气体膜分离用过渡金属有机络合物聚酰亚胺杂化材料的研究

用三苯二醚四酸二酐 (HQDPA)或二苯酮四酸二酐 (BTDA)与二氨基二苯甲烷 (MDA)缩聚合成出聚酰胺酸溶液 ,将此溶液与过渡金属有机络合物共混 ,再经热亚胺化即可制备出一类新型的气体膜分离用过渡金属有机络合物 聚酰亚胺杂化材料 .对所得杂化材料的各项性能进行了研究 ,结果表明 ,制得的杂化材料保持了聚酰亚胺良好的力学性能、耐热性能和耐溶剂性能 .用广角X 射线衍射和液体天平对所得材料的结构进行了表征 ,结果表明 ,过渡金属有机络合物的加入能够增加聚酰亚胺材料的分子链间距 .因此 ,与相应的聚酰亚胺相比 ,杂化材料的透气系数增大而透气选择性变化不大 .     

溶胶-凝胶法制备聚酰亚胺/二氧化钛感光杂化材料

高聚物 -无机物纳米杂化材料的研究已成为当今高分子化学和物理、无机化学和材料化学等许多学科交叉的前沿领域 [1] .聚酰亚胺因其特有的优越性能而成为聚合物中的热选材料 ;感光聚酰亚胺除具备常规聚酰亚胺的优良性能 ,还由于可在材料上直接刻蚀图形 ,简化工艺步骤 [2 ] ,作为通信产业中光波导、光联接等装置的材料而受到市场的关注 .目前有很多关于无机材料 Ti O2 和 Si O2 用于电光领域材料[3～ 5] 及其与聚合物形成的杂化材料用于制作光波导、光联结等电光领域的文献 [6,7] 报道 ,但很少见到可直接刻蚀图形的无机 /聚酰亚胺杂化材料 […     

UV固化丙烯酸酯化有机硅及杂化材料的研究与应用

丙烯酸酯化有机硅及杂化材料因兼具有机硅材料的优异性能和光固化的高效、节能及环保等特点而得到广泛的应用。文章综述了光敏性丙烯酸酯化有机硅单体的种类、结构特点及其制备方法,分析了紫外光（UV）固化后聚合物及其杂化材料的性能,介绍了它们的研究与应用现状及其发展前景。     

聚酰亚胺／SiO_2杂化材料的硅核磁共振波谱和电光性质的研究

以含氟的二胺5,5’-(六氟异丙基)-二-(2-氨基苯酚)(6FHP)及二酐4, 4’-(六氟异丙基)-苯二酸酐(6FDA)或均苯四甲酸酐(PMDA)为单体,以分散红 1(DR1)为活性生色分子合成具有非线性光学特性的含氟聚酰亚胺,并采用溶胶-凝胶(Sol-Gel)法合成相应的聚酰亚胺／SiO2杂化材料．采用固态29 Si MAS NMR谱研究了含氟聚酰亚胺／SiO2杂化材料的交联结构,结果表明杂化材料中是以T3、Q3、Q4结构为主,说明在杂化材料中形成了交联网状结构．采用衰减全反射(ATR)测定了聚酰亚胺和杂化材料在832 nm处的电光系数,其值分别为 32、28、34和29 pm／V,结果表明具有较高的电光系数．     

铂纳米簇/聚酰亚胺杂化膜反应器的制备及其在催化苯部分加氢中的应用

研究了铂纳米簇/光敏性聚酰亚胺(Pt/PSPI)杂化膜在苯部分加氢制环己烯反应中的催化性能. 通过微波加热法还原氯铂酸, 制备了单分散 Pt 纳米簇, 并将其掺入到光敏性聚酰胺酸基体中, 通过热亚胺化法得到 Pt/PSPI 杂化膜. 透射电镜表明, 铂纳米颗粒平均粒径为 3.7 nm. 用 Pt/PSPI 催化液相苯加氢反应, 环己烯选择性达到 72.4%.     

光敏聚酰亚胺的最新进展

综述光敏聚酰亚胺作为感光高分子的最新进展，着重叙述了有机硅改性光敏聚酰亚胺，自增感光敏聚酰亚胺和含氟光敏聚酰亚胺的制备方法和性能研究。     

杂化材料的制备、性能及应用

较详细地介绍了杂化材料的概念及其制备方法、性能和应用。重点是有机高分子－无机杂化材料的制备、性能及应用。     

PMDA-6FHP-DR1/SiO2杂化纳米材料的结构设计和合成

以含氟的二胺5,5′ (六氟异丙基) 二 (2 氨基苯酚)及均苯四甲酸酐(PMDA)为单体,首先合成了经酰胺化的主链上带有活性羟基的含氟聚酰亚胺,再通过Mitsunobu反应将活性生色分子分散红1(DR1)共价链接到聚酰亚胺的侧链骨架上,合成了含氟聚酰亚胺.采用溶胶 凝胶(Sol Gel)技术,并利用偶联剂γ 氨丙基三乙氧基硅烷(APTES)制备带有发色团的和含有硅氧烷端分子的聚酰胺酸,其中的Si(OR)3基经水解、缩合后,与正硅酸乙酯(TEOS)在催化剂作用下反应,经杂化、凝胶后,得到光学透明且热稳定性高的有机/无机杂化材料.将制得的含氟聚酰亚胺/SiO2杂化材料,采用红外光谱(FT IR)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射(XRD)、示差扫描量热法(DSC),对材料的结构、表面形貌、热性能进行了表征.     

有机无机杂化膜材料的制备技术

有机无机杂化膜兼有机膜韧性和无机膜耐高温性能,具有优良的气体渗透选择性,成为高分子化学和材料科学等领域的研究热点.本文综述了近年来有机无机杂化膜材料的制备技术进展,着重探讨了溶胶-凝胶法制备聚酰亚胺类杂化膜材料的研究状况,并作了简要述评。     

聚合物纳米杂化高性能光功能材料

近年来材料科学与技术的不断发展,对光学材料提出了高性能化和多功能化的需求,为此,研究者们结合传统有机聚合物光学材料和无机光学材料的优势,提出了备受关注的聚合物纳米粒子杂化的策略.本文首先概述了针对杂化材料透光性进行控制的杂化方法,指出杂化方法的选择很大程度上与材料性质尤其是纳米相的性质相关,而杂化方法的目的则在于实现纳米杂化材料的透光性控制,纳米杂化光功能材料实现功能的前提即为透光性.随后,分别介绍了聚合物纳米杂化策略在高折射率材料与发光材料中的应用.对于高折射率材料,总结了提升材料折射率的不同策略.对于发光材料,总结了基于聚合物相和纳米相之间不同的相互作用而采用各种杂化方式以及相关的性能提升.接下来,讨论了聚合物纳米杂化光功能材料在光学和机械、热学、表面性能方面的调控手段和性能提升的策略.最后,提出了下一代光学杂化材料所面临的困难与挑战,以进一步推动这一领域的发展.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.