基于苝酸酯受体光伏器件的性能表征

近十几年来,基于有机聚合物半导体材料的太阳能电池,由于具有价格低廉,易于加工,不受材料种类限制和易于制备大面积柔性器件等优点,而受到极大关注．自从1992年发现从共轭聚合物的基态到富勒烯存在光诱导电子转移现象以来,有机聚合物太阳能电池的研究取得了较大进展,研究较多的是共轭聚合物为给体(D),富勒烯为受体(A)的体系,能量转换效率可达3．3％,苝酸酯是一类液晶材料,其结构高度有序且含有4个吸电子的酰基,使得它们适合电子传输,且在普通有机溶剂中具有良好的溶解性,与共轭聚合物有较好的相容性,因此可制成薄膜,本文的研究表明,苝酸酯也是一类良好的电子受体,与共轭聚合物给体匹配,可用于制备光伏器件——太阳能电池。     

POLYMER-SUPPORTED RARE EARTH CATALYSTS FOR STYRENE POLYMERIZATION

The neodymium complex supported on styrene-maleic anhydride copolymer (SMA·Nd) has been prepared for the first time and found to be a highly effective catalyst for the polymerization of styrene. The SMA·Nd polymeric complex is characterized by IR and its catalytic activity, and the polymerization features have been investigated in comparison with that of the conventional Ziegler-Natta catalysts. When [Nd]=1×10~(-3) mol/L, [M]=5mol/L, Al/Nd=170(mol ratio) and CCl_4/Nd=50(mol ratio), the polymerization conversion of styrene gets to 51.6% in six hours, and the catalytic activity reaches 1852 gPS/gNd, which is much higher than that of conventional rare earth catalysts. The polymerization reaction has an induction period and shows some characteristics of chain polymerization. The polymerization rate is the first order with respect to the concentration of styrene monomer. Addition of FeCl_3 does not suppress the polymerization.     

反应性复合乳液的合成、表征及其交联反应

利用种子半连续乳液聚合方法合成了核层或壳层带有环氧基以及壳层带有羧基的3种不同核/壳结构的乳胶粒子,通过物理共混带环氧基和羧基的乳胶粒子,得到了两种反应性复合乳液.利用透射电镜和激光动态光散射对乳胶粒子进行了表征,其粒径分布较窄,粒径分布的多分散系数为0.062,平均粒径约76 nm,乳胶粒子具有明显的核/壳结构.通过胶膜的凝胶率和膨胀率的测定和红外光谱分析对反应性复合乳液中乳胶粒子的扩散及交联反应进行了研究,并探讨了不同核壳结构复合乳液对涂膜机械性能的影响.研究表明,当反应性复合乳液中的环氧基和羧基分别分布在乳胶粒子的核层和壳层时,有利于聚合物分子链的充分扩散和化学交联反应的进行,从而提高涂膜的物理化学性能,当甲基丙烯酸缩水甘油酯(GMA)含量为10 wt%时,涂膜的拉伸强度达20.3 MPa.     

稀土聚乙炔电化学

本文研究了稀土聚乙炔在水溶液中进行电化学掺杂和化学掺杂,及稀土聚乙炔的电位;用掺杂后的稀土聚乙炔作为水溶液体系一次电池的阴极,以镁作阳极构成半塑料电池;并研究了以稀土聚乙炔作为有机电解质体系可再充式电池的阴极,以锂作阳极的化学电源的电性能。     

COORDINATION COPOLYMERIZATION OF STYRENE WITH MALEIC ANHYDRIDE BY RARE-EARTH COORDINATION CATALYSTS

The study on coordination copolymerization of styrene (S) with maleic anhydride (MA) by rare-earth coordination catalysts, NdL_3-Al(i-Bu)_3, has been successfully carried out for the first time. Some features, kinetic behavior, and mechanism of the SMA copolymerization by Nd(naph)_3-Al(i-Bu)_3 system are described and discussed. The copolymex of styrenemaleic anhydride prepared by the NdL_3-Al(i-Bu)_3 systems in benzene at 50℃ is an alternating-rich white powder having high number-average molecular weight of 6—8.5×10~5. The overall activation energy for the polymerization was found to be 10.5KJ/mol. The polymerization was not suppressed by addition of hydroquinone. The catalytic activity of various ligands in NdL_3 for the copolymerization decreases in the following order: Nd (naph)_3>Nd-(P_(507))_3～NdCl_3-6H_2O>Nd(P_(204))_3>Nd(acac)_3. 3H_2O. The experimental results are explained based on a mechanism to be the coordination-type copolymerization in terms of the participation of a monomer-monomer c     

乙炔在三异丙醇钕盐络合催化体系中的定向聚合

本文研究了乙炔在三异丙醇钕盐[Nd(O-i-Pr)_3]-三烷基铝(AIR_3)-第Ⅲ组份(Ⅲ)络合催化体系中定向聚合的规律。发现在所用稀土络合催化体系中,催化活性不仅与第Ⅲ组份(Ⅲ)添加量有关,而且与铝和钕的摩尔比[AlR_3/Nd(O-i-Pr)_3]有着密切的关系,每种添加剂各有其显示最佳添加效应的铝、钕摩尔比和添加量。同时发现,聚乙炔的顺式含量,除与温度有关外,亦符合上述规律。从而进一步提高了稀土络合催化体系的活性以及聚乙炔膜的顺式含量,在30～5℃制得了高顺式(90—99.5％)具有金属光泽的银色聚乙炔薄膜。此外,本文用红外光谱、顺磁共振、扫描电子显微镜、X衍射、热分析及电阻率、密度测定等对聚乙炔膜进行了表征。     

STUDIES ON ION IMPLANTATION AND ELECTRICAL PROPERTIES OF POLYACETYLENE FILMS

The effects of ion implantation on ployacetylene films PA have been studied with Ar~+, Fe~+, C1~+, I~+, Na~+ and K~+ ions in the energy range of 15—30 keV. The changes of PA films in the electrical conductivity, due to chemical doping and ion implantation in relation to their structure and depth profiles of impurities, were measured through infrared (ATR/FTIK), Rutherford backscattering spectrometry (RBS) and the four probe technique. In all cases, ion implantation of active ions exhibits the same effects as chemical doping. The formation of p-n junction is observed at the interface of implanted region and chemical doped PA substrate. The mechanism of interaction process between ion beam and polymer is also discussed.     

醋酸丙炔酯低聚物的合成及其湿敏性

采用新的过渡金属钯σ 键合炔酯单体络合物 [Pd(C≡CCH2 OOCCH3 ) 2 (PPh3 ) 2 ](PPA) ]作为催化剂 ,合成了主链含π 共轭结构、可溶的醋酸丙炔酯低聚物 (OPAT) ,其重均分子量为 4 50 0 ,聚合度约为 4 5.研究了这一新聚合反应的特征、动力学行为和产物的湿敏特性 .聚合反应的表观速率方程为 :Rp=kp[PAT]1.5[PPA]1.5,其中表观速率常数kp=6 58× 1 0 -4 L2 mol-2 s-1,表观活化能为 1 1 0 2kJ/mol.低聚物经无水三氯化铁掺杂后 ,在几乎全部湿度范围内 (RH % :1 1 %～ 96% )显示良好湿敏响应 .     

可溶性聚对二乙炔苯的合成与表征

一些π-共轭高聚物由于具有优良的荧光性能或三阶非线性光学性能而引起了人们极大的兴趣,合成新型可溶性π-共轭高聚物的研究已成为近年来的研究热点.对二乙炔苯的聚合研究已有报道.