过氧化苯甲酰在不同杂质作用下的热分解行为  

Thermal Decomposition Behavior of Benzoyl Peroxide in Presence of Different Impurities

作　　者：崔晓花 胡继文[1,2] 桂雪峰 CUI Xiaohua;HU Jiwen;GUI Xuefeng(Guangzhou institute of Chemistry,Chinese Academy of Sciences,CAS Engineering Laboratory for Special Fine Chemicals,Guangzhou 510650,China;CASH GCC Shaoguan Research Institute of Advanced Materials,CASH GCC(Nanxiong)Research Institute of Advanced Materials Co.Ltd.,Nanxiong 512400,China;University of Chinese Academy of Sciences,Beijing 100049,China)

机构地区：[1]中国科学院广州化学研究所中国科学院新型特种精细化学品工程实验室,广东广州510650 [2]国科广化韶关新材料研究院国科广化(南雄)新材料研究院有限公司,广东南雄512400 [3]中国科学院大学,北京100049

出　　处：《广州化学》2024年第4期1-11,I0001,共12页Guangzhou Chemistry

基　　金：国家自然科学基金(51173204、51503124、21404121、214041222);广东省科学技术专项基金(201909146221089);广州市科学技术项目(202102021194);清远科技项目(2022YFJH004)。

摘　　要：采用实验和理论相结合的方法系统研究过氧化苯甲酰(BPO)的放热特性及硫酸(H_(2)SO_(4))和氢氧化钠(NaOH)对其放热行为的影响。首先,通过差示扫描量热法(DSC)和加速量热法(ARC)对不同体系的热失控风险进行详细研究,以识别和量化热危险性及其分解反应的特征。在此基础上,根据苏黎世危害分析(ZHA)标准对其热危害进行等级评估。其次,采用KAS法和FWO等模型方法求解动力学参数以进一步阐明热解的内在特性。此外,借助气相色谱-质谱法(GC-MS)对热解产物的组成进行鉴定,并辅以量子化学计算,推断出BPO和掺杂杂质体系的热解路径,揭示杂质对BPO热解的内在影响机制。结果表明:BPO的分解具有自催化特性;H_(2)SO_(4)和NaOH的引入依次提高了BPO的热稳定性,且降低了平均放热量,但显著缩短了绝热诱导期的持续时间,增加了热失控的可能性;H_(2)SO_(4)和NaOH均改变了BPO的热解路径,且甲苯和苯酚产物是促进BPO进一步加速热解的本质原因。此研究可为实际应用提供更为精准的理论指导。In this work,a combined experimental and theoretical approach was used to systematically investigate the exothermic characteristics of benzoyl peroxide(BPO)and the effects of sulfuric acid(H_(2)SO_(4))and sodium hydroxide(NaOH)on its exothermic behavior.Firstly,the thermal runaway risks of different systems were investigated in detail by differential scanning calorimetry(DSC)and accelerating rate calorimetry(ARC)to identify and quantify thermal hazards and characterize their decomposition reactions.On this basis,the thermal hazard levels were evaluated by the Zurich Hazard Analysis(ZHA)standard.Secondly,modeling methods such as KAS method and FWO were employed to solve the kinetic parameters to further elucidate the intrinsic properties of pyrolysis.Additionally,the composition of pyrolysis products was characterized via gas chromatography-mass spectrometry(GC-MS)and supplemented with quantum chemical calculations to infer the pyrolysis pathway of BPO in order to reveal the intrinsic mechanism of the influence of impurities on the pyrolysis of BPO.The results indicate that the decomposition of BPO is autocatalytic in nature.And the introduction of H_(2)SO_(4) and NaOH sequentially improves the thermal stability of BPO and reduces the total heat release,but significantly shortens the duration of the adiabatic induction period and increased the potential for thermal runaway.H_(2)SO_(4) and NaOH altered the pyrolysis pathway of BPO,and toluene and phenol products were the intrinsic cause of further accelerated pyrolysis of BPO.This study can provide more precise theoretical guidance for practical application.

关 键 词：过氧化苯甲酰 杂质 热危害 分解机理 

分 类 号：O622.6[理学—有机化学]