硅胶负载的双高分子-钯催化剂的研究——Ⅰ.硅胶负载的聚[4(2)-乙烯吡啶]-聚[苯乙烯-顺丁烯二酸]-钯催化剂的合成及其催化加氢性能

 合成了硅胶负载的聚(4-乙烯吡啶)或聚(2-乙烯吡啶)-聚(苯乙烯-顺丁烯二酸)-钯催化剂(P4VP-PSM-Pd/SiO₂和P2VP-PSM-Pd/SiO₂),研究了合成条件、组成等对其催化性能的影响及对丙烯酸甲酯的催化加氢性能。发现,同时含两种高分子的催化剂比只含一种高分子的催化剂具有较高的催化活性,催化剂在常温常压下对丙烯酸甲酯的氢化反应具有很高的催化活性和选择性,且能重复使用,表现出良好的稳定性。同时还研究了其它因素对催化剂性能的影响。     

Synthesis of Fluoroalkylated Heterocycles via the Reaction of 3-(1-Hydropolyfluoroalkenyl)-1-oxo-2,4,1-benzoxazines with Dinucleophilic Reagents

The reaction of 3-(1-hydropolyfluoroalkenyl)-1-oxo-2,4,1-benzoxazines 1 with some dinucleophiles was inves-tigated.7-Fluoroalkyl-2,3-dihydro-1,4-diazepine[1,2-d]quinazolin-11-ones 2,2-fluoroalkylisoxazolo[3,2-b]quin-azolin-9-ones 3 and 2-fluoroalkylbenzoimidazoles 4 were obtained from the reaction of 1 with 1,2-diaminoethane,hydroxylamine hydrochloride and 1,2-diaminobenzene respectively.     

Ionic Liquid Based Electrolyte with Mesoporous Silica SBA-15 as Framework for Quasi-solid-state Dye-sensitized Solar Cells

Quasi-solid-state electrolytes were fabricated with mesoporous silica SBA-15 as a framework material. Ionic conductivity measurements revealed that SBA-15 can enhance the conductivity of the quasi-solid-state electrolyte. The diffusion coefficients of polyiodide ions such as Ⅰ3ˉ and Ⅰ5ˉ which were confirmed by Raman spectroscopic measurement, were about twice larger than that of I-. The optimized photoenergy conversion efficiency of dye-sensitized solar cells （DSSC） with the quasi-solid-state electrolyte was 4.3% under AM 1.5 irradiation at 75 mW·cm^-2 light intensity.     

二氯化二(N-甲基-N′-苄基-乙二胺)(二水)合镍的合成及其与瓜环相互作用的研究

以氯化镍与N-甲基-N′-苄基-乙二胺(NMEA)反应合成了配合物二氯化二(N-甲基-N′-苄基-乙二胺)二水合镍([Ni(NMEA)₂·(H₂O)₂]·Cl₂)。利用元素分析、IR光谱、NMR对其结构进行了表征。通过1H NMR和UV-Vis光谱研究了该配合物与六、七、八元瓜环的相互作用，并且考察了其动力学行为。结果表明六、七元瓜环与配合物能形成物质的量比为2∶1的超分子结构，而八元环与配合物的作用则具有不同的模式。     

凝胶渗透色谱法测定聚丙烯腈共聚物分子量中宽分布校正法的应用

应用宽分布校正法对凝胶渗透色谱(GPC)进行了校正，将校正曲线用于聚丙烯腈(PAN)共聚物分子量的计算。对扣除色谱峰扩展效应前后的测试结果与乌氏粘度法测得的数据进行比较。结果表明，应用宽分布校正法时，必须扣除色谱峰扩展效应，才能得到较为准确的测试结果。     

Studies on Natural CXN Zeolite： Modification, Framework De-alumination and Ion-exchange

A natural CXN zeolite (stilbite, type code-STI) discovered in China was modified with NH4^ exchange by using ammonium salt and calcinations (procedure Ⅰ), or with NH4 exchange followed by treatment with acid (procedure Ⅱ). The coordination state of Si and A1 atoms in the framework, the property of ion exchange, and the adsorption of the H-STI zeolite samples prepared by different modification procedure were investigated with XRD,EDX,^29Si and ^27Al MAS NMR, Ag^ ion exchange and Ne adsorption. The results of the investigations indicate that different procedure of the modification made variety on the distribution of the framework Si atoms and A1 atoms,the content of non-framework aluminum, and the blocking channels and the shielding effect to the positions of the exchangeable cations. The H-STI zeolite prepared by the procedure Ⅱ possesses high ion exchange capacity, open and perfect pore system, and high thermal stability.     

STUDY ON HIGHLY ACTIVE ZIEGLERNATTA CATALYSTS FOR POLYMERIZATION OF OLEFINS

In this paper, highly active Ziegler-Natta catalysts of MgCl_2 supported TiCl_4 for synthesis ofpolyolefins, using di-n-butyl phthalate (DNBP) as internal donor and diphenyl dimethoxyl silane(DPDMS) as external donor, have been prepared. The conditions controlling the treatment ofsupport were studied. The interactions of various components present in the catalysts and theirinfluences on catalytic performance were investigated. It is found that by using DNBP and DPDMSas internal and external donors together the polymer products with higher isotactic index can beobtained. Plausible structure model and mechanism were proposed.     

STUDIES ON THE POLYMERIZATION OF ACRYLONITRILE INITIATED BY METAVANADATE-CONTAININ G ANION EXCHANGER-THIOUREA REDOX SYSTEM

The polymerization of acrylonitrile (AN) in aqueous nitric acid initiated by metavanadate-containing anion exchange resin (PV)-thiourea (TU) redox system at 20—40℃. has been investigated. The overall rate of polymerization (R_p) is given byR_p=1.92×10~4e~(-6.860/RT) [AN]~(1.2) [PV]~(0.44) [TU]~(1.0)[HNO_3]~(1.0)The kinetic parameters differed from those of V~(5+)-TU system indicated that the generation of the primary radicals is mainly a difffusion-controlled reaction. The effect of macromolecular field arisen from the polymer matrix exerts a great influence on the polymerization process.     

含茂基及酰亚胺基镧系金属有机化合物的合成

在室温下由邻苯二甲酰亚胺[phthalimide, H(Pht)]与Cp3Ln在四氢呋喃溶液中反应, 合成了六个新化合物: Cp2Ln(pht),CpLn(pht)2, (Cp=cyclopentadienyl; Ln=Yb, Er, Dy;pht=phthalimido)。它们均经元素分析、红外光谱和质谱鉴定, 为非溶剂化的桥式二聚体结构。     

分散共聚法制备特殊形态高分子微球的研究

以聚乙二醇 (PEG)大分子单体为反应性稳定剂 ,在丙烯腈的分散共聚反应中添加少量苯乙烯以形成疏水性核 ,制备得到了亚微米级高分子微球 .透射电子显微镜研究表明 ,该高分子微球具有特异的形态结构 .同时研究了分散共聚体系中各种反应因素对微球形态和直径的影响 ,结果表明 ,苯乙烯单体的添加量、PEG大分子单体的浓度及分子量、混合溶剂的组成对微球直径和形态均有明显的影响 .X 射线光电子能谱 (XPS)研究结果表明 ,微球表面聚集有亲水性PEG链 ,核为疏水的聚 (丙烯腈 苯乙烯 ) ,即形成的特异形态的PEG接枝高分子微球亦为复合型结构