含氨基酸侧链的有机硅高分子催化剂 ⅩⅤ.γ-(L-酪氨酰胺基)丙基硅氧烷钯催化剂的合成加氢活性及其结构表征

本文报导了四种不同N/Pd摩尔比的聚γ-(L-酪氨酰胺基)丙基硅氧烷钯催化剂的合成及其催化加氢活性,这类催化剂与聚γ-((L-酷氨酸)丙基硅氧烷钯催化剂相比较,虽然均具有类似的N→Pd配位的活性中心组成,但它们对底物的加氢活性则明显不同,前者对丙烯腈、丙烯酸、环己烯和1-癸烯的催化活性比后者高,对苯乙烯则相反。N/Pd摩尔比、反应温度、溶剂以及体系的pH值对催化活性的影响,两者的情况大致相同,标题催化剂对衣康酸的催化加氢,产物的光学纯度为30％。     

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.     

盐类对4-氯-4′-羟基二苯砜钾盐真空熔融聚合的影响

聚苯砜醚是一种综合性能比较好、可在180℃长期使用的热塑性工程塑料,在国内外受到一定的重视。我们与武汉化工原料厂协作,对4-氯-4′-羟基二苯砜钾盐真空熔融缩聚合成聚苯砜醚的途径进行过一些探索,得到了较好的结果。但是,在实践中发现,由于这一反应速度快,放出的热量大而集中,在真空中聚合热不易导出,随着单体用量     

双氮桥联1,10-菲咯啉大环化合物分子构型的从头算研究

应用规范不变原子轨道法(GIAO)在RHF/6-31G**和B3LYP/6-31G**水平上计算了质子化双氮桥联1,10-菲咯啉大环化合物(H4HAPP2+)C2h和C2h构型的1HNMR,并用TDDFT法计算了H4HAPP2+电子光谱.结果表明,B3LYP/6-31G*优化的C2h构型为较优构型,经谐振频率验证无虚频,C2h构型是H4HAPP2+合理的对称性构型.     

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.     

新型含二茂铁有机配合物的合成及其电化学性质

以二茂铁为起始原料,经氯汞化反应、溴代反应、Suzuki偶联反应、水解反应和取代反应等5步反应合成了一种新型的含二茂铁结构单元的有机配合物(7),其结构经1H NMR、13C NMR、IR和HR-MS(ESI-TOF)表征。电化学研究结果表明:化合物6的E1/2小于化合物7,具有较高的氧化还原活性。     

STUDIES ON ENHANCED CONDUCTIVITY OF STRETCHED CONDUCTING POLYMERS

A physical model of series of the conductivity on chain and the interchain conductivitybetween chains is proposed to explain enhanced conductivity of stretched conducting polymers.This model suggests that the enhanced conductivity for stretched conducting polymers might bedue to increasing of the interchain conductivity between chains along the elongation direction afterdrawing processes if the conductivity on chain is assumed much larger than that of the interchainconductivity between chains. According to this model, it is expected that the temperaturedependence of conductivity measured by four-probe method for stretched conducting polymers iscontrolled by a variation of the interchain conductivity between chains with temperature, whichcan be used to explain that a metallic temperature dependence of conductivity for stretchedconducting polymers is not observed although the conductivity along the elongation direction isenhanced by two or three orders of magnitude.     

MgF2对Mn4+掺杂锗酸盐红色荧光粉发光的影响

3.5MgO·0.5MgF₂·GeO₂：Mn⁴⁺作为优异热稳定性和良好发光性能的红色荧光粉而被市场应用,然而,该粉体中MgF₂的作用影响机理尚不明晰,阻碍其性能进一步优化和发展。采用高温固相法制备了系列Mn⁴⁺激活的锗酸盐荧光粉,通过对比加入MgF₂、H₃BO₃（助熔剂）,研究了该粉体的结构、形貌、发光性能等变化规律,阐明了MgF₂的发光影响作用。研究表明,加入MgF₂、H₃BO₃和不加任何助熔剂时的样品,其最佳烧结温度分别为1 150、1 250和1 350 ℃,上述温度下发光强度均为最佳值,其中加入MgF₂、H₃BO₃的样品在最佳温度处生成了纯相。MgF₂的添加,一方面同H₃BO₃一样作为助熔剂对生成纯相、提高样品结晶度起了积极的作用;另一方面,通过研究分析,确认F^-离子成功掺杂进入晶格,促使样品生成的晶体结构为Mg₁₄Ge₅（O, F）₂₄。加入MgF₂、H₃BO₃在最佳烧结温度的样品的荧光寿命分别为0.93和0.75 ms。     

Analysis of secondary electron emission using the fractal method

Based on the rough surface topography with fractal parameters and the Monte–Carlo simulation method for secondary electron emission properties, we analyze the secondary electron yield(SEY) of a metal with rough surface topography. The results show that when the characteristic length scale of the surface, G, is larger than 1 × 10^-7, the surface roughness increases with the increasing fractal dimension D. When the surface roughness becomes larger, it is difficult for entered electrons to escape surface. As a result, more electrons are collected and then SEY decreases. When G is less than 1 × 10^-7,the effect of the surface topography can be ignored, and the SEY almost has no change as the dimension D increases. Then,the multipactor thresholds of a C-band rectangular impedance transfer and an ultrahigh-frequency-band coaxial impedance transfer are predicted by the relationship between the SEY and the fractal parameters. It is verified that for practical microwave devices, the larger the parameter G is, the higher the multipactor threshold is. Also, the larger the value of D,the higher the multipactor threshold.     

新型全息用光致聚合物的研究

研制了一种新型全息用光致聚合物材料,其成膜树脂为胺固化环氧体系,全息记录组分为光引发自由基聚合体系.用新合成的高效光敏染料DEAMC做光敏剂,通过配方调整,制备了一系列的样片,以457 nm的蓝光为记录光,632.8 nm的红光为探针光,研究了样片的衍射效率、灵敏度、折射率调制度等全息性能.结果表明,通过调整材料的配方组成、各组分的含量及样片的膜厚等因素,可以优化样片的全息性能.对样片的信噪比损失(LSNR)测试结果表明,在全息存储的曝光量范围内对样片曝光引起的图像信噪比损失仅有0.40 dB,说明样片的光学质量高,在全息存储上将具有很好的应用前景.