Study of the effect of BDMA catalyst in the epoxy novolac curing process by isothermal DSC

Epoxy novolac/anhydride cure kinetics has been studied by differential scanning calorimetry under isothermal conditions. The system used in this study was an epoxy novolac resin (DEN431), with nadic methyl anhydride as hardener and benzyldimethylamine as accelerator. Kinetic parameters including the reaction order, activation energy and kinetic rate constants, were investigated. The cure reaction was described with the catalyst concentration, and a normalized kinetic model developed for it. It is shown that the cure reaction is dependent on the cure temperature and catalyst concentration, and that it proceeds through an autocatalytic kinetic mechanism. The curing kinetic constants and the cure activation energies were obtained using the Arrhenius kinetic model. A suggested kinetic model with a diffusion term was successfully used to describe and predict the cure kinetics of epoxy novolac resin compositions as a function of the catalyst content and temperature. Copyright © 2003 Society of Chemical Industry     

过氧化甲乙酮合成研究

论述了过氧化甲乙酮的合成方法，用阳离子交换树脂催化剂代替传统的无机酸催化剂。考察了离子交换树脂用量、反应温度对反应产率、活性氧含量的影响及溶剂对产品稳定性的影响。     

镁钴铝类水滑石催化合成安息香甲醚

采用共沉淀法制备了镁钴铝类水滑石化合物(MgCoAl-HTLcs),并用 X 射线衍射、扫描电子显微镜、NH_3程序升温脱附等方法对 MgCoAl-HTLcs 进行了表征,并以 MgCoAl-HTLcs 为催化剂催化苯甲醛与甲醇反应合成安息香甲醚,研究了n(Mg):n(Co):n(Al)、催化剂用量、原料配比、反应温度、反应时间对合成反应的影响。表征结果显示,MgCoAl-HTLcs 的晶相完整,表面主要为弱酸、弱碱性。催化合成安息香甲醚的适宜条件为:MgCoAl-HTLcs 催化剂用量0.10 g(约为原料总质量的0.23%),n(Mg):n(Co):n(Al)=0.4:1.6:1.0,V(苯甲醛):V(甲醇)=3:50,反应温度50℃,反应时间150 min。在此条件下,苯甲醛的平衡转化率达77.49%,安息香甲醚选择性接近100%。为洁净合成安息香甲醚开辟了一条新的途径。     

由碳五馏分合成甲基叔戊基醚工艺的研究

以催化裂化C_5馏分与工业甲醇为原料,D005型大孔强酸型阳离子交换树脂为催化剂,采用筒式膨胀床双反应器,考察了甲基叔戊基醚的合成工艺条件。一阶反应器的操作条件为：循环比为2：1,醇烯比为1.2：1,入口温度为70℃,空速为6 h~(-1),平均转化率为53.63%；二阶反应器的操作条件为：入口温度为50℃,空速为1.2h~(-1),平均转化率为71.32%,全调合方案可以使催化裂化汽油的辛烷值平均提高0.55个单位。     

反应精馏法制备高纯度醋酸甲酯

在中试反应精馏塔中以浓硫酸为催化剂进行了醋酸与甲醇反应制备醋酸甲酯的试验。反应精馏塔的精馏段为填料,反应段为立体催化精馏塔板,采用连续操作,考察了回流比、甲醇进料位置、停留时间、催化剂用量对反应精馏的影响。试验结果表明,当回流比为1.2、甲醇进料位置为第11～15块塔板、停留时间为2.2～2.5h、催化剂与醋酸的质量比为1.07∶100时,塔顶醋酸甲酯的质量分数达到99.50%以上,醋酸的转化率达到99.85%以上。     

溶液中微量甲基异丁基酮的分析方法

研究了微量甲异丁基酮在氟氧铌酸（H2NbOF5)及氟钽酸（H2TaF7)溶液中存在的形式，找到利用碘仿-硫代硫酸钠联合滴定的方法，来标定微量甲基异丁基酮在H2NbOF5及H2TaF7溶液中的含量，本方法在钽铌冶炼过程中操作简便易行且结果重现性好。     

Decreasing miscibility with greater heterogeneity in ternary polymer blend: poly(cyclohexyl methacrylate), poly(α‐methyl styrene) and poly(4‐methyl styrene)

A ternary blend system comprising poly(cyclohexyl methacrylate) (PCHMA), poly(α‐methyl styrene) (PαMS) and poly(4‐methyl styrene) (P4MS) was investigated by thermal analysis, optical and scanning electron microscopy. Ternary phase behaviour was compared with the behaviour for the three constituent binary pairs. This study showed that the ternary blends of PCHMA/PαMS/P4MS in most compositions were miscible, with an apparent glass transition temperature (T_g) and distinct cloud‐point transitions, which were located at lower temperatures than their binary counterparts. However, in a closed‐loop range of compositions roughly near the centre of the triangular phase diagram, some ternary blends displayed phase separation with heterogeneity domains of about 1 µm. Therefore, it is properly concluded that ternary PCHMA/PαMS/P4M is partially miscible with a small closed‐loop immisciblity range, even though all the constituent binary pairs are fully miscible. Thermodynamic backgrounds leading to decreased miscibility and greater heterogeneity in a ternary polymer system in comparison with the binary counterparts are discussed. © 2003 Society of Chemical Industry     

甲醛与甲酸甲酯的偶联反应 Ⅰ.杂多酸的催化作用

研究了４种杂多酸（磷钨酸、硅钨酸、磷钼酸和硅钼酸）对甲醛和甲酸甲酯偶联反应的催化作用；对反应条件进行了考察。结果表明，磷钨酸和硅钨酸对该反应具有较高的催化活性；而氧化性强的钼系杂多酸的活性较低。水对甲醛和甲酸甲酯的偶联反应具有不利影响。将杂多酸在３００℃进行热处理后，其活性显著增强。     

A method for the preparation of PMMA-SiO2 nanocomposites with high homogeneity

It is possible to optimize the performance of the inorganic-organic composites dispersing the inorganic component in the organic matrix on a nanomiter length scale. If dry the inorganic phase cannot be intimately dispersed during the incorporation in the matrix. When the particle surface is organically modified, and the incorporation is made starting from a liquid dispersion (particles in polymer solution), the resulting composites exhibit an excellent homogeneity. Here, monolithic [poly(methyl methacrylate)/monodisperse silica particles] nanocomposites have been prepared and characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), dynamic light scattering (DLS), micro-hardness, and differential scanning calorimetry (DSC).