Metathesis of Butylene-2 and Ethylene to Propylene over 3.0Mo/(Hβ+ γ-Al203) Catalysts with Different γ-Al203 Contents

A series of 3. 0Mo/(Hβ γ-Al2O3) samples with γ-Al2O3 contents in the range of 0-100% (mass fraction) was studied by means of XRD, NH3-TPD, TPR and BET determinations for characterizing their structures. The Hβ zeolite structure in the 3. 0Mo/Hβ sample can be effectively stabilized by adding some γ-Al2O3to Hβ zeolite. γ-Al2O3 mainly favors the formation of polymolybdate or multilayered Mo oxide, while Hβmainly forms the Al2(MoO4)3 species, as evaluated by the TPR technique. When used as the catalyst for the metathesis of butylene-2 and ethylene to propylene, there exists a close correlation between the specific surface area and stability of the catalyst. The specific surface area of the catalyst shows the maximum when (Hβ γ-Al2O3) contains 30%γ-Al2O3, which is in agreement with that of the time needed for the reaction stablization. In the case of maximum surface area, the rate of coke deposition is the minimum.     

稀土三元催化剂作用下正辛酸缩水甘油酯-二氧化碳-环氧丙烷的三元共聚合研究

本工作研究了稀土三元催化剂(三氯乙酸稀土配合物/二乙基锌/甘油)催化下的正辛酸缩水甘油酯、二氧化碳和环氧丙烷三元共聚合。红外光谱、核磁共振和差示扫描结果表明所获得的聚合物是一种新型的三元共聚物。随着反应单体中正辛酸缩水甘油酯比例的增加,所得聚合物在20℃下的断裂伸长率由二氧化碳－环氧丙烷共聚物的31.0%增大到二氧化碳－正辛酸缩水甘油酯共聚物的983.9%,相应的玻璃化转变温度由39.6℃降低至-12.3℃。所得三元共聚物中长碳链侧基单元含量为5.6%时,其断裂伸长率就已经达到481.1％,而拉伸强度仍然维持在24.9MPa的较高水平。     

MgCl_2晶型对丙烯聚合MgCl_2载体催化剂活性的影响

ＭｇＣｌ_２晶型对丙烯聚合ＭｇＣｌ_２载体催化剂活性的影响张明辉，肖世镜中国科学院化学研究所，北京，１００８０）关键词丙烯聚合、ＭｇＣｌ２、载体催化剂近年来，有关ＭｇＣＩ。载体催化剂的研究报道和综述文章不少，但涉及载体晶型对催化剂结构性能的影响却少见．...     

双金属氰化物催化二氧化碳与环氧丙烷聚合

研究了双金属氰化配合物(DMC)催化剂催化二氧化碳(CO2)与环氧丙烷(PO)的共聚及PO的均聚反应,考察了DMC催化剂的诱导现象。结果表明,共聚时DMC催化的诱导期比均聚短,尤其是在低CO2压力(1.0MPa)下更明显,诱导期由均聚时的45min缩短为共聚时的15min。共聚时诱导期随CO2压力升高而增加,当反应压力由1.0MPa升高至7.0MPa时,诱导期由15min增至40min。PO与CO2共聚时的引发现象不同于PO均聚:共聚引发时温度和压力突然异常升高并迅速降低至引发前的状态,而均聚引发时温度突然升高后逐渐下降。由此可知CO2能促进DMC催化剂的活化。     

丙烯选择氧化铋钼铁复氧化物催化剂组成,结构及性能的研究

采用XRD、Raman、XPS及催化剂性能评价等手段,考察了Bi_3(FeO_4)(MoO_4)_2和Fe_2(MoO_4)_3分别存在及两者共存时对Bi-Mo复氧化物体系催化性能的影响.结果表明,这两种含Fe物种的存在都有助于改善Bi-Mo系复氧化物催化剂对丙烯选择氧化反应的催化性能.但两者在作用机理上有所不同.Fe_2(MoO_4)_3本身无催化活性,但在反应条件下可部分还原为FeMoO_4形成Fe~(3+)/Fe~(2+)氧化还原对;且其地结构上与α-Bi_2(MoO_4)_3相匹配,这些因素都有助于促进催化体系中电子和氧物种的传递及催化剂表面活性中心的再生,从而提高催化性能.Bi_3(FeO_4)(MoO_4)_2在反应条件下也可形成Fe~(3+)/Fe~(2+)氧化还原对,但由于其Fe~(3-)所处的化学环境与Fe_2(MoO_4)_3很不相同,且Fe的含量也不及Fe_2(MoO_4)_3,因此它在促进催化体系中电子和氧物种的传递及催化剂表面活性中心的再生等方面的性能较差,但它对提高催化剂表面的活性中心(Bi-Mo对)数目有贡献.     

甲苯定向硝化的理论研究

运用密度泛函理论(DFT)B3LYP方法，在6-31G~(* *)基组水平上，全优化计算 了硝酰阳离子NO_2~+对苯和从0-，m-,p-位进攻甲苯亲电取代硝化后应，求得4条反 应途径上包括反应物、过渡态和Wheland中间体共(4×3)12个反应驻点σ络合物的 分子几何、电子结构、能量和IR光谱等性质，阐明了反应中无同位素效应的实验事 实，求得各反应途径的活化能排序：p-＞o-＞PhH＞m-和σ络合物(R,TSak或INT)的 相对稳定化能排序：p-ArCH_3-NO_2~+＞o-ArCH_3-NO_2~+＞m-ArCH_3-NO_2~+＞ PhH-NO_2~+，从而阐明了甲基对苯环致活(或致钝)以及增加甲苯硝化络合物稳定性 的双重功能，对甲苯定向硝化的理论预示与实验结果相吻合。     

POLYMERIZATION OF ETHYLENE AND PROPYLENE WITH VCL4-BUTYLLITHIUM CATALYSTS

Polymerization of ethylene and propylene with VCl₄-BuLi (Bu = n-Bu, sec-Bu, tert-Bu) catalysts was investigated. The VCl₄-BuLi catalysts were found to initiate the polymerization of ethylene and propylene. The VCl₄-BuLi catalysts gave an ultra high molecular polyethylene. The effect of the Li /V mole ratio on the polymerization of ethylene with the VCl₄-BuLi catalysts was observed, an the catalyst gave an optimum rate at the Li/V ratio of about 3.0. The polyethylene obtained with the VCl₄-BuLi catalyst was found to be a linear structure. In the polymerization of propylene with the VCl₄-BuLi catalyst, the polymers contain mm contents of 56–66% were produced.     

Selectivity optimization for the capillary gas chromatographic analysis of bacterial cellular fatty acids

Summary The importance of selectivity in the capillary gas chromatographic analysis of the cellular fatty acids of micro-organisms is underestimated. The analysis on apolar silicone phases can lead to erratic elucidation of the fatty acid structure. Qualitative errors have been detected in commercially available standards on which computer matching identification techniques are based. Using highly polar capillary columns of the cyanopropyl silicone type, the errors could be elucidated. The exact identification of the hydrolysis products of bacteria is a must for chemotaxonomic studies applying chromatographic techniques. The fatty acid methyl ester profiles can also contain other chemical components which are very important taxonomic markers. Fatty aldehydes, for example, are main components in someClostridium species. Fractionation techniques are described for selective enrichment of fatty aldehydes and hydroxy fatty acids.Dedicated to Prof. Dr. A Liberti on the occasion of his 70th birthday     

Bis-substituted benzo-15-crown-5 ethers as ion carriers in potassium ion-selective electrodes

Lipophilic bis-substituted ester and ether derivatives of benzo-15-crown-5 have been synthesised. The correlation between the structure and potentiometric ion-selectivity has been studied in PVC membrane ion-selective electrodes. An ion-selective potassium sensitive electrode based on 4,5-bis (biphenyloxymethyl)benzo-15-crown-5 exhibited the best electrode properties. The detection limit was loga _K = -5.4; logK _K,Na ^ppot = -3.5. The effect of the lipophilicity of neutral carriers upon electrode performance has been also discussed.