含酞菁功能基聚苯胺的合成及性能研究：Ⅰ.酞菁铜磺酸掺杂聚苯胺的合成与表

以耐晒翠蓝为原料合成了酞菁铜磺酸（ＣｕＰｃＳ）,用其对本征态聚苯胺分别在水相和油相中进行掺杂,获得了具有酞菁功能基了聚苯胺的分子结构。该聚合物具有优良的溶解性能和成膜能力,电导率达到１０Ｓ／ｍ,红外谱图证实了所合成产物的结构,紫外吸收分析表明,用酞菁铜磺酸掺杂聚苯胺后在可见光区、近红外区具有较强的吸收,可大幅度提高其光电导性能。     

含酞菁功能基聚苯胺的合成及性能研究Ⅰ.酞菁铜磺酸掺杂聚苯胺的合成与表征

以耐晒翠蓝为原料合成了酞菁铜磺酸(CuPcS),用其对本征态聚苯胺分别在水相和油相中进行掺杂,获得了具有酞菁功能基聚苯胺的分子结构.该聚合物具有优良的溶解性能和成膜能力,电导率达到10S/m,红外谱图证实了所合成产物的结构,紫外吸收分析表明,用酞菁铜磺酸掺杂聚苯胺后在可见光区、近红外区具有较强的吸收,可大幅度提高其光电导性能.     

PMLG／PDMSA—B—A型三嵌段共聚膜的微相结构

在Ｌ－谷氨酸－γ－甲酯与聚二甲基硅氧烷合成ＰＭＬＧ／ＰＤＭＳＡ－Ｂ型嵌段共聚膜的基础上,进一步成功合成了Ａ－Ｂ－Ａ型嵌段膜。用ＩＲ、Ｘ－Ｒａｙ等测试方法确认了不同共聚组成ＭＳｉＭ膜的相区的结构及特征,结果表明：Ａ、Ｂ组份不仅存在的不同的微相结构,而且在其介面区域的ＰＭＬＧ（Ａ组份）部分还产生了无规线团结构。     

聚苯胺的光学吸收及其染料增感作用研究EI

对笔者合成的不同结构与性能的聚苯胺因电子或极子跃迁而引起的可见 -近红外区的吸收特性进行了研究。详细讨论了掺杂聚苯胺分子构象对其光学吸收的影响。对该聚合物的染料增感作用研究发现 ,孔雀绿、酞菁铜和分散橙对于该聚合物均有增感作用 。     

酞菁铜羧酸掺杂聚苯胺薄膜制备表征及光电性研究

成功制备了酞菁铜羧酸掺杂聚苯胺(PANI)薄膜.红外光谱测试结果说明酞菁铜羧酸的羧基和聚苯胺的氨基发生了酸碱中和反应,即成功的对聚苯胺进行了掺杂.紫外可见光谱说明酞菁铜羧酸掺杂后PANI在紫外区有强吸收峰,在可见光区吸收变宽.光电性能测试结果表明掺杂后酞菁铜使聚苯胺对光的敏感性增强,更容易受光子的激发,因而具有更优越的光电性.     

敏化剂修饰纳米晶TiO2多孔膜电极的光电化学行为

在TiO2纳米晶多孔膜电极上,修饰了合成的RuL2(SCN)2(L＝2,2′-bipyridine-4,4′-dicarboxylic acid)及聚苯胺,用光电化学方法研究了该纳米晶TiO2/敏化剂多孔膜电极的光电转换机理,并比较了两类敏化复合电极的光电转换效能.用染料或聚苯胺修饰纳米晶多孔膜电极后,可使该复合电极在可见光区吸收增加,光电流增强,且起始波长红移至＞600 nm,从而提高了宽禁带半导体电极的光电转换效率.     

可生物降解PCL/PEG嵌段共聚物的合成与表征

研究了以辛酸亚锡为催化剂的ε－己内酯与聚乙二醇在１１０℃的熔体开环聚合制备ＰＣＬ／ＰＥＧ嵌段共聚物,分频加入ε－己内酯对嵌段聚合物的分子量有大幅度提高,研究了催化剂量、反应时间及ＰＥＧ分子量对ＰＣＬ／ＰＥＧ嵌段共聚物合成反应的影响。     

高分子p—n异质结太阳电池的研究

用合成的十二烷基苯磺酸（ＤＢＳＡ）掺杂的聚苯胺（ＰＡｎ）导电材料和Ｂｅｉ染料组合，采用涂覆技术，研制成ＳｎＯ２／ＰＡｎ膜／Ｂｅｉ染料薄层／Ａｌ栅电极结构和Ａｌ／ＰＡｎ导电基片／Ｂｅｉ染料薄层／Ａｌ栅电极结构的ｐ－ｎ异质结太阳电池，测定了该电池的光电效应和伏安特性，在４．７２ｍＷ／ｃｍ＾２的氙灯照射下，开路电压Ｖｏｃ达４００ｍＶ短路电流Ｉｓｃ为１０μＡ，填充因子可达５７．４％，光电转换效率为０．０９     

CuPc／ZnS多层复合薄膜的光电性能研究

本文首次报道了用真空热蒸发法制备ＣｕＰｃ／ＺｎＳ交替多层复合薄膜,研究ＣｕＰｃ和ＺｎＳ的层数以及制备工艺对薄膜光电性能和结构的影响。利用光电导特性测量仪、紫外可见光谱仪和Ｘ射线衍射仪等设备分析了复合薄膜的结构和光电性能,探讨了有机／无机复合薄膜的光电导机理,提出了理论模型。     

共聚法引入甲基对聚苯胺结构及电导率的影响

通过间甲基苯胺与苯胺在右旋樟脑磺酸水性介质中进行化学氧化共聚得到它们各自的均聚物及共聚物,在聚苯胺链段上引入甲基来改变产物的结构与电导率。用FT-IR、UV-Vis、XRD、SEM方法表征聚合物的分子链结构与微观形貌,用四探针法测定聚合物电导率。结果表明,所得聚合物为直径100nm左右的短纤维,聚苯胺分子链上甲基的引入削弱了苯环之间的π-π共轭,使FT-IR、UV-Vis光谱特征峰发生蓝移。在单体总浓度一定的条件下,可通过调节单体比例将聚合物的电导率控制在0.02～6.50S/m的范围内。XRD谱图分析表明,甲基还具有诱导聚苯胺分子链取向的作用,使聚苯胺链聚集态规整性提高。     

可溶性聚苯胺/聚乙烯醇掺杂氧化石墨烯复合材料的制备

通过加入十二烷基苯磺酸钠(SDBS)制备了可溶性的聚苯胺/聚乙烯醇掺杂氧化石墨烯导电复合材料。通过XRD、SEM、TEM、FT-IR、TGA、CV对合成的复合材料进行了表征和分析,结果表明聚苯胺/聚乙烯醇能够插入到氧化石墨烯的层间和包裹在氧化石墨烯的表面形成复合物。用十二烷基苯磺酸钠掺杂的聚苯胺/聚乙烯醇/氧化石墨烯材料具有很好的溶解性和导电性能,将复合物进行还原和再次用酸掺杂之后,发现复合材料的导电性得到进一步提升。     

The effect of carbon nanotube dispersion on CO gas sensing characteristics of polyaniline gas sensor

Polyaniline is one of the most promising conducting polymers for gas sensing applications due to its relatively high stability and n or p type doping capability. However, the conventionally doped polyaniline still exhibits relatively high resistivity, which causes difficulty in gas sensing measurement. In this work, the effect of carbon nanotube (CNT) dispersion on CO gas sensing characteristics of polyaniline gas sensor is studied. The carbon nanotube was synthesized by Chemical Vapor Deposition (CVD) using acetylene and argon gases at 600 degrees C. The Maleic acid doped Emeradine based polyaniline was synthesized by chemical polymerization of aniline. CNT was then added and dispersed in the solution by ultrasonication and deposited on to interdigitated AI electrode by solvent casting. The sensors were tested for CO sensing at room temperature with CO concentrations in the range of 100-1000 ppm. It was found that the gas sensing characteristics of polyaniline based gas sensor were considerably improved with the inclusion of CNT in polyaniline. The sensitivity was increased and response/recovery times were reduced by more than the factor of 2. The results, therefore, suggest that the inclusion of CNT in MA-doped polyaniline is a promising method for achieving a conductive polymer gas sensor with good sensitivity, fast response, low-concentration detection and room-operating-temperature capability.     

Hierarchical composites of conductivity controllable polyaniline layers on the exfoliated graphite for dielectric application

Hierarchical composites of polyaniline fibers on the surface of exfoliated graphite were synthesized by chemical oxidation method. The conductivity of polyaniline fibers was controlled by doping and dedoping procedures. The morphology, structure and chemical character of doped and dedoped hierarchical composites were systemically investigated by SEM, TEM, XRD, FT-IR, XPS and conductivity measurement. After dedoping procedure, polyaniline/exfoliated graphite composites were used to improve dielectric property of the electroactive polymer poly(vinylidene fluoride). The dielectric constant and loss tangent of composites were 17 and 0.06 (10³ Hz) when the polyaniline/exfoliated graphite loading was 3 wt%. Of great interest was that the dielectric loss tangent of composites showed inherent low loss of poly(vinylidene fluoride) because insulating polyaniline fibers on the surface of exfoliated graphite effectively prevented direct contact of exfoliated graphite flakes in poly(vinylidene fluoride) matrix.     

聚苯胺复合膜的制备及性质

用溶液共混法制备聚苯胺与聚酰胺的复合膜,并研究了复合膜的性能。将化学氧化法制备的本征态聚苯胺用樟脑磺酸(PANI—CSA)掺杂后,与基体聚合物聚酰胺-66,聚酰胺-1010或聚酰胺-11同时溶解在间甲酚溶剂中,干法浇膜,制得的复合膜的电导率处于10^-6S／m～10^2S／m范围,导电阈值2％。DSC法对复合膜热性能和结晶性能进行了研究。采用三种不同pH值的溶液对复合膜进行了处理,对其导电性能的变化进行了测试。     

Influence of conductive electroactive polymer polyaniline on electrochemical performance of LiMn1·95Al0·05O4 cathode for lithium ion batteries

Conductive electroactive polymer polyaniline is utilized to substitute conductive additive acetylene black in the LiMn_1·95Al_0·05O₄ cathode for lithium ion batteries. Results show that LiMn_1·95Al_0·05O₄ possesses stable structure and good performance. Percolation theory is used to optimize the content of conductive additive in cathode. It shows that the conductivity of cathode reaches its maximum value when the content of conductive additives is 15 wt%. This is in agreement with the results of charge and discharge experiments. The application of polyaniline can evidently enhance the electrochemical performance of cathode. The discharge capacity of cathode using 15 wt% polyaniline is 95·9 mAh g^???1 at the current density of 170 mA g^???1. The charge transfer resistance under different depths of discharge of cathode is much lower compared with the use of acetylene black. It can be concluded that the application of polyaniline in cathode can greatly improve the electrochemical performances of LiMn_1·95Al_0·05O₄ cathode.     

Interfacial polymerization to high-quality polyacrylamide/polyaniline composite hydrogels

Conducting polymer hydrogels composed of polyacrylamide (PAAm) and polyaniline (PAn) have been successfully synthesized through the interfacial polymerization. Compared to the conventional preparation methods, the interfacial polymerization is much more economical and effective because the PAn formed at the water/organic-solvent interface assembles spontaneously and exclusively into the PAAm hydrogel. In contrast to conventional materials, the resulting PAAm/PAn composite hydrogel exhibits high qualities including homogeneous structure, enhanced mechanical toughness, high electrical conductivity and the ability to reversibly interconvert between the doped and dedoped states. As-described interfacial polymerization for the fabrication of conducting polymer hydrogels does not depend on specific kinds of organic solvents or acid dopants.     

原位聚合法制备炭黑/聚甲基丙烯酸酯导电复合材料

通过原位聚合法制备了炭黑/聚甲基丙烯酸甲酯(CB/PMMA)、炭黑/聚甲基丙烯酸丁酯(CB/PB-MA)和炭黑/聚甲基丙烯酸2-乙基己酯(CB/PEHMA)三种导电复合材料,研究了这三种聚合物基体对复合材料的导电性影响。结果表明:由于炭黑的阻聚作用,当复合材料的炭黑含量增加时,均聚物的数均分子量呈下降趋势,多分散性系数PDI变大。而且炭黑粒子表面发生了接枝聚合反应,这有利于炭黑粒子在聚合物基体中的分散。当聚合物基体的玻璃化温度Tg较高时,复合材料逾渗阈值较低。     

Metal oxalate complexes as novel inorganic dopants: Studies on their effect on conducting polyaniline

Doped polyaniline materials with metal oxalate complexes of Cr, Fe, Mn, Co and Al were synthesized byin situ chemical oxidative polymerization of aniline using potassium perdisulphate as oxidant in aqueous sulphuric acid medium. These polymer materials were characterized by chemical analyses, spectral studies (UV-visible and IR), X-ray diffraction and thermal techniques and also by conductivity measurements by four-probe technique. The presence of complex anion in polyaniline material was confirmed by chemical and spectral analyses. The yield and conductivity of metal oxalate doped polyanilines were found to be high when compared to the simple sulphate ion doped polyaniline prepared under similar condition. UV-visible and IR spectral features not only confirmed the polyaniline doping by complex anions but also substantiated their facilitating effect on conductivity. The X-ray diffraction patterns indicated some crystalline nature in metal oxalate doped polyaniline and amorphous in polyaniline sulphate salt. The conductivity of the polymer samples strongly depended on the degree of crystallinity induced by complex counter anions as dopant. All the polymer materials, as evident from TGA curves, were observed to undergo three-step degradation of water loss, de-doping and decomposition of polymer. Further, the thermal stability of polyaniline was found to improve on doping with metal oxalate complex.