文献类型：期刊文献

中文题名：TG-DSC-MS联用研究不同气氛下腰果壳油改性热塑性酚醛树脂的热裂解特性

英文题名：Investigation on Thermal Decomposition Behaviors of Cashew Nut Shell Liquid Modified Thermoplastic Phenolic Resin by TG-DSC-MS Coupling Techniques at Different Atmospheres

作者：戴燕[1,2] 谭卫红[1,2] 胡立红[1,2] 马艳[1,2] 蔡燕燕[1,2]

第一作者：戴燕

机构：[1]中国林业科学研究院林产化学工业研究所生物质化学利用国家工程实验室国家林业局林产化学工程重点开放性实验室江苏省生物质能源与材料重点实验室,江苏南京210042;[2]中国林业科学研究院林业新技术研究所,北京100091

年份：2014

卷号：33

期号：4

起止页码：387-394

中文期刊名：分析测试学报

外文期刊名：Journal of Instrumental Analysis

收录：CSTPCD;;北大核心:【北大核心2011】；CSCD:【CSCD2013_2014】；

语种：中文

中文关键词：腰果壳油;热塑性酚醛树脂;热分解;热重-差示扫描量热-质谱联用技术;动力学

外文关键词：cashew nut shell liquid; thermoplastic phenolic resin; thermal decomposition; TG -DSC - MS technique ; kinetics

分类号：O657.63

摘要：采用热重-差示扫描量热-质谱联用技术（TG-DSC-MS）研究了腰果壳油改性热塑性酚醛树脂在不同气氛下热分解过程中质量、能量、气体产物的变化规律,利用Coats-Redfern法计算了腰果壳油改性热塑性酚醛树脂热分解的动力学参数.结果表明,裂解气氛能显著影响样品的热解过程：与氮气气氛下相比,样品在空气气氛下的失重区间总数和主失重区温度范围均增加,且有2个主失重区,裂解更加完全;氮气气氛下,在主失重区表现明显的吸热效应,而在空气气氛下,第Ⅰ主失重区的热效应与升温速率有关,第Ⅱ主失重区放热明显;在反应深度α为0.10～0.90的区间内,分别采用一级四段、一级六段对样品在氮气、空气气氛下的热裂解过程进行模拟,得到氮气气氛下各段的平均活化能为17、65、32、13 kJ＆#183;mol-1,空气气氛下各段的平均活化能为72、23、14、12、19、57 kJ＆#183;mol-1.不同气氛下,MS总离子流图信号强度与TG曲线的变化规律具有一致性,但气氛种类对裂解产物种类和相对含量有较大影响：惰性气氛（Ar气）下,样品更容易裂解成烷基酚（苯酚、甲基苯酚、乙基苯酚、二甲苯酚、三甲苯酚）、烷基苯（苯、甲苯、二甲苯、三甲苯、乙基甲苯）等芳香烃类和烷烃类（甲烷、丙烷、丁烷、戊烷、己烷）等气态产物,芳香烃化合物为主产物,生成量在305～333℃达到第一个峰值,408～460℃附近达到第二峰值;而在有氧的空气气氛中,CO2、H2O和甲酸为主要气体产物,释放量明显比惰性气氛下大,芳香烃类化合物只在第一个主失重区有逸出,种类和释放量明显较少,且未检测到烷烃类化合物.
The thermal decomposition behaviors, including weight loss, heat flow and gaseous de- composition products of cashew nut shell liquid（CNSL） modified thermoplastic phenolic resin were in- vestigated by TG - DSC - MS coupling techniques at different kinds of atmosphere. The kinetic pa- rameters of CNSL modified thermoplastic phenolic resin were obtained from equation Coats - Redfern. The results showed that the atmosphere had an obvious effect on the pyrolysis of sample. Compared with that at N2 atmosphere, two major weight loss steps at air atmosphere existed, the total weight loss steps and temperature zones both also increased, and the thermal decomposition was more com- plete. At N2 atmosphere, the major weight loss zone showed endothermic in the DSC curves at differ- ent heating rates. At air atmosphere, the thermic response depended on the heating rates in the first major weight loss stage, but appearing exothermic in the second weight loss stage. The pyrolysis ki-netics could be simplified as a model of a first - order reaction with four sections model at N2 atmos- phere and another model of a first - order reaction with six sections at air atmosphere while ot value varied from 0. 10 to 0.90. In N2 atmosphere, the activation energies at different stages were 17, 65, 32, 13 kJ · mo1-1, respectively, and in air atmosphere, the activation energies at different stages were 72, 23, 14, 12, 19, 57 kJ ~ mo1-1, respectively. The signal intensity of ion current varied with temperature, and the atmosphere had an obvious effect on the gaseous decomposition products. In inert atmosphere（Ar）, CNSL modified thermoplastic phenolic resin more easily cracked into aro- matic hydrocarbons, e.g. benzene, toluene, dimethylbenzene, trimethylbenzene, ethyholuene, ethylbenzene, phenol, methyl phenol, dimethylphenol, trimethylphenol, and alkanes, e.g. etha- nol, methane, propane, butane, hexane, pentane. The aromatic hydrocarbons were the main gas products, which productions were up to a peak at 305 -333 ℃ and another peak at 408 -460 ℃, respectively. In air atmosphere, the gaseous products were mainly H20, CO2 and formic acid. Fur- thermore, the relative contents of HEO, CO2 and formic acid increased obviously. Only a few of aro- matic hydrocarbons, e.g. benzene and phenol were detected in the first major weight loss stage with- out any alkanes.