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.     

新型斑蝥素羧酸衍生物的合成及其抗癌活性

以DMSO为溶剂,5-氟脲嘧啶(5-Fu)为修饰物,对去甲斑蝥素(2)酸酐环部分进行结构修饰,合成了一个新型的去甲斑蝥素羧酸衍生物(3),其结构经1H NMR和IR表征。采用L9(34)正交试验考察了原料比,反应温度,反应时间及溶剂用量对反应的影响。结果表明,在最佳反应条件[2 0.5 mmol,n(2)∶n(5-Fu)=1.2,于140℃反应6 h,DMSO用量15 mL]下制备的3收率为78.2%。采用MTT法研究了体外3对人肝癌细胞HepG2的抑制活性。结果表明,3在用药量为250μmol·L-1时对HepG2的抑制率为89.5%,其IC50为232.4μmol·L-1。     

反相离子对抑制色谱法分析聚酰亚胺树脂溶液单体成分

使用C18反相液相色谱柱,以乙腈和水作为流动相,以甲基磺酸作为离子对试剂,并加入高氯酸钠以增强离子强度,采用等度洗脱,建立了单体反应物原位聚合型（PMR型）的聚酰亚胺树脂溶液中单体成分分析的反相离子对抑制液相色谱法。并对树脂单体材料的纯度以及PMR型树脂溶液中的单体及单体异构体成分进行了分析。     

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...     

DDBT类可溶性聚酰亚胺的合成与性能研究

由二甲基-5,5'-3,7-二苯并噻吩二胺（DDBT）和3,3',4,4'-二苯砚四羧酸二酐（DSDA）、2,2'-双（3,4-二羧酸）六氟丙烷二酐（……FDA）、均苯四羧酸二酐（PMDA）、联苯四羧酸二酐（BPDA）等多种二酐单体进行缩聚反应制备了新型可溶性聚酰亚胺。测定了其特性粘度为0.6-0.9dL/g;DDBT与DSDA、6FDA反应得到的聚酰亚胺在非质子强极性溶剂中具有良好的溶解性。用IR、热力学分析等手段对DDBT类聚酰亚胺进行了表征,并对可溶性DDBT-DSDA聚酰亚胺膜作了进一步的研究,推导出了苯在DDBT-DSDA聚酰亚胺膜中动态吸附初期的吸附方程。实验结果表明DDBT-DSDA聚酰亚胺膜对苯具有特殊的亲和力。     

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.     

含异山梨醇结构单元聚酰亚胺的合成与表征

以异山梨醇为原料,合成了含异山梨醇的二胺单体.将该单体与4,4′-(六氟异丙基)双邻苯二甲酸二酐(6FDA)反应,制备了含异山梨醇结构单元的聚酰亚胺.采用红外光谱、氢核磁共振、紫外光谱和热分析等手段,对产物的结构、热性能及光学性能等进行了表征.结果表明,所得到的聚酰亚胺具有较好的热稳定性和光学性能、并在极性溶剂中具有较好的溶解性.     

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.     

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。     

原子转移自由基聚合法用于以单分散树脂为基质的强阳离子交换色谱固定相的制备及其色谱性能研究

以7μm单分散交联聚甲基丙烯酸环氧丙酯树脂表面键合溴异丁酰溴为引发剂,以CuCl/CuCl2/2,2-联二吡啶(Bpy)为催化体系,采用封闭体系,在氮气保护下,以乙烯基苯磺酸钠(NaSS)为单体、N,N-二甲基甲酰胺(DMF)水溶液为溶剂,制备了强阳离子交换色谱(SCX)固定相,并用元素分析与红外光谱法对其进行了表征....     

Properties of polyimide films doped with copper complexes

Polyimide films based on either 3, 3′, 4, 4′-benzophenone tetracarboxylic acid dianhydride or pyromellitic dianhydride with 4,4′-oxydianiline have been doped with copper(I) and copper(II) complexes. High-quality, flexible, glass-cast films have been obtained which exhibit increased softening temperatures and lower polymer decomposition temperatures. The atmosphere and glass sides of the films are quite different. The copper(I) dopant is oxidized on the air side of the film, while the glass side contains predominantly copper (I). In the copper(II) case most of the copper appears on the air side as a silvery substance in the Cu(II) state. Chemical as well as ion etching can remove this material. Electrical resistivity of the copper(II)-doped films is decreased by three to five orders of magnitude relative to the polymer alone.     

Amine–quinone polyimide: A new high‐temperature polymer and its use to protect iron against corrosion

A new diamine monomer was synthesized by the Michael addition of 4,4′‐methylene dianiline with 1,4‐benzoquinone. The monomer was condensed with 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride to give a polyamic acid that was soluble in NMP. The polyamic acid was cast onto iron and thermally imidized to yield the amine–quinone polyimide (AQPI‐2). AQPI‐2 had a thermal decomposition temperature of 540 °C (10% TGA weight loss in N₂) and a glass transition at 292 °C, values typical of polyimides. The degradation of the coating on iron after exposure to 0.1 M NaCl electrolyte was followed by electrochemical impedance spectroscopy. Under these conditions a conventional polyimide failed after 3 days exposure, while AQPI‐2 survived more than 24 days exposure. The adhesive bond between the amine–quinone polyimide and the iron surface was so strong that it could not be broken by the electrolyte. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2893–2899, 2000     

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.     

聚酰亚胺碳分子筛气体分离膜的研究进展

聚酰亚胺碳分子筛膜由于具有较高的热稳定性、耐化学性、气体渗透性和选择性,而受到广泛关注。根据近年来聚酰亚胺碳分子筛膜在气体分离方面的研究现状,详细介绍了填充改性、对前驱体进行预处理和聚酰亚胺单体改性的研究成果,并展望了聚酰亚胺碳分子筛分离膜的发展趋势,以期为未来高效分离膜的研发提供参考。     

聚甲基丙烯酸甲酯-聚甲基丙烯酸两亲性嵌段共聚物的制备及自组装形态的研究

以2-溴异丁酸乙酯为引发剂, 氯化亚铜/联二吡啶为催化剂, 通过原子转移自由基聚合(ATRP)获得分子链末端含一个α-溴原子的聚甲基丙烯酸甲酯(PMMA-Br), 以此为大分子引发剂引发甲基丙烯酸铅[Pb(MA)₂]单体进行ATRP反应, 制得P[MMA-b-Pb(MA)_2]嵌段共聚物, 将此共聚物在盐酸中进行离子交换即得聚甲基丙烯酸甲酯-聚甲基丙烯酸的两亲性嵌段共聚物[P(MMA-b-MAA)]. 用FTIR, GPC, NMR和SEM方法对共聚物进行了表征.     

甲基丙烯酸(N,N-二甲氨基)乙酯的自引发催化氧化聚合

作为一种自身还原性单体,甲基丙烯酸(N,N-二甲氨基)乙酯(DMAEMA)可与部分氧化剂构成氧化还原引发剂体系,并引发自身的聚合.为验证该假设,进行了以CuCl2络合物催化DMAEMA的本体氧化聚合.动力学研究表明,所得聚合物的分子量随着聚合时间的延长而逐渐增加.核磁波谱分析表明,低转化率下所得低聚物同时含有甲基丙烯酸酯末端和C-Cl端基,显示DMAEMA的二甲氨基(N-CH3)被CuCl2氧化成单体自由基(N-CH2·),并通过原子转移自由基聚合(ATRP)机理形成聚合物.由于叔胺广泛地用作ATRP的络合物,由此可见,在传统ATRP体系中,来自CuCl2/叔胺的氧化还原引发不可忽略.     

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.     

On the interaction of ascorbic acid and the tetrachlorocuprate ion [CuCl4]2- in CuCl nanoplatelet formation from an ionic liquid precursor (ILP)

The formation of CuCl nanoplatelets from the ionic liquid precursor (ILP) butylpyridinium tetrachlorocuprate [C(4)Py](2)[CuCl(4)] using ascorbic acid as a reducing agent was investigated. In particular, electron paramagnetic resonance (EPR) spectroscopy was used to evaluate the interaction between ascorbic acid and the Cu(II) ion before reduction to Cu(I). EPR spectroscopy suggests that the [CuCl(4)](2-) ion in the neat IL is a distorted tetrahedron, consistent with DFT calculations. Addition of ascorbic acid leads to the removal of one chloride from the [CuCl(4)](2-) anion, as shown by DFT and the loss of symmetry by EPR. DFT furthermore suggests that the most stable adduct is formed when only one hydroxyl group of the ascorbic acid coordinates to the Cu(II) ion.     

Asymmetrische Katalysen, 73. Mitt. Enantioselektive Decarboxylierung von Methylphenylmalonsäure-Derivaten mit Cu(I)/Alkaloid-Katalysatoren

Summary Methylphenylmalonic acid was decarboxylated to yield 2-phenylpropionic acid with an optical induction of 36% ee using catalytic amounts of CuCl and an excess of (+)-cinchonine in acetonitril. Methylphenylmalonic acid hemiethylester gave ethyl 2-phenylpropionate of 20% ee with catalytic amounts of CuCl and (+)-cinchonine, respectively. The tetraethylammonium salt of methylphenylmalonic acid could be decarboxylated in the presence of CuCl, (+)-cinchonine, and chiral carboxylic acids, the best result of 27% ee being obtained with malic acid.

     

含氟苯乙炔苯胺封端聚酰亚胺的合成与性能研究

设计并合成了一种含氟苯乙炔苯胺封端剂4-苯乙炔基-3-三氟甲基苯胺(3FPA),使用3FPA与4,4′-(六氟异丙基)双邻苯二甲酸二酐(6FDA)和对苯二胺(p-PDA)制备了计算分子量为5000的聚酰亚胺树脂3FPA-PI-50,并对树脂溶液、树脂模塑粉和树脂模压件的制备与性能进行了研究,实验结果表明3FPA-PI-50树脂溶液具有良好的储存稳定性,成型后树脂具有优异的热性能和热氧化稳定性,后固化后树脂玻璃化转变温度为404℃,5%热失重温度大于530℃.此外树脂具有低的介电常数和吸水率.