含氟共聚芳醚酮的合成与性能研究

通过三步反应合成新的含氟双酚单体4-氟苯基对苯二酚,在该含氟双酚单体中加入不同比例的间苯二酚与4,4'-二氟二苯酮经亲核缩聚反应制备了一系列新型共聚芳醚酮.用傅立叶变换红外光谱仪、差示扫描量热仪、热失重分析仪及广角X射线衍射仪等对聚合物的结构和性能进行了表征和研究.结果表明,该共聚物为非晶态,具有优异的耐热性能,其玻璃化转变温度(Tg)在123～159℃、氮气中5%热失重温度在510℃以上;且具有良好的溶解性,室温下能溶解于N-甲基吡咯烷酮、N,N-二甲基乙酰胺、氯仿等有机溶剂.     

含芴可交联聚芳醚酮的合成

以4,4′-二氟二苯甲酮、双酚芴和二烯丙基双酚A为单体,调整双酚芴和二烯丙基双酚A的摩尔比,通过亲核取代逐步加成反应合成了一系列含芴可交联的聚芳醚酮（PAEK）;用红外光谱仪、核磁共振波谱仪、差示扫描量热仪、热重分析仪对所制备的含芴可交联PAEK的结构、热交联行为、热稳定性等进行了表征。结果表明,所制备的聚合物可通过热引发交联,交联后的聚合物具有优良的耐热性能,交联后聚合物的耐溶剂性能得到提高,最高凝胶含量达到97.5 %。     

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。     

氰基含量对聚芳醚腈砜性能的影响

以2,6-二氟苯甲腈、4,4’-二氯二苯砜、4,4’-二羟基二苯砜以及间苯二酚为主要原料,改变它们的摩尔配比合成了不同氰基含量的聚芳醚腈砜。研究了氰基含量对聚芳醚腈砜的合成工艺、聚集态结构、热氧稳定性以及玻璃化转变温度的影响。     

新型聚芳醚砜共聚物的制备及其性能

以4,4’-二氯二苯砜、4,4’-二羟基二苯砜和2,4-二羟基二苯砜为单体,通过缩聚合成一系列主链含异构体醚键单元的聚芳醚砜共聚物,利用核磁共振碳谱(13C NMR)、差示扫描量热分析(DSC)和高压毛细管流变仪对产物进行了测试和分析。对比不同产物的熔体黏度、玻璃化转变温度和力学性能,发现随着共聚单元含量的增加,聚芳醚砜共聚物的流动性逐渐提高,玻璃化转变温度逐渐降低,并且屈服点伸长率和缺口冲击强度均逐渐提高。这一结果对实际应用中提高聚芳醚砜树脂流动性和韧性、降低热加工温度等具有重要的指导意义。     

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。     

含氟磺化聚芳醚酮质子交换膜的制备与性能研究

以六氟双酚A(6FBPA),4,4′-二氟二苯酮(DFBP)和3,3′-二磺酸钠基-4,4′-二氟二苯酮(SDFBP)为单体,调整单体DFBP与SDFBP的摩尔投料比,通过缩合共聚反应合成了一系列离子交换容量不同的含氟磺化聚芳醚酮共聚物(SPEK-6Fs)。采用红外(FT-IR)、核磁共振氢谱(1H-NMR)对共聚物的结构进行了表征,同时对所制备的质子交换膜的吸水率、尺寸稳定性、甲醇透过率、质子电导率及抗氧化性能等进行了一个综合的评价。结果表明:所合成的聚合物具有较高的分子量,可通过溶液浇铸成膜法制备成柔韧、透明的膜,所制备的膜具有良好的尺寸稳定性,在同等测试条件下,具有与杜邦公司Nafion 117膜相当的质子电导率,同时,其甲醇渗透率比Nafion 117膜低1~2个数量级。     

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。     

邻甲基二氮杂萘联苯型聚醚酮的合成及表征

以自制的新型类双酚单体４－（３－甲基－４－羟基苯基）－２，３－二氮杂萘－１一酮，与４，４′－二氟二苯酮反应，合成了新型聚芳醚酮。初步探讨了聚合条件；用核磁共振、红外光谱分析研究了双酚单体及聚合物的结构；用ＤＳＣ、ＴＧＡ分析了聚合物的耐热性。实验结果表明，此类双酚单体具有与双酚类似的活性，可以进行聚合反应，由此合成的材料具有优异的综合性能：４００℃以下聚合物几乎没有热损失；对溶剂的溶解性能优于其它聚醚酮；力学性能良好。由于主链上引入了甲基基团，为拓宽材料的应用范围提供了一个潜在的功能基团。     

聚芳醚腈砜碳布层压板和玻璃布层压板的研制

本文以２,６－二氟苯甲腈和４,４－二羟基二苯砜为主要原料合成了聚芳醚腈砜利用ＩＲ、＾１３Ｃ－ＮＭＲ和热分析等手段对其结构和热性能进行了表征。以取长醚腈砜为基体树脂采用特殊的溶液浸胶工艺,一次邓要制我含量达４５％的预浸料。制得的碳布层压板和玻璃布层压板皆具有优异的力学性能和热性能,可在１８０℃使用。     

Synthesis and characterization of poly(aryl ether sulfone)s with metallophthalocyanine pendant unit

A series of novel poly(aryl ether sulfone) copolymers containing dicyanophenyl group were prepared by the reaction of bis(4‐chlorophenyl)sulfone with (3,4‐dicyano) phenylhydroquinone and 4,4′‐isopropylidenediphenol. On this basis, a series of poly(aryl ether sulfone)s containing metallophthalocyanine units were synthesized by the reaction of poly(aryl ether sulfone)s containing dicyanophenyl group with excessive amounts of 1,2‐dicyanobenzene and the corresponding metal salt in quinoline. All these copolymers were found to have high glass transition temperature and thermal stability. These copolymers were found to be soluble in common solvents, and capable of forming transparent films by solution casting. The copolymers containing metallophthalocyanine units showed strong optical absorption in the visible region, and exhibited blue photoluminescence in solution. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3457–3461, 2006     

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     

Preliminary investigation of poly(ether sulfone)/poly(aryl ether ketone) containing 1,4‐naphthalene blends

The blends of poly(ether sulfone) and poly(aryl ether ketone) containing 1,4‐naphthalene were prepared by melt mixing in a Brabender‐like apparatus. The specimens for measurements were made by compression molding under pressure and then were water‐quenched at room temperature. The tensile strength, tensile modulus, elongation at break, thermal analysis, and scanning electron microscopy were each measured. The dependence of tensile strength, tensile modulus, and elongation at break on blend systems was obtained. The effects of composition and miscibility on the mechanical properties are discussed. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 472–476, 2006     

Poly(aryl ether sulfide)s by sulfide-activated nucleophilic aromatic substitution polymerization

Poly(aryl ether sulfide)s have been produced by nucleophilic aromatic substitution with phenoxide nucleophiles bisphenol A and bisphenol AF, and the activated arylfluorides bis(4-fluorophenyl)sulfide and 2,7-difluorothianthrene. The resulting polymers are thermally stable, amorphous materials that have been characterized by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and gel permeation chromatography (GPC). Moderate molecular weights have been achieved, representative of greater than 98% conversion of arylfluorides. The poly(aryl ether thianthrene)s are flame resistant and self extinguish within 0.2 s upon removal from a flame source. TGA of the poly(aryl ether thianthrene)s in an inert atmosphere result in a char yield greater than 50% at 750 °C. The flame resistant properties are more effectively modeled by TGA in an inert atmosphere as compared to TGA in an air atmosphere. The poly(aryl ether thianthrene)s are found to have high refractive index values, 1.61-1.70, depending on wavelength and bisphenol composition.     

Fluorinated poly(aryl thioether)s and poly(aryl sulfone)s derived from 2,3,4,5,6‐pentafluorobenzoic acid

Poly(aryl thioether)s (F‐PTEs) containing 2,3,5,6‐tetrafluoro‐1,4‐phenylene moiety and polar moiety, such as 1,3,4‐ozadiazole, ether ketone, and amide groups, were synthesized by nucleophilic aromatic substitution reaction of aryl fluorides and 4,4′‐thiobisbenzenthiol. F‐PTEs were amorphous with good thermal properties including high glass transition temperature (T_g) and thermal stability, solubility, and hydrophobicity. F‐PTEs were transformed into poly(aryl sulfone)s (F‐PSs) by the oxidation reaction with hydrogen peroxide in acetic acid. Because of the sulfone group, the T_gs of the F‐PSs were 30–40°C higher than those of the corresponding F‐PTEs. F‐PSs maintained solubility in polar aprotic solvents and exhibited hydrophobicity in spite of the content of polar sulfone groups due to the highly substituted fluorine atoms. These F‐PTEs and F‐PSs were a new class of high‐performance polymers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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.     

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     

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     

Synthesis and properties of amphiphilic poly(ethylene oxide)-grafted cardo poly(aryl ether sulfone) copolymers

A series of comb-type amphiphilic copolymers (PES-g-PEO) with a stiff poly(aryl ether sulfone) backbone and flexible PEO side chains was synthesized via a “grafting onto” technique. By controlling the monomer feed ratios, high molecular weight copolymers with a range of PEO side chain content were prepared and used to form tough and flexible membranes. The PES-g-PEO membranes displayed high thermal stability (T_d > 230 °C) and good mechanical properties. The water contact angles of the PES-g-PEO membranes ranged from 60.5° to 66.7°, 20° lower than those of poly(aryl ether sulfone) membranes (82-86°), indicating that the PEO side chains improved the hydrophilicity of the membranes. Wide-angle X-ray diffraction results indicated that the PES-g-PEO membranes possessed an amorphous structure, that is, crystallization of the PEO side chains did not occur. The Li-ion conductivity reached 2.26 × 10⁻⁴ S/cm at room temperature, much higher than that of the pure PEO-based system (10⁻⁶ S/cm), due to the presence of the amorphous PEO side chains between the PES backbones, which provided an effective Li-ion transport pathway.