基于［bmim］［BF4］相转移催化的氟代碳酸乙烯酯高效合成

doi:10.11949/0438-1157.20231271

摘要/Abstract

摘要：

氟代碳酸乙烯酯（FEC）是锂电池电解液添加剂的重要组分之一，其工业制备方法主要为卤素交换法，即氯代碳酸乙烯酯（CEC）与氟化钾（KF）通过取代反应制备FEC。该工艺中，取代反应速率受限于KF相际传质速率，且CEC易发生消去反应生成碳酸亚乙烯酯副产物。针对上述问题，研究了相转移催化剂（PTC）结构对KF相际传质速率和CEC制FEC主副反应能垒的影响规律和调控机制。优化条件下，PTC为[bmim][BF₄]（1-丁基-3-甲基咪唑四氟硼酸盐），溶剂为乙腈，反应温度为乙腈回流温度（81.6℃），n（KF）∶n（CEC）=2.5∶1，此时FEC收率高达91.94%（摩尔分数）。密度泛函理论计算表明，在乙腈中[bmim][BF₄]能与KF形成配合物，增加K⁺和F^-的核间距并降低KF的溶解自由能，从而强化相际传质并降低取代反应能垒，实现CEC经KF取代高效制备FEC。

关键词: 离子液体, 相转移催化, 配合物, 传质, 氟代碳酸乙烯酯, 密度泛函理论

Abstract:

As one of the key components in lithium battery electrolyte additives, fluoroethylene carbonate (FEC) is primarily produced industrially using the halogen exchange process. During the FEC synthesis, a substitution reaction between potassium fluoride (KF) and chloroethylene carbonate (CEC) occurs, the rate of which has been limited by the interphase mass transfer of KF. Meanwhile, the CEC is susceptible to an elimination reaction to form by-product of vinylene carbonate. To address these issues, the effect of phase transfer catalyst (PTC) structure on the interphase mass transfer of KF and reaction energy barriers were investigated. It was revealed that the optimized conditions consist of [bmim][BF₄] (1-butyl-3-methylimidazolium tetrafluoroborate) as the PTC, acetonitrile as the solvent, a reaction temperature of 81.6℃, and a KF∶CEC molar ratio of 2.5∶1. Under the optimized reaction conditions, an unprecedently high yield of FEC (91.94%, molar fraction) was achieved. Density functional theory calculations suggested that the [bmim][BF₄] can form complexes with the KF in acetonitrile to increase the nuclear distance between K⁺ and F^- and decrease the free energy of solvation of KF. As a result, the interphase mass transfer of KF was facilitated and the energy barrier of the substitution reaction between KF and CEC was reduced, which contributed to the efficient production of FEC from CEC.

Key words: ionic liquids, phase transfer catalysis, complexes, mass transfer, fluoroethylene carbonate, density functional theory

中图分类号:

TQ 072

蒋方涛, 钱刚, 周兴贵, 段学志, 张晶. 基于［bmim］［BF₄］相转移催化的氟代碳酸乙烯酯高效合成[J]. 化工学报, 2024, 75(4): 1543-1551.

Fangtao JIANG, Gang QIAN, Xinggui ZHOU, Xuezhi DUAN, Jing ZHANG. Efficient synthesis of fluoroethylene carbonate via phase transfer catalysis using [bmim][BF₄][J]. CIESC Journal, 2024, 75(4): 1543-1551.

图/表 8

图1 CEC、EC、FEC标准曲线以及原料、产物色谱分析

Fig.1 Gas chromatograph calibration curves of CEC, EC and FEC and component identification of reactant and product

图2 无相转移催化剂时SN2取代和E2消去反应机理

Fig.2 Mechanism of SN2 substitution and E2 elimination reaction in the absence of phase transfer catalyst

图3 反应温度、反应物摩尔比n(KF)∶n(CEC)、反应溶液含水量、反应溶剂类型对反应结果的影响

Fig.3 Effects of reaction temperature, molar ratio of n(KF)∶n(CEC), water content, and solvent type on reaction results

图4 反应溶液中水分对SN2氟氯取代反应能垒的影响

Fig.4 Effect of water in reaction medium on the energy barriers of the SN2 substitution reaction

表1 不同氟源对反应结果的影响

Table 1 Effect of fluorine source on the reaction result

氟源	时间/h	收率/%(摩尔分数)	核间距/Å	S_N2/ (kcal/mol)	E2/ (kcal/mol)
F^-	—	—	—	14.72	10.74
CsF	0.5	74.77	2.7230	20.30	18.93
KF	8.0	79.97	2.4243	24.15	24.52
NaF	8.0	—	2.0754	28.55	29.66

表2 不同PTC对反应结果的影响

Table 2 Effect of different PTC on the reaction result

序号	PTC	n(PTC)∶n(CEC)	时间/ h	转化率/ %	收率/% (摩尔分数)
1	—	—	8.0	93.89	82.21
2	[bmim][BF₄]	0.15	6.0	99.33	89.80
3	[bmim][BF₄]	0.2	6.0	99.26	91.94
4	[bmim][BF₄]	0.25	6.0	99.59	89.02
5	[bmim][SbF₆]	0.2	6.0	72.53	51.39
6	[bmim][OMS]	0.2	6.0	72.20	27.24
7	[C4MPr][BF₄]	0.2	6.0	79.34	73.12
8	[C4PyM][BF₄]	0.2	6.0	83.21	65.27
9	四丁基氯化铵	0.2	8.0	46.71	4.94
10	四丁基氯化磷	0.2	8.0	28.07	0.72
11	PEG800	0.2	8.0	35.66	19.36
12	18-冠醚-6	0.2	8.0	41.78	9.80
13	β-环糊精	0.2	8.0	82.13	66.37

图5 [bmim][BF4]作用下SN2、E2过渡态结构以及有无[bmim][BF4]时SN2取代、E2消去反应能垒

Fig.5 Transition state structures of SN2 and E2 with [bmim][BF4] and the reaction energy barriers of SN2 and E2 with or without [bmim][BF4]

表3 ［bmim］［BF4］和KF在乙腈溶剂中活化及氟化反应数据

Table 3 Activation and fluorination reaction data of ［bmim］［BF4］ and KF in acetonitrile solvent

序号	过程	ΔG/(kcal/mol)
1	KF(s) KF(g)^①	46.40
2	KF(g) KF(solv)	-21.04
3	KF(solv)+[bmim][BF₄] KF([bmim][BF₄])	-7.50
4	KCl(s) KCl(g)^①	41.91
5	KCl(g) KCl(solv)	-22.60
6	KCl(solv)+[bmim][BF₄] KCl([bmim][BF₄])	-0.90
7	KCl(solv)+HF+[bmim][BF₄] (KCl-HF)([bmim][BF₄])	-1.31
8	TS-KF(solv)-S_N2	24.15
9	TS-KF([bmim][BF₄])-S_N2	25.74
10	TS-KF(solv)-E2	24.52
11	TS-KF([bmim][BF₄])-E2	27.42

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基于［bmim］［BF₄］相转移催化的氟代碳酸乙烯酯高效合成

Efficient synthesis of fluoroethylene carbonate via phase transfer catalysis using [bmim][BF₄]

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