Ring-opening polymerization of macrocyclic aryl ether ketone oligomers containing the 1,2-dibenzoylbenzene moiety

Facile ring-opening polymerization of cyclic aryl ether oligomers containing the 1,2-dibenzoylbenzene moiety to form high molecular weight linear polymers in the presence of a nucleophilic initiator is described. The polymerization can be initiated in the melt in the presence of a nucleophilic initiator such as potassium carbonate, cesium fluoride, and alkali phenoxides. Various alkali phenoxides were investigated as potential nucleophilic initiators. The polymerization reaction rate in the melt increases in the order of K⁺ > Na⁺ > Cs⁺, and in the order of ⁻OPhPhO⁻ > PhO⁻ > PhOPhO⁻ > PhPhO⁻. However, the polymerization in an aprotic dipolar solvent is faster in the presence of cesium phenoxide than in the presence of potassium phenoxide. Polymerization of the cyclic oligomers in solution demonstrates that the ring-opening polymerization proceeds via a chain-growth mechanism and involves a transetherification reaction between linear and cyclic aryl ether oligomers. The ring-chain equilibrium is much more favorable towards linear polymers. Since little or no ring strain exists in the cyclic system, the transetherification reactions are indiscriminate with regards to cyclic or linear chains and the interchain equilibration is also a facile process during polymerization. This intermolecular transetherification has been demonstrated by using low molecular weight aryl ethers to control the molecular weight of the polymer formed via ring-opening polymerization. © 1996 John Wiley & Sons, Inc.     

Isothermal melt and cold crystallization kinetics of poly(aryl ether ketone ether ketone ketone)

The isothermal melt and cold crystallization kinetics of poly(aryl ether ketone ether ketone ketone) are investigated by differential scanning calorimetry over two temperature regions. The Avrami equation describes the primary stage of isothermal crystallization kinetics with the exponent n ≈ 2 for both melt and cold crystallization. With the Hoffman–Weeks method, the equilibrium melting point is estimated to be 406 °C. From the spherulitic growth equation proposed by Hoffman and Lauritzen, the nucleation parameter (K_g) of the isothermal melt and cold crystallization is estimated. In addition, the K_g value of the isothermal melt crystallization is compared to those of the other poly(aryl ether ketone)s. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1992–1997, 2000     

含间苯连接的聚醚醚酮酮的等温结晶过程和形态结构

用透射电子显微镜和电子衍射方法研究了含间苯连接的聚醚醚酮酮（PEEKmK）溶液浇铸薄膜的等温结晶过程和形态结构．结果表明，PEEKmK无论从玻璃态结晶还是从熔体结晶均能形成2种不同取向的结晶形态结构，即平放片晶和侧放片晶；前者c轴垂直于膜平面，后者c轴平行于膜平面．其结晶发展过程为先形成平放单晶状片晶，随着时间的增长，在单晶上开始生长侧放片晶，逐渐发展形成球晶，最终形成2种不同取向的单晶和球晶共存的结晶形态结构．     

几种甲基取代的聚醚酮酮的合成与表征

聚芳醚酮是一类热、电、机械性能优异的热塑性工程塑料,其合成方法有亲电取代法和亲核取代法．近年来,通过改变主链上醚酮键的比例和次序以及在主链上引入ｓｐ３杂化原子团,如砜基、烷基,对其进行结构上的改性研究已有很多报道［１４］．另一种结构上的改性研究是在...     

含三苯基氧磷结构聚芳醚醚酮酮的合成与表征

以苯酚、对二溴苯及苯基磷酰二氯为原料合成出二(4-苯氧基苯基)苯基氧磷(BPOPPO)。 三氯化铝(AlCl₃)为催化剂,通过缩聚反应,BPOPPO与对苯二甲酰氯(TPC)反应制备出一种含有三苯基氧磷结构的聚醚醚酮酮(P-PEEKK)树脂。 采用傅里叶变换红外光谱仪(FT-IR)、差示扫描量热仪(DSC)、热重分析仪(TGA)和广角X射线衍射(WAXD)等技术手段对P-PEEKK树脂的结构和性能进行表征。 结果表明,P-PEEKK树脂属于非晶聚合物,玻璃化转变温度(T_g)较高,为190.5 ℃;热分解温度(T_5%)为515 ℃,耐热性能较好;极限氧指数(LOI)为42,阻燃性能好,为难燃材料;易溶解于氯仿、1,2-二氯乙烷、N,N-二甲基乙酰胺等有机溶剂中,溶解性能较好,便于涂膜加工;拉伸强度为62 MPa,力学性能较好。     

Thermal behavior and phase behavior in blends of liquid crystalline poly(aryl ether ketone) and poly(aryl ether ether ketone) containing thioether units

Thermal behavior and phase behavior in blends of liquid crystalline poly(aryl ether ketone) with lateral methoxy groups (M-PAEK) and poly(aryl ether ether ketone) containing thioether units (S-PEEK) have been investigated by differential scanning calorimetry (DSC) and polarized light microscopy (PLM) techniques. The results indicate that the composition of the blends has great effect on the phase behavior and morphology. Thin films of pure M-PAEK and S-PEEK crystallized from the melts exhibit typical mosaic and spherulitic structures, respectively. For the blends with higher M-PAEK contents (> 50%), an unusual ring-banded spherulite with structural discontinuity is formed. The bright core and rings of the ring-banded spherulites under PLM are composed of M-PAEK phase, while the dark rings consist mainly of S-PEEK phase. For the 50:50 M-PAEK/S-PEEK blend, the ring-banded spherulites and S-PEEK spherulites coexist, which implies that a partial phase separation between the two components takes place in the melting state. In S-PEEK-rich blends, a volume-filled spherulite is produced. In addition, the effect of isothermal crystallization temperature on the phase behavior, especially the ring-banded spherulite formation in the blends, is discussed.     

Synthesis and Characterization of Soluble Reactive Copoly (aryl ether ketone ketone)

Poly (aryl ether ketone)s are a category of high performance engineering plastics, widely used in electronic, electric, and military industries1. For their general excellent properties, many new products are developed. In recent years, much attention has been paid to synthesize soluble or reactive poly (aryl ether ketone)2,3. In this letter, we report the synthesis of a novel soluble reactive copoly (aryl ether ketone ketone) from 2,2-p-hydroxyphenyl-iso-propane 3, functionalized chemical 1, a…     

Glass transition and miscibility in blends of two semicrystalline polymers: Poly(aryl ether ketone) and poly(ether ether ketone)

Binary melt‐blended mixtures of two aryl ether ketone polymers (i.e., a new poly(aryl ether ketone) (code name PK99) and poly(ether ether ketone) (PEEK), have been studied. Polymer miscibility in glassy amorphous (or melt) domains has been demonstrated for the binary blend comprising of two aryl‐ether‐ketone‐type semicrystalline polymers. Composition‐dependent, single T_g was observed within full composition range in the PK99/PEEK blends, and the narrow T_g breadth also suggests that the scale of mixing was fine and uniform. To better resolve any possible overlapping T_g's, physical aging was imposed on a comparison set of blend samples for the purpose of improving detectability of overlapped multiple transitions if existing. The result still showed one single T_g. The relative sharp T_g and lack of cloud point transition suggest that the scale of molecular intermixing is good. Phase homogeneity was further confirmed using optical and scanning electron microscopy. The X‐ray diffractograms suggest that isomorphism does not exist in the PK99/PEEK blends and that the crystal forms of the respective polymers remain distinct and unchanged by the miscibility in the amorphous region. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1485–1494, 1999     

Stress-enhanced transport of toluene in poly aryl ether ether ketone (PEEK)

The transport of fluids in the semicrystalline polymer, poly(aryl ether ether ketone) (PEEK), was investigated. Both solubility and rate of penetration of toluene into PEEK are markedly increased by the application of an external stress. The induction period (i.e., the time for the sorption to begin) is a function of applied stress as well as temperature and crystallinity. At 22°C in 29% crystalline PEEK the induction period was reduced from more than 2000 h to approximately 10 h whereas the solubility of toluene was increased from 9 to 44 wt % upon the application of an external tensile stress of 30 MPa. A critical stress (i.e., a stress value below which the stress-enhanced effects are not observed) was determined. The critical stress is a strong function of crystallinity and temperature. © 1996 John Wiley & Sons, Inc.     

氧化偶联聚合方法合成电活性聚芳醚酮

通过氧化偶联聚合方法成功地合成出电活性聚芳醚酮. 该反应条件温和, 操作简单, 室温下即可进行. 用红外光谱、核磁共振谱、高效凝胶渗透色谱、循环伏安、热失重、X射线衍射等技术对所合成的聚合物进行了表征, 并探讨了聚合物的性能.     

含间苯基聚醚醚酮酮的合成与性能研究

含间苯基聚醚醚酮酮的合成与性能研究林权，王一凡，张万金，吴忠文，尹玖梅（吉林大学化学系，长春，１３００２３）（中国科学院长春应用化学研究所）关键词聚醚醚酮酮，间苯基，熔点，玻璃化转变温度聚芳醚酮类高聚物具有优异的热、电、机械性能．全对苯基位聚醚醚酮酮...     

(夹)二氧蒽改性聚芳醚酮酮

共聚物;合成;(夹)二氧蒽改性聚芳醚酮酮     

Synthesis, structure and ring-opening polymerization of macrocyclic arylates containing phthalic unit

A series of maerocyclic arylate diraers have been selectively synthesized by an interfacial polyconden-sation of o-phthaloyldichloride with bisphenols A combination of GPC,FAB-MS,1H and 13C NMR unambiguously confirmed the cyclic nature Although single-crystal X-ray analysis of two such macrocycles reveals no severe strain on the cyclic structures,these macrocycles can undergo facile melt polymerization to give high molecular weight polyary-lates.     

含联苯结构聚醚醚酮酮共聚物和共混物的制备及性能研究

聚醚醚酮（PEEK）是八十年代初投入市场的全芳香结构热塑性耐高温特种工程塑料，它的7’。一143“C，Tm一334C“‘，最大结晶度为48％，典型制品结晶度为20％～30％［”．PEEK可用通常的设备成型，其制件、纤维、涂料及复合材料在电子电器、机械设备、交通运输、宇航、原子能工程、军事等领域有广泛的用途［’j．聚醚醚酮酮（PEEKK）是继PEEK之后，由德国Hoechst公司开发出来的又一种全芳香结构热塑性耐高温特种工程塑料［‘j．为了研究该类聚合物的结构和性能的关系，我们在实验室中合成了PEEKK和含联苯结构聚醚醚酮酮（PE－＊…     

Novel fluorinated poly(aryl ether ketone)s

Two novel fluorinated monomers were prepared and polymerized with biphenols to produce amorphous, thermally stable poly(aryl ether ketone)s. The properties of the fluorinated polymers are compared to those of unfluorinated, amorphous poly(aryl ether ketone)s. The presence of fluorine in the polymers was found to cause a decrease in glass transition temperature and Young's moduli, however, no increase in thermal stability was observed. The fluorinated polymers are soluble in common organic solvents such as chloroform and methylene chloride at room temperature, and also show solubility in solvents containing a ketonic moiety, such as acetone. Evidence of polymer branching through fluorines considered to be unreactive under the polymerization conditions was found. Efforts were made to evaluate the reactivity of fluorine atoms under the polymerization conditions using both molecular modeling and ¹⁹F-NMR to ascertain if such branching could be avoided. © 1995 John Wiley & Sons, Inc.     

新型热致型液晶苯代聚芳醚酮的单畴液晶行为

通过偏光显微镜研究了在外力场作用下新型热致型液晶苯代聚芳醚酮的向列相单畴液晶行为。结果表明，聚合物在剪切力作用下形成条带织构，强外力场能使介晶基元沿基质表面平行排列，形成均匀织构的单畴区。由于裂纹的存在，观察到了四条和六条黑刷的纹影织构。     

聚芳醚酮醚酮酮类聚合物的结晶与多晶型

晶体结构;聚芳醚酮醚酮酮类聚合物的结晶与多晶型     

聚芳醚酮类聚合物晶体结构醚酮等效性的研究

半结晶的聚芳醚酮类聚合物 ( PAEKs)因其性能优异而在机械、航天等高技术领域中得到广泛应用 .有关其晶体结构的研究亦有许多文献报道[1～ 11] ,而醚基与酮基在晶体结构方面是否等效一直存在争议 .虽然醚酮等效性的观点已被广泛接受 [4～ 8] ,但对于聚合物主链中含联苯基团的 PAEKs的醚酮等效性的研究则复杂得多 .文献 [1 ]报道醚酮等效性在主链含有联苯基团时不再成立 .本文首次发现醚酮等效性在主链含有联苯基团时在适当条件下仍可成立 ,并对聚芳醚酮类聚合物晶体结构的醚酮等效性问题进行了系统阐述 .1　实验部分　　样品联苯聚醚酮 …     

稀土催化异戊二烯-马来酸酐交替共聚

研究了含氟基团的引入对聚醚醚酮（PEEK）的介电常数、溶解性、结晶性和力学性能等的影响，结果表明，这种含氟聚芳醚酮在保持PEEK良好机械性能的条件下，介电常数达到2．7，且频率依赖性小，成膜性能好，成本比相应的含氟PI低5－10倍，有望成为一种极有实用价值的电子封装材料，同时利用合成的含氢氟单体合成了一系列不同－CF3取代基含量的聚芳醚酮共聚物，研究了聚芳醚酮共聚物的介电常数与聚合物结构单元中－CF3取代基含量的关系，结果表明，聚芳醚酮共聚物的介电常数的介电常数随聚合结构单元中－CF3取代基含量的增加而线性降低。     

含氟聚芳醚酮的合成与性能研究

研究了含氟基团的引入对聚醚醚酮(PEEK)的介电常数、溶解性、结晶性和力学性能等的影响.结果表明,这种含氟聚芳醚酮在保持PEEK良好机械性能的条件下,介电常数达到2.7,且频率依赖性小,成膜性能好,成本比相应的含氟PI低5～10倍,有望成为一种极有实用价值的电子封装材料.同时利用合成的含氟单体合成了一系列不同-CF₃取代基含量的聚芳醚酮共聚物,研究了聚芳醚酮共聚物的介电常数与聚合物结构单元中-CF₃取代基含量的关系.结果表明,聚芳醚酮共聚物的介电常数随聚合物结构单元中-CF₃取代基含量的增加而线性降低.