1,2-二乙炔基四苯基乙硅烷与1,2-二乙炔基四甲基乙硅烷的共聚及其光解

１，２－二乙炔基四苯基乙硅烷与１，２－二乙炔基四甲基乙硅烷在催化剂铑（Ⅰ）络合物［氯化三－（三苯基膦）铑］的作用下得到一种新的含硅共聚物。实验证明此共聚物的主链是有规交替结构。研究了固体薄膜及其溶液的光解作用，并测定了ＳｂＦ５蒸气处理后的共聚物薄膜的导电性。     

有机锂化合物中化学键的性质——-反式1,2-二锂代乙烷、1,2-二锂代乙烯和1,2-二锂代乙炔分子中化学键的abinitio研究

用从头计算法计算了电荷密度图和各从是分子轨道的键强参数.结果表明,三个标题化合物的稳定构型都存在双桥式四中心键.追其原因是:这种构型有利于Li的2p轨道的吸电子效应,这种效应可使C-Li键增强.此外,也发现这三个化合物中C-C键的强度大于C=C键,而后者又比C=C键为强,本文亦讨论了这种"反常"的原因.     

(μ-FcC≡CH)Co2(CO)6簇合物羰基取代衍生物的合成和分子结构

The substituted reactions of (μ-FcC≡CH)Co₂(CO)₆ with PPh₃, AsPh₃ and dppm have been studied and three new substituted derivatives have been obtained. The compounds were characterized by elemental analysis, IR, ¹H NMR, MS and X-ray crystallography. They have the following formula: (μ-FcC≡CH)Co₂(CO)_6-nL[n=1, L=PPh₃（2）, AsPh₃（3）; n=2, L=dppm (4)]. The cluster 2 crystallizes in monoclinic, space group P2₁/n, with a=1.342 4(8) nm, b=1.305 4(8) nm, c=1.875 0(9) nm, β=103.084(9)°, V=3.201(3) nm³, Z=4, F(000)=1 480, D_c=1.515 g·cm^-3, μ=15.62 cm^-1; final R indices [I > 2σ(I)]: R₁=0.040 9, ωR₂=0.076 9; S=1.007, Δρ_max=463e·nm^-3, Δρ_min=-395 e·nm^-3. The cluster 3 crystallizes in monoclinic, space group P2₁/n, with a=1.341 0(4) nm, b=1.307 9(4) nm, c=1.912 0(5) nm, β=103.043(5)°, V=3.267(15) nm³, Z=4, F(000)=1 552, D_c=1.574 g·cm^-3, μ=24.87 cm^-1; final R indices[I> 2σ（I）]：R₁=0.0437, ωR₂=0.078 2; S=0.995, Δρ_max=530 e·nm^-3, Δρ_min=-444 e·nm^-3. CCDC: 221860, 2; 221863, 3.     

聚（2，5－二甲氧基对苯乙炔）的可溶性前聚物合成及表征

研究了合成聚（２，５－二甲氧圣对苯乙炔）的有机可溶性前聚物的反应条件与单体转化率和前聚物产率的关系。实验结果表明：ＮａＯＨ是聚合反应的有效引发剂。适宜的反应条件为：单体与ＮａＯＨ摩尔比为１：１，单体浓度０．０５～０．２ｍｏｌ／Ｌ聚合时间２ｈ，温度低于５℃。正已烷、石油醚作为有机提取剂可有效提高前聚物产率，用ＩＲ、ＵＶ－Ｖｉｓ、￣１ＨＮＭＲ、ＴＧＡ和ＤＳＣ对前聚物进行了表征。     

1,4—双（取代苯乙炔基）苯电子光谱的溶剂效应

1,4-双(取代苯乙炔基)苯是较好的荧光物质并有良好的激光转换效率。本文测定了1,4-双(苯乙炔基)苯1和1,4-双[(4-叔丁基苯基)乙炔基]苯2在14种溶剂中的紫外吸收光谱和荧光发射光谱,并用多元回归QSAR程序研究了它们的溶剂效应。 1 实验 UV谱用Beckman DU-8B紫外可见分光光度计测定。荧光光谱在MPF-4荧光仪上测得。     

乙炔和三乙氧基硅烷的硅氢加成反应研究

制备了氯铂酸-异丙醇、氯铂酸-聚甲基乙烯基硅氧烷和氯铂酸-三苯基膦三种催化剂,评价了它们在乙炔与三乙氧基硅烷的硅氢加成反应中的催化活性及选择性;并考察了反应温度、乙炔流量、氯铂酸-聚甲基乙烯基硅氧烷与三乙氧基硅烷摩尔比、PPh3/H2PtCl6摩尔比等因素对产物收率的影响.结果表明,氯铂酸-聚甲基乙烯基硅氧烷对该反应表现出较高的催化活性,在催化剂与三乙氧基硅烷摩尔比为1.2×10-4∶1,T=80℃,乙炔流量=120 mL/min的条件下反应,产物乙烯基三乙氧基硅烷的选择性为100%,收率可达97.5%.     

二苯乙炔类液晶的合成

以碘代烷基苯（或联苯）与烷基苯乙炔为中间体，采用二价镍为催化剂的方法合成了二苯乙炔类液晶化合物。其相变过程通过差热分析测试，该类化合物表现出优良的液晶性能。     

Preparation and Characterization of Carbon Nanotubes-Coated Cordierite for Catalyst Supports

The carbon nanotubes-coated cordierite (CNTs-cordierite) was fabricated by pyrolysis of ethine on cordierite with iron catalyst, which was penetrated into the cordierite substrate by vacuum impregnation. The cordierite substrate, carbon naontubes, and CNTs-cordierite were characterized by SEM. TEM/HREM. BET, and TGA. The results show that the carbon nanotubes were distributed uniformly on the surface of cordierite. A significant increase in BET surface area and pore volume was observed, and a suitable pore-size distribution was obtained. On the CNTs-cordierite, carbon nanotubes penetrated into the cordierite substrate, which led to a remarkable stability of the CNTs against ultrasound maltreatment. Growth time is an important factor for thermostability and texture of the sample. The mass increased but the purity decreased with the growth time, which caused the exothermic peak shift to low temperature, and the corresponding full width half maximum (FWHM) of the peak in DTG increased.     

含Bi、Mg的硅酸铜催化剂的制备及其催化性能

以硝酸铋、硅酸钠和MgO-SiO₂复合微球为原料,分别采用共沉淀法和浸渍-沉淀法制备了含Bi、Mg的硅酸铜催化剂，其结构经SEM，低温N₂吸附-脱附、XRD和XPS表征。研究了催化剂在甲醛乙炔化合成1,4-丁炔二醇反应中的催化性能。结果表明：采用共沉淀法制备的催化剂具有高比表面积、孔径和孔体积，炔化反应活性高，1,4-丁炔二醇选择性大于96%。催化剂表面的活性组分主要为无定形硅酸铜，分散度与稳定性较好，活性组分Cu和Bi不易流失。     

碳纳米管对非晶态NiB合金催化剂性能的影响

采用化学还原法制备了非晶态NiB合金，用CNTs-1、CNTs-2、y-Al2O3作载体制备了负载型非晶态NiB合金催化剂．以乙炔选择性加氢为目标反应考察了催化活性和选择性，用TEM、TPD等方法对催化剂进行了表征．TEM结果表明，粒径为8～10nm的NiB粒子均匀分散在CNTs-1外表面，大部分粒径为12～14nm的NiB颗粒在CNTs-2内腔生长，而y-Al2O3载体未能有效提高NiB分散度．用CNTs-1将NiB负载化，明显提高了NiB催化剂乙炔加氢活性．CNTs-1、CNTs-2和y-Al2O3载体对比，CNTs-2作载体促进了催化剂对氢的吸附，减弱了乙炔的吸附，提高了加氢活性和乙烯选择性．