可溶性含氟聚芳醚酰胺的合成与性能研究

以自制的高纯二胺单体1,4-双(4.氨基-2-三氟甲基苯氧基)苯与3种商品化二酸单体经缩聚反应制得了一系列新型含氟聚芳醚酰胺(PEA).该含氟PEA表现出优良的溶解性能,室温下不仅可以溶于N-甲基-2-吡咯烷酮、N,N-二甲基乙酰胺、N,N-二甲基甲酰胺等强极性溶荆中,而且还可以溶于吡啶、四氢呋喃、环己酮等低沸点溶剂中.由该聚合物所制得的薄膜无色透明,截断波长在334～364nm之间,加400nm后具有高度透明性.该舍氟PEA还表现出良好的介电性能,介电常数为2.43-2.93(1 MHz).     

含3,3’,5,5’-四甲基结构的新型聚芳酰胺的合成与表征

摘 要：本文从分子设计的角度出发,以苯甲醛和2,6-二甲基苯胺为原料,经过一步法合成一种含四甲基结构的二胺单体。利用Yamazaki磷酰化法,将自制的二胺单体分别与对苯二甲酸（PTA）、间苯二甲酸(IPA)和二羧基联苯醚(OBA)三种二酸单体经一步缩聚得到了三种新型可溶性芳香聚芳酰胺,特性黏度在0.57~0.84dL/g之间。该聚芳酰胺表现出优异的溶解性能和光学性能：室温下不仅可以溶于高沸点的N-甲基-2-吡咯烷酮（NMP）、N, N-二甲基乙酰胺(DMAc)、N, N-二甲基甲酰胺(DMF)和二甲基亚砜(DMSO)中,还能溶于低沸点的氯仿（CHCl3）等有机溶剂中,而且大部分聚合物在这类溶剂中的溶解度可达10 wt% 以上。所制得的聚芳酰胺薄膜颜色浅、透明性高,截断波长在312~345 nm之间,500 nm处的透过率均超过80%。此外,该系列聚芳酰胺还表现出良好的热学性能和机械性能：玻璃化转变温度在338℃以上,空气和氮气中10%热失重在380℃和408℃以上;其薄膜的拉伸强度、断裂伸长率和起始模量分别在64~81MPa、8.0%~9.2 %和1.4~2.0GPa之间。     

基于酚酞结构共聚型高可溶性聚酰亚胺的合成与性能

以邻甲酚酞与2-氯-5-硝基三氟甲苯为起始原料,通过两步有机反应——芳香亲核取代和氧化还原反应得到芳香二胺单体——4,4"-(2,2’三氟甲基)-二氨基苯氧基-3,3"-二甲基酚酞。利用共聚改性的思路,由两种二胺单体〔4,4"-(2,2"三氟甲基)-二氨基苯氧基-3,3"-二甲基酚酞和2,6-二氨基甲苯〕与一种二酐单体3,3",4,4"-二苯醚四甲酸二酐（ODPA）通过不同投料比以一步法高温缩聚制备得到同时含酚酞、三氟甲基和烷基结构系列共聚型聚酰亚胺。该系列共聚型聚酰亚胺具有优异的溶解性,在室温下不仅可溶于常见的高沸点溶剂：N-甲基吡咯烷酮（NMP）,N,N-二甲基乙酰胺（DMAc）、N,N-二甲基甲酰胺（DMF）和二甲基亚砜（DMSO）,在低沸点溶剂氯仿（CHCl3）、二氯甲烷（CH2Cl2）和四氢呋喃（THF）中也表现出优异的溶解性,可便利地通过其溶液浇筑制备得到系列高性能聚酰亚胺膜材料。该类膜材料玻璃化转变温度在275~314 ℃,其在N2和O2氛围中热失重10%时的温度分别为477~507 ℃和477~49 0 ℃。该类膜材料具有低的介电常数和良好的力学性能：其在1 MHz下介电常数在2.69~2.92之间,拉伸强度、弹性模量和断裂伸长率分别在80~92 MPa、1.2~1.8 GPa和9.2 %~13.5%之间。     

MM-HPPZ/NDA/TPA聚芳酰胺的合成与性能

采用新型的含间甲基取代杂萘联苯结构的二胺2-(4-氨基苯基)-4-[2-甲基-4-(4-氨基苯氧基)卜2,3-二氮杂萘-1-酮为单体,与2,6-萘二甲酸(NDA)进行溶液缩聚制备了新型聚芳酰胺,以对苯二甲酸(17PA)为第三单体对聚芳酰胺进行了共缩聚改性,并研究了TPA的含量及结构对聚芳酰胺性能的影响。n(NDA)/n（TPA)为4：6时,共聚物特性黏数最大为1．70dL/g。合成的聚芳酰胺具有良好的溶解性,可溶于N-甲基吡咯烷酮、N,N-二甲基乙酰胺等非质子极性溶剂中,玻璃化转变温度大于320℃,5％热失重温度大于435℃。     

含氟聚酰亚胺的制备及性能研究

采用新型含氟二胺单体2,2-双[4-(4-氨基苯氧基苯)]六氟丙烷(HFBAPP),通过两步法缩聚反应得到一类新型含氟及非共面结构的可溶性聚酰亚胺,并对其结构和性能进行表征。结果表明,该聚酰亚胺具有较好的溶解性,能较好的溶于常规有机溶剂,如N,N-二甲基乙酰胺(DMAc)、N,N-二甲基甲酰胺(DMF)等;耐热性能突出,玻璃化转变温度高于352℃,氮气中5%热失重温度在477℃以上。     

新型含磷可溶性共聚芳酰胺的合成

以双（对-羧苯基）苯基氧化膦（BCPPO）,对苯二甲酸（TPA）和4,4′-二氨基二苯醚（ODA）为原料,通过Yamazaki膦酰化法合成聚芳酰胺。研究了反应温度、单体浓度和溶剂体系对聚合物相对分子质量的影响,确定了聚合反应的最佳工艺条件为：单体摩尔浓度为0．3mol／L,N-甲基呲咯烷酮（NMP）的用量是呲啶的3倍,聚合反应的温度为110℃。采用红外光谱对合成聚合物进行了结构表征,合成的聚芳酰胺可溶于N-甲基吡咯烷酮（NMP）、N,N-二甲基甲酰胺（DMF）、N,N-二甲基乙酰胺（DMAC）等有机溶剂中。     

基于酚酞结构高可溶性聚酰亚胺的合成与性能

以百里香酚酞、对氟硝基苯为起始原料,通过芳香亲核取代和氧化还原反应得到新型芳香二胺单体5,5’-二异丙基-4,4’-二氨基苯氧基-2,2’-二甲基酚酞。该二胺单体分别与3,3’,4,4’-二苯醚四甲酸二酐、3,3’,4,4’-二苯酮四羧酸二酐和3,3’,4,4’-联苯四甲酸二酐以一步法高温缩聚制得了一系列同时含酚酞Cardo结构及异丙基和甲基侧基的高可溶性聚酰亚胺(PI-1、PI-2和PI-3)。该系列聚酰亚胺具有优异的溶解性,室温下不仅可溶于高沸点溶剂N-甲基吡咯烷酮、N,N-二甲基乙酰胺、N,N-二甲基甲酰胺、二甲基亚砜,而且能溶于低沸点溶剂氯仿,二氯甲烷和四氢呋喃,可通过其溶液浇铸制得一系列高性能聚酰亚胺薄膜。所制聚酰亚胺薄膜具有较高的光学透明性,截断波长在324～365 nm之间,450 nm的透过率在56%～78%之间。该系列薄膜玻璃化转变温度在266～289℃之间,在N₂和O₂下10%热失重温度均≥432℃。其拉伸强度在77～95 MPa之间,断裂伸长率在9.1%～13.0%之间,1 MHz下介电常数为2.79～3.01 F/m,...     

萃取精馏分离环己烷-环己烯溶剂的筛选

通过一个简单的汽液平衡装置,研究了N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、二甲基亚砜、γ-丁内酯、N-甲酰基吗啉溶剂以及混合溶剂在萃取精馏分离环己烷-环己烯过程中的分离性能。结果发现二甲基亚砜单独作为溶剂时表现出最佳的分离性能。溶解性好的溶剂往往分离性能一般,而分离性能好的溶剂又存在溶解性差的问题。进一步通过萃取精馏实验证明了溶剂的实际分离效果由溶剂的分离性能与溶解性共同决定。结果表明:二甲基亚砜和N,N-二甲基甲酰胺混合溶剂表现最佳的实际分离效果。     

新型含吡啶环二胺及其可溶透明性氟化聚酰亚胺的合成与表征

以4-三氟甲基苯甲醛和3-(4-硝基苯氧基)苯乙酮(m,p-NPAP)为原料,通过改进的Chichibabin反应制备了硝基化合物4-(4-三氟甲基苯基)-2,6-双[3-(4-硝基苯氧基)苯基]吡啶(m,p-3FPNPP),再用Pd/C和水合肼将m,p-3FPNPP进行还原,成功制备了一种新型含吡啶环的芳香二胺4-(4-三氟甲基苯基)-2,6-双[3-(4-胺基苯氧基)苯基]吡啶(m,p-3FPAPP)。以m,p-3FPAPP作为二胺,3,3′,4,4′-二苯醚四羧酸二酐(ODPA)作为二酐,N,N-二甲基甲酰胺(DMF)为溶剂,通过常规的两步法,经热或者化学亚胺化形成聚酰亚胺,制得了一种新型的含吡啶环聚酰亚胺。所得聚酰胺酸和聚酰亚胺的粘度分别为0.78 dL/g和0.65 dL/g。化学亚胺化所得的聚酰亚胺速溶于常见有机溶剂如DMF、N,N-二甲基乙酰胺(DMAc)、N-甲基-2-吡咯烷酮(NMP)、四氢呋喃(THF)等。制得了柔韧的聚酰亚胺膜,膜有很好的热稳定性,玻璃化转变温度(Tg)为234.4℃,氮气氛中10%失重温度为575.3℃,膜有很好的光学透明性,截止波长为369 nm,同时,膜还有较好的力学性能,拉伸强度为96.4 MPa,拉伸模量为1.63 GPa,断裂伸长率为9.2%,膜的吸水率为0.68%。     

一种芳香族双季铵盐的合成

本文以N,N-二甲基苯胺、1,4-二溴丁烷为原料制备出二溴代-N,N-双(二甲基苯基)丁二胺。实验考察了该双季铵盐的合成工艺条件,从反应时间、所用溶剂、反应物之间物料比等因素对合成产物的影响,筛选出了较为适宜的反应条件。     

Synthesis and characterization of novel polyamides derived from 1,4-bis((4-amino-2-(trifluoromethyl)phenoxy)methyl)cyclohexane and aromatic dicarboxylic acids

A new aromatic diamine with a trifluoromethyl pendent group, 1,4-bis((4-amino-2-(trifluoromethyl)phenoxy)methyl)cyclohexane, was successfully synthesized in two steps from 1,4-cyclohexanedimethanol and 2-chloro-5-nitrobenzotrifluoride as starting materials. And the newly obtained diamine with various aromatic dicarboxylic acids, including isophthalic acid (IPA), 2,2-bis(4-carboxy-phenyl)hexafluoropropane (6FA) and 4,4′-oxydibenzoic acid (OBA), were polymerized, respectively via the usual Yamazaki reaction to prepare a series of fluorinated polyamides. The resulting polymers had inherent viscosities ranging from 1.85 to 2.36 dL/g. All the polymers showed outstanding solubility and could be easily dissolved in amide-type polar aprotic solvents [e.g., N-methyl-2-pyrrolidone (NMP), DMAc, and DMF] and even dissolved in less polar solvents (e.g., pyridine, and tetrahydrofuran). These polymers could also be easily be cast into transparent, tough and flexible films with tensile strengths of 76.5–82.3 MPa, Young’s moduli of 1.64–1.85 GPa, and elongations at break of 10–12%. In addition, these polyamides films exhibited low dielectric constants of 2.37–2.53 at 100 MHz, low water absorptions in the range of 1.54–2.13%, and high transparency with an ultraviolet–visible absorption cut-off wavelength in the 326–333 nm range. Furthermore these polyamides still retained good thermal stability. These combined outstanding features make these obtained polyamides competitive for advanced microelectronic applications.     

Polyamides containing quinoxaline moiety

A new quinoxaline moiety containing aromatic diamine; 2,3-bis[4-(4-aminophenoxy)phenyl]quinoxaline (APQ) was synthesized starting from 4-methoxybenzaldehyde and was characterized by IR, ¹H, ¹³C NMR and Mass spectrometry. Five new polyamides were synthesized by polycondensation of various aliphatic diacid / aromatic diacids namely, azelaic acid, bis(4-carboxyphenyl)dimethylsilane, 4,4′-oxybis(benzoicacid), isophthalic acid and terephthalic acid with APQ by Yamazaki’s phosphorylation method using triphenyl phosphite as condensing agent. The polyamides were characterized by IR spectroscopy, solubility tests, inherent viscosity, X-ray diffraction technique, differential scanning colorimetry and thermogravimetric analysis. The polyamides had inherent viscosities in the range 0.39–0.45 dL/g in N, N-dimethylacetamide at 30?±?0.1?°C. The polyamides were soluble in polar aprotic solvents such as N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone. X-Ray diffraction studies showed that polyamides were amorphous in nature. The polyamides showed glass transition temperatures in the range 104–205?°C, according to differential scanning calorimetry. Thermogravimetric analysis exhibited initial decomposition temperatures above 348?°C; indicating that these polyamides possessed excellent thermal stability.     

Preparation and morphology distinguishing of novel ZnO ultrafine particle filled nanocomposites contain new poly(amide-imide) via ultrasonic process

New triptycene-containing polyamides were prepared from 1,4-bis(4-carboxyphenoxy)triptycene with aromatic diamines or from 1,4-bis(4-aminophenoxy)triptycene with aromatic dicarboxylic acids via the phosphorylation polyamidation reaction. These polyamides were essentially amorphous and showed a significantly increased solubility as compared with their analogs without the triptycene units. All the polyamides could be solution-cast into flexible and tough films. They also showed good thermal stability with glass transition temperatures of 252?C295?°C and 10?% weight loss temperatures higher than 540?°C. These polyamides are considered to be promising processable high-temperature polymeric materials.     

Synthesis and characterization of novel fluorinated polyimides derived from 4,4′-[2,2,2-trifluoro-1-(3,5-ditrifluoromethylphenyl)ethylidene]diphthalic anhydride and aromatic diamines

A novel fluorinated aromatic dianhydride, 4,4′-[2,2,2-trifluoro-1-(3,5-ditrifluoromethylphenyl) ethylidene] diphthalic anhydride (9FDA), was synthesized, which was employed to polycondense with various aromatic diamines, including 4,4′-oxydianiline, 1,4-bis(4-aminophenoxy) benzene, 3,4′-oxydianiline and 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene to produce a series of fluorinated aromatic polyimides. The fluorinated polyimides obtained had inherent viscosities ranged of 0.61-1.14 dL/g and were easily dissolved both in polar aprotic solvents and in low boiling point common solvents. High quality polyimide films could be prepared by casting the polyimide solution on glass plate followed by thermal baking to remove the organic solvents and volatile completely. Experimental results indicated that the fluorinated polyimides exhibited good thermal stability with glass transition temperature ranged of 245-283 °C and temperature at 5% weight loss of 536-546 °C. Moreover, the polyimide films showed outstanding mechanical properties with the tensile strengths of 87.7-102.7 MPa and elongation at breaks of 5.0-7.8%, good dielectric properties with low dielectric constants of 2.71-2.97 and low dissipation factor in the range of 0.0013-0.0028.     

Organosoluble and light-colored fluorinated semialicyclic polyimide derived from 1,2,3,4-cyclobutanetetracarboxylic dianhydride

In this study, the alicyclic dianhydrides 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) was polymerized with seven kinds of fluorinated aromatic diamines, 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl (1), 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene (2), 1,4-bis(4-amino-2-trifluoromethylphenoxy)diphenyl (3), 1,4-bis(4-amino-2-trifluoromethylphenoxy) diphenyl ether (4), 2,2-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane (5), 4,4′-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfone (6), and 2,7-bis(4-amino-2-trifluoromethylphenoxy)naphthalene (7), via a two-step polycondensation procedure to prepare seven kinds of fluorinated semialicyclic polyimides (PI) PI-1 ∼ PI-7. The structures of these polyimides were confirmed by infrared spectroscopy (IR). Solubility of the polyimides was tested in various organic solvents and their thermal properties were investigated by dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA). Ultraviolet-visible spectra (UV-vis) and near infrared absorption spectra (NIR) were obtained to evaluate the optical properties of these polyimides. The obtained polyimides PI-1 ∼ PI-7 displayed excellent solubility in a variety of organic solvents; they were readily soluble in amide-type polar solvent. These polyimide films exhibited good optical transparency in the visible light region (400–700 nm) with the transmittance higher than 80% at 450 nm, and these polyimide films showed little absorption at the optocommunication wavelengths of 1.30 and 1.55 μm. These polyimides showed good thermal stability with the 10% thermal decomposing temperatures higher than 443°C in nitrogen and the glass transition temperatures higher than 265°C. In addition, the effect of the structure of fluorinated diamines on the properties of polyimide films was also compared. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and characterization of aromatic-alipathic polyamides containing tetraphenylthiophene units into the backbone

Summary Aromatic-aliphatic polyamides were prepared from 2, 5-bis(4-carboxyethylcarbonylphenyl)-3,4-diphenylthiophene (BCDT) with few commercial diamines by using Yamazaki's phosphorylation reaction. The polymers were obtained in good yields and were characterized by solubility tests, viscosity measurements, IR spectroscopy, thermal analysis and X-ray diffraction studies. These polyamides had inherent viscosities in the range of 0.35 to 0.70 dl/g and were amorphous in nature. All the polyamides were readily soluble in solvents such as N,N-dimethylacetamide, N-methyl-2-pyrrolidinone, N,N-dimethylformamide, nitrobenzene, hexamethylphosphoramide, m-cresol, sulphuric acid and did not lose weight below 300°C in air. NCL Communication No:-4815     

一类高透明含氟共聚型聚酰亚胺的合成与表征

以2,2′-双(三氟甲基)-4,4′-二氨基联苯(TFMB)、4,4-二氨基二苯醚(ODA)和3, 3′,4,4′-二苯醚四甲酸二酐(ODPA)为原料,间甲酚为溶剂,按不同的配比,采用一步法制备了一系列低成本含氟共聚型聚酰亚胺CPI-1～CPI-4,进一步制备成膜。通过红外光谱仪、核磁共振波谱仪对该系列含氟聚酰亚胺的结构进行了表征确认。采用UV光度计、TGA、DSC、拉伸性能试验机对其溶解性能、光学性能、热性能、机械性能进行了测试。结果表明,该系列含氟聚酰亚胺室温下能溶于二甲基亚砜(DMSO)、N,N-二甲基乙酰胺(DMAc)、三氯甲烷(CHCl_3)等有机溶剂,具有较好的溶解性和成膜性。所制薄膜具有优良的光学透明性,在紫外光波长400nm时的透光率均在70%以上。CPI-1～CPI-4的起始分解温度均大于500℃,N_2氛围下800℃的质量残留百分数均在52%以上,玻璃化转变温度在166～170℃。此外,CPI-1～CPI-4薄膜的拉伸强度在89.8～105.3MPa,弹性模量在1.3～1.7 GPa,断裂伸长率在9.7%～18.4%,表现出较好的机械性能。     

Synthesis and characterization of novel soluble fluorinated aromatic polyamides derived from fluorinated isophthaloyl dichlorides and aromatic diamines

Two series of fluorinated aromatic polyamides derived from two novel monomers, 5-(4-trifluoromethylphenoxy)isophthaloyl dichloride (3FPC) and 5-(3,5-bistrifluoromethyl-phenoxy)isophthaloyl dichloride (6FPC) with various aromatic diamines were synthesized and characterized. Experimental results indicated that the fluorinated aromatic polyamides showed good solubility in many organic solvents. The solubility of the polyamides was affected by the trifluoromethyl substituents and the pendent phenoxy groups in the polymer backbone. The fluorinated polyamides have good thermal stability with the glass transition temperature of 206-285 °C, the temperature at 5% weight loss of 442-460 °C in nitrogen. The polyamide films also exhibited good mechanical properties and excellent electrical and dielectric properties. The fluorinated groups in the polymer backbone have played an important role in the improvement of electrical and dielectric performance of polymer.     

Synthesis and Characterization of Polyamides Based on s-Triazine Moiety

Seven polyamides containing s-triazine rings in the main chain were synthesized by high temperature polycondensation of 2-(β-naphthylamino)-4,6-bis(naphthoxy-3-carbonyl chloride)-s-triazine [NANCCT] with various aromatic diamines such as 4,4′-diaminodiphenyl [DADP], 4,4′-diaminodiphenylamide [DADPA], 4,4′-diaminodiphenylsulphone [DADPS], 4,4′-diaminodiphenylsulphonamide [DADPSA], 4,4′-diaminodiphenyl methane [DADPM], 2,4-diamino toluene [DAT] and p-phenylene diamine [PPDA]. All the polyamides were characterized by solubility tests, density measurements, viscosity measurements, IR spectra, NMR spectra, and thermogravimetric analysis. The polyamides had inherent viscosities in the range 0.88–1.16 g/dL in N,N′-dimethyl formamide at room temperature (30°C). All the polyamides showed good thermal stability at high temperatures and most of them were soluble readily at room temperature in polar solvents.