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十溴二苯醚热解动力学及在聚苯乙烯中的热解行为
引用本文:关国强,刘旭,陈烈强,蔡明招. 十溴二苯醚热解动力学及在聚苯乙烯中的热解行为[J]. 化工学报, 2012, 63(11): 3537-3545. DOI: 10.3969/j.issn.0438-1157.2012.11.023
作者姓名:关国强  刘旭  陈烈强  蔡明招
作者单位:1. 过程节能与传热强化教育部重点实验室, 华南理工大学, 广东 广州 510640;2. 华南理工大学化学与化工学院, 广东 广州 510640
摘    要:十溴二苯醚(decaBDE)是多种聚苯乙烯(PS)类塑料阻燃添加剂,其热解动力学对开发新型高效的电子塑料安全处置技术具有十分重要的意义,为此采用普适积分法成功关联了氮气中decaBDE的热解动力学参数。结果表明:固体decaBDE在306℃时熔融为液相并在400~450℃进一步汽化为气相,热重/红外(TG/IR)分析表明,其气相产物组成具有与decaBDE相同的红外特征;decaBDE热解过程可用三维扩散模型关联。进而通过对比分析decaBDE、PS和含decaBDE的阻燃PS样品的TG实验结果,发现阻燃塑料样品在热解时存在decaBDE与PS间的相互作用,表现为热解起始温度的降低和终止温度的升高。TG/IR分析表明:阻燃塑料样品的热解气相产物中不存在游离的HBr,decaBDE热解时产生的活性基团改变了PS的降解反应历程,使其气相产物具有与1,3-二苯基丁烷类似的红外特征。

关 键 词:十溴二苯醚  聚苯乙烯  热解动力学  普适积分法  热重红外分析  
收稿时间:2012-03-12
修稿时间:2012-05-03

Kinetics of thermal decomposition of decabromodiphenyl ether and interaction with polystyrene in pyrolysis
GUAN Guoqiang , LIU Xu , CHEN Lieqiang , CAI Mingzhao. Kinetics of thermal decomposition of decabromodiphenyl ether and interaction with polystyrene in pyrolysis[J]. Journal of Chemical Industry and Engineering(China), 2012, 63(11): 3537-3545. DOI: 10.3969/j.issn.0438-1157.2012.11.023
Authors:GUAN Guoqiang    LIU Xu    CHEN Lieqiang    CAI Mingzhao
Affiliation:1. Key Laboratory of Enhanced Heat Transfer and Energy Conservation, Ministry of Education, Southern China University of Technology, Guangzhou 510640, Guangdong, China;2. School of Chemistry and Chemical Engineering, Southern China University of Technology, Guangzhou 510640, Guangdong, China
Abstract:Decabromodiphenyl ether(decaBDE)is one of the most popular flame retardants used with polystyrene.The interest in the thermal decomposition of decaBDE has intensified due to its potential production of polybrominated dibenzo-p-dioxins(PBDD)or dibenzofurans(PBDF)in the thermal recycle of plastic waste.Kinetics of thermal decomposition of decaBDE was studied by non-isothermal thermogravimetric analysis(TGA).The three-dimensional diffusion model was found to be the best correlation of TGA data by the general integration method.The activity energy and logarithmic pre-exponential factor were found to be 122.7 kJ·mol-1 and 74.3 s-1 in TGA of decaBDE.In the process of thermal decomposition of decaBDE in the atmosphere of nitrogen,solid decaBDE melt at 306℃ and then vaporized in the temperature range of 400-450℃.When PS was blended with decaBDE,the decomposition temperature of the mixture was lower than that of virgin PS and a higher temperature was needed to complete pyrolysis.The infrared spectral characteristics of 1,3-diphenylbutane was detected in the pyrolysis vapor-phase products of the mixture,whereas styrene was usually found in the pyrolysis product of PS.It indicated that the active groups released from decaBDE changes the path of depolymerization in thermal decomposition of PS.
Keywords:decabromodiphenyl ether  polystyrene  thermal decomposition kinetics  general integration method  TG/IR
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