硫代樟脑光化学反应的理论研究

运用量子化学方法优化了硫代樟脑的最低5个电子态(S₀, T₁, S₁, T₂和S₂)的结构, 并计算了它们的相对能量. 计算结果表明: S₁, T₁和T₂态的能量非常接近, 而S₂的能量远远高于T₂态, 这与之前对几种小的硫代羰基化合物的研究结论一致. 确定了硫代樟脑分子在T₁态发生β-插入反应和类Norrish II型反应的机理, 计算的势垒相对于S₀的振动零点分别为314.1和332.6 kJ/mol. 在400 nm波长的光的照射下, 分子被激发到S₁态, 此时分子没有足够的能量发生反应, 只能通过内转换回到基态. 当激发光波长在254 nm时, 硫代樟脑分子被激发到S₂态, 这时候体系有了足够的内部能量使反应发生. 实验上已经观察到此激发光波长下, 气态硫代樟脑可以发生β-插入反应和类Norrish II型反应.     

FREE STANDING FILM OF POLYANILINE

A free standing film of polyaniline as large as 18 cm×18cm×0.002 cm can be obtained by evaporation of a solution of the chemically synthesized base in NMP. Its structure was examined by the elemental analysis, IR, U.V.-visible spectra, XPS, DSC, SEM and X-ray scattering and its conducting behavior as well as electrochemical properties were studied. Results show that the composition, structure of main chain, physical properties of the free standing film of polyanilme is similar to that of the powder. However, some differences in its electronic structure, conductivity at room temperature and potential of redox couple between the flee standing film and powder are observed, which may be due to cross-linking of the film of polyaniline.     

CATIONIC CONDUCTIVITY FOR THE CROSSLINKED P [OLIGO (OXYETHYLENE) METHACRYLATE-COoMETHACRYLOYL ALKYLSULFONIC ACID LITHIUM]

Crosslinked copolymers with single Li~+-ionic conductivity were prepared from oligo (oxyethylene) methacrylate (MEO_n), methacryloyl alkylsulfonic acid lithium (SAMLi), and oligo (oxyethylene) dimethacrylate (DMEO_n). Li~+-ionic conductivity of the copolymer is improved by crosslinking and presented as a function of polymerization degree (n) in MEO_n, comonomeric salt concentration (O/Li), and crosslinking degree. The crosslinked copolymer P (0.7 MEO_(14)-0.3DMEO_(14)-SHMLi) without other small molecular additives exhibits an optimum Li~+-ionic conductivity of 1.2×10~(-6) S/cm at 25℃. Dc polarization test in the cell composed of Li/copolymer/Li shows a constant dc ionic conductivity which closes gradually to the ac one with decreasing dc polarization potential.     

PHOTO-INDUCED DOPED POLYANILINE BY THE VINYLIDENE CHLORIDE AND METHYL ACRYLATE COPOLYMER AS PHOTO ACID GENERATOR

The emeraldine base form of polyaniline (PANI) can be doped by a photo-induceddoping method. In this method a copolymer of vinylidene chloride and methyl acrylate(VCMAC) was used as photo acid generator which can release proton when it is exposedto ultraviolet light (λ= 254 nm). The structure of PANI-VCMAC system before and afterirradiation was characterized by elemental analysis, IR, XPS, and SEM images. Resultsobtained indicate that the photo-induced doping characteristics, such as doping positionand type of charge carriers, are similar to that of PANI doped with HCl. The poor room-temperature conductivity (～10~(-5)S/cm) of PANI-VCMAC system after irradiation maybe due to low doping degree (～pH= 3) and the difference in morphology as compared withPANI-HCl film.     

膨胀石墨/聚苯胺/Fe_3O_4复合材料的制备及吸波性能

采用原位聚合方法制备了膨胀石墨/聚苯胺(EG/PANI)复合材料,将Fe_3O_4负载于EG/PANI表面,得到具有电磁吸收性能的EG/PANI/Fe_3O_4复合材料.通过扫描电子显微镜(SEM)、X射线衍射仪(XRD)、傅里叶变换红外光谱仪(FTIR)及矢量网络分析仪(VNA)等对复合材料的形貌、成分和吸波性能进行了研究.吸波性能分析结果表明,当掺杂浓度为0.05 mol/L,匹配厚度d=2 mm时,样品的最小反射损耗(RLmin)在8.64 GHz处达到-37 dB.随着掺杂浓度的增加,最小反射损耗峰向低频移动,对应的匹配厚度逐渐变厚.材料的介电弛豫极化、涡流损耗及λ/4模型的干涉相消现象出现的双峰,使EG/PANI/Fe_3O_4复合材料在电磁波吸收领域有一定的应用前景.