氟代碳酸乙烯酯的合成

Synthesis of Fluoroethylene Carbonate

以偶氮二异丁腈(AIBN)为引发剂,硫酰氯(SO2Cl2)为氯化剂,对碳酸乙烯酯(EC)进行氯化,合成了氯代碳酸乙烯酯(CEC);在反应温度65℃,硫酰氯滴加时间72 min,反应时间90 min,n(EC)∶n(SO2Cl2)=1∶1.3,n(AIBN)∶n(EC)=1∶200的条件下,CEC的收率达85.81%。以氟化钾(KF)为氟化剂在溶剂中对CEC进行氟化,得到锂离子电池电解液添加剂氟代碳酸乙烯酯(FEC);在反应温度75℃,反应时间1.5～2 h,n(CEC)∶n(KF)=1∶1.3,V(CEC)∶V(乙腈)=1∶1的条件下,FEC的收率达71.86%。采用红外光谱及气质联用分析对产物进行了结构表征。

Chloroethylene carbonate（CEC） was prepared by chlorination of ethylene carbonate（EC） with sulfuryl chloride as chlorinating agent and azobisisobutyronitrile（AIBN） as an initiator.CEC reacted with potassium fluoride（KF） which functioned as a fluorinating agent in a solution to give fluoroethylene carbonate（FEC）.The optimum technological conditions for preparing CEC were as follows：the reaction taking place at 65 ℃;sulfuryl chloride was added into the reaction solution in drops in 72 min and reacted for 90 min;the molar ratio of ethylene carbonate（EC） and sulfuryl chloride was 1∶1.3;the amount of substance ratio of AIBN to EC was n（AIBN）∶n（EC）=1∶200.The yield of CEC could reach 85.81% under such reaction conditions.The optimum technological conditions for preparing FEC were as follows：acetonitrile was chosen as the solvent,the reaction temperature was 75 ℃,the reaction time was 1.5~2 h,and the molar ratio of CEC to KF was 1∶1.3,the molar ratio of CEC and acetonitrile was 1∶1.Under these reaction conditions,the yield of FEC could reach 71.86%.The product was characterized by means of IR and GC-MS.