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     

加氢渣油催化裂化七集总动力学模型的建立

以加工加氢渣油的茂名石化3^＃重油催化裂化装置的工业数据为基础，针对加氢渣油的特点，提出了以渣油四组分作为划分原料集总基础的催化裂化七集总动力学模型。通过变尺度法（B-F-G-S）和龙格库塔法确定动力学参数，并通过工业实测数据验证，表明该模型具有良好的拟合性和外推性，较好地反映了加氢渣油催化裂化反应规律。     

合成吡啶类化合物用催化剂的再生行为研究

对合成吡啶类化合物用的失活催化剂上的结焦物进行了元素分析 ,并着重对失活催化剂的再生行为进行了研究。得到了不同失活程度催化剂的再生曲线及相同失活程度、不同再生条件下的再生曲线。经回归求得了一简单的再生反应动力学经验方程式 ,其中反应级数为碳含量的 1.16 5级 ,活化能为 4 2 .5 72kJ/mol,计算值与实验值的平均相对误差为 6 .5 %。     

Rate of ammonia oxidation in a synthetic saline wastewater by a nitrifying mixed‐culture

Most of the kinetic studies on nitrification have been performed in diluted salts medium. In this work, the ammonia oxidation rate (AOR) was determined by respirometry at different ammonia (0.01 and 33.5 mg N‐NH₃ L^?1), nitrite (0–450 mg N‐NO₂^? L^?1) and nitrate (0 and 275 mg N‐NO₃^? L^?1) concentrations in a saline medium at 30 °C and pH 7.5. Sodium azide was used to uncouple the ammonia and nitrite oxidation, so as to measure independently the AOR. It was determined that ammonia causes substrate inhibition and that nitrite and nitrate exhibit product inhibition upon the AOR. The effects of ammonia, nitrite and nitrate were represented by the Andrews equation (maximal ammonia oxidation rate, r_AOMAX, = 43.2 [mg N‐NH₃ (g VSS_AO h)^?1]; half saturation constant, K_SAO, = 0.11 mg N‐NH₃ L^?1; inhibition constant K_IAO, = 7.65 mg N‐NH₃ L^?1), by the non‐competitive inhibition model (inhibition constant, K_INI, = 176 mg N‐NO₂^? L^?1) and by the partially competitive inhibition model (inhibition constant, K_INA, = 3.3 mg N‐NO₃^? L^?1; α factor = 0.24), respectively. The r_AOMAX value is smaller, and the K_SAO value larger, than the values reported in diluted salts medium; the K_IAO value is comparable to those reported. Process simulations with the kinetic model in batch nitrifying reactors showed that the inhibitory effects of nitrite and nitrate are significant for initial ammonia concentrations larger than 100 mg N‐NH₄⁺ L^?1. Copyright © 2005 Society of Chemical Industry     

Lipase‐catalyzed dynamic kinetic resolution of (R,S)‐fenoprofen thioester in isooctane

A lipase‐catalyzed enantioselective hydrolysis process under in situ racemization of the remaining (R)‐thioetser substrate with trioctylamine as the catalyst was developed for the production of (S)‐fenoprofen from (R,S)‐fenoprofen 2,2,2‐trifluoroethyl thioester in isooctane. Detailed investigations of trioctylamine concentration on the enzyme activation and the kinetic behavior of the thioester in racemization and enzymatic reactions were conducted, in which good agreement between the experimental data and theoretical results was observed. © 2002 Society of Chemical Industry     

Moderate antioxidative efficiencies of flavonoids during peroxidation of methyl linoleate in homogeneous and micellar solutions

The relative reactivities as well as the stoichiometric coefficients for a number of flavonoids, catechols, and—for comparison—standard phenolic antioxidants were determined by analyzing the kinetics of oxygen consumption in organic and micellar systems, with peroxidation initiated by lipid- and water-soluble azo initiators. The results demonstrated that the flavonoids did not behave as classic phenolic antioxidants such as α-tocopherol, but showed only moderate chain-breaking activities. The results were in line with other structure-activity relationship studies on the importance of the B-ring catechol structure, the 2,3-double bond, and the 3,5-hydroxy groups. The data are discussed in view of possible explanations of the deviations flavonoids reveal in their behavior compared with regular phenolic antioxidants.     

On the curing of a vinylester-urethane hybrid resin

Curing kinetics of a vinylester-urethane hybrid (VEUH) resin consisting of vinylester resin (VE) diluted in styrene and novolac type polyisocyanate (NPI) have been studied by differential scanning calorimetry (DSC). As VEUH is crosslinked via free radical polymerisation between the vinyl functions of styrene and VE, and polyaddition reaction between the secondary -OH groups of VE and -NCO of NPI, it was necessary to study these reactions separately. This was achieved by studying the curing with and without incorporating the NPI. The curing reaction was monitored by measuring the heat of reaction under isothermal and dynamic temperature conditions. Models describing the curing were developed, which are in good agreement with the experiments. A comparison between the curing of the VEUH and the VE resin without NPI leads to the conclusion that the curing of the VEUH as accessed by DSC is dominated by the radical polymerisation of styrene with VE although the two reactions are not time separated.     

A new approach to the mechanism of chlorine evolution: Separate examination of the kinetic steps using ac impedance on a rotating thin ring electrode

In the absence of a bulk diffusion effect, it is shown for the first time that the impedance spectra for the chlorine evolution reaction on a rotating thin ring electrode comprise three consecutive semicircles in the capacitive half of the complex plane. The first (highest frequency) semicircle is due to the charge-transfer resistance for chloride discharge and the simultaneous chlorine adsorption coupled to the double-layer capacitance. The second semicircle (around 5 Hz) is due to the adsorption and desorption of a chlorine intermediate. The third (lowest frequency, around 0.5 Hz) semicircle is due to the relaxation of surface oxygen species. The impedance data allow the steps of the overall reaction to be examined individually. On a Pt surface the rate of chloride discharge and simultaneous chlorine adsorption (the admittance of the first semicircle) is first order with respect to chloride concentration and has a potential-dependence close to 58 mV/decade. The rate of the adsorption and desorption process (the admittance of the second semicircle) is second order with respect to chloride concentration, and has a potential dependence close to 30 mV/decade. The time constant for the adsorption/desorption processes is ca 20 ms, independent of electrode potential in the range studied. These features are consistent with a mechanism in which a faster discharge reaction (Cl⁻ Cl_ad + e) is followed by a slower surface combination reaction (2Cl_ad → Cl₂), but inconsistent with mechanisms in which ion + atom desorption is predominant, the initial chloride discharge is slow, or a unipositively charged chlorine species is involved.     

On the kinetics of the autoxidation of fats: influence of pro‐oxidants,antioxidants and synergists

The influence of minor amounts of pro‐ and anti‐oxidants on the kinetics of the autoxidation of fat has been evaluated. The reaction rates of oxygen with the substrates were found to follow the same basic equation, hitherto established for pure substrates. There is evidence that the surface of the reaction vessel also acts as a reaction catalyst and its effect is proportional to the area of glass in contact with lipids. Oxidation is enhanced by trace metal ions as well as by surface‐active compounds (e.g. hydroperoxides and sterols). Antioxidants such as α‐tocopherol and butylated hydroxyanisole inhibit the oxidation by delaying the start of oxygen consumption (the induction period) while retarders like amino acids only decrease the rate of oxidation. Thus pro‐ and anti‐ oxidants affect either the start or the rate of oxygen consumption. The empirical formula dx/dt = k [O₂] (1‐x/n) f′(t) was found applicable to the different stages of oxidation.