聚苯胺/离子液体/蒙脱土纳米复合材料的制备及其导电性能研究

采用1-羧甲基-3-甲基咪唑氯化盐离子液体对钠化蒙脱土进行插层改性,然后用苯胺的盐酸溶液进行二次插层,以过硫酸铵为氧化剂,盐酸溶液为掺杂剂,使进入离子液体/蒙脱土(CMMIm/MMT)层间的苯胺(An)发生氧化聚合反应,制备了一种具有良好导电性的聚苯胺/离子液体/蒙脱土复合材料(PANI/CMMIm/MMT).用红外光谱、X-射线衍射,热重分析和DSC对样品进行了表征.结果表明当离子液体/蒙脱土用量为7.5%、盐酸浓度为1mol/L、过硫酸铵与苯胺的摩尔比为1∶1、0℃下反应6h时制备的PANI/CMMIm/MMT纳米复合材料电导率最高,达到了0.3S/cm,是相同条件下聚苯胺/钠化蒙脱土纳米复合材料电导率的2.5倍,聚苯胺的7.5倍.     

苯胺的化学聚合

本文研究了氧化剂浓度、聚合溶液酸浓度、苯胺浓度以及氧化剂种类对苯胺化学氧化聚合的影响.结果表明,聚合条件的改变强烈地影响聚合物收率、电导率以及分子结构.本文初步给出了合成具有较高电导率聚苯胺的实验条件范围.     

复合氧化剂在合成导电聚苯胺中的应用

以苯胺为原料 ,采用 (NH4) 2 S2 O8和碳酸酯类过氧化物组成的复合氧化剂 ,在常温条件下 ,合成了电导率达 5.8s/cm、产率达 82 %的聚苯胺。     

原位氧化聚合制备导电PAn-PC和PAn-SIR复合膜

以聚碳酸酯（PC）和硅橡胶（SIR）为基体浸泡于苯胺（An）的盐酸溶液中,然后经氧化剂（NH4）2S208（APS）或FeCl3在基体中原位氧化聚合,制备导电聚苯胺（PAn）复合材料PAn-PC和PAn-SIR。研究了聚合反应的工艺条件对复合材料导电性能的影响,确定了合适的制备条件。采用扫描电镜（SEM）及荧光光谱对复合膜进行表征。     

聚苯胺/纳米二氧化锰复合材料Ⅰ.原位氧化合成制备

用固相合成法制备了纳米二氧化锰(nm-MnO2),并通过原位聚合法制备了聚苯胺／纳米二氧化锰复合材料。研究结果表明：在苯胺／nm-MnO2的盐酸反应体系中,nm-MnO2可以使苯胺氧化聚合。在一定的nm-MnO2用量下,聚苯胺的产率随苯胺添加量的增加而下降,nm-MnO2在产物中的含量也随之下降,且含量很低。在苯胺：／nm-MnO2／过硫酸铵的反应体系中,研究了Nm-MnO2通过两种不同的加料方式原位制备PA-NI／nm-MnO2复合材料的合成条件。第一种方式为nm-MnO2和过硫酸铵同时与苯胺混合,一起参与苯胺的氧化聚合。第二种方法是先将过硫酸铵和苯胺混合,3min后再将nm-MnO2加入反应体系中。研究表明：第一种加料方式得到的队NI／nm-MnO2中nm-MnO2的含量很低;第二种加料方式可以得到高nm-MnO2含量(w=0．14-0．73)的产物,其电导率约10^-4S／cm。     

二氧化锰氧化制备聚苯胺及其超级电容性能

以二氧化锰为氧化剂在酸水体系中化学氧化制备了聚苯胺(PANI),考察了聚合条件对产率的影响。采用红外光谱、扫描电镜等手段对PANI的结构与形貌进行了表征,采用电化学工作站对其电化学电容性能进行了测试。结果表明:PANI产率随着体系中氧化剂用量的增加、苯胺用量的减少、反应温度的降低和反应时间的延长而增加,制备的聚苯胺主要是翡翠亚胺型聚苯胺,并以颗粒形式存在,大小在100 nm左右,局部有团聚现象,颗粒间堆积蓬松;该聚苯胺作为超级电容器活性电极材料,具有较好的电化学电容性能,最高比电容达到178 F/g。     

掺杂质子酸的类型对聚苯胺结构和电导率的影响

采用化学氧化聚合法以苯胺为单体，过硫酸铵为氧化剂，在不同质子酸的水溶液中合成聚苯胺，考察质子酸对聚苯胺电性能影响，并通过傅立叶红外吸收光谱（FTIR）和紫外可见光吸收光谱（UV－vis)研究聚苯胺掺杂前后结构的变化。结果表明，龙质子酸掺杂后聚 胺具有导电性是因为其分子链上电荷离城形成了共轭结构，具有不同质子酸中生成的聚苯胺氧化程度不同；分子链共轭程度与掺杂酸对阴离子大小有关，掺杂质子酸对阴离子越大，聚苯胺分子链共轭程度越大，电导率也就越高。     

复合酸掺杂导电聚苯胺的性能研究

以苯胺为单体、过硫酸胺为氧化剂,由化学氧化聚合法在磺基水杨酸和硫酸的复合酸的水溶液中合成导电聚苯胺,并通过压片法、激光粒度分析、扫描电镜、差热分析及红外光谱对掺杂态聚苯胺的电导率、表面形貌及结构进行了研究.结果表明,复合酸掺杂聚苯胺的热稳定性比仅用硫酸掺杂聚苯胺的有了很大的提高;所得导电聚苯胺的粒度分布比较均匀(平均粒径约15.4μm);复合酸掺杂使聚苯胺分子链上的电荷呈离域化,掺杂程度提高.     

反应温度对衣康酸掺杂聚苯胺性能的影响

以衣康酸为掺杂剂,过硫酸铵为引发剂,采用化学氧化聚合法在不同的反应温度下合成聚苯胺(PANI)。计算其产率和电导率,并测定掺杂态聚苯胺的各项性能指标。通过电阻测试、傅立叶红外光谱测试(FT-IR)、紫外-可见光谱测试(UV-vis)、电子探针分别对产物的导电性、化学结构、紫外可见光谱和微观形貌进行了表征。结果表明,低温有利于减缓链终止的速度使得产物分子链较长,从而使载流子的传输更容易进行,产物电导率高;而温度高于10℃会使聚苯胺氧化断链,使产物电导率下降。以反应温度为10℃时电导率最高,为1.29×10-2(S·cm-1),且具有最高的产率为111.2%,微观形貌为纳米棒状结构。     

原位聚合法制备聚酰胺/聚苯胺复合导电纤维

研究了原位聚合法制备聚酰胺/聚苯胺导电纤维,并对制备的复合纤维进行红外及光学显微镜测试,结果表明聚苯胺与纤维成功复合。对制备的复合纤维进行电导率测试,采用控制单一变量法探讨了苯胺单体在不同的条件下聚合对纤维电导率的影响,并讨论了反应温度对聚合过程和电导率的影响,得出最佳的工艺条件为:纤维经30%的甲酸溶液预处理20min,苯胺单体浓度为0.8M,氧化剂过硫酸铵浓度为1M,掺杂酸为盐酸,浓度为0.8M,冰水浴条件,反应时间为4h,得到的聚酰胺/聚苯胺导电纤维的电导率为3.7S/m。     

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.