含稠杂环结构聚醚酮酮的合成与性能研究（1）

以吩噻恶（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。     

亲电聚合法合成甲基取代聚芳醚酮酮的研究

由间甲基二苯醚（ＭＰＥ）和对苯二甲酰氯（ＴＰＣ）、间苯二甲酰氯（ＩＰＣ）、２,５－二氯对苯二甲酰氯（ＤＣＣ）等芳二酰氯在１,２－二氯乙烷（ＤＣＥ）中,以无水ＡｌＣｌ３为催化剂,在Ｎ－甲基吡咯烷酮（ＮＭＰ）存在下,进行亲电缩聚反应,合成了五种不同结构的甲基取代的聚醚酮酮（ＭｅＰＥＫＫ）。用ＩＲ、ＤＳＣ和ＷＡＸＤ等方法对聚合物进行了分析表征,结果表明：聚合物的对数比浓粘度在０．５～０．６８ｄＬ／ｇ之间,与ＰＥＫＫ相比,ＭｅＰＥＫＫ的结晶度、熔融温度、热分解温度均有所下降,但聚合物仍具有很好的耐热性,其溶解性得到了明显的改善。     

聚醚酮酮的合成及性能研究

在温和条件下,以１,２－二氯乙烷为溶剂,无水三氯化铝为催化剂,二苯醚和对苯二甲醚为原料合成了高分子量的聚醚酮酮（ＰＥＫＫ）并找到了用浓盐酸脱除催化剂,乙醇提纯聚合物的有效途径,测试了ＰＥＫＫ的主要物理和化学性能,其中ＰＥＫＫ的特性粘度可达０．８－１．０,达到工程材料的要求。     

聚醚酮酮的合成与性能研究

在温和条件下,以1,2-二氯乙烷为溶剂、无水三氯化铝为催化剂、二苯醚和对苯二甲酰氯为原料合成了高分子量的聚醚酮酮(PEKK),并找到了用浓盐酸脱除催化剂、乙醇提纯聚合物的有效途径。测试了PEKK的主要物理和化学性能,其中PEKK的特性粘度可达0.8～1.0,达到了工程材料的要求。     

聚醚酮酮和磺化聚醚酮酮的热稳定性研究

用差热分析法,差示扫描量热法、换失重法,等热分析方法对聚醚酮酮和磺化聚醚酮酮的热稳定及其差异进行了研究,结果表明聚醚酮酮有更好的热稳定性。     

新型耐高温杂环聚醚砜酮酮材料的研究

合成一种新型热塑性耐高温杂环聚醚砜酮酮材料（ＰＰＥＳＫＫ）,研究了材料的热性能、力学性能、电性能、溶解性能、摩擦性能及膜性能。结果表明,ＰＰＥＳＫＫ为一类具有较高耐热性、综合性能优良、成本低的机械工程塑料。     

聚醚酮酮和磺化聚醚酮酮物理性能的研究

研究了聚醚酮酮(PEKK)和磺化聚醚酮酮(SPEKK)的密度、吸水率、耐溶剂性能和电性能,用X—射线衍射研究了结晶度的大小,用差热分析、差示扫描量热分析和热失重法进行了热性能的研究,并对模压成型条件进行了探讨。与磺化聚醚酮酮相比,聚醚酮酮的密度略大,吸水率较小,耐溶剂性能好,结晶度大,熔点及热分解温度较高。     

杂环取代联苯聚醚酮的流变行为

用日本岛津ＡＧ－２０００Ａ毛细管流变仪，研究了自制的杂环取代联苯型聚醚酮的流变行为。求出了表观流动活化能，考察了巴氏效庆和非牛顿行为，对其加工行为进行了分析。     

芳香环状聚醚酮的合成研究进展

芳香环状聚醚酮的合成是应现代高技术领域对先进复合材料的需求而发展起来的研究领域。综述了芳香环状聚醚酮的合成研究进展、合成方法,并分析各种合成方法的优势。     

高性能航天航空材料——聚醚酮酮

主要综述了聚醚酮酮(PEKK)的物理性能、合成方法和在航天航空领域的应用     

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。     

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     

特种工程塑料聚芳醚酮

介绍了聚芳醚酮的发展概况、分类及其物化性能;重点对PEEK的性能及应用进行详细阐述;概述了PEEK 的最新研究成果,并指出其今后发展趋势。     

Synthesis of a new electroactive poly(aryl ether ketone)

In this communication, we report for the first time the synthesis of a new electroactive poly(aryl ether ketone) derived from the phenyl-capped aniline tetramer. The general properties are studied by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The polymer has high serving temperature and good thermal stability. And its chemical oxidation process was studied by UV-Vis spectra. It was found the polymer was oxidized to its EB form and then to the pernigraniline oxidation state, which is same as the PANI.     

Synthesis and properties of novel poly(aryl ether ketone)s containing both diphenyl moiety and amide linkages in the main chains

New monomers, 4,4′-bis(4-phenoxybenzoyl)diphenyl (BPOBDP) and N,N′-bis(4-phenoxybenzoyl)-p-phenylenediamine (BPBPPD), were conveniently synthesized via simple synthetic procedures from readily available materials. A series of novel poly(aryl ether ketone)s containing both diphenyl moiety and amide linkages in the main chains were prepared by electrophilic Friedel-Crafts solution copolycondensation of isophthaloyl chloride (IPC) with a mixture of BPOBDP and BPBPPD, over a wide range of BPOBDP/BPBPPD molar ratios, in the presence of anhydrous AlCl₃ and N-methylpyrrolidone (NMP) in 1,2-dichloroethane (DCE). All the polymers are semicrystalline and had remarkably increased T_gs over commercially available PEEK and PEKK due to the incorporation of the diphenyl moiety and amide linkages in the main chains. The polymers with 40-60 mol% BPBPPD had not only high T_gs of 183-189 °C, but also moderate T_ms of 314-328 °C, which are very suitable for the melt processing. These polymers had tensile strengths of 107.4-111.5 MPa, Young's moduli of 2.20-2.45 GPa, and elongations at break of 11.3-13.5% and exhibited high thermal stability and good resistance to organic solvents.     

含氯侧基聚芳醚酮醚酮酮的合成与表征

以α-萘酚为原料，通过和4，4′-二氟二苯酮在N，N-二甲基乙酰胺（DMAC）及K2CO3中的缩合反应制备了一种含萘环的新型芳醚单体4，4′-二（α-萘氧基）二苯酮（DNBP），将其分别与2，5-二氯对苯二甲酰氯（DCTPC）。对苯二甲酰氯（TPC）等芳二酰氯通过在NMP/AlCl3/ClCH2CH2Cl复合溶剂/催化剂体系中的低温溶液进行亲电共缩聚反应，合成了一系列在分子主链芳环上引入侧基氯原子的同时，又在主链中引入刚性萘环结构的新型聚芳醚酮醚酮酮无规共聚物。     

含三氟甲基聚芳醚酮的合成与表征

以六氟双酚A和4,4′–二氟二苯酮为原料,以N–甲基吡咯烷酮为溶剂采用新的合成工艺合成含三氟甲基聚芳醚酮,采用傅里叶变换红外光谱、核磁共振波谱及X射线衍射等对聚合物的结构和性能进行分析和表征。结果表明,采用新工艺合成的聚芳醚酮与传统工艺合成的树脂的热性能基本一致,具有良好的耐热性能,其玻璃化转变温度为162.6℃,氮气中5%热失重温度为517.1℃;80 kHz下含三氟甲基聚芳醚酮的介电常数为1.55,具有良好的电绝缘性;室温下能溶解于N–甲基吡咯烷酮、氯仿、四氢呋喃等有机溶剂。     

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     

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。     

Crosslinkable fully aromatic poly(aryl ether ketone)s bearing macrocycle of aryl ether ketone

A novel bisphenol monomer, (3-methoxy)phenylhydroquinone, was synthesized via a three-step synthetic procedure. The cyclization of the bisphenol monomer and 4,4-difluorobenzophenone was carried out under pseudo high dilution condition. Two types of fully aromatic poly(aryl ether ketone)s were prepared by copolymerization of macrocycle of aryl ether ketone (MACEK) containing hydroxyphenyl, 4,4′-(hexafluoroisopropylidene)diphenol (HFBPA), and 4,4-difluorobenzophenone. The copolymers have high molecular mass, good solubility and high glass transition temperatures. The copolymers are crosslinkable in the presence of basic initiator and the glass transition temperatures of the copolymers increased greatly after the curing. These cured copolymers exhibit excellent thermal stability, and the 5% weight loss temperatures are around 500 °C in nitrogen.