聚碳硅烷/二乙烯基苯陶瓷前驱体交联样品的制备

研究了聚碳硅烷交联样品的制备过程，着重讨论了用二乙烯基苯交联聚碳硅烷的条件。结果表明：选择熔点为200℃，摩尔质量为1500g/mol作为熔融纺丝，生产碳化硅纤维前驱体用的聚碳硅烷，以二乙烯基苯为交联剂，氯铂酸异丙醇溶液为催化剂，聚碳硅烷与二乙烯基苯的质量比不能低于1：0．2，二乙烯基苯的用量为20％－40％，交联反应温度120℃时，制成的聚碳硅烷／二乙烯基苯陶瓷前驱体交联样品性能良好。     

直链烷基苯生产工艺及市场分析

通过对大量资料的收集与整理，简述了全球直链烷基苯的生产工艺及应用情况，重点介绍了目前全球最新的直链烷基苯生产工艺——固体酸烷基化生产工艺(DETAL工艺)。同时对全球范围内直链烷基苯的供应与需求情况进行了介绍，并对直链烷基苯的未来市场进行了分析与预测。     

Diffusion and sorption of benzene vapor through polybutadiene‐, polybutadiene/styrene‐, and polybutadiene/acrylonitrile‐based polyurethanes

A series of polyurethane (PU) films made from toluene diisocyanate (TDI), 1,4‐butanediol (BDO), and hydroxyl‐terminated polybutadiene (HTPB), hydroxyl terminated polybutadiene/styrene (HTBS), or hydroxyl terminated polybutadiene/acrylonitrile (HTBN) was synthesized by solution polymerization. The absorption of benzene vapor was found mainly in the soft phase. The equilibrium adsorption (M_∞) was reduced with increasing hard segment content for all the PUs. The values of M_∞ were in the sequence of HTBN‐PUs > HTBS‐PUs > HTPB‐PUs, which could be explained by the different interaction parameters between soft segments and benzene. The HTBN‐PU film showed the lowest degree of phase segregation and had more hard segments intermixed in the soft phase, restricting the movement of soft segments, and therefore resulted to non‐Fickian behavior, while the HTPB‐PU is antithetical. FTIR and atomic force microscopy were utilized to identify the hydrogen bonding behavior and morphology change of the PU films before and after the absorption of benzene vapor. The tensile strength of the HTBN‐PUs showed a greater decrease than that of HTBS‐PUs and HTPB‐PUs after absorbing benzene vapor. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2984–2991, 2004     

密度泛函方法的ZSM-5分子筛上苯与乙烯烷基化反应机理研究

采用密度泛函(DFT)方法对于ZSM-5分子筛上苯与乙烯的烷基化反应机理进行研究。选取了包含酸性质子的8T原子簇模型代表ZSM-5分子筛的部分结构。采用B3LYP/6-31G(d)水平从生成能与反应活化能角度对于烷基化反应发生时可能存在的2种联合机理和一种分步机理进行了计算与比较。结果表明,联合反应机理中乙烯的质子化和C-C键的形成同时发生,而分步机理开始于乙醇盐中间体的生成,随后与苯反应生成反应产物。分步机理中乙醇盐中间体生成步骤的活化能(124.55 kJ/mol)低于联合机理的反应活化能(168.98 kJ/mol和156.06 kJ/mol),而烷基化步骤的活化能(209.35 kJ/mol)高于联合机理的反应活化能,由此可以推断ZSM-5分子筛上苯与乙烯的烷基化反应时2种机理同时发生,存在竞争关系。     

Alkylation of Benzene with Isopropyl Alcohol over SAPO-5 Catalyst in an Integral Pressure Reactor

The alkylation of benzene with isopropyl alcohol was studied in an integral pressure reactor over silicon substituted aluminophosphate molecular sieves, SAPO-5. The influence of various process parameters such as temperature, pressure, time on stream, weight hourly space velocity, and mole ratio of reactants on cumene yield and selectivity were investigated. The activity of SAPO-5 was compared with that of Hbeta for this reaction under similar conditions and in the same reactor. At pressures higher than atmospheric, almost the theoretical maximum yields of cumene were achieved on this SAPO-5. Among the diisopropyl benzenes formed by the alkylation of cumene, the meta-isomer was found to form in a significant amount followed by the para-isomer. The ortho-isomer with relatively high strain energy of 4.26 kcal/mol was almost negligible. The cumene yield goes through a maximum in the temperature range 498-543 K studied. Cumene selectivity was found to decrease at higher temperatures, higher pressures and lower benzene to isopropanol mole ratios.     

苯和乙烯一步法合成苯乙烯反应研究

首次采用苯和乙烯在无氧存在下, 于多种固体酸和金属负载HZSM-5分子筛催化剂上反应直接得到苯乙烯与其它固体酸相比, HZSM-5分子筛催化剂表现出最高的反应活性和较高的对苯乙烯的选择性。HZSM-5分子筛负载不同金属后, 苯乙烯的选择性均有明显提高, 其中以Co/HZSM-5、Fe/HZSM-5和Pd/HZSM-5催化剂显示出较高的反应活性和苯乙烯选择性。反应温度、苯烯比、金属负载量、液空速、催化剂的焙烧及还原温度均会不同程度地影响反应转化率和产物分布。     

二乙酸亚碘酰苯及羟基对甲苯磺酰氧碘基苯的合成研究

通过碘化苯直接与 2 6 %～ 30 %的过氧化氢溶液和醋酸酐反应 ,合成了二乙酸亚碘酰苯 ,该反应避免直接使用较高浓度的过乙酸 ,且操作简单方便 ,产物收率较好 ,纯度高。同时也可不必分离出二乙酸亚碘酰苯直接加入对甲苯磺酸反应 ,得到羟基对甲苯磺酰氧碘基苯。     

SDBS的表面张力对天然气水合物生成的影响

利用德国KRUSS公司生产的界面张力仪K11中的板法测定十二烷基苯磺酸钠在不同温度(5,10,20,30,35℃)和不同浓度下(100,400,800,1200,1600,2000 mg/L)的表面张力,确定有利于天然气水合物合成的最佳浓度为1 200 mg/L,这在工业应用中有着重要的参考价值,同时分析了表面活性剂加速天然气水合物生成的机理。     

Catalytic conversion of methane to benzene over Mo/ZSM-5

Dehydroaromatization of methane to benzene occurs over a 2 wt% Mo/ZSM-5 catalyst at 700C under non-oxidizing conditions. Following an initial induction period, during which CH₄ reactant reduces the original Mo⁶⁺ ions in the zeolite to Mo₂C and deposition of coke occurs, a benzene selectivity of 70% at a CH₄ conversion of 8–10% could be sustained for more than 16 h. X-ray photoelectron spectroscopy and X-ray powder diffraction measurements indicate that the reduced Mo is highly dispersed in the channels of the zeolite. Initial activation of CH₄ reactant occurs on Mo₂C sites, leading to the formation of C₂H₄ as the primary product. The latter then undergoes subsequent oligomerization reactions on acidic sites of the zeolite to form aromatic products.     

Crystalline complex between poly(γ-methyl l-glutamate) and dimethyl phthalate

The crystalline complex between poly(γ-methyl l-glutamate) (PMLG) and dimethyl phthalate (DMP) has been formed in films cast from a solution in dichloroethane. It has the stoichiometry of 1 mol of DMP to three or four residues of PMLG and shows two definite characteristics in X-ray diffraction patterns; one is the large hexagonal unit cell with the edge of around 28 Å and another the ‘extra’ 5.07 Å meridional reflection which can not be interpreted by a PMLG α-helical conformation. The structural examination for the films with various DMP contents is carried out by X-ray, viscoelastic, and d.s.c. measurements and the following structure is proposed for the crystalline complex. Four PMLG are associated to form a group which is hexagonally packed and DMP molecules, located in the gaps between groups, form a specific favourable helical structure along PMLG chains in which the van der Waals stacking of benzene rings of DMP is significant.