含三氟甲基聚酰亚胺的合成与性能研究

通过在4,4′-二氨基二苯醚(4,4-′ODA)单体中引入三氟甲基合成了一种新型二胺单体2-三氟甲基-4,4′-二氨基二苯醚(3FODA),该单体具有良好的溶解性和高的反应活性,使用3FODA替代4,4′-二氨基二苯甲烷(MDA)制备了PMR热固性聚酰亚胺树脂.树脂溶液高浓度低粘度,具有室温下良好的储存稳定性;树脂具有很好的加工性能,成型后的模压件显示了优异的热性能和耐热氧化稳定性,玻璃化转变温度在336~379℃之间;此外树脂具有较好的电性能和较低的吸水率.     

新型乙炔封端聚酰亚胺的制备及性能

用双酚A型二醚二酐(BPADA)和3-乙炔基苯胺(m-APA)进行缩聚反应合成了乙炔基封端的聚酰亚胺预聚体, 并对预聚体的熔体黏度、稳定性和热性能等进行研究. 结果表明, 此类预聚体具有较宽的加工窗口和较低的加工温度, 适合模压成型工艺制备树脂基复合材料. 预聚体经250 ℃固化后显示了优异的热性能, 动态力学分析显示其玻璃化转变温度为363 ℃, 在氮气和空气气氛下5%热失重温度分别为490和492 ℃.     

4-苯乙炔基苯胺封端聚酰亚胺树脂的合成与性能研究

使用4-苯乙炔基苯胺(4-PEA)作为反应性封端剂,和3,3′,4,4′-二苯醚四酸二酐(ODPA),3,3′,4,4′-联苯四酸二酐(BPDA),1,4-双(4′-氨基-2′-三氟甲基苯氧基)苯(BTPB)和3,4′-二氨基二苯醚(3,4-′ODA)反应合成了系列4-苯乙炔基苯基封端的聚酰亚胺低聚物,对低聚物的化学结构、热性能和熔体粘度以及固化后树脂的热性能等进行了研究.实验结果表明,低聚物均具有一定的结晶性,含有ODPA的聚酰亚胺低聚物较之含有BPDA的低聚物具有更低的熔体粘度,且出现最低熔体粘度的温度更低;固化后的树脂表现出良好的热性能,含有BPDA的树脂具有更高的玻璃化转变温度;系列低聚物中二胺单体的比例对于低聚物的熔体粘度和固化后树脂的热稳定性有一定影响.     

用于树脂传递模塑成型的苯乙炔封端的酰亚胺预聚体制备

采用4-苯乙炔苯酐(4-PEPA)、1,3-二(3-氨基苯氧基-4′-苯酰基)苯(BABB)和4,4′-双(3-氨基苯氧基)二苯甲酮(APBP)合成了两种苯乙炔苯酐封端的聚酰亚胺预聚体PI-1和PI-2, 并对预聚体的熔体黏度、稳定性、固化后树脂的热稳定性能和机械性能等进行了研究. 结果表明, 制备的预聚体具有较高产率(>95%); 与其它PEPA封端的聚酰亚胺相比, 两种预聚物在较低温度(200 ℃)时均具有很低的熔体黏度(1 Pa·s)和良好的熔体黏度稳定性, 固化后玻璃化温度达到300 ℃以上, 可适用于树脂传递模塑(RTM)成型制备耐高温高性能树脂基复合材料, 且在成型工艺上有了很大改善; 固化后的树脂具有优异的热稳定性能和良好的机械性能.     

萘乙炔基封端的含硅聚酰亚胺的制备与性能

为了获得兼具良好热性能和加工性能的聚酰亚胺树脂,设计合成了不对称二胺(3-氨基-苯基)-(4’-氨基-苯基)-乙炔(AMPA),含萘环的封端剂3-(萘-1-乙炔基)苯胺(NAA)以及含硅二酐双(3,4-二羧基苯基)二甲基硅烷二酐.为研究结构与性能的关系,引入4,4’-双邻苯二甲酸酐(ODPA)和间氨基苯乙炔(APA)为对照二酐和封端剂,制备了一系列分子链中含硅和内炔基团的聚酰亚胺树脂PI-Si-Ⅰ(以APA为封端剂)和PI-Si-Ⅱ(以NAA为封端剂),以及与之相对照的树脂PI-O-Ⅰ和PI-O-Ⅱ(二酐单体为ODPA). PI-Si树脂在常见溶剂如四氢呋喃中具有很好的溶解度,而PI-Si-Ⅱ树脂更是具有低的熔体黏度和100℃宽的加工窗口.热失重的结果显示固化树脂具有良好的耐热性能,5 wt%热失重温度(T_d5)在547℃左右,质量残留率在79%左右;热裂解分析结果表明在聚酰亚胺主链中引入的硅和内炔基团在高温环境中形成硅氧硅结构和苯环等刚性结构,从而提高树脂的耐热性.     

全内炔型含硅聚三唑树脂的制备与性能

采用格氏试剂法制备了苯乙炔封端型含硅芳炔(PTPSA),并采用傅里叶转换红外光谱(FT-IR)、核磁共振氢谱(~1 H-NMR)和差示扫描量热法(DSC)表征了其结构。以PTPSA和1,3,5-三叠氮甲基-2,4,6-三甲基苯(TAMIMB)为原料,制备了新型全内炔型含硅聚三唑树脂(P-PTA3)。利用FT-IR、DSC、动态力学分析(DMA)和热重分析(TGA)研究了树脂的固化行为及热性能,通过测试凝胶时间随贮存时间的变化研究了树脂溶液的贮存稳定性。结果表明:树脂固化物的玻璃化转变温度(Tg)可达304℃,失重率5%时的温度(Td5)达330℃以上。P-PTA3树脂溶液在35℃和25℃下贮存时间分别超过20d和40d。单向碳纤维T700/P-PTA3复合材料常温下的弯曲强度为1 875MPa,弯曲模量为135.5GPa,180℃下弯曲强度保留率为75%。     

苯乙炔封端的可交联含氟聚芳醚的合成及性能

从光电集成器件对于材料性能的需要出发 ,我们相继合成了一系列可溶性的含氟聚芳醚和聚芳醚酮[1～ 5] .为了满足器件的多层化制备过程以及使器件成型后具有优异的性能 ,本文在间三氟甲基苯取代的聚芳醚 (1 1 F- PAE)中引进可交联的苯乙炔端基 ,合成了可热交联的高含氟量聚芳醚 ,并对其性能进行了初步研究 .1　实验部分1 .1　试剂与仪器　 4-苯乙炔苯酚 (PEP)按文献 [6 ]方法制备 ;3 -氟甲基苯代对苯二酚 (3 F- PH)按文献[2 ]方法制备 ;十氟联苯 ,Aldrich公司 ,99%;无水碳酸钾 ,A.R.级 ,天津化学试剂厂 ;甲苯 ,A.R.级 ,北京化工厂 ;N-…     

三(3-乙炔基苯胺)-苯基硅烷改性含硅芳炔树脂的性能

以苯基三氯硅烷、3-氨基苯乙炔为原料,通过胺解反应合成了三(3-乙炔基苯胺)苯基硅烷(SZTA),并通过傅里叶变换红外光谱(FT-IR)和核磁共振氢谱(1 H-NMR)表征了其结构。随后通过熔融共混的方法制备了不同配比的改性含硅芳炔树脂(PSA/SZTA),借助黏度计、流变仪、差示扫描量热仪(DSC)、电子万能试验机、热重分析仪(TG)等考察了改性树脂的工艺性能、固化特性、弯曲性能、热稳定性能和热解动力学等。结果显示,引入SZTA后,改性PSA树脂的黏度降低62%;改性PSA树脂固化物的弯曲强度最高达到34.6MPa,比未改性的PSA树脂提高了约54%;且改性树脂固化物在N_2中的5%热失重温度(T_(d5))均高于500℃,保持了良好的耐热性能;PSA/SZTA-20固化物的热解表观活化能(Ea)的平均值为249kJ/mol。     

基于甲基三苯乙炔基硅烷的新型聚三唑树脂的制备与性能

首先采用格氏试剂法合成了甲基三苯乙炔基硅烷(MTPES),通过傅里叶变换红外光谱(FT-IR)、核磁共振氢谱(1 H-NMR)对其结构进行了表征。然后以MTPES和4,4’-二叠氮甲基联苯(BAMBP)为原料制备了新型聚三唑树脂(MPTA)。利用FT-IR和差示扫描量热(DSC)研究了MPTA树脂的固化行为,通过动态力学热分析(DMA)和热重分析(TG)研究了炔基与叠氮基配比对树脂热性能的影响,并通过测试凝胶时间随贮存时间的变化研究了树脂及其四氢呋喃(THF)溶液的贮存稳定性。结果表明,固化后的树脂玻璃化转变温度(Tg)达到236℃,在氮气中的5%热失重温度(T_(d5))在320℃左右。MPTA树脂在35℃和25℃下分别贮存7d和20d后,100℃下树脂的凝胶时间分别为40min和25min,MPTA树脂的THF溶液在同样条件下贮存28d后,凝胶时间分别为54min和61min,具有比现有聚三唑树脂更好的贮存稳定性。单向T700碳纤维-MPTA复合材料常温下的弯曲强度为1 660 MPa,弯曲模量为129 GPa,150℃下的弯曲强度保留率为70%。     

4-苯乙炔苯酐封端聚酰亚胺树脂的合成与性能研究

使用3,3′,4,4′-二苯醚四酸二酐(ODPA)、3,3′,4,4′-联苯四酸二酐(BPDA)、1,3-双(4-氨基苯氧基)苯(1,3,4-APB)、3,4′-二氨基二苯醚(3,4′-ODA)和反应性封端剂4-苯乙炔苯酐(4-PEPA)合成了设计分子量为5000的系列苯乙炔基封端的聚酰亚胺低聚物,并使用XRD、DSC、TGA、FT-IR、DMA和流变仪等对低聚物的化学结构、热性能和熔体性能,固化后树脂的热性能和力学性能进行了测试.研究结果表明基于ODPA的低聚物具有低的熔体粘度和良好的熔体粘度稳定性,固化后的树脂具有很高的热失重温度,较高的玻璃化转变温度以及良好的力学性能尤其是高的断裂伸长率(>10%);基于BPDA的低聚物具有一定的结晶性,其结晶熔融温度与苯乙炔基固化交联温度相近,影响了材料的成型工艺性能.     

耐高温交联侧基苯乙炔封端酰亚胺预聚体

合成了含有苯乙炔基的二胺单体 3,5-二氨基-4'-苯乙炔苯甲酮(DPEB), 并与3,3',4,4'-联苯四酸二酐(s-BPDA)和1,4-双(4'-氨基苯氧基)-2-(苯基)苯(p-TPEQ)进行了缩聚反应, 以4-苯乙炔苯酐作为封端剂, 合成了交联侧基苯乙炔封端酰亚胺预聚体(n=4). DSC测试结果表明, 引入交联侧基后预聚体依然保持着较宽的加工窗口. 利用所合成的预聚体在370℃热压1 h制备了热固性薄膜. DMA测试结果表明, 引入交联侧基的预聚体树脂具有更高的玻璃化转变温度, 并且其储存模量在玻璃化转变后有很好的保持.     

Meltable phenylethynyl-capped oligoimide resins derived from 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene and 3,4′-oxydianiline

A series of meltable oligoimide resins with controlled molecular weights by reactive phenylethynyl endcapping groups have been prepared by the thermal polycondensation of 3,3′,4,4′-biphenyltetracarboxylic dianhydride (s-BPDA) with the aromatic diamine mixtures consisting of different mole ratios of 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene (1,4,4-6FAPB) and 3,4′-oxydianiline (3,4′-ODA) in the presence of 4-phenylethynylphthalic anhydride (PEPA) as molecular weight-controlling and reactive endcapping reagent. Experimental results indicated that the molecular weight-controlled oligoimide resins were mixtures containing a series of biphenylethynyl-endcapped oligoimides with different chemical structures and different molecular weights. The typical oligoimide resins could be melted at temperatures of 300 °C to yield stable molten fluid with melt viscosity of 13.4 Pa s, which was suitable for melt processing. The molten oligoimide resins could be further polymer chain extended and crosslinked by thermal curing of the reactive phenylethynyl groups to give strong and tough thermosetted polyimides. Thus, the oligoimide resin with calculated molecular weight of 2500 exhibited not only good meltability with low melt viscosity, but also high melt stability and fluidability at temperatures of <300 °C. After thermal curing, the obtained thermosetted polyimide showed high glass transition temperature (>316 °C, DMA), excellent thermal stability with initial thermal decomposition temperature of 588 °C and good mechanical properties with flexural strength of 159.1 MPa, flexural moduli of 3.3 GPa, tensile strength of 94.7 MPa and elongation at breakage of 9.0%.     

3‐Phenylethynyl phthalimide end‐capped imide oligomers and the cured polymers

In the past decades, 4‐phenylethynyl phthalic anhydride (4‐PEPA) has been the most important endcapper used for thermoset polyimide. As the isomer of4‐PEPA, 3‐phenylethynyl phthalic anhydride (3‐PEPA) has attracted our interest. In this article, 3‐PEPA was synthesized and a comparative study with 4‐PEPA on curing temperature, curing rate, thermal and mechanical properties of oligomers and cured polymers was presented. The new phenylethynyl endcapped model compound, N‐phenyl‐3‐phenylethynyl phthalimide, was synthesized and characterized. The molecular structure of model compound was determined via single‐crystal X‐ray diffraction and the thermal curing process was investigated by Fourier transform infrared. Differential scanning calorimetry clearly showed that the model compound from 3‐PEPA had about 20 °C higher curing onset and peak temperature than the 4‐PEPA analog. This result was further proved by the dynamic rheological analysis that the temperature of minimum viscosity for oligomers end‐capped with 3‐PEPA was above 20 °C higher than that of the corresponding 4‐PEPA endcapped oligomers with the same calculated number average molecular weight. The cured polymer from 3‐PEPA displayed slightly higher thermal oxidative stability than those from 4‐PEPA by thermogravimetric analysis. The thermal curing kinetics of 3‐PEPA endcapped oligomer (OI‐5) and 4‐PEPA endcapped oligomer (OI‐6) fitted a first‐order rate law quite well and revealed a similar rate acceleration trend. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4227–4235, 2008     

Phenylethynyl-terminated Imide Oligomers Modified by Reactive Diluent for Resin Transfer Molding Application

To meet the processing requirements of resin transfer moulding(RTM)technology,reactive diluent containing m-phenylene moiety was synthesized to physically mixed with phenylethynyl terminated cooligoimides with well-designed molecular weights of 1500-2500 g/mol derived from 4,4’-(hexafluoroisopropylidene)diphthalic anhydride(6 FDA),3,4’-oxydianiline(3,4’-ODA)and m-phenylenediamine(m-PDA).This blend shows low minimum melting viscosity(<1 Pa·s)and enlarged processing temperature window(260–361℃).FPI-R-1 stays below 1 Pa·s for2 h at 270℃.The relationship between the molecular weight of the blend and its melting stability was first explored.Blending oligoimides with lower molecular weights exhibit better melting stability.Upon curing at 380℃for 2 h,the thermosetting polyimide resin demonstrates superior heat resistance(T_g=420-426℃).     

异构化对二苯醚二酐/二苯醚二胺聚酰亚胺结晶行为的影响

合成了一系列基于4,4-′ODPA,3,4-′ODPA以及3,3-′ODPA 3种异构二苯醚二酐单体的异构聚酰亚胺,以苯酐(PA)作为封端剂来控制分子量.用DSC和WAXD为主要手段研究了这几种异构聚酰亚胺的结晶行为.研究发现聚酰亚胺4,4-′ODPA/ODA(二苯醚二胺)在分子量较低的情况下能够在热处理,退火或剪切作用下结晶.并且升高热处理温度和延长热处理时间有利于结晶的完善,在玻璃化温度以上施加剪切能够加速聚酰亚胺的结晶.而对于其他的两种异构体3,4-′ODPA/ODA以及3,3-′ODPA/ODA无论是经过热处理还是施加外力剪切都未能使其结晶.     

Phenylethynyl terminated oligoimides derived from 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride and their adhesive properties

A series of phenylethynyl terminated oligoimides based on 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride (DSDA), m-phenylene diamine (m-PDA) or/and 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene (6FAPB) with calculated molecular weight of 5000 g mol⁻¹ were synthesized. The effect of molecular structure on solubility and melt viscosity of oligoimides as well as the thermal properties of cured polyimide resins was investigated. Experimental results indicated that the oligoimides have good solubility in strong polar solvents to afford homogeneous solutions with the solid content as high as 50 wt%. The oligoimides exhibited better solubility and lower minimum melt viscosity at relatively lower temperature with the incorporation of flexible 6FAPB. These oligoimides could be thermally cured at 320-380 °C to give thermosetted resins. The cured resins have good thermal stability with the glass transition temperatures of 278-329 °C and the onset decomposition temperatures higher than 500 °C. Adhesive properties of polyimides adhered to stainless steel at various conditions were evaluated by lap shear strength test. It was found that the LSS at room temperature increased with the molar ratio of 6FAPB increasing. The polyimides with combination of rigid and flexible structures exhibited good adhesive properties. With the increasing of curing temperature, the lap shear strength of polyimides at elevated temperature maintained at a high level due to the formation of strong bond.     

Modeling of oxidative development in PMR-15 resin

A multidisciplinary approach focused on models and processes to predict the performance and life expectancy of high-temperature polymer matrix composite (HTPMC) materials used in a variety of aerospace applications is being developed. Emphasis is on the implementation and extension of hierarchical models to represent the polymer behavior/properties as a function of the degradation state. Neat resin specimens of high-temperature polyimide PMR-15 have been evaluated for various aging conditions. Characterization of the properties of the polyimide is focused on development of a constitutive law for use in a micromechanical analysis to predict the behavior of PMR-15 reinforced composites. Thermo-oxidative aging is simulated with a diffusion-reaction model in which temperature, oxygen concentration and weight loss effects are considered. One-dimensional simulations illustrate oxidative layer growth for neat resin specimens. Comparisons and correlations with experimental observations of oxidation layer growth are presented.     

一种含三氟甲基取代不对称芳香二胺及其可溶性透明聚醚酰亚胺 的合成与表征

以2,6-二甲基苯酚和4-硝基苯甲酰氯为起始原料, 经三步有机反应设计合成了一种含氟不对称芳香二胺: (4’-(4’’-胺基-2’’-三氟甲基苯氧基)-3’,5’-二甲基苯)-(4-胺基苯)甲酮(3); 并由该二胺单体和二苯醚四酸二酐经一步法缩聚制备了一种新型含氟聚醚酰亚胺, 其特性粘度为0.68 dL/g. 该聚醚酰亚胺表现出优良的溶解性能和光学性能: 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剂中, 还能溶于低沸点的氯仿、四氢呋喃、二氯甲烷等溶剂中; 由该聚合物溶液所制的薄膜无色透明, 截断波长在352, 400 nm后具有高的透明性. 此外该聚醚酰亚胺还表现出良好的热性能和机械性能: 玻璃化转变温度在288 ℃, 氮气中起始分解温度在508 ℃; 该聚合物薄膜的拉伸强度为91 MPa, 断裂伸长率在10%～15%, 起始模量为1.7 GPa.     

SYNTHESIS AND PROPERTIES OF POLY-1,3,5-TRIAZINES

Two new polytriazines: poly[2-methyl-4, 6-(4,′4″-diphenylene)-1, 3, 5-triazine] (Ⅰ) and poly[2-phenyl-4, 6-(4′, 4″-diphenylene)-1, 3, 5-triazine] (Ⅱ) were synthesized from the solution condensation of biphenyl-4, 4′-diamidine dihydrochloride with acetic anhydride and biphenyl-4, 4′-diamidine with benzaldehyde respectively. These two polymers were characterized by TGA, DTA, elemental analysis and IR spectroscopy. They exhibited good thermal oxidative stability as shown by the fact that the powders of these polymers suffered 5.4%, 2.4% weight loss after isothermal aging in air at 300℃for 200 hours. The decomposition temperature of (Ⅱ) was 583℃in air and 590℃in N_2. These linear poly-1, 3, 5-triazines were soluble in concentrated sulfuric acid, phosphoric acid and trifluoroacetic acid whereas the erosslinked poly-1, 3, 5-triazines reported in the literature were insoluble and infusible.It is interesting that these polymers can form complexes with metal halides as determined by X-ray photoelectron spectroscopy (XPS). The polymer metal complex (Ⅲ). PdCl_2 possesses catalytic activity for hydrogenation.