitigating the dendrites formation and ameliorating the parasitic reactions of Zn metal anodes for high-performance Zn ion batteries.

高磺化度芳香聚醚醚酮的合成与表征

用 3 ,3’-二磺酸钠基 -4 ,4 -二氟二苯酮合成了具有高磺化度的荷电聚醚醚酮 .用红外吸收光谱及 DSC对其进行了表征 .研究了共聚物的组成、热稳定性、溶解性。

含二氮杂萘酮结构聚芳醚酮和聚芳醚砜研究进展

综述了含二氮杂萘酮结构的聚芳醚酮和聚芳醚砜的结构性能及其合成、改性、应用研究进展。

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。

3,3′-二磺化-4,4′-二氟二苯砜二钠盐的合成与表征

以工业级4,4′-二氟二苯砜(DFDPS)为原料,利用升华方法进行纯化处理后,采用发烟硫酸直接磺化,通过改变反应物计量比、反应温度、反应时间等参数,系统研究了3,3′-二磺化-4,4′-二氟二苯砜二钠盐(SDFDPS)的制备方法。采用HPLC、UV、1HNMR及FTIR对磺化产物结构及纯度进行了表征,由此得到最佳的磺化条件为:反应物摩尔比(SO3:DFDPS)为3.0:1,在110℃下反应20h。在此反应条件下的磺化产物中未发现单磺化产物以及未磺化的原料DFDPS。经过乙醇/水两次重结晶后,总收率达到75%。以合成的SDFDPS为原料合成了磺化度60%的磺化聚芳醚砜聚合物,该聚合物具有较高的相对黏度,同样也表明了SDFDPS的高纯度。