含苯并咪唑单元可溶性聚酰亚胺的合成和性能

合成了一种刚性芳香二胺单体3,3',5,5'-四甲基-4,4'-二胺基苯基甲苯(BDAP),与6-氨基苯基-2-氨基苯并咪唑(BIA)组成混合二胺,分别与4种商品化的二酐单体(均苯四酸二酐(PMDA)、联苯四酸二酐(BPDA)、二苯酮四酸二酐(BTDA)和二苯醚四酸二酐(ODPA))一步法缩聚合成了一系列可溶性聚酰亚胺.采用FTIR,1H-NMR,UV-Vis,DMA和TGA等测试方法对所制备的聚酰亚胺进行了表征.结果表明,所制备的聚酰亚胺具有良好的溶解性能,能够在NMP和DMAc等常规溶剂中溶解;耐热性及力学性能优良,玻璃化转变温度超过410℃,分解温度在500℃以上.     

新型含酯基结构的具有低线膨胀系数和吸水性的聚酰亚胺的合成

将2种主链中含有酯基结构的二胺单体:二(4-氨基苯基)对苯二甲酸酯(BPTP)和4-氨基苯基-4-氨基对苯甲酸酯(APAB),与几种常见的酸酐聚合,合成了一系列主链中含有酯基结构的新型聚酰亚胺膜材料.结果表明,所制备的聚酰亚胺薄膜表现出优良的热稳定性、机械性能和低吸水性,其中聚合物的表观玻璃化转变温度高达526℃,在空气和N2气气氛下5%的热失重温度分别在498和507℃以上,表明薄膜具有非常优异的热性能.由于聚合物主链中引入酯基结构而表现出低的线膨胀系数和吸水率.     

基于三蝶烯结构D3h对称性聚酰亚胺的合成及性能研究

以四氯邻氨基苯甲酸和蒽经Diels-Alder反应得到1,2,3,4-四氯三蝶烯,再经硝化、还原得到2,6-二氨基-13,14,15,16-四氯三蝶烯二胺单体.该二胺与双酚A二酐(BPADA)、六氟二酐(6FDA)和3,3’,4,4’-二苯甲酮四羧酸二酐(BTDA)经两步法缩聚得到系列聚酰亚胺.对2,6-二氨基-13,14,15,16-四氯三蝶烯二胺单体进行了1H-NMR,13C-NMR,FTIR表征,对所合成聚酰亚胺进行了1H-NMR、FTIR结构表征及溶解性、热性能、特性粘度、BET等测试.结果表明,含四氯三蝶烯结构的聚酰亚胺具有优异的溶解性,能溶于DMAc、DMF、NMP、THF、吡啶、间甲酚等有机溶剂,其中基于双酚A二酐和六氟二酐的聚酰亚胺在室温下能溶于氯仿中.聚合物具有良好的热性能,在0~300℃之间没有发现其玻璃化转变温度以及10%的热失重温度均高于500℃.聚合物可形成颜色较浅的透明薄膜,其中基于双酚A二酐的聚酰亚胺薄膜为无色透明.基于六氟二酐的聚酰亚胺BET比表面积为370 m2/g,是一种新型多孔聚合物.     

原位一步法制备BTDA/4,4′-ODA/4,4′-SDA聚酰亚胺表面银化薄膜

采用原位一步自金属化的方法制备了具有反射性和导电性的表面银(Ag)化的聚酰亚胺(PI)薄膜,PI是由一种二酐(3,3′,4,4′-四羧基二苯酮酐,BTDA)和两种二胺(4,4′-二氨基二苯醚,4,4′-ODA与4,4′-二氨基二苯硫醚,4,4′-SDA)三元共聚而得,系统研究了4,4′-SDA的引入对薄膜性能及相态结构的影响.结果表明,4,4′-SDA的加入有助于银的还原和迁移,并利于薄膜导电性的提高,薄膜的反射率在两种二胺单体4,4′-ODA与4,4′-SDA的摩尔比为1比1时达到最佳.     

原位一步法制备BTDA/4,4′-ODA/4,4′-SDA 聚酰亚胺表面银化薄膜

采用原位一步自金属化的方法制备了具有反射性和导电性的表面银(Ag)化的聚酰亚胺(PI)薄膜,PI是由一种二酐(3,3′,4,4′-四羧基二苯酮酐,BTDA)和两种二胺(4,4′-二氨基二苯醚,4,4′-ODA与4,4′-二氨基二苯硫醚,4,4′-SDA)三元共聚而得,系统研究了4,4′-SDA的引入对薄膜性能及相态结构的影响.结果表明,4,4′-SDA的加入有助于银的还原和迁移,并利于薄膜导电性的提高,薄膜的反射率在两种二胺单体4,4′-ODA与4,4′-SDA的摩尔比为1比1时达到最佳.     

含二氮杂萘酮结构磺化聚酰亚胺共聚物的合成及其膜性能研究

将磺化二胺单体4,4′-二(4-氨基苯氧基)联苯-3,3′-二磺酸(BAPBDS),含二氮杂萘酮结构的二胺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(DHPZDA)和1,4,5,8-萘四甲酸二酐(NTDA)进行缩合聚合反应,通过改变磺化二胺单体BAPBDS的含量,合成了一系列不同磺化度的聚酰亚胺(SPIs).采用FT-IR,1H-NMR表征了聚合物的结构,热重分析仪(TGA)研究了聚合物的耐热稳定性.以间甲酚为溶剂,通过溶液浇铸法成膜研究了该系列聚合物膜的性能.结果表明,与其它磺化聚酰亚胺相比,该系列磺化聚酰亚胺的溶解性以及在高温下(80℃)水解稳定性有较大提高.     

燃料电池用磺化聚酰亚胺质子交换膜材料的制备与性质

以联萘二酐、磺化二胺和含咪唑基团的非磺化二胺单体为原料,制备了一系列高相对分子质量的磺化聚酰亚胺,该类聚合物具有优异的溶解性和良好的成膜性.得到的质子交换膜具有优异的水解稳定性.苯并咪唑碱性基团的存在提高了磺化聚酰亚胺质子交换膜膜的溶胀稳定性和热稳定性、降低了膜的甲醇透过率.质子导电率测试结果表明,IEC值为2.55mequiv·g-1的膜室温条件下的质子导电率为0.121 S·cm-1,高于在相同测试条件下Nafion 117膜的质子导电率(0.09 S·cm-1).     

柔性OLED显示用聚酰亚胺基板的合成与性能

合成了一种含吡啶结构的刚性二胺,2-(4-氨基苯基)-5-氨基吡啶(PD),将其与二氨基二苯醚(ODA)以及均苯四甲酸二酐(PMDA)共聚,调控分子链中刚性与柔性结构单元的比例,制备出一系列聚酰亚胺共聚物.结果表明:随着聚酰亚胺中含吡啶结构的刚性二胺PD含量增加,玻璃化转变温度显著提高(Tg450℃),热膨胀系数逐渐降低(CTE5×10~(-6)K~(-1),50～400℃).同时,聚酰亚胺薄膜的拉伸强度提高(1.25倍),模量显著增加(4.53倍),但仍保持较高的断裂伸长率(35%).利用广角X射线衍射(WAXD)分析聚合物聚集态结构表明,含吡啶结构刚性二胺(PD)的引入使聚酰亚胺分子链倾向于有序排列和紧密堆积,结晶度增加.因此,通过调控聚合物链中刚性二胺(PD)含量可使PI薄膜同时达到优异的尺寸稳定性、高耐热性、高强度以及较好的柔韧性,此类PI有望应用于柔性OLED显示领域.     

不同比例的s-BPDA/i-BPDA型聚酰亚胺共聚结构与性能关系

由不同比例的二酐单体3,3′,4,4′-联苯四酸二酐(s-BPDA)/2,2′,3,3′-联苯四酸二酐(i-BPDA)与二胺单体4,4′-二氨基二苯醚(4,4′-ODA)制得了一系列共聚可溶聚酰亚胺. 采用DSC 、TGA和拉伸等测试方法对所得共聚聚酰亚胺进行了表征, 实验结果表明, 所得聚酰亚胺具有优异的力学性能和热稳定性, 并且随着i-BPDA含量的增加, 聚酰亚胺的溶解性提高, 玻璃化转变温度(Tg)升高, 中间体聚酰胺酸的固有黏度降低.     

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...     

Poly(ether‐imide) and related sepiolite nanocomposites: investigation of physical,thermal, and mechanical properties

Novel poly(ether‐imide) and sepiolite nanocomposites were synthesized based on a unique diamine monomer with the aim of improving physical and mechanical properties of final polyimide films. The diamine was polycondensed with 4,4′‐(hexafluoroisopropylidene) diphthalic anhydride to produce related poly(ether amic acid) prepolymer. Pure poly(ether‐imide) and nanocomposite films were prepared via thermal imidization process of poly(ether amic acid). Coexistence of ether, pyridine, and phenylene functional groups in the diamine chemical structure resulted in flexible polyimide films with significant thermal, physical, and mechanical properties. Thermal stability, glass‐transition temperature, dimensional stability, and tensile properties of polymer and nanocomposites were studied and compared. Morphology of nanocomposites was also investigated using scanning and transmission electron microscopic methods to study the distribution and dispersion behavior of sepiolite nanofibers in the polyimide matrix. By introduction of sepiolite nanoparticles, overall improvement of properties was observed in respect to pure polyimides. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis and characterization of soluble polyimides based on a new fluorinated diamine: 4-Phenyl-2,6-bis[3-(4′-amino-2′-trifluoromethyl-phenoxy) phenyl] pyridine

A new kind of pyridine-containing aromatic diamine monomer, 4-phenyl-2,6-bis[3-(4′-amino-2′-trifluoromethyl-phenoxy) phenyl] pyridine (m-PAFP), was successfully synthesized by a modified Chichibabin reaction of 3-(4′-nitro-2′-trifluoro-methyl-phenoxy)-acetophenone with benzaldehyde, followed by a catalytic reduction. A series of fluorinated pyridine-bridged aromatic poly(ether-imide)s were prepared from the resulting diamine monomer with various aromatic dianhydrides via a conventional two-step thermal or chemical imidization method. The inherent viscosities values of these polyimides were in the range of 0.56-1.02 dL/g, and they could be cast and thermally converted into transparent, flexible, and tough polyimide films. The polyimides displayed higher solubility in polar solvents such as NMP, DMSO and m-cresol. The polyimides had good thermal stability, with the glass transition temperatures (T_g) of 187-211 °C, the temperatures at 5% weight loss of 511-532 °C, and the residue at 800 °C in air was higher than 50%. These films also had dielectric constants of 2.64-2.74 at 10 MHz and low water uptake 0.53-0.66%. Wide-angle X-ray diffraction measurements revealed that these polyimides were predominantly amorphous. Moreover, the polymer films of these novel polyimides showed outstanding mechanical properties with the tensile strengths of 90.1-96.6 MPa, elongations at breakage of 8.9-10.7% and tensile modulus of 1.65-1.98 GPa.     

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.     

硫醚型芳香族二胺单体的合成及应用

以对氨基硫酸及４，４＇－二氯基二苯砜为原料合成了含硫醚键芳香族二胺单体：，用它制备的聚酰亚胺显示了良好的耐热性能。     

Preparation of ultrathin films of aromatic polymides by vapor deposition polymerization from N-silylated aromatic diamines or aromatic tetracarboxylic dithioanhydride

A novel method for the preparation of ultrathin films of aromatic polyimides was developed through vapor deposition polymerization from combinations of monomer pairs of either N,N′-bis (trimethylsilyl)-substituted aromatic diamines and pyromellitic dianhydride or aromatic diamines and pyromellitic dithioanhydride. Both diamine component and tetracarboxylic dianhydride component were evaporated simultaneously at a stoichiometric molar ratio under vacuum, giving a deposited film on a substrate, which consisted of a polyamic acid derivative formed by the ring-opening polyaddition. The deposit was then converted to polyimide by thermal imidization at a relatively lower temperature, compared with a conventional method using the parent diamine and tetracarboxylic dianhydride. The properties of polyimide ultrathin films such as thermal stability, chemical resistance, and dielectric behavior were almost the same as those of the polyimide films prepared by a conventional method.     

Influence of Steric Hindrance Between Hydrogen Atoms of Linkage Groups and Adjacent Phenyls on Properties of Polyimide

A diamine monomer 4,4′-methylenedianiline(MDA) was introduced to modify the polyimide of pyromellitic dianhydride(PMDA) and 4,4′-oxydianiline(ODA) by polycondensation. A series of polyamic acids was synthesized from MDA and ODA of different molar ratios with PMDA of sum mole of moles of MDA and ODA, and polyimide films were obtained by thermal imidization. Polyimide(PI) films were characterized by tensile testing, dynamic mechanical analysis(DMA), thermal gravimetry analysis(TGA), Fourier transform infrared spectroscopy (FTIR), wide X-ray diffraction(WAXD) and molecular simulation. With the increase of MDA content, the tensile strength and thermal decomposition temperature remained generally stable compared with those of PMDA/ODA polyimide. Unexpectedly, the glass transition temperature(T_g) and Young’s modulus increased from 388.7 ℃ and 2.37 GPa to 408.3 ℃ and 5.74 GPa, respectively. The results of WAXD and molecular simulation indicate the steric hindrance among hydrogen atoms of the linkage groups and adjacent phenyls enhanced the properties of the polyimide modified with MDA.     

Synthesis and characterization of novel polyimides derived from unsymmetrical diamine:2-Amino-5-[4-(2’-aminophenoxy)phenyl]-thiazole

A new kind of thiazole-containing unsymmetrical ortho-diamine monomer,2-amino-5-[4-(2’- aminophenoxy)phenyl]-thiazole(o-AAPPT),was synthesized by four steps,using 4-hydroxyacetophenone as starting material.A novel thiazole-containing polyimide was prepared from the resulting diamine o-AAPPT with BTDA via a conventional one-step method.The resulting polyimide exhibits excellent solubility,film-forming capability and high thermal and thermo-oxidative stability.     

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.     

Insights into MWCNTs/polyimide nanocomposites: from synthesis to application as free-standing flexible electrodes in low-cost micro-supercapacitors

In the pursuit to enlarge the library of polyimide materials for energy applications, new polyimide/MWCNTs composite films have been developed by MWCNTs-assisted polycondensation reaction of a hydroxyl and triphenylmethane-containing diamine with benzophenone tetracarboxylic dianhydride targeting to highlight their electrical storage capability as flexible electrodes in micro-supercapacitors (mSCs). The Fourier-transform infrared spectroscopy, proton nuclear magnetic resonance, UV–vis, fluorescence, and Raman spectroscopies were used to demonstrate the evolution of interfacial interactions between MWCNTs and the precursors (diamine monomer and intermediate polyamidic acid) and polyimide matrix that proved to be the origin of MWCNTs homogeneous dispersion. Thus, composite films incorporating 1, 3, 5, and 10 w.t.% MWCNTs were obtained and thoroughly investigated with regard to their morphology, mechanical behavior, thermal stability, and electrical conductivity. The electrochemical performance of these composites was first analyzed in a classical three-electrode cell by cyclic voltammetry and galvanostatic charge-discharge in both aqueous and organic electrolyte systems. By far, the best electrical storage capacity was obtained with the composite polyimide film containing 10% MWCNTs that was further used as both active material and current collector in a flexible symmetric mSC realized by a straightforward and low-cost procedure. In the attempt to better exploit the advantages of this composite film, it was layered with a graphite-containing paint and tested as an electrode in a flexible mSC, which provided satisfactory results. To our knowledge, this is the first report on the electrical charge storage capability of a polyimide/MWCNTs free-standing film as a flexible electrode in mSCs, which do not require time- and resource-consuming processing steps.     

Synthesis of a new pyridine-containing diamine and related polyimide

<正>A new kind of aromatic diamine monomer containing pyridine unit,2,6-bis[4-(4-aminophenoxy)phenoxy]pyridine(BAPP),was synthesized in three steps,using hydroquinone as starting material.A novel pyridine-containing polyimide was prepared from the resulting diamine BAPP with 4,4'-oxydiphthalic anhydride(ODPA) via a conventional two-step thermal imidization method.The resulting polyimide exhibits excellent solubility,film-forming capability and high thermal resistance.