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碳酸亚乙烯酯的合成工艺

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碳酸亚乙烯酯(VC)作为一种锂离子电池添加剂,可以显著提高锂离子电池的循环性能.因此高纯度VC的工业化生产具有十分重要的意义和价值.以氯代碳酸乙烯酯(CEC)为反应原料、三乙胺(TEA)为缚酸剂、碳酸二甲酯(DMC)为反应溶剂、2,6-二叔丁基-4-甲基苯酚(BHT)和四丁基溴化铵(TBAB)以及吩噻嗪(PTZ)为辅料,合成了纯度较高的VC,并通过红外和核磁对其结构进行了表征.研究了反应温度、反应时间、溶剂和三乙胺用量以及三乙胺滴加速率对β-消除反应的影响,并对其反应动力学进行了验证.研究结果表明:当CEC用量为62.50 g、DMC用量为89.09 g、TBAB用量为1.00 g、BHT用量为0.50 g、PTZ用量为0.50 g、TEA用量为68.24 mL时,为合成VC的最佳工艺条件.在此最优条件下,CEC转化率为68.10%,VC的纯度为98.27%,VC收率为66.92%.经验证,该反应为吸热反应,反应动力学级数为一级.
Synthesis Technology of Vinylidene Carbonate
Vinylene carbonate(VC),as a lithium-ion battery additive,can significantly improve the cycling performance of lithium-ion batteries.Therefore,the industrialized production of high-purity VC is of great significance and value.VC with high purity was synthesized in this study by using vinyl chloroethylene carbonate(CEC)as raw material,triethylamine(TEA)as acid binding agent,dimethyl carbonate(DMC)as solvent,2,6-di-tert-butyl-4-methylphenol(BHT),tetrabutylammonium bromide(TBAB)and phenothiazine(PTZ)as excipients,and the structural characteristics of the structure were determined by infrared and nuclear magnetic characterization.The results showed that when the dosage of CEC was 62.50 g,DMC was 89.09 g,TBAB was 1.00 g,BHT was 0.50 g,PTZ was 0.50 g and TEA was 68.24 mL,the optimum conditions for the synthesis of VC were obtained;Under this optimal conditions,the conversion rate of CEC was 68.10%,the purity of VC was 98.27%,and the yield of VC was 66.92%.It has been verified that the reaction is endothermic,the kinetic order of the reaction is first order.

chloroethylene carbonatevinylene carbonateβ-elimination reactionsynthesisthermo-dynamic analysiskinetic analysis

魏玉玉、刘辉、冯齐云、张传伟、张琦、凌奇、刘建路

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山东海化股份有限公司技术研发中心,山东潍坊 262737

氯代碳酸乙烯酯 碳酸亚乙烯酯 β-消除反应 合成 热力学分析 动力学分析

山东省企业技术创新资助项目山东海化集团有限公司科技项目

202360700605SDHH-KJXM 2023 7 JSYFZX

2024

合成化学
四川省化学化工学会 中国科学院成都有机化学研究所

合成化学

CSTPCD
影响因子:0.42
ISSN:1005-1511
年,卷(期):2024.32(8)