四溴双酚a -二（2,3-二溴丙基醚）热分解行为的研究：主要热解产物的演化机制

IF 7.3 2区环境科学与生态学 Q1 ENVIRONMENTAL SCIENCES

Environmental Pollution Pub Date : 2025-07-16 DOI:10.1016/j.envpol.2025.126838

Shi Yan , Yang Long , Liming Tai , Yan Zhu , Jinbao Huang , Hong Wang , Jiankai Ou , Wenjing Duan

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The calculation results of bond dissociation energy (BDE) show that, in the initial reaction, the value of BDE required for ether bond cleavage is the lowest, followed by C<sub>2</sub>-Br bond and C-CH<sub>3</sub> bond cleavage, and the required BDEs are 271.2 kJ/mol, 281.0 kJ/mol, and 305.0 kJ/mol, respectively. The unimolecular elimination of hydrogen bromide (HBr) is the main reaction in the concerted reaction, and the breaking of ether bonds is the main competitive reaction, leading to the formations of 3-bromopropene, 2,3-bromopropene, and tetrabromobisphenol-A. The participation reactions of hydrogen radicals mainly involve abstract reactions and substitution reactions, and HBr is mainly derived from the abstraction reaction, which has a lower reaction energy barrier (14.9–29.6 kJ/mol). 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引用次数: 0

摘要

四溴双酚a -双（2,3-二溴丙基醚）（TBBPA-DBPE）是一种新型阻燃剂，广泛应用于电子设备中。在其降解过程中，会产生一些有毒的溴化化合物并释放到环境中，对人类健康和生态环境造成极大危害。对于TBBPA-DBPE热解机理的深入理论研究相对较少，因此本文采用密度泛函数理论方法对TBBPA-DBPE热降解产物的演化机理进行了详细的研究。键解离能（BDE）计算结果表明，在初始反应中，裂解醚键所需的BDE值最低，其次是C2-Br键和C-CH3键，所需BDE值分别为271.2 kJ/mol、281.0 kJ/mol和305.0 kJ/mol。协同反应以单分子消除溴化氢（HBr）为主要反应，醚键断裂为主要竞争反应，生成3-溴丙烯、2,3-溴丙烯和四溴双酚a。氢自由基的参与反应主要包括抽象反应和取代反应，HBr主要来源于抽象反应，反应能垒较低（14.9 ~ 29.6 kJ/mol）。取代反应主要是氢自由基取代溴自由基，苯环上的取代反应所需活化能低于丙基上的。热解的主要溴化产物为HBr、1,2,3-三溴丙烷、2,3-二溴丙烷、3-溴丙烯、溴苯酚。本研究结果有利于加深对热过程中TBBPA-DBPE演化机理的认识，有效控制含溴产物等有害污染物的排放。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Investigation on tetrabromobisphenol A-bis(2,3-dibromopropyl ether) thermal decomposition behaviours: Evolutionary mechanisms of main pyrolysis products

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Investigation on tetrabromobisphenol A-bis(2,3-dibromopropyl ether) thermal decomposition behaviours: Evolutionary mechanisms of main pyrolysis products

Tetrabromobisphenol A-bis(2,3-dibromopropyl ether) (TBBPA-DBPE), as a new type of flame retardant, is widely used in electronic equipment. During its degradation process, some toxic brominated compounds can be produced and released into the environment, causing great harm to human health and the ecological environment. There are relatively few in-depth theoretical studies on the pyrolysis mechanism of TBBPA-DBPE, therefore, the evolution mechanism of thermal degradation products of TBBPA-DBPE is studied in detail by using the density functional theory method in this paper. The calculation results of bond dissociation energy (BDE) show that, in the initial reaction, the value of BDE required for ether bond cleavage is the lowest, followed by C₂-Br bond and C-CH₃ bond cleavage, and the required BDEs are 271.2 kJ/mol, 281.0 kJ/mol, and 305.0 kJ/mol, respectively. The unimolecular elimination of hydrogen bromide (HBr) is the main reaction in the concerted reaction, and the breaking of ether bonds is the main competitive reaction, leading to the formations of 3-bromopropene, 2,3-bromopropene, and tetrabromobisphenol-A. The participation reactions of hydrogen radicals mainly involve abstract reactions and substitution reactions, and HBr is mainly derived from the abstraction reaction, which has a lower reaction energy barrier (14.9–29.6 kJ/mol). Substitution reactions are mainly the substitution of bromine radicals by hydrogen radicals, and the activation energy required for substitution reactions on the benzene ring is lower than that on the propyl group. The main pyrolysis brominated products are HBr, 1,2,3-tribromopropane, 2,3-dibromopropane, 3-bromopropene, bromophenol. The results of this study are conducive to deepening the understanding of the evolution mechanism of TBBPA-DBPE during the thermal process and effectively controlling the emissions of harmful pollutants such as bromine-containing products.

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来源期刊

Environmental Pollution 环境科学-环境科学

CiteScore

16.00

自引率

6.70%

发文量

2082

审稿时长

2.9 months

期刊介绍： Environmental Pollution is an international peer-reviewed journal that publishes high-quality research papers and review articles covering all aspects of environmental pollution and its impacts on ecosystems and human health. Subject areas include, but are not limited to: • Sources and occurrences of pollutants that are clearly defined and measured in environmental compartments, food and food-related items, and human bodies; • Interlinks between contaminant exposure and biological, ecological, and human health effects, including those of climate change; • Contaminants of emerging concerns (including but not limited to antibiotic resistant microorganisms or genes, microplastics/nanoplastics, electronic wastes, light, and noise) and/or their biological, ecological, or human health effects; • Laboratory and field studies on the remediation/mitigation of environmental pollution via new techniques and with clear links to biological, ecological, or human health effects; • Modeling of pollution processes, patterns, or trends that is of clear environmental and/or human health interest; • New techniques that measure and examine environmental occurrences, transport, behavior, and effects of pollutants within the environment or the laboratory, provided that they can be clearly used to address problems within regional or global environmental compartments.