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     

Structure and properties of CE/CTBN/EP blends: II. Effect of EP on the mechanical properties and thermostability of the CE/CTBN system

Carboxyl‐terminated butadiene‐acrylonitrile rubber (CTBN) has often been used to improve the toughness of cyanate ester (CE) resin while sacrificing modulus and thermostability. In this paper, the addition of the appropriate amount of epoxy resin (EP) to the CE/CTBN system is shown to not only increase the modulus and thermostability of the blend, but also improve the toughness. The values of impact strength showed a maximum for the CE/CTBN/EP 100/5/5 blend. The temperature of 10 % weight loss (T₁₀) improves from 376 °C for CE/CTBN 100/5 to 407 °C for the CE/CTBN/EP 100/5/2.5 blend. It is proposed that addition of the appropriate amount of EP can decrease the mobility and increase the stability of CTBN via the reaction between the terminal carboxyl group of CTBN and the hydroxyl group of EP. But a very high EP concentration will decrease the crosslinking density of CE, consequently reducing the mechanical properties and thermostability of the blends. Copyright © 2004 Society of Chemical Industry     

Synthesis and characterization of new thermally stable poly(ester‐imide)s derived from 2,2′‐bis(4‐trimellitimidophenoxy)biphenyl and 2,2′‐bis(4‐trimellitimidophenoxy)‐1,1′‐binaphthyl and various aromatic dihydroxy compounds

A series of new alternating aromatic poly(ester‐imide)s were prepared by the polycondensation of the preformed imide ring‐containing diacids, 2,2′‐bis(4‐trimellitimidophenoxy)biphenyl (2a) and 2,2′‐bis(4‐trimellitimidophenoxy)‐1,1′‐binaphthyl (2b) with various aromatic dihydroxy compounds in the presence of pyridine and lithium chloride. A model compound (3) was also prepared by the reaction of 2b with phenol, its synthesis permitting an optimization of polymerization conditions. Poly(ester‐imides) were fully characterized by FTIR, UV‐vis and NMR spectroscopy. Both biphenylene‐ and binaphthylene‐based poly(ester‐imide)s exhibited excellent solubility in common organic solvents such as tetrahydrofuran, m‐cresol, pyridine and dichloromethane. However, binaphthylene‐based poly(ester‐imide)s were more soluble than those of biphenylene‐based polymers in highly polar organic solvents, including N‐methyl‐2‐pyrrolidone, N,N‐dimethylacetamide, N,N‐dimethylformamide and dimethyl sulfoxide. From differential scanning calorimetry thermograms, the polymers showed glass‐transition temperatures between 261 and 315 °C. Thermal behaviour of the polymers obtained was characterized by thermogravimetric analysis, and the 10 % weight loss temperatures of the poly(ester‐imide)s was in the range 449–491 °C in nitrogen. Furthermore, crystallinity of the polymers was estimated by means of wide‐angle X‐ray diffraction. The resultant poly(ester‐imide)s exhibited nearly an amorphous nature, except poly(ester‐imide)s derived from hydroquinone and 4,4′‐dihydroxybiphenyl. In general, polymers containing binaphthyl units showed higher thermal stability but lower crystallinity than polymers containing biphenyl units. Copyright © 2005 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。     

尿素醇解合成碳酸酯类化合物技术进展

综述了用尿素醇解合成碳酸酯类化合物的技术进展 ,重点介绍尿素醇解合成碳酸二甲酯研究现状以及与其它工艺路线的比较 ,另外也介绍了尿素醇解合成长碳链脂肪族和芳香族类碳酸酯的研究进展。     

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。     

2-甲基-3-甲苯基喹唑啉-4-酮盐酸盐的合成研究

以邻氨基苯甲酸为原料，以不同的中间体和不同的脱水剂对2-甲基-3-甲苯基喹唑啉-4-酮的合成进行研究比较，寻找较佳的合成路径。