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.     

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。     

钛酸钾晶须填充新型聚芳醚酮的性能

用溶液共沉析的方法制备了含二氮杂萘结构的聚芳醚酮／钛酸钾晶须复合材料，晶须表面用偶联剂处理。研究了复合材料的拉伸强度，冲击强度，弯曲强度，形态及热性能，结果表明，复合材料的冲击强度和弯曲强度随晶须含量的增加而增高，而拉伸强度却呈下降趋势，热重分析显示，随晶须含量的增加，复合材料的热稳定性提高。     

间位苯基取代聚芳醚砜醚酮酮的合成与性能研究

以4,4′-二苯氧基二苯砜(DPODPS)、对苯二甲酰氯(TPC)和间苯二甲酰氯(IPC)为单体,无水AlCl3/二氯乙烷(DCE)/N,N-甲基甲酰胺(DMF)为催化溶剂体系,通过低温溶液共缩聚反应,合成系列聚芳醚砜醚酮酮(PESEKKs),用IR、DSC、WAXD、TG等技术对聚合物进行了结构和性能的表征,研究结果表明,随着高分子主链中间位苯基结构单元的增加,对共聚玻璃化转变温度(Tg)和热分解温度(Td)影响不大,熔融温度(Tm)和结晶则逐渐降低,但仍保持良好的耐热性,溶解性等到很大改善。     

聚芳醚酮的改性研究

综述了特种工程塑料聚芳醚酮改性研究的进展,主要介绍了聚芳醚酮结构改性的三大类方法:主链上引入其他基团、主链上引入大侧基及共聚改性。研究表明,通过结构改性可以在保持聚芳醚酮高的耐热性能和力学性能的基础上有效地改善其加工性能和在有机溶剂中的溶解性。同时简介了聚芳醚酮与聚酰亚胺、聚醚砜、聚苯硫醚等高性能树脂以及不同种类的聚芳醚酮间共混改性的研究状况。     

聚芳醚酮/含甲基侧基聚芳醚砜醚酮酮的合成与表征

以2，2’-二甲基-4,4'-二苯氧基二苯砜(o-CH3-DPODPS)、二苯醚(DPE)和对苯二甲酰氯(TPC)为单体，在无水A1C13、1，2-二氯乙烷和N，N-二甲基甲酰胺存在下，通过低温溶液缩聚反应。合成了一系列新型含甲基侧基的聚芳醚酮／聚芳醚砜无规共聚物。用FT-IR，WAXD，DSC和TG等方法对聚合物进行了表征。结果表明，随着2,2'-二甲基-4，4'-二苯氧基二苯砜含量的增加，共聚物的玻璃化转变温度逐渐提高，熔融温度则逐渐下降。     

聚芳醚砜酮纤维的热性能

采用DSC、TG测定了含联苯结构聚芳醚砜酮 (PPESK)纤维的热性能 ,结果表明 ,纤维的玻璃化温度随砜酮比的增大而提高 ,纤维的起始分解温度大于 463℃。当砜酮比为 15 / 85 ,5 0 / 5 0 ,75 / 2 5时 ,纤维的玻璃化温度分别为 2 5 7.62 ,2 78.64 ,2 79.71℃ ;热分解活化能分别为 15 0 .8,2 19.9,195 .5kJ/mol;热分解反应级数分别为 1,1.76,1级     

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。     

新型高性能聚芳醚酮类热塑性聚合物的研究进展与应用

聚芳醚酮类树脂是近10年来国外发展的一类新型高性能热塑性聚合物,具有优良的高温机械性能、电气性、难燃性、成型加工性、耐化学腐蚀性及抗辐射性。是一类前途广阔的工程塑料。本文详细介绍了这类材料的发展概况、品种、性能及其在机械、汽车、电子电器、医学、化学化工及航天航空等领域的应用。     

亲电聚合路线合成含氯取代基的聚芳醚酮酮的研究

对苯二甲酰氯、2,5-二氯对苯二甲酰氯和二苯醚,在无水三氯化铝、1,2-二氯乙烷和N,N-二甲基甲酰胺存在下,通过傅-克(Friedel-Crafts)酰化缩合反应,合成了新型的含氯取代基的聚芳醚酮酮(简称PEKKC)。用红外光谱、X-射线衍射、扫描电镜、差示扫描量热、热失重及耐溶剂试验等对聚合物进行了表征。研究结果表明苯环上的氯取代基能显著降低聚合物的熔融温度、结晶度及表观形态的致密度,PEKKC具有和PEKK相似的耐热性及耐溶剂、抗化学腐蚀性。     

Rheological properties in blends of poly(aryl ether ether ketone) and liquid crystalline poly(aryl ether ketone)

Rheological properties of the blends of poly(aryl ether ether ketone) (PEEK) with liquid crystalline poly(aryl ether ketone) containing substituted 3‐trifluoromethylbenzene side group (F‐PAEK), prepared by solution precipitation, have been investigated by rheometer. Dynamic rheological behaviors of the blends under the oscillatory shear mode are strongly dependent on blend composition. For PEEK‐rich blends, the systems show flow curves similar to those of the pure PEEK, i.e., dynamic storage modulus G′ is larger than dynamic loss modulus G″, showing the feature of elastic fluid. For F‐PAEK‐rich systems, the rheological behavior of the blends has a resemblance to pure F‐PAEK, i.e., G″ is greater than G′, showing the characteristic of viscous fluid. When the PEEK content is in the range of 50–70%, the blends exhibit an unusual rheological behavior, which is the result of phase inversion between the two components. Moreover, as a whole, the complex viscosity values of the blends are between those of two pure polymers and decrease with increasing F‐PAEK content. However, at 50% weight fraction of PEEK, the viscosity‐composition curves exhibit a local maximum, which may be mainly attributed to the phase separation of two components at such a composition. The changes of G′ and G″ with composition show a trend similar to that of complex viscosity. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4040–4044, 2006     

Synthesis and properties of poly(aryl ether ketone ketone)/poly(aryl ether ether ketone ketone) copolymers with pendant cyano groups

2,6‐Diphenoxybenzonitrile (DPOBN) was synthesized by reaction of phenol with 2,6‐difluorobenzonitrile in N‐methyl‐2‐pyrrolidone in the presence of KOH and K₂CO₃. Poly(aryl ether ketone ketone)/poly(aryl ether ether ketone ketone) copolymers with pendant cyano groups were prepared by the Friedel–Crafts electrophilic substitution reaction of terephthaloyl chloride with varying mole proportions of diphenyl ether and DPOBN using 1,2‐dichloroethane as solvent and N‐methyl‐2‐pyrrolidone as Lewis base in the presence of anhydrous AlCl₃. The resulting polymers were characterized by various analytical techniques, such as FT‐IR, differential scanning calorimeter, thermal gravimetric analysis, and wide‐angle X‐ray diffraction. The crystallinity and melting temperature of the polymers were found to decrease with increase in concentration of the DPOBN units in the polymer. Thermogravimetric studies showed that all the polymers were stable up to 514°C in N₂ atmosphere. The glass transition temperature was found to increase with increase in concentration of the DPOBN units in the polymer when the molar ratios of DPOBN to DPE ranged from 10/90 to 30/70. The copolymers containing 30–40 mol % of the DPOBN units exhibit excellent thermostability at (350 ± 10)°C and have good resistance to acidity, alkali, and organic solvents. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3601–3606, 2007     

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.     

聚醚醚酮表面壳聚糖的固定

通过紫外光接枝和湿化学法连用在聚醚醚酮 （PEEK）表面固定上具有抑菌杀菌作用的壳聚糖。结果表明,相比未改性的PEEK表面,改性后材料表面亲水性提高;通过扫描电子显微镜和X射线光电子能谱分析证明壳聚糖成功接枝在了PEEK薄膜表面;随着壳聚糖浓度的提高,材料表面的壳聚糖接枝率增加。     

新型含偶氮结构聚芳醚砜醚酮酮的合成与表征

在无水AlCl3及N-甲基吡咯烷酮(NMP)/1,2-二氯乙烷(DCE)复合溶剂的存在下,将含砜基芳二醚类单体与含偶氮苯结构芳二甲酰氯进行低温付-克缩聚反应,合成了一类新型含偶氮结构聚芳醚砜醚酮酮树脂。用IR、TG、WAXD及元素分析等技术进行了结构表征和性能测试。结果表明:所合成的聚合物树脂具有预期结构且为非晶态聚合物;在N2气氛中质量损失5%的温度(Td)分别为445～463℃;聚合物除了能在浓硫酸、CF3COOH/CHCl3等强极性质子型溶剂中溶解外,还能溶解于N-甲基吡咯烷酮(NMP)、N,N-二甲基甲酰胺(DMF)、二甲基亚砜(DMSO)等强极性非质子型溶剂中,也能在普通溶剂,如氯仿(CHCl3)、1,2-二氯乙烷(DCE)、四氢呋喃(THF)等中溶解。     

Synthesis and characterization of novel poly(aryl ether ketone ketone)s containing the o‐dibenzobene moiety

The synthesis of a novel chloro monomer containing the 1,2‐dibenzoylbenzene moiety was described. The chloro monomer was reacted with 4‐(4‐hydroxyphenyl)‐1(2H)‐phthalazinone compound in the presence of excess anhydrous potassium carbonate in an aprotic solvent (Sulfolane), and high molecular weight amorphous poly(aryl ether ketone ketone) was synthesized. The polymers with high glass transition temperature were soluble in solvents such as chloroform and nitrobenzene at room temperature and easily cast into flexible, colorless, and transparent films. The 5% weight loss of the polymers was >400 °C. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1487–1492, 2001     

含稠杂环结构聚醚酮酮的合成与性能研究(I)

以吩噻（ＯＳＰ）、对苯二甲酰氯（ＴＰＣ）和二苯醚（ＤＰＥ）为单体,在无水ＡｌＣｌ３／ＣＨ２ＣｌＣＨ２Ｃｌ／ＤＭＦ催化剂／溶剂体系中,由亲电缩聚反应合成了含稠杂环结构的聚醚酮酮共聚物,并对其基本性能进行了测定。结果表明,含ＯＳＰ结构单元ＰＥＫＫ的Ｔｇ比全对苯基位ＰＥＫＫ高４２℃以上。且随ＯＳＰ结构单元含量的增加,共聚物Ｔｇ逐渐提高,而Ｔｍ、结晶度却逐渐下降,仍具有很好的耐热性和耐溶剂性。