新型聚芳醚酮的研究进展

介绍了聚芳醚酮的合成路线与性质,并讨论了其改性的研究方向和进展,例如利用共聚共混对其改性,在聚 芳醚酮的主链中引入大的侧基破坏其规整性,以及研制含氟的新型聚合物。     

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。     

含三苯基磷结构双酚A型聚芳醚酮的合成与表征

以环丁砜为溶剂,由双（4-（对氟苯甲酰基）苯基）苯基氧化膦和双酚A通过亲核缩聚反应合成了主链含磷聚芳醚酮。采用红外光谱和核磁共振等方法对产品的结构进行了表征,研究了磷基团的引入对聚芳醚酮的电性能、力学性能、耐热性、阻燃性和溶解性的影响。结果表明,磷基团的引入对聚芳醚酮的阻燃性能起到了较明显的提高作用,降低了聚合物分子链的规整性,减小了分子间的相互作用,改善了聚芳醚酮的溶解性能,使其在室温下可溶于CH2Cl2,CHCl3等多种极性溶剂。     

高性能聚芳醚酮的发展及应用

综述了聚醚酮、聚醚醚酮、聚醚醚酮酮、聚醚酮酮、聚醚酮醚酮酮等5类高性能聚芳醚酮的性能、合成方法及其改性研究进展等,并介绍了聚芳醚酮的应用情况,指出聚芳醚酮的发展趋势是通过开发新的合成技术或者改性途径,在不影响其主要性能的前提下降低生产成本.     

耐高温含氟聚芳醚酮和聚芳醚砜的合成与性能研究

通过三步反应合成新的含氟双酚单体3,4-二氟苯基对苯二酚,由该含氟双酚单体、4-氟苯基对苯二酚、邻苯基对苯二酚分别与4,4′-二氟二苯酮、4,4′-二氯二苯砜经亲核缩聚反应,制备了一系列新型聚芳醚酮和聚芳醚砜。采用 FT-IR、DSC、TGA及XRD手段等对聚合物的结构和性能进行了表征和研究,结果表明：合成的聚芳醚酮和聚芳醚砜具有优异的耐热性能,玻璃化转变温度分别在150~159 ℃和177~196 ℃之间,氮气中5 %热失重温度分别在527 ℃和507 ℃以上。合成的聚芳醚酮和聚芳醚砜具有良好的溶解性,室温下能溶解在N-甲基吡咯烷酮、二甲基乙酰胺、氯仿等有机溶剂中。     

高性能特种工程塑料的发展与功能化研究

作者结合自己在高性能特种工程塑料—聚芳醚腈(PEN)及其复合材料的研究,就特种工程塑料的发展、改性及其功能化技术回顾与展望,重点对聚芳醚腈树脂及其性能相当的聚芳醚酮进行了概述。     

高性能特种工程塑料改性研究进展

着重介绍了聚芳醚酮、聚芳酰胺及聚苯硫醚改性方法及研究进展,从化学改性方面阐明了通过引入一些化学基团,如柔性基团、刚性基团或者较大侧基来改善其某些性能,或通过改变其平面结构和破坏规整度来实现改性;从物理改性方面可以通过共混填充等来实现改性,通过改性优化性能来扩展应用领域是十分必要的.     

二种双邻位甲基取代的聚芳醚酮类树脂的合成与性能

合成二种双邻位甲基取代的聚芳醚酮类聚合物,聚芳醚酮醚酮酮(DM-PEKEKK)和聚芳醚酮酮醚酮酮(DM-PEKKEKK),用FT-IR、1H NMR、DSC、WAXD、TG等技术对其进行表征,研究表明:较之于未取代的PEKEKK和PEKKEKK玻璃化转变温度和溶解性能大幅度提高,热分解温度有所下降,但均在450℃以上.     

高生物活性聚醚醚酮化学改性研究进展

由于聚醚醚酮（PEEK）表面疏水及生物惰性，用作骨科材料难以与周围细胞、骨组织结合。通过化学改性在PEEK分子链中引入具有生物活性的功能化基团是提高其表面细胞黏附、增殖和成骨分化能力最有效的方式。基于功能化基团引入位置的不同，本文将PEEK化学改性分为苯环位改性、酮基位改性和共聚改性等三种，并且重点综述了这些不同化学改性方法的原理和特性及其对PEEK材料生物活性的影响。苯环位改性主要是通过强酸处理引入羧基等官能团，但会残留含硫或含硝化合物，对细胞有一定的毒害作用；酮基位改性是通过胺类、硼氢化钠等试剂与酮基反应，进一步接枝引入功能化基团，但是会破坏PEEK主链上的醚酮比，影响物理性能和热性能。通过亲电、亲核及卤代改性等共聚方式在PEEK侧链引入功能化基团，能保持聚合物主链醚酮比基本不变，同时提升材料生物活性，具有良好的应用前景。在化学改性的基础上，研究多种功能基团的协同作用，进一步引入物理改性，优化面向不同场景的综合性能，是拓宽其在医疗领域应用的发展趋势。     

聚芳醚酮的表面修饰及其在生物医用领域的应用

综述了特种工程塑料聚芳醚酮的表面修饰方法及其在生物医用领域的应用。重点介绍了选择性湿化学法和等离子体处理等聚芳醚酮表面改性方法及通过固定细胞外基质的生物功能化途径;最后,介绍了聚芳醚酮及改性聚芳醚酮在细胞培养基体、椎间融合器、关节摩擦面等临床植入体方面的应用进展,并对聚芳醚酮在生物医用领域的发展前景进行了展望。     

Synthesis and curing behavior of macrocycle‐terminated poly(aryl ether ketone)s

BACKGROUND: The introduction of poly(ether ether ketone)‐based carbon‐fiber composites accelerated the application of poly(ether ether ketone)s in advanced composite materials. In order to improve the compatibility and processability with reinforced components, polymers with low melt viscosity are preferable. RESULTS: Novel fully aromatic macrocycle‐terminated poly(aryl ether ketone)s (MCPAEKs) were prepared by condensation of macrocyclic aryl ether ketone dimers containing hydroxyphenyl groups and fluorine end‐capped poly(aryl ether ketone) oligomers. Compared with liner poly(aryl ether ketone)s, MCPAEKs showed much lower melt viscosities at low temperature. In the presence of caesium fluoride, the crosslinking reaction of MCPAEKs afforded fully aromatic thermoset poly(aryl ether ketone)s by ring‐opening reaction. CONCLUSION: The MCPAEKs exhibited high thermal stability due to their wholly aromatic structures. After crosslinking, the glass transition temperatures and complex melt viscosities of the polymers were increased greatly. Although there was some residual cesium fluoride or phenoxides produced by ring‐opening reaction, the thermoset poly(aryl ether ketone)s obtained had good thermal stability with temperatures at 5% weight loss above 475 °C. Copyright © 2009 Society of Chemical Industry     

聚芳醚酮化学改性研究进展

介绍了聚芳醚酮的物理化学性质,主要对近年来研究的热点超支化聚醚酮改性、化学改性和磺化改性等进行了综述.     

车用燃料电池质子交换膜的制备及性能

合成了一系列具有不同支化度的磺化聚芳醚砜材料,并对其结构和性能进行了表征。所制备的磺化的支化聚芳醚砜材料的分子量可达7.00×105以上,并且分子量分布在1.17左右,拉伸强度可达20.55~28.81 MPa。随着聚合物支化度的增加,聚合物的热稳定性得到改善,在550℃下的热失重可降低至39%~45%。高支化的磺化聚芳醚砜薄膜的氧化稳定性也得到改善,80℃下的使用寿命可提高至7.25 h。支化的磺化聚芳醚砜薄膜的吸水率和质子传导率都较高。80℃下高支化度的聚芳醚砜薄膜的质子传导率可达0.33 S/cm。对其微观形貌进行观测发现,支化聚芳醚砜中的支化结构可对周围的亲水磺酸基团起支撑作用,促使其发生团聚而形成连续的质子通道。     

Miscible blends of poly(aryl ether ketone)s and polyetherimides

A new class of high performance engineering resins, poly(aryl ether ketone)s, has emerged with a property balance not offered by existing polymeric materials. Blends of poly(aryl ether ketone)s with other polymers have not been described in the open literature, although several patents have revealed interesting and important properties of certain blend combinations. Ultem polyetherimide has been found to be miscible over the entire composition range and as a consequence is a very effective heat distortion temperature builder, particularly if the poly(aryl ether ketone) is allowed to crystallize. Crystallization kinetics and mechanical properties were studied as a function of blend composition and poly(aryl ether ketone) melting point. The blends exhibited a maximum in toughness at intermediate compositions along with an accompanying maximum in poly(aryl ether ketone) crystallinity. The chemical resistance of the polyetherimide is significantly improved with the addition of a poly(aryl ether ketone). In organic chemicals, the improvement was expected when tensile stress was plotted vs. log time to rupture. However, in aqueous bases, the resistance of the blends was much greater than anticipated. This property profile suggests that these blends will be useful as thermoplastic composite matrix resins.     

Synthesis and characterization of novel poly(aryl ether ketone)s with metallophthalocyanine pendant unit from a new bisphenol containing dicyanophenyl side group

A new bisphenol, (3,4-dicyano)phenylhydroquinone was prepared via a three-step reaction. Then a series of novel poly(aryl ether ketone) copolymers containing dicyanophenyl groups were prepared by the reactions of 4,4′-difluorobenzophenone with (3,4-dicyano)phenylhydroquinone and 4,4′-isopropylidenediphenol. After that, a series of poly(aryl ether ketone)s with metallophthalocyanine pendants were synthesized via the reactions of poly(aryl ether ketone)s containing dicyanophenyl with excessive amounts of 1,2-dicyanobenzene and the corresponding metal salt in quinoline. These resulting copolymers were found to have high glass transition temperatures and high thermal stability. They have good solubility and are capable of forming tough films. These copolymers show strong optical absorption in the visible region and exhibit strong blue photoluminescence.     

Adhesion characteristics of imide-aryl ether ether ketone block copolymers with poly(ether-imide)

Imide-aryl ether ether ketone block copolymers were prepared and the adhesion characteristics with poly(ether-imide) were investigated. The copolymers were prepared via the poly(amic alkyl ester) precursor to the polyimides which is hydrolytically stable and may be isolated and characterized prior to imidization. Solutions of the copolymers were cast and cured to effect the imidization, producing clear tough films which showed two transitions, indicative of a multiphase morphology. Mixtures of the copolymers with poly(ether-imide) also produced clear films, and the shift in the T_g of the aryl ether ether ketone component of the block copolymer indicated miscibility with the poly(ether-imide) within this phase. This miscibility of the poly(ether-imide) with the aryl ether ether ketone component of the block copolymer produced significant improvements in the adhesion of the thermoplastic poly(ether-imide) with the rigid polyimide copolymer.     

Kinetic study of the thermal degradation of poly(aryl ether ketone)s containing 2,7‐naphthalene moieties

The degradation of poly(aryl ether ketone) containing 2,7‐naphthalene moieties was subjected to dynamic and isothermal thermogravimetry in nitrogen and air. The dynamic experiments showed that the initial degradation temperature, temperature for 5% weight loss, and temperature corresponding to the maximum degradation rate of poly(aryl ether ketone) containing 2,7‐naphthalene moieties were a little higher than those of poly(ether ether ketone) and almost independent of the 2,7‐naphthalene moiety content. The thermal stability of poly(aryl ether ketone) containing 2,7‐naphthalene moieties in air was substantially less than that in nitrogen, and the degradation mechanism was more complex. The results obtained under the isothermal conditions were in agreement with the corresponding results obtained in nitrogen and air under the dynamic conditions. In the dynamic experiments, the apparent activation energies for the degradation processes were 240 and 218 kJ/mol in nitrogen and air for the second reaction stage as the heating rate was higher than 5°C/min. In the isothermal experiments, the apparent activation energies for the degradation processes were 222 and 190 kJ/mol in nitrogen and air, respectively. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Surface modification of poly(aryl ether ether ketone) film by remote oxygen plasma

Surface modification of poly(aryl ether ether ketone) (PEEK) film surfaces by oxygen plasma treatment was investigated. Two procedures, the direct plasma treatment and the remote oxygen plasma treatment, were used as oxygen plasma treatments, and the efficiency of the hydrophilic modification was discussed. The direct and remote oxygen plasma treatments lead to degradation of the PEEK film as well as hydrophilic surface modification. The degradation disturbs the surface modification. The remote oxygen plasma treatment rather than the direct oxygen plasma is suitable for the hydrophilic surface modification of the PEEK film. The remote oxygen plasma treatment at 10 W for 60 s forms predominantly C—O groups rather than C=O groups as an oxygen-containing group on the PEEK surface and gives a highly hydrophilic surface with a contact angle of 44 degrees. © 1998 John Wiley & Sons, Inc. J Appl Polm Sci 68:271–279, 1998