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.     

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     

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。     

耐高温聚芳醚砜的合成与表征

以联苯甲醛与2,6-二甲基苯酚为原料合成了一种新型双酚单体,与4,4’-二氟二苯砜进行缩聚,得到了一种新型含联苯结构的聚芳醚砜聚合物。测试了聚合物的溶解性,并用^1H NMR、DSC、TGA、GPC等方法进行了表征。结果表明,所合成的聚合物在NMP、DMF、DMSO等强极性非质子溶剂及CH2C12、THF、CHCl3等普通溶剂中具有较好的溶解性;具有高的摩尔质量（Mn=4．3×10^4g／mol）;玻璃化温度（Tg）为261℃,5％的热分解温度为421℃,说明其具有突出的耐高温性能。     

新型特种工程塑料聚芳醚砜酮和聚芳醚砜热分解动力学及寿命预测

采用逐步聚合方法制备了新型特种工程塑料含二氮杂萘酮结构的聚芳醚砜酮［PPESK(1/1)］和聚芳醚砜(PPES).利用热失重(TGA)分析仪,氮气氛围中,多重加热扫描速率下的不定温法对PPESK(1/1)及PPES进行热分解动力学研究.根据Satava法得出,聚合物PPESK(1/1)分解反应机理为随机成核和随后生长,反应级数n=1;而聚合物PPES的热分解反应机理为相界面反应模式,反应级数n＝2.同时采用经典动力学方程Friedman、Kissinger-Akahira-Sunose(KAS)及Ozawa方程计算了热分解动力学参数(E_a,lnZ).重点考察升温速率、不同酮/砜比对PPESK（1/1）热稳定性影响,并且根据得到的动力学参数推测其在高温使用条件下的使用寿命及对热分解反应过程中“动力学补偿效应”（KCE）进行分析.     

聚芳醚腈砜的结构与热性能的研究

本文采用红外光谱方法对聚芳醚腈砜的结构进行了分析,并与间苯型聚芳醚砜的结构作了对比,利用ＴＧＡ,ＤＴＡ等热分析测试,对不同分子量聚芳醚腈砜的热氧稳定性,玻璃化转变温度等热性能进行了研究。     

聚芳醚砜酮纺丝溶液流变性能研究

研究了含二氮杂萘酮结构聚芳醚砜酮 (PPESK)的 N-甲基吡咯烷硐 (NMP)溶液体系的粘度对浓度、温度和切变速率以及砜酮比的依赖性。结果表明 ,该溶液的粘度随剪切速率的提高而降低 ,为非牛顿流体 ;粘度随溶液浓度的增大而增大 ,与浓度的高次幂成正比 ,随砜酮比的增加而下降 ;温度对粘度的影响服从 Arrhenius公式。用该溶液纺制的纤维经测定力学性能较好。     

纳米改性含氟聚芳醚酮聚合物的研制

文章从单体合成入手,通过纳米改性剂催化聚合制取纳米杂化高聚物。并以此为基体树脂开发研制出纳米瓷膜涂料。由于该目标产品突出地表现了卓越的耐高温高压热蒸汽渗透、高硬度超耐磨、抵御恶劣环境下允质腐蚀等一系列优异的理化性能,为石油天然气田井管道用的特种防护涂层提供了新型聚合物材料。     

纳米改性含氟聚芳醚酮聚合物的研制

文章从单体合成入手,通过纳米改性剂催化聚合制取纳米杂化高聚物,并以此为基体树脂开发研制出纳米瓷膜涂料。由于该目标产品突出地表现了卓越的耐高温高压热蒸汽渗透、高硬度超耐磨、抵御恶劣环境下介质腐蚀等一系列优异的理化性能,为石油天然气田井管道用的特种防护涂层提供了新型聚合物材料。     

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 a novel phthalazinone poly(aryl ether sulfone ketone) with carboxyl group

Soluble, thermally stable phthalazinone poly(aryl ether sulfone ketone)s (PPESKs) containing a carboxyl group in its side chain have been synthesized by the nucleophilic displacement reaction of 4‐(4‐hydroxylphenyl)‐1(2H)‐phthalazinone with bis(4‐chlorophenyl) sulfone, 4,4′‐difluoro‐benzophenone, and phenolphthalin. The polymerization reactions were conducted in sulfolane in the presence of K₂CO₃ to give high molecular weight polymers, which are soluble in solvent such as nitrobenzene and pyridine at room temperature and easily cast into flexible, yellow, and transparent film. The polymers are amorphous with high glass transition temperature. The decomposition temperature of the polymers are >400°C, which indicates high thermal stability. The crosslinking reaction of PPESK can occur by using dicyandiamide (Dicy) as curing agent. The apparent energy (ΔE) is 52.2 kJ/mol and reaction order (n) is close to 1.0. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1111–1114, 2003     

Synthesis and properties of poly(aryl ether sulfone ether ketone ketone) (PESEKK)

4,4′‐bis(Phenoxy)diphenyl sulfone (DPODPS) was synthesized by reaction of phenol with bis(4‐chlorophenyl) sulfone in tetramethylene sulfone in the presence of NaOH. Two poly(aryl ether sulfone ether ketone ketone)s (PESKKs) with high molecular weight were prepared by low temperature solution polycondensation of DPODPS and terephthaloyl chloride (TPC) or isophthaloyl chloride (IPC), respectively, in 1,2‐dichloroethane and in the presence of aluminum chloride (AlCl₃) and N‐methylpyrrolidone (NMP). The resulting polymers were characterized by various analytical techniques, such as FT‐IR, ¹H‐NMR, DSC, TG, and WAXD. The results show that the T_g and T_d of PESEKKs are much higher, but its T_m is lower than those of PEKK. The other results indicate that PESEKKs exhibit excellent thermostabilities at 300 ± 10°C. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 489–493, 2005     

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     

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。     

Preparation and characterization of soluble copoly(aryl ether ketone)s containing hindering structures

New copoly(aryl ether ketone)s have been synthesized by polycondensation of 2,2′,3,3′,6,6′‐hexaphenyl‐4,4′‐diphenol, 2,2′‐p‐hydroxyphenyl‐iso‐propane, and 4,4′‐difluorobenzophenone. The technology of ¹³C‐NMR was used to determine contents of the two bisphenols in the copolymers. Chain structure was characterized by illustrating average block length (L_A, L_C) in terms of portion of the triads (AKA, CKC, AKC). The obtained copoly(aryl ether ketone)s have the properties of excellent solubility, high heat‐resistance, good tensile strength, and good selectivity for gas permeability. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 20–24, 2000     

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