PMDA-ODA型聚酰亚胺纤维的热稳定性研究

通过干法纺丝制备了聚酰亚胺(PI)纤维,采用热失重(TGA)测试分析了其热稳定性能.TGA测试表明,均苯四甲酸酐-4,4.二氨基二苯醚(PMDA-ODA)型PI纤维500℃之前不发生分解,其热分解稳定性要优于P84纤维.并利用Kissinger和Flynn-Wall-Ozawa方法计算并比较了PI和P84纤维在空气中热...     

以BAPP为原料的热塑性PI薄膜的合成及性能

以芳香长链二胺2,2-双[4-(4-氨基苯氧基)苯基]丙烷(BAPP)为二胺原料,与最具商业价值的四种酸酐均苯四甲酸二酐(PMDA)、3,3′,4,4′-联苯四酸二酐(BPDA)、3,3′,4,4′-二苯酮四酸二酐(BTDA)、3,3′,4．4′-二苯醚四酸二酐(ODPA)为二酸酐原料,采用二步溶液缩聚法制得了一系列均聚和共聚聚酰亚胺薄膜。利用FTIR表征了聚酰亚胺的结构,并用DSC、TOA、TMA DMA等手段测得了不同聚酰亚胺的Tg、5%与10%热失重温度、线膨胀系数、拉伸强度、断裂延伸率、热压粘接T型剥离强度等性能数据。     

均苯型共聚聚酰亚胺薄膜的制备及其性能

以2,2′-双[3-苯基-4(4-氨基苯氧基)苯基]丙烷(BPAPOPP)、4,4′-二胺基二苯醚和均苯四甲酸酐为原料,采用两步法共缩聚制备了一系列共聚聚酰亚胺薄膜.采用红外光谱仪、差示扫描量热仪等分析了薄膜的结构,利用静态热机械分析仪分析了薄膜的性能.结果表明:制备的聚酰亚胺薄膜具有较低的玻璃化转变温度;随着BPAP...     

基于异构三苯二醚二酐的热塑性共聚酰亚胺的合成

以2,2′,3,3′–三苯二醚四甲酸二酐(3,3′–HQDPA)、3,3′,4,4′–三苯二醚四甲酸二酐(4,4′–HQDPA)为二酐单体,邻苯二甲酸酐为封端剂,与4,4′–二氨基二苯醚(4,4′–ODA)进行无规共聚。通过改变二酐的比例,用两步法制备了一系列热塑性共聚酰亚胺粉料,并对其热性能、溶解性能、熔体性能等进行了表征,与均聚酰亚胺进行了比较。结果表明,聚合物均具有良好的热稳定性,热分解5%的温度在空气中为500~521℃,在氮气中为507~538℃;随着3,3′–HQDPA含量的增加,玻璃化转变温度(Tg)由223℃升高至257℃,溶解性也逐渐提高。与均聚物相比,共聚物的熔体流动性有了显著地提高。可以通过调控异构二酐的比例来调控共聚酰亚胺的Tg、溶解性和熔体流动性,满足材料在不同应用上的要求,当二酐的比例为1∶1时,共聚酰亚胺的熔体流动性最好,可作为高性能、易加工的热塑性工程塑料使用。     

共聚共混改性聚酰亚胺的摩擦磨损性能研究

为了改善传统均苯四甲酸酐(PMDA)–4,4′-二胺基二苯醚(ODA)型聚酰亚胺(PI)的摩擦性能,分别以共聚和共混两种方式,引入柔性二胺单体芳香杂环二胺(DAMI),从分子结构制备不同ODA/DAMI物质的量之比的共聚和共混改性PI。并用摩擦磨损试验机、扫描电子显微镜、万能试验机以及X射线衍射仪等分析共聚和共混改性PI的结构和性能。结果表明,当ODA/DAMI物质的量之比分别为3∶1和5∶1时,共聚和共混改性PI具有最优的综合摩擦磨损性能,摩擦系数分别为0.273和0.280,磨损率分别为9.28×10–14,11.2×10–14 m3/(N·m)。共聚改性PI的摩擦系数随摩擦时间的增加变化比较稳定,其在兼顾磨损率和摩擦系数方面比共混改性PI更具优势。共聚和共混法改性PI磨损机理相似,主要为粘着磨损、磨粒磨损和疲劳磨损。随DAMI含量增加,两种改性PI的拉伸强度、拉伸弹性模量和玻璃化转变温度均呈下降趋势,当DAMI含量较高时,两种改性PI结晶取向增加,磨损率急剧升高。     

共缩聚聚酰胺酸和聚酰亚胺的微波辐射合成研究

在N,N′-二甲基甲酰胺(DMF)溶剂中,选用3,3,′4,4′-二苯酮四羧酸二酐(BTDA)、均苯四甲酸酐(PMDA)和4,4′-二氨基二苯醚(ODA)为单体,微波辐射低温溶液缩聚合成一种共缩聚聚酰亚胺的前驱体聚酰胺酸(PAA),然后亚胺化脱水环化生成共缩聚聚酰亚胺(PI)。通过特性黏数([η])、红外光谱(FT-IR)和热重分析(TGA)对聚合物进行了结构表征和性能测试。结果表明,微波辐射溶液聚合能够提高PAA的特性黏数及产率,微波的引入大大缩短了反应时间;IR表明,在1778 cm-1和1723 cm-1处观察到聚酰亚胺特征峰;TG表明,PI在氮气中535℃左右开始降解,10%热失重温度(Td10%)为587℃。     

2L-FCCL用聚酰亚胺复合膜的制备与性能

采用2,2′-双[4-(4-氨基苯氧基)苯基]丙烷(BAPP)、4,4′-二氨基二苯醚(ODA)和3,3′,4,4′-二苯酮四酸二酐(BTDA)合成BAPP/ODA/BTDA型聚酰亚胺(PI)的前驱体聚酰胺酸(PAA)溶液,将该溶液涂覆于3,3′,4,4′-联苯四甲酸二酐(BPDA)/ODA型PI基膜上,通过去溶剂和热亚胺化制备PI复合膜,将复合膜的热塑面与铜箔复合,热压制得二层挠性覆铜板(2L-FCCL)。研究了BAPP/ODA/BTDA型PI、BPDA/ODA型PI、PI复合膜及2L-FCCL的性能。结果表明:BAPP/ODA/BTDA型PI薄膜的玻璃化转变温度为238℃,耐热性能优异,PI复合膜在280℃,15MPa下与铜箔层压50~60min制得的2F-FCCL剥离强度大于0.8N/mm,且经360℃焊锡浴测试未分层、未起泡,耐热性能和剥离强度均满足工业要求。     

含苯环侧基三元共聚PI的合成及其表征

以4,4’-二胺基二苯醚(ODA)、2,2’-双[3-苯基-4(4-氨基苯氧基)苯基]丙烷(BPAPOPP)和均苯四甲酸酐(PMDA)为单体,采用溶液共缩聚方法合成了一系列共聚聚酰亚胺(PI)薄膜;采用傅里叶红外光谱仪(FTIR)、差示扫描量热仪(DSC)等分析了PI薄膜的结构和性能。结果表明:随着高聚物中柔性体系含量的增加,PI薄膜的热学性能和力学性能都有一定程度降低;但其加工性能得到了改善。     

部分环化三元共聚聚酰胺酸初生纤维的制备

采用均苯四甲酸酐（PMDA）和4,4’-二氨基二苯醚（ODA）、对苯二胺（PPDA）在溶剂N,N’-二甲基乙酰胺（DMAc）中低温共聚,并在PAA中继续加入一定量酰亚胺化试剂,从而合成部分环化聚酰胺酸（PAA）,以甲醇和水混合溶液为凝固浴通过干湿法纺丝纺制出部分环化PAA纤维。研究了不同浓度的凝固浴、不同量的环化剂对初生纤维结构与力学性能的影响。乙酸酐与二胺摩尔比为0．7,40％甲醇水溶液为凝固浴时,制备PAA初生纤维强度达1．530cN／dtex。     

含氰基聚酰亚胺薄膜的制备及其热分解动力学

以4-[3,5-双(4-氨基苯氧基)苯氧基]邻苯二甲腈和3,3′,4,4′-联苯四甲酸二酐为原料,经聚酰胺酸热酰亚胺化制备含氰基的聚酰亚胺(CN-BP-PI)薄膜。采用傅里叶变换红外光谱、热重分析、差示扫描量热法对CN-BP-PI薄膜进行了分析。采用动态热重法研究了CN-BP-PI的分解动力学,用积分法结合常见固相热分解反应动力学函数来判断热分解的动力学函数。由Ozawa,KAS,Kissinger,Achar,Coats-Redfern,MacCallum-Tanner,van Krevelen方程求热分解反应的动力学参数。转化率为0.2~0.8时所得CN-BP-PI在氮气中热分解反应的表观活化能为119.68~215.61 kJ/mol,平均活化能为136.35 kJ/mol,指前因子平均值为8.52×107 s-1。     

Residual stress and mechanical properties of polyimide thin films

Four different structure polyimide thin films based on 1,4‐phenylene diamine (PDA) and 4,4′‐oxydianiline (ODA) were synthesized by using two different dianhydrides, pyromellitic dianhydride (PMDA) and 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA), and their residual stress behavior and mechanical properties were investigated by using a thin film stress analyzer and nanoindentation method. The residual stress behavior and mechanical properties were correlated to the morphological structure in polyimide films. The morphological structure of polyimide thin films was characterized by X‐ray diffraction patterns and refractive indices. The residual stress was in the range of ?5 to 38 MPa and increased in the following order: PMDA‐PDA < BPDA‐PDA < PMDA‐ODA < BPDA‐ODA. The hardness of the polyimide films increased in the following order: PMDA‐ODA < BPDA‐ODA < PMDA‐PDA < BPDA‐PDA. The PDA‐based polyimide films showed relatively lower residual stress and higher hardness than the corresponding ODA‐based polyimide films. The in‐plane orientation and molecularly ordered phase were enhanced with the increasing order as follows: PMDA‐ODA < BPDA‐ODA < BPDA‐PDA ～ PMDA‐PDA. The PDA‐based polyimides, having a rigid structure, showed relatively better‐developed morphological structure than the corresponding ODA‐based polyimides. The residual stress behavior and mechanical properties were correlated to the morphological structure in polyimide films. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Structure and properties of novel PMDA/ODA/PABZ polyimide fibers

A series of random copolyamic acid were synthesized from various ratios of two diamines 4, 4′‐oxydianiline (ODA) and 2‐(4‐aminophenyl)‐5‐aminobenzimidazole (PABZ) by polycondensation with pyromellitic dianhydride (PMDA) in N‐methyl‐2‐pyrrolidone (NMP). Their inherent viscosities were in the range of 1.89–2.91 dl/g. The polyamic acid (PAA) solution drops were spun into fibers by the wet spinning process. The polyimide (PI) fibers were obtained from PAA fibers after drawn and treated in heating tube. The fibers were characterized by fourier transform infrared (FTIR), wide X‐ray diffraction (WAXD), scanning electron microscope (SEM), thermal gravimetry analysis (TGA), dynamic mechanical analysis (DMA), and tensile testing. WAXD showed these PI fibers were basically amorphous. The tensile strength and initial modulus of the PI fiber reached 1.53 and 220.5 GPa when diamine ratio of PABZ/ODA was 7/3, which were almost three times and 30 times over that of the PMDA/ODA PI fibers. TGA showed that the PI fibers were thermally stable with 10% weight losses recorded in the range of 492–564°C under nitrogen atmosphere, and their glass transition temperature (T_g) were found to be 410–440°C by DMA with increasing PABZ content from 30 to 70%. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

亚胺化工艺对聚酰亚胺性能影响的研究

以4,4’-二氨基二苯醚ODA和均苯四甲酸二酐PMDA为原料分别采用溶液-固相亚胺化和化学亚胺化法制备了2种聚酰亚胺(PI)树脂。通过FT-IR、DSC、TGA、溶解性能等对PI树脂进行测试与表征。FT-IR表明,2种方法均形成了酰亚胺结构,DSC和TGA分析表明化学亚胺化法得到的PI的热性能优于溶液-固相亚胺化PI。溶解性测试表明溶液-固相亚胺化PI要优于化学亚胺化PI。()()     

Adhesion of polyimide to silicon and polyimide

The characteristics of the adhesions of polyimide to silicon and to polyimide and the autohesion of a polyimide blend have been investigated. As found, the peel strength of pyromellitic dianhydride–4,4′-oxydianiline (PMDA–ODA) on silicon can be greatly improved by blending with 20 or 40% benzophenone tetracarboxylic dianhydride–p-phenylene diamine (BPDA–PDA). Exposing in air for a 2 day period resulted in a serious deterioration in adhesion for the pure PMDA–ODA system, while in no deterioration for the blend systems. Regardless of adhesion or autohesion, the resulting peel strength decreased markedly with the increase of the curing temperature. It was also found that based on the same curing temperature the diffusion of NMP is much faster in the film of PMDA–ODA than in the blend containing 20% BPDA–PDA. Beside curing temperature, imide-to-imide compatibility seems to play an important role in affecting the adhesion characteristics. © 1993 John Wiley & Sons, Inc.     

聚酰胺酸纺丝溶液的流变性能研究

由均苯四酸二酐(PMDA)和4,4'-二氨基二苯醚(ODA)在N,N-二甲基乙酰胺(DMAc)中共聚合制得聚酰亚胺前驱体——聚酰胺酸的纺丝溶液,采用哈克流变仪研究了溶液的流变性能。结果表明:聚酰胺酸溶液属于切力变稀的非牛顿流体;溶液的表观黏度随溶液温度的升高而降低,随溶液浓度的升高或聚合物特性黏度的增大而增大。溶液温度的升高、浓度的降低或聚合物特性黏度的减小均使得聚酰胺酸溶液呈现切力变稀行为的临界剪切速率变大,使得溶液的非牛顿指数增大,同时使得溶液的结构黏度指数减小。溶液的黏流活化能随剪切速率的增加或随溶液浓度的增高而下降。     

喷涂聚氨酯-脲-酰亚胺弹性体的合成及应用

以均苯四甲酸酐(PMDA)、碳化二亚胺改性MDI(L-MDI)、聚醚多元醇、蓖麻油、端氨基聚醚、小分子二胺等合成了喷涂聚氨酯-脲-酰亚胺弹性体。通过ATR、TGA、DMA、SEM、力学性能等测试,发现当A组分中NCO基质量分数在13%左右,多元醇(GEP)/蓖麻油(CTO)质量比为80∶20时,产品具有较好的力学性能和施工性能,且PMDA含量增加对产品耐热性有改善,储能模量、损耗模量也均有提高,但对损耗因子影响不明显。该弹性体应用于卫浴产品获得了良好的效果。     

PPD对PAA溶液性质及其纤维结构的影响

以均苯四酸二酐(PMDA)和4,4,-二氨基二苯醚(ODA)以及PMDA,ODA和对苯二胺(PPD)共聚合成聚酰胺酸(PAA),经湿法纺丝制备PAA纤维.研究了PPD的引入对PAA原液性质及其纤维形态结构的影响.结果表明:PAA的特性粘数随着PPD含量增加而提高;PPD的引入使PAA的凝固性能及其纤维力学性能提高;凝固浴为水/乙醇,水含量较高时,含有PPD的PAA纤维截面结构变得疏松多孔;凝固浴为水/N甲基吡咯烷酮,水体积分数为70%～80%时,得到致密无孔的改性PAA纤维.     

聚酰胺酸酰亚胺化条件及其对聚酰亚胺力学性能的影响

采用均苯四酸二酐(PMDA)和4,4'-二氨基二苯醚(ODA)为单体,N-甲基吡咯烷酮(NMP)为溶剂,合成了黏度为1.87 dL/g的聚酰胺酸(PAA)。对聚酰胺酸分别进行了热酰亚胺化和化学酰亚胺化处理,研究了完全酰亚胺化所需的条件以及不同酰亚胺化方式对聚酰亚胺(PI)纤维条断裂强度的影响;对PAA初生纤维条进行拉伸和酰亚胺化处理的顺序不同,所得到的聚酰亚胺(PI)纤维条的力学性能不同,采用先酰亚胺化再拉伸的方法能得到力学性能更优异的聚酰亚胺(PI)纤维条。     

Imide-aryl ether benzothiazole copolymers

Summary Imide-aryl ether benzothiazole random copolymers were investigated. A new diamine containing preformed benzothiazole rings was prepared by a thiazole activated nucleophilic aromatic substitution reaction. The synthesis involved the reaction of 2,6-(bis(4-fluorophenyl))benzo[1,2,4,5]bisthiazole with 3-aminophenol in the presence of K ₂ CO ₃ in N-methylprrolidone (NMP) to afford bis(3-aminophenoxy)phenylbenzo [1,2,4,5]bisthiazole in high yield. This new diamine was readily purified and co-reacted with various compositions of 4,4-oxydianiline (ODA) and pyromellitic dianhydride (PMDA) producing a series of imide-ary ether benzothiazole random copolymers. Films were cast and cured (350°C) to effect imidization, affording tough films with moduli significantly higher than PMDA/ODA polyimide. The thermal stability of the copolymers was good with thermal decomposition temperatures in the 480 to 510°C range, and the thermal expansion coefficients were lower than PMDA/ODA polymide and in the 25–30 ppm range.