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     

Valorisation of waste fractions from autohydrolysis of selected lignocellulosic materials

Non‐isothermal processing of lignocellulosic materials in aqueous media (autohydrolysis reaction) under mild conditions leads to solutions containing valuable chemicals (oligosaccharides, sugars and acetic acid) and other, undesired, compounds (belonging to the extractive and acid‐soluble lignin fractions) which have to be removed in further purification treatments. Liquors obtained by non‐isothermal autohydrolysis of Eucalyptus globulus wood and corncobs under a variety of operational conditions were extracted with ethyl acetate in order to remove non‐saccharide components, and the suitability of the fraction dissolved in the organic phase was assayed for possible utilisation as an antioxidant. The yield and antioxidant activity of ethyl acetate extracts (measured by the α,α‐diphenyl‐β‐picrylhydrazyl (DPPH) radical scavenging capacity) showed a strong dependence on the autohydrolysis conditions. The antioxidant activity of extracts obtained under selected operational conditions compared well with synthetic antioxidants. © 2003 Society of Chemical Industry     

Morphology and properties of poly[2‐methoxy‐5‐(2′‐ethyl‐hexyloxy)‐para‐phenylene vinylene]/silica nanoparticle hybrid films

Poly[2‐methoxy‐5‐(2′‐ethyl‐hexyloxy)‐para‐phenylene vinylene] (MEH‐PPV)/silica nanoparticle hybrid films were prepared and characterised. Three kinds of materials were compared: parent MEH‐PPV, MEH‐PPV/silica (hybrid A films), and MEH‐PPV/coupling agent MSMA/silica (hybrid B films), in which MSMA is 3‐(trimethoxysilyl) propyl methacrylate. It was found that the hybrid B films could significantly prevent macrophase separation, as evidenced by scanning electron and fluorescence microscopy. Furthermore, the thermal characteristics of the hybrid films were largely improved in comparison with the parent MEH‐PPV. The UV‐visible absorption spectra suggested that the incorporation of MSMA‐modified silica into MEH‐PPV could confine the polymer chain between nanoparticles and thus increase the conjugation length. The photoluminescence (PL) studies also indicated enhancement of the PL intensity and quantum efficiency by incorporating just 2 wt% of MSMA‐modified silica into MEH‐PPV. However, hybrid A films did not show such enhancement of optoelectronic properties as the hybrid B films. The present study suggests the importance of the interface between the luminescent organic polymers and the inorganic silica on morphology and optoelectronic properties. Copyright © 2004 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。     

新型香料苹果酯-B的合成

以硫酸高铈为催化剂,通过乙酰乙酸乙酯和1,2-丙二醇反应合成了苹果酯-B,研究了各有关因素对产品收率的影响。实验表明,硫酸高铈是合成苹果酯-B的良好催化剂,在酯醇物质的量比为1∶1.25、催化剂用量为0.3g/0.1mol乙酰乙酸乙酯、环己烷10mL、反应时间2h的条件下,苹果酯-B的收率可达91.5%。     

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。     

An attempt to compare the performance of bioscrubbers and biotrickling filters for degradation of ethyl acetate in gas streams

This study presents a comparison of the efficiency of a bioscrubber and a biotrickling filter (BTF) for the removal of ethyl acetate (EA) vapour from a waste gas stream, under the same operating conditions. The maximum EA elimination capacity achieved in the bioscrubber was 550 g m^?3 h^?1 with removal efficiency higher than 96%. For higher EA loadings the bioscrubber was oxygen limited, which caused incomplete EA biodegradation. When pure oxygen was fed to the bioscrubber at a rate of 0.02 L min^?1, the bioscrubber recovered and could treat higher EA loadings without any oxygen limitation. The BTF achieved EA elimination capacity of 600 g m^?3 h^?1 with removal efficiency higher than 97% and the dissolved oxygen concentration remained substantially higher than in the bioscrubber. However, severe channelling and blockage of the spray nozzle occurred due to the excessive biomass growth. Overall, the bioscrubber system was easier to operate and control than the BTF, while an enhancement of the oxygen mass transfer in the bioscrubber could potentially increase its performance by up to three times. Copyright © 2005 Society of Chemical Industry     

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。