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.

SYNTHESIS AND CRYSTALLIZATION BEHAVIOR OF POLY(ETHER ETHER KETONE ETHER KETONE)(PEEKEK)

In this paper, the synthesis and crystallization behavior of poly(ether ether ketone ether ketone) (PEEKEK) are reported. PEEKEK was prepared from 4,4'-bis(p-fluorobenzoyl) diphenyl ether (4,4'-FBDE) and hydroquinone along the nucleophilic substitution route. The thermal properties were investigated by using DSC and TGA. The crystallization behavior of PEEKEK under several conditions, i.e., crystallization from the molten state (melt crystallization), crystallization from a quenched sample (cold crystallization) and crystallization induced by exposing glassy sample to methylene chloride (solvent-induced crystallization) has also been investigated. The results show that crystallization of PEEKEK could be induced by the above methods, and no polymorphism was found. The differences in the crystallization of PEEKEK induced by the above methods are seen in their degree of crystallinity.

Synthesis and characterization functionalized poly(ether ether ketone)s with carboxylic groups

A novel type of aromatic poly（ ether ether ketone） s with carboxyl groups were prepared by polycondensation of 4,4-bis（4-hydroxyphenyl）pentanoic acid with difluoro-monomers. Their mo- lecular structures were determined by ^1H-NMR and IR, respectively. Their molecular weights were measured by gel permeation chromatography （ GPC ）, which showed that all the polymers had high molecule weights （ 〉 42 000）. Due to the long side chains of polymers, all the polymers had good solubility （soluble in NMP, DMAc, THF, etc. ）. The differential scanning calorimeter （DSC） detected their excellent glass transition temperatures （ Tg ） up to 195 ℃. The Tg increased with the content of carboxylic units in the polymer chains, because the interactions of H bonds increased with increasing content of carboxylic. The polymers could form transparent and flexible films, which make them a candidate for membrane materials.

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.

Ionic liquids as green reaction media for synthesis of poly(aryl ether ketone)s

Poly(aryl ether ketone)s (PAEKs) were successfully synthesized via nucleophilic aromatic substitution (SNAR) mechanism, using ionic liquids as green reaction media. The influence of various reaction parameters including monomer concentration, dehydration time, polymerization temperature and duration, IL's cations and anions nature, upon PAEKs molecular weight was investigated. In addition, the peculiarities of hydrogen-bonding ability of ILs were investigated. The interaction of 2,2-bis(4-hydroxyphenyl) propane (bisphenol A) with ILs has a strong influence on PAEKs synthesis. Various moderate molecular weight PAEKs have been obtained in high yields with molecular weights ranging from 10000 to 18000g mol-1.

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。

含磷双酚S型共聚醚醚酮的合成研究

以9,10-二氢-9-氧杂-10-磷酰杂菲-对苯二酚(DOPO-HQ),4,4’-二氟二苯甲酮(DFK)和双酚S(DDS)为单体,通过溶液缩聚合成了含磷双酚S型聚醚醚酮。探讨了聚合条件,包括溶剂的类型、反应时间、反应物浓度等对最终聚合产物性能的影响,最终得到的产物特性黏度最高为1．04 dL·g-1,并使用了元素分析、红外光谱、DSC (DSC测试显示其玻璃化转变温度为194．88℃,远高于一般的聚醚醚酮)等测试手段对共聚物的结构和性能进行了表征。

Synthesis and Optical Properties of Hyperbranched PAEKs Containing Porphyrin and Its Metal Derivatives

Novel functional hyperbranched poly（aryl ether ketone）s （HPAEKs） bonded with nonlinear optical chromophores （meso-tetrakis（4-hydroxyphenyl） porphyrin, THPP and its metal derivatives） were synthesized and characterized by IH-NMR and UV-Vis absorption spectra. The incorporation of chromophores into HPAEKs endowed HPAEKs novel NLO and OL properties. Indeed, dendritic architecture allowed for maximum dispersion of the chromophores, avoided aggregation, more optical limiting property was obtained. Simultaneously, they retained the excellent properties of the materials, particularly in thermal stability. Their optical properties were evaluated by nonlinear optical analyses and optical limiting. The results showed that these polymers possessed good optical limiting （OL） property and large nonlinear optical （NLO） susceptibilities （ca. 10-12 esu）. All polymers containing chromophores presented excellent thermal stability （DT5 〉 524.17 ℃）.

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.

甲基取代的新型聚醚醚酮及其共聚物的合成、表征和性能研究

设计合成了一种甲基侧基取代的可溶性聚芳醚酮均聚物 PETMDEK,同时合成了一系列不同比例的无规共聚物 PETMDEK-PEDEK,考察了共聚组成对聚合物性能的影响 .随着共聚物中可溶性 PETMDEK组分的不断增加 ,其聚集态结构也发生变化 ,出现从结晶→液晶→结晶→无定形固体的转变 ,同时溶解性也由可溶向不溶转变 .本文还侧重研究了 PETMDEK组分摩尔分数为 2 0 %的无规共聚物的热致液晶行为 .

新型可溶性聚芳醚酮的合成与表征

Two novel poly(aryl ether ketone)s based on (3 methyl)phenylhydroquinone were synthesized via aromatic nucleophilic substitution reaction. The high molecular polymers were easily obtained because of the high reaction activity of bisphenol monomer. The traces of DSC showed that the T gs of m TPEEK and m TPEEKK were 421 and 432 K, respectively. The two polymers exhibit a high thermal stability and good solubility. The transparent and flexible films were readily prepared with chloroform solution. The film of m TPEEK had a low dielectric constant( ε =2 7).

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。

通过A_2+B_3反应制备超支化聚芳醚酮荧光材料

用3-二甲氨基苯酚与超支化聚芳醚酮(HPETFDEK-F)的末端氟发生反应,制得荧光超支化聚芳醚酮(FHPETFDEK).采用1H NMR,FTIR,DSC和TGA等方法对所得到的聚合物结构和热性能进行了表征.研究了FHPETFDEK的紫外吸收及荧光发射光谱,发现其具有荧光行为.

可自交联超支化聚醚醚酮的合成与热性能研究

Fluoro-terminated hyperbranched（poly（aryl） ether ketone）（HPOP-PEEK-F） with 4-phenoxyphenyl side groups was prepared from A2（2-（4-phenoxyphenyl）-1,4-diphenol） and B3（1,3,5-tris[4-（4-flourobenzoyl） phenoxy]benzene） with a function group ratio of 0.48:1（A2:B3）.The chemical structure of HPOP-PEEK-F was confirmed by FTIR and（）1H-NMR.The degree of branching（DB） of HPOP-PEEK-F was 0.66 determined by（）1H-NMR measurements.The phenyl ethynyl-terminated hyperbranched poly（ether ether ketone）（HPOP-PEEK-PEP） was prepared by the end-capping approach.The HPOP-PEEK-PEP showed high glass transition temperature than HPOP-PEEK-F,but exhibited lower thermal stability.After cross-linking,the glass transition temperature,thermal stability and anti-chemical corrodibility of HPOP-PEEK-PEP were all improved.

一种新型磺化聚醚醚酮的合成、表征和性能

以特丁基对苯二酚、 3 ,3′-二磺酸钠基 -4,4′-二氟二苯酮和 4,4′-二氟二苯酮为单体 ,制备了具有高磺化度的聚醚醚酮 .该系列聚合物可溶 ,并具有良好的成膜性 .

含二氮杂萘酮结构聚芳醚腈酮酮的合成及表征

以5种含杂萘联苯结构的单体与2，6-二氯苯腈、1，4-二（4-氟代苯甲酰基）苯为原料进行亲核缩聚反应，制备了一系列含有杂萘联苯结构的新型聚芳醚腈酮酮树脂．其特性粘度在0．51～1．15dL·g^-1之间．采用FT-IR，示差扫描量热仪（DSC），热重分析仪（TGA）对聚合物的结构和性能进行了表征，结果表明，聚芳醚腈酮酮的玻璃化转变温度（Tg）在252～294℃之间，10％热失重温度（Td）在457℃以上，具有优异的耐热性能．聚芳醚腈酮酮均可溶解于N-甲基吡咯烷酮（NMP）、N，N-二甲基乙酰胺（DMAc）、和氯仿等极性非质子型有机溶剂中，聚合物均可溶解于NMP后浇铸得到透明的、韧性好的薄膜．

联苯型二氮杂萘酮聚醚酮酮的合成及性能

以自制的新型氯代双酮单体 ,与新型联苯型二氮杂萘酮类双酚单体经亲核取代反应 ,合成了一系列新型聚芳醚酮酮聚合物 ,对其聚合条件作了初步探讨 ;并利用核磁共振、红外光谱分析研究了双酮单体及聚合物的结构 ,利用 DSC对聚合物的耐热性进行了分析。实验结果表明 ,该类双酮单体具有足够的活性与类双酚进行聚合反应 。

不同单体对合成聚芳醚酮酮(PEKK)结构与性能的影响研究

以1,4-二(4-苯氧基苯甲酰基)苯(p-EKKE)、1,3-二(4-苯氧基苯甲酰基)苯(m-EKKE)、二苯醚(DPE)分别与对苯二甲酰氯(TPC)、间苯二甲酰氯(IPC)亲电共缩聚,合成全对位、全间位、对间位取代及交替聚芳醚酮酮(p-PEKK、i-PEKK、p/i-PEKK、a-PEKK),用FT-IR、DSC、WAXD、TG、SEM等技术对p-EKKE和m-EKKE以及PEKKs的结构与性能进行了分析表征.结果表明,随着1,3-苯基含量的增加,共聚物的熔融温度(Tm)和玻璃化转变温度逐渐降低,而热分解温度变化不大;p/i-PEKK交替共聚物较之于无规共聚物,有较好的链规整性和较高的结晶度;WAXD分析表明,共聚物p-PEKK的结晶衍射峰和小分子模型化合物p-EKKE基本相同,同属正交晶系,全间位取代的i-PEKK在熔融冷却过程中很难再次结晶,转变为非晶聚集态,其2θ角和m-EKKE针状结晶基本相同,属三斜晶系.

新型可溶性聚芳醚腈酮的合成及其在绝缘漆领域的应用

以4种含杂萘联苯结构的类双酚单体分别与2，6-二氯苯腈、4，4-二氟酮进行亲核缩聚反应，制备了一系列新型含杂萘联苯结构的聚芳醚腈酮树脂。研究了不同类双酚单体结构对聚合物性能的影响。所制备聚合物均具有较高的分子量，特性粘度在0．50dL／g以上，可溶解于N-甲基吡咯烷酮（NMP），N，N-二甲基乙酰胺（DMAc），氯仿等极性非质子型有机溶剂中。聚合物的结构以FT-IR进行表征；利用差示扫描量热仪（DSC）和热重分析仪（TGA）研究了聚合物的耐热性能，结果表明，该类聚芳醚腈酮树脂具有优异的耐热性能，玻璃化转变温度（Tg）在255～277℃之间，10％热失重温度（Td）在498℃以上。由该系列聚芳醚腈酮材料制成的绝缘漆具有良好的电绝缘性能，较高的机械强度，良好的柔韧性和附着力。