含哒嗪环聚酰亚胺的合成及性能表征

以马来酸酐为原料与水合肼反应得到哒嗪酮,再与三氯氧磷反应制备3,6-二氯哒嗪中间体,哒嗪中间体与间氨基苯酚通过亲核取代反应合成了一种新的二胺单体——3,6-二(3-氨基苯氧基)哒嗪.通过1HNMR,FTIR及HPLC-MS确证了哒嗪二胺及中间体的结构.这种哒嗪二胺单体与6种芳香二酐单体——均苯四甲酸二酐(PMDA)、3,3',4,4'-联苯四甲酸二酐(BPDA)、4,4-六氟异丙基邻苯二甲酸酐(6FDA)、3,3',4,4'-二苯甲酮四甲酸二酐(BTDA)、3,3',4,4'-二苯醚四甲酸二酐(ODPA)和双酚A型二醚二酐(BPADA)通过两步法聚合制备了一系列的聚酰亚胺,并对其结构和性能进行了研究.结果表明,聚酰胺酸的比浓对数黏度为0.37~0.50 dL/g,该系列聚酰亚胺膜具有良好的热稳定性和机械性能,玻璃化温度(Tg)为188~241℃,氮气氛围下5%和10%热失重分别为421~448℃和447~473℃,拉伸强度(TS)高达102 MPa,断裂伸长率(EB)为2.0%~6.5%.紫外可见光谱测试得到的截止波长(λcut-off)为367~389 nm.     

聚酰亚胺纤维及其纺丝工艺研究进展

聚酰亚胺纤维由于其优良的性能,已成为高技术纤维领域的研究热点之一.本文归纳了聚酰亚胺纤维的聚合单体,主要有二酐单体(均苯四甲酸酐、联苯四甲酸酐、二苯醚四酸二酐、二苯酮四酸二酐等)和二胺单体(二氨基二苯醚、对苯二胺、间苯二胺等).另外,还有第三单体,如嘧啶环二胺、氯化对苯二胺、二氨基二苯醚等,综述了聚酰亚胺纤维的主要纺丝...     

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.     

含全氟环丁烷环可溶性聚酰亚胺的合成与表征

以乙酰氨基苯酚为原料,经过BrCF2CF2Br氟烷基化、Zn催化脱卤、热环化二聚,以及水解去保护,合成了一种含全氟环丁烷环的二胺单体1,2,3,3,4,4-六氟-1,2-双[4-(氨基)苯氧基]环丁烷.用该单体分别与酯环二酐双环[2·2·1]辛烷-2,3,5,6-四羧基2,3,5,6-二酐(BHDA)、芳香性二酐3,3′,4,4′-联苯四酸二酐(BPDA)和3,3′,4,4′-二苯酮四酸二酐(BTDA)通过“一步法”制备了3种新型含全氟环丁烷环聚酰亚胺.通过粘度测试、溶解性实验、FT-IR、热失重分析(TGA)和差热扫描量热(DSC)分析等手段,对所合成的聚酰亚胺的结构与性能进行了表征.结果显示该类聚酰亚胺可溶于大多数常用极性有机溶剂,热分解温度高于480℃,其中两种聚合物玻璃化温度低于150℃,表明含全氟环丁烷环聚酰亚胺具有良好的溶解性和可加工性.     

含磷聚酰亚胺纤维的制备及其力学与阻燃性能

采用廉价的三苯基氧膦和混酸合成了一种含磷二胺单体,二（3-氨基苯基）苯基膦氧(DAPPO)。在4,4′-二胺基二苯醚（ODA）、3,3′,4,4′-联苯四酸二酐（BPDA）和均苯四酸二酐（PMDA）聚合体系中引入该单体,制备含磷聚酰亚胺纤维。热失重分析（TGA）结果表明,聚酰亚胺纤维的热稳定性随含磷量的增加而明显提高。当n（DAPPO）：n（ODA）为7：93时,纤维的极限氧指数达到了43,说明纤维的阻燃性能显著提高。     

含磷聚酰亚胺纤维的制备与性能

合成了一种含磷二胺单体, 二(4-胺基苯氧基)苯基膦氧(DAPOPO). 该单体与4,4'-二胺基二苯醚(ODA)、 均苯四酸二酐(PMDA)和3,3',4,4'-联苯四酸二酐(BPDA)共聚得到聚酰胺酸溶液, 通过干喷湿纺法纺丝得到聚酰胺酸纤维, 聚酰胺酸纤维经过热亚胺化和热牵伸得到含磷的聚酰亚胺纤维. 利用纤维强度仪、 扫描电子显微镜、 热失重分析仪和氧指数测定仪等研究了含磷聚酰亚胺纤维的力学性能、 形貌、 热稳定性能和阻燃性能. 结果表明, 随着含磷量的增加, 纤维的热稳定性明显提高, 而极限氧指数从35上升到了45, 说明纤维的阻燃性能得到很大提高.     

侧链含邻苯二甲酰亚胺的聚酰亚胺液晶垂直取向剂的制备与表征

以邻苯二甲酰亚胺和溴代正辛烷为原料,合成了功能性二胺单体N-辛基-4(3,5-二氨基苯甲酰基)-氨基邻苯二甲酰亚胺(D8).用此单体与3,3’-二甲基-4,4’-二氨基二苯甲烷(DMMDA)、3,3’,4,4’-二苯醚四甲酸二酐(ODPA)共缩聚,采用低温缩聚-化学亚胺化方法,通过调节共聚物组成制备了5种聚酰亚胺(PI).利用FTIR、NMR、UV-Vis与DSC等手段对合成的二胺单体及聚酰亚胺进行了结构表征和性能测试;研究了其摩擦取向性能、透光性能、溶解性能和耐热性能.结果表明,5种聚酰亚胺均可溶于常见极性溶剂,如NMP、THF等;随着D8含量的增加,PI膜对液晶分子取向时的预倾角逐渐增大至垂直,当D8含量大于20%,且经过5次摩擦后,预倾角仍能保持在89°以上.此外实验所得PI透过率大于80%,玻璃化转变温度在260℃以上.     

含氟及硫醚基团聚酰亚胺光波导材料的合成及表征

通过分子设计,合成了含三氟甲基及硫醚基团的二胺单体4,4'-双(4-胺基-2-三氟甲基苯硫基)二苯硫醚(6FSEDA),利用其与6种芳香二酐单体:3,3',4,4'-联苯四羧酸二酐(BPDA)、4,4'-氧双邻苯二甲酸酐(ODPA)、3,3',4,4'-二苯酮四酸二酐(BTDA)、4,4'-(六氟异丙基)-苯二酸酐(6FDA)、3,3',4,4'-二苯硫醚四酸二酐(DTDA)及3,3',4,4'-二苯砜四酸二酐(DSDA)经一步法合成了一系列含氟及硫醚基团的聚酰亚胺(PI),并对其结构与性能进行了研究.结果表明,该系列PI的玻璃化温度Tg(DSC)在199.8～231.7℃范围,5%和10%热失重的温度(N2氛围)分别在491℃和517℃以上,在400～700 nm的可见光波长范围内具有优异的光学透明性,在光通讯波段(1310 nm和1550 nm处)均无明显吸收,且在这两个波长处测得的平均折射率范围分别为1.5401～1.6142和1.5389～1.6124,在波长632.8 nm测得的双折射范围为0.0012～0.0045.可见,含氟及硫醚基团聚酰亚胺薄膜具有良好的热稳定性和光学性能.     

含五元杂环的聚酰亚胺的合成与性能研究

以多聚磷酸为溶剂,4-氨基苯甲酸与硫代氨基脲反应制得一种含噻二唑环的二胺单体4-(5-对氨基苯基)-1,3,4-噻二唑苯胺(2); 2与均苯四酸二酐反应合成了含五元杂环的聚酰亚胺(3),其结构和性能经¹H NMR, FT-IR和TGA表征,并研究了3的溶解性能。结果表明：3的热稳定性较好,T_5%为402 ℃。 3在二甲基亚砜、DMF和N-甲基吡咯烷酮等溶剂中溶解性较好。     

三明治结构含铅聚酰亚胺材料的制备与辐射屏蔽性能研究

采用离子交换法合成了以化学方式键合铅离子的二胺单体4,4'-二氨基-1,1'-联二苯-2,2'-二磺酸铅BDSA(Pb),并与二胺单体4,4'-二氨基-二苯醚(ODA),二酐单体均苯四甲酸酐(PMDA)在溶剂N-甲基-2-吡咯烷酮(NMP)中完成缩聚反应,通过改变2种二胺单体的摩尔比,采用热亚胺法和流延法逐层浇筑的工艺,制备出了一系列侧基键合铅离子的三明治结构的聚酰亚胺复合材料PI(Pb),试图解决传统物理共混方法制备的复合材料中易出现的铅元素分布不均匀、机械性能差的科学问题.实验结果表明:以纯PI为参照物,制备的PI(Pb)复合材料对~(241)Am(59.5 keV)、~(238)Pu(79.9、176.7 keV)等中低能γ射线具有很好的屏蔽效果,而且具备优良的耐辐照性能、优异的热稳定性能和良好的力学性能.     

ORGANO-SOLUBLE FLUORINATED POLYIMIDES DERIVED FROM α,α-BIS(4-AMINO-3,5- DIMETHYLPHENYL)-4''-FLUOROPHENYL METHANE AND VARIOUS AROMATIC DIANHYDRIDES

Organo-soluble fluorinated polyimides were synthesized by the polycondensation of a new aromatic diamine α,αbis(4-amino-3,5-dimethylphenyl)-4'-fluorophenyl methane with several aromatic dianhydrides. The one-step polymerization polyimides could be soluble not only in polar aprotic solvents, such as N-methyl-2-pyrrolidinone, and N,Ndimethylacetamide, but also in common organic solvents, such as chloroform, cyclopentanone, m-cresol and so on. The polyimide films show excellent transparency with the UV-Vis cut-off lengths of 310-360 nm and light transmittances of higher than 80% in the visible region. In addition, the polyimides exhibit good thermal stability with an initial decomposition temperature (Td) higher than 530℃ and have more than 60% of residual weight retentions at 700 ℃.     

主链含邻位取代单元及吡啶环聚酰亚胺的合成与性能

以o-羟基苯乙酮、对氯硝基苯和苯甲醛为原料,通过亲核取代反应、改进的Chichibabin反应以及水合肼催化还原合成了一种新型含邻位取代单元及吡啶环的芳香二胺4-苯基-2,6-双[3-(4-氨基苯氧基)苯基]吡啶(o,p-PAPP).以N,N-二甲基甲酰胺(DMF)为溶剂,将o,p-PAPP分别与3,3',4,4'-二苯醚四羧酸二酐(ODPA)、2,2-双[4-(3,4-二羧基苯氧基)苯基]丙烷二酐(BPADA)、3,3',4,4'-二苯酮四甲酸二酐(BTDA)及均苯四甲酸二酐(PMDA)通过常规的两步法,合成了4种聚酰亚胺.用FTIR、DSC、TGA、XRD、溶解性测试、UV-Vis和荧光光谱对聚合物的结构和性能进行了表征.FTIR结果表明,所得的聚合物在1780,1720和1380cm-1左右出现了聚酰亚胺的特征吸收峰.实验所得的PI能很好地溶解于常见有机溶剂(如DMF,DMAC,DMSO,NMP,THF,CHCl3),在氮气氛中,PI的10%失重温度(T10)为444.2～467.5℃,800℃时的残余质量(Rw)为49.6%～58.3%.同时PI分子主链中的吡啶环结构使其具有良好的紫外光吸收性能,经HCl质子化后,在460 nm附近出现非常强的荧光发射峰.     

ORGANO-SOLUBLE FLUORINATED POLYIMIDES DERIVED FROM a,a-BIS(4-AMINO-3,5- DIMETHYLPHENYL)-4′-FLUOROPHENYL METHANE AND VARIOUS AROMATIC DIANHYDRIDES

 Organo-soluble fluorinated polyimides were synthesized by the polycondensation of a new aromatic diamine -bis(4-amino-3,5-dimethylphenyl)-4′-fluorophenyl methane with several aromatic dianhydrides. The one-step polymerization procedure was conducted at 180℃ in m-cresol, producing the polyimides with inherent viscosities of 0.680.76 dL•g1. The polyimides could be soluble not only in polar aprotic solvents, such as N-methyl-2-pyrrolidinone, and N,N-dimethylacetamide, but also in common organic solvents, such as chloroform, cyclopentanone, m-cresol and so on. The polyimide films show excellent transparency with the UV-Vis cut-off lengths of 310360 nm and light transmittances of higher than 80% in the visible region. In addition, the polyimides exhibit good thermal stability with an initial decomposition temperature (Td) higher than 530℃ and have more than 60% of residual weight retentions at 700℃.     

含氧膦结构的可溶性感光聚酰亚胺合成与表征

聚酰亚胺(PI)是一类综合性能优异的功能性材料,广泛应用于航天、航空及电子工业等领域[1].感光聚酰亚胺可以采用光刻工艺,大大简化了其应用加工程序[2,3],因而备受人们所青睐.含查尔酮结构的聚合物对UV辐射敏感度高和化学稳定性好,最近被广泛的研究和应用[4～7].主链含查尔酮结     

Soluble and Colorless Polyimides from Alicyclic Diamines

Abstract

A series of novel polyimides was synthesized from alicyclic diamines and various aromatic dianhydrides by one-step polymerization in m-cresol without a catalyst. The polymerization was conducted for 4 hours with refluxing, which was enough to obtain the polymers with high molecular weight. The inherent viscosities of the resulting polyimides were in the range of 0.30 ～1.29 dL/g. The prepared polyimides showed excellent thermal stabilities and good solubility. All the polymers were readily soluble in common organic solvents such as chloroform, tetrachloroethane (TCE), dimethylacetamide (DMAc), etc and the glass transition temperatures were observed at 199 to 311°C. UV-visible spectra were obtained to measure the transparency of polymer films. All the polymers showed high transmission above 90% in the wavelength of 400 ～700 nm.     

可溶性侧链含萘聚酰亚胺的合成与性能

以萘甲醛和2,6-二甲基苯胺或苯胺为原料合成了2种含萘的二胺单体, 进一步与二苯醚四酸二酐(ODPA)经高温溶液缩聚, 得到2种侧链含萘的聚酰亚胺, 对聚合物进行了核磁共振谱、 傅里叶变换红外光谱及溶解性、 耐热性、 憎水性、 机械性能等结构与性能的测试. 结果表明, 含醚侧链含萘的聚酰亚胺具有优异的溶解性, 良好的耐热性, 较好的憎水性与机械性能. 另外, 通过静电纺丝的方法制备了侧链含萘的聚酰亚胺纤维, 研究了纤维的形貌与憎水性.     

含二苯甲烷结构四元共缩聚杂萘聚芳酰胺的合成与性能

采用自制二胺1,2-二氢-2-(4-氨基苯基)-4-[4-(4-氨基苯氧基)-苯基]-二氮杂萘-1-酮、商品二胺4,4′-二氨基二苯甲烷和对苯二胺与对苯二甲酰氯进行低温溶液缩聚反应,改变三种二胺的比例,得到了一系列共聚酰胺树脂,其特性粘数为1·24~2·32dL/g,用FT-IR、1H-NMR手段研究了聚合物的结构;利用DSC和TGA研究了聚合物的耐热性能,结果表明,该类聚合物具有较高玻璃转化温度(301℃以上);氮气气氛中5%热失重温度在438℃以上;用一定比例的二胺制得的聚合物分别能溶于N-甲基吡咯烷酮、N,N-二甲基乙酰胺等非质子极性溶剂中并浇注得到韧性薄膜.     

Synthesis and characterization of novel fluorinated polyimides derived from 1,1′-bis(4-aminophenyl)-1-(3-trifluoromethylphenyl)-2,2,2-trifluoroethane and aromatic dianhydrides

A novel fluorinated aromatic diamine 1,1′-bis(4-aminophenyl)-1-(3-trifluoromethylphenyl)-2,2,2-trifluoroethane (6FDAM) was synthesized in a simple procedure, which was then employed to prepare a series of fluorinated polyimides with commercial aromatic dianhydrides, such as pyromellitic dianhydride (PMDA), 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane (6FDA), 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA) and 4,4′-oxydiphthalic anhydride (ODPA). The polyimides exhibited good solubility in strong dipolar solvents such as NMP, DMAc, DMF and m-cresol as well as some of low boiling point organic solvents of THF and CHCl₃, etc. Experimental results indicated the polyimides possessed low moisture adsorptions of 0.42-0.95%, low dielectric constant of 2.71-2.95 at 1 MHz, high dielectric strength of 92.0-122.6 kV/mm and good optical transparency with cutoff wavelengths of UV-vis at 330-375 nm. The polyimides also exhibited good mechanical properties as well as excellent thermal and thermo-oxidative stability. The fluorinated polyimides possessed better solubility, lower dielectric constant and water adsorption as well as higher optical transparency than the representative non-fluorinated polyimide derived from PMDA and 4,4′-oxydianiline (ODA).     

Synthesis and characterization of soluble polyimides from 2,2-bis(4-aminophenyl)cycloalkane derivatives

New aromatic diamines [(1) and (2)] containing polycycloalkane structures between two benzene rings were synthesized by HCl-catalyzed condensation reaction of aniline hydrochloride and corresponding polycycloalkanone derivatives. The structures of diamines were identified by ¹H-NMR, ¹³C-NMR, FTIR spectroscopy, and elemental analysis. The polyimides were synthesized from the obtained diamines with various aromatic dianhydrides by one-step polymerization in m-cresol. The inherent viscosities of the resulting polyimides were in the range of 0.34–1.02 dL/g. The polyimides showed good thermal stabilities and solubility. All the polymers were readily soluble in N-methyl-2-pyrrolidone, m-cresol, tetrachloroethane, etc. Some of them were soluble even in chloroform at room temperature. The glass transition temperatures were observed in the range of 323–363°C, and all of the polymers were stable up to 400°C under nitrogen atmosphere. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3449–3454, 1999     

一类新型杂环聚芳酰胺的合成与性能研究

采用二氮杂萘类双酚 4 (4 羟基苯基 ) 2 ,3 二氮杂萘 1 酮 (DHPZ)与对氯苯腈反应制得二腈化合物 ,进一步水解为二酸 .以此新型二酸与不同二胺聚合制得的聚芳酰胺均具有较高的耐热性能 ,其Tg 在 2 91～318℃ ,且易溶于极性非质子溶剂中 .聚合物的特性粘数为 1 17～ 1 5 0dL g(2 5℃ ,0 5 %inNMP) ,对所得聚酰胺进行性能研究 ,其拉伸强度为 71～ 86MPa ,断裂伸长率为 8%～ 13% ,拉伸模量为 0 86～ 1 0 2GPa ,电阻系数数量级为 10 1 4～ 10