| 引用本文: | 庞素艳,段杰斌,江进,姜成春,马军.KMnO4氧化降解阻燃剂四氯双酚A的动力学、氧化产物及反应路径[J].哈尔滨工业大学学报,2018,50(8):20.DOI:10.11918/j.issn.0367-6234.201706036 |
| PANG Suyan,DUAN Jiebin,JIANG Jin,JIANG Chengchun,MA Jun.Degradation of flame retardant tetrachlorobisphenol A by potassium permanganate: Kinetics, oxidation products and reaction pathways[J].Journal of Harbin Institute of Technology,2018,50(8):20.DOI:10.11918/j.issn.0367-6234.201706036 |
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| KMnO4氧化降解阻燃剂四氯双酚A的动力学、氧化产物及反应路径 |
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庞素艳1,段杰斌1,江进2,3,姜成春4,马军2,3
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(1. 哈尔滨理工大学 化学与环境工程学院, 哈尔滨150040; 2. 哈尔滨工业大学 环境学院, 哈尔滨150090;3. 城市水资源与水环境国家重点实验室(哈尔滨工业大学), 哈尔滨150090;4. 深圳职业技术学院 建筑与环境工程学院, 广东 深圳 518055)
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| 摘要: |
| 为探讨KMnO4氧化降解阻燃剂四氯双酚A(TCBPA)的动力学、氧化产物及反应路径, 在不同pH条件下, 研究KMnO4氧化降解TCBPA的动力学规律, 利用三重四级杆液相质谱联用仪(LC-MS/MS)对KMnO4降解TCBPA的氧化产物进行检测分析, 并推测反应路径.结果表明, KMnO4氧化降解TCBPA的二级反应速率常数k(40.1~981.7 L/(mol·s))随着pH的升高先增加而后降低, 在接近pKa(7.5/8.5)时最大.子找母质谱扫描方法(LC-MS/MS-PIS)测得KMnO4氧化降解TCBPA产生4个主要产物, 质量数(m/z 35)分别为219/221(Ⅰ)、201/203(Ⅱ)、379/381/383/385(Ⅲ&Ⅲ′)、523/525/527/529/531/533(Ⅳ).KMnO4氧化降解TCBPA的反应路径为TCBPA首先发生一电子反应形成酚氧自由基, 并进一步断裂形成碳正离子中间体, 然后反应形成产物4-(2-羟基异丙基)-2, 6-二氯苯酚(Ⅰ)、4-异丙烯-2, 6-二氯苯酚(Ⅱ)和两个聚合产物(Ⅲ&Ⅲ′和Ⅳ).
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| 关键词: KMnO4 四氯双酚A 动力学 氧化产物 反应路径 |
| DOI：10.11918/j.issn.0367-6234.201706036 |
| 分类号:X703 |
| 文献标识码:A |
| 基金项目:国家自然科学基金(51578203) |
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| Degradation of flame retardant tetrachlorobisphenol A by potassium permanganate: Kinetics, oxidation products and reaction pathways |
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PANG Suyan1,DUAN Jiebin1,JIANG Jin2,3,JIANG Chengchun4,MA Jun2,3
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(1. College of Chemical and Environmental Engineering, Harbin University of Science and Technology, Harbin 150040, China; 2. School of Environment, Harbin Institute of Technology, Harbin 150090, China; 3. State Key Laboratory of Urban Water Resource and Environment (Harbin Institute of Technology), Harbin 150090, China; 4. School of Civil and Environmental Engineering, Shenzhen Polytechnic, Shenzhen 518055, Guangdong,China)
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| Abstract: |
| The purpose of this article was to investigate the kinetics, oxidation products and reaction pathways for the degradation of flame retardant tetrachlorobisphenol A (TCBPA) by aqueous potassium permanganate. Experiments were conducted to examine the reaction kinetics of potassium permanganate with TCBPA under the condition with potassium permanganate in excess over a wide pH range, determine the brominated oxidation products and theorize the reaction pathways of TCBPA by aqueous potassium permanganate using liquid chromatography-triple quadrupole mass spectrometry (LC-MS/MS). The results showed that the degradation of TCBPA followed the second-order kinetics and the rate constants (40.1-981.7 L/(mol·s)) increased with the increase of pH and reached the maximum near the pKa (7.5/8.5) of TCBPA, after which they decreased gradually. Four chlorinated oxidation products were detected by the precursor scan approach of liquid chromatography tandem mass spectrometry (LC-MS/MS-PIS), the oxidation products of m/z 219/221(Ⅰ), 201/203(Ⅱ), 379/381/383/385(Ⅲ&Ⅲ′), 523/525/527/529/531/533(Ⅳ), respectively. Reaction pathways mainly involves the initial one-electron oxidation of TCBPA to phenolic radical and subsequent release and further reactions of 2, 6-dibromo-4-isopropylphenol carbocation intermediate, leading to the formation of 4-(2-hydroxyisopropyl)-2, 6-dibromophenol and 4-isopropylene-2, 6-dibromophenol) as well as two polymeric products(Ⅲ&Ⅲ′and Ⅳ).
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| Key words: potassium permanganate tetrachlorobisphenol A kinetics oxidation products reaction pathways |
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