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

参考文献 33

1	Horstmann B, Shi J Y, Amine R, et al. Strategies towards enabling lithium metal in batteries: interphases and electrodes[J]. Energy & Environmental Science, 2021, 14(10): 5289-5314.
2	Zhang X Q, Cheng X B, Chen X, et al. Fluoroethylene carbonate additives to render uniform Li deposits in lithium metal batteries[J]. Advanced Functional Materials, 2017, 27(10): 1605989.
3	Markevich E, Salitra G, Aurbach D. Fluoroethylene carbonate as an important component for the formation of an effective solid electrolyte interphase on anodes and cathodes for advanced Li-ion batteries[J]. ACS Energy Letters, 2017, 2(6): 1337-1345.
4	Liu Q C, Xu J J, Yuan S, et al. Artificial protection film on lithium metal anode toward long-cycle-life lithium-oxygen batteries[J]. Advanced Materials, 2015, 27(35): 5241-5247.
5	胡华坤, 薛文东, 霍思达, 等. 锂离子电池电解液SEI成膜添加剂的研究进展[J]. 化工学报, 2022, 73(4): 1436-1454.
	Hu H K, Xue W D, Huo S D, et al. Review of SEI film forming additives for electrolyte of lithium ion battery[J]. CIESC Journal, 2022, 73(4): 1436-1454.
6	任章顺, 朱志峰, 袁胜芳, 等. 氟代碳酸乙烯酯的合成与精制进展[J]. 化学推进剂与高分子材料, 2015, 13(6): 39-44.
	Ren Z S, Zhu Z F, Yuan S F, et al. Progress in synthesis and purification of fluoroethylene carbonate[J]. Chemical Propellants & Polymeric Materials, 2015, 13(6): 39-44.
7	吕俊奇, 阎子祯, 周羿凝, 等. 氟代碳酸乙烯酯的制备和精制工艺最新进展[J]. 化学推进剂与高分子材料, 2023, 21(2): 30-44.
	Lyu J Q, Yan Z Z, Zhou Y N, et al. Recent advances in preparation and purification process of fluoroethylene carbonate[J]. Chemical Propellants & Polymeric Materials, 2023, 21(2): 30-44.
8	Starks C M. Phase-transfer catalysis(Ⅰ): Heterogeneous reactions involving anion transfer by quaternary ammonium and phosphonium salts[J]. Journal of the American Chemical Society, 1971, 93(1): 195-199.
9	Pozzi G, Quici S, Fish R H. Fluorous phase transfer catalysts: from onium salts to crown ethers[J]. Journal of Fluorine Chemistry, 2008, 129(10): 920-929.
10	Shirakawa S, Maruoka K. Recent developments in asymmetric phase-transfer reactions[J]. Angewandte Chemie (International Ed. in English), 2013, 52(16): 4312-4348.
11	Greer A J, Jacquemin J, Hardacre C. Industrial applications of ionic liquids[J]. Molecules, 2020, 25(21): 5207.
12	姚桂, 段正康, 贺玉平, 等. 氟代碳酸乙烯酯的合成[J]. 精细化工, 2012, 29(4): 394-397.
	Yao G, Duan Z K, He Y P, et al. Synthesis of fluoroethylene carbonate[J]. Fine Chemicals, 2012, 29(4): 394-397.
13	李云峰, 王永勤. 氟代碳酸乙烯酯的合成工艺研究[J]. 河南化工, 2018, 35(7): 29-31.
	Li Y F, Wang Y Q. Study on the synthetic process of fluoroethylene carbonate[J]. Henan Chemical Industry, 2018, 35(7): 29-31.
14	Frisch M J, Trucks G W, Schlegel H B, et al. Gaussian 09 Rev. E.01[CP]. Wallingford: Gaussian Inc., CT., 2009.
15	Zhao Y, Truhlar D G. The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals[J]. Theoretical Chemistry Accounts, 2008, 120(1): 215-241.
16	Weigend F, Ahlrichs R. Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: design and assessment of accuracy[J]. Physical Chemistry Chemical Physics: PCCP, 2005, 7(18): 3297-3305.
17	Hariharan P C, Pople J A. Accuracy of AH _n equilibrium geometries by single determinant molecular orbital theory[J]. Molecular Physics, 1974, 27(1): 209-214.
18	Petersson G A, Bennett A, Tensfeldt T G, et al. A complete basis set model chemistry(Ⅰ): The total energies of closed-shell atoms and hydrides of the first-row elements[J]. The Journal of Chemical Physics, 1988, 89(4): 2193-2218.
19	Marenich A V, Cramer C J, Truhlar D G. Universal solvation model based on solute electron density and on a continuum model of the solvent defined by the bulk dielectric constant and atomic surface tensions[J]. The Journal of Physical Chemistry B, 2009, 113(18): 6378-6396.
20	Grimme S, Antony J, Ehrlich S, et al. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu[J]. The Journal of Chemical Physics, 2010, 132(15): 154104.
21	Maeda S, Harabuchi Y, Ono Y, et al. Intrinsic reaction coordinate: calculation, bifurcation, and automated search[J]. International Journal of Quantum Chemistry, 2015, 115(5): 258-269.
22	Oh Y H, Yun W, Kim C H, et al. Inter- and intra-molecular organocatalysis of S_N2 fluorination by crown ether: kinetics and quantum chemical analysis[J]. Molecules, 2021, 26(10): 2947.
23	Silva S L, Valle M S, Pliego J R. Nucleophilic fluorination with KF catalyzed by 18-crown-6 and bulky diols: a theoretical and experimental study[J]. The Journal of Organic Chemistry, 2020, 85(23): 15457-15465.
24	O'Hair R A J, Davico G E, Hacaloglu J, et al. Measurements of solvent and secondary kinetic isotope effects for the gas-phase S_N2 reactions of fluoride with methyl halides[J]. Journal of the American Chemical Society, 1994, 116(8): 3609-3610.
25	Liu X, Yang L, Zhang J X, et al. Competition of F/OH-induced S_N2 and proton-transfer reactions with increased solvation[J]. The Journal of Physical Chemistry A, 2018, 122(49): 9446-9453.
26	Anslyn E V, Dougherty D A. Modern Physical Organic Chemistry[M]. Sausalito, Calif.: University Science, 2006.
27	Tang W Q, Zhao J H, Jiang P, et al. Solvent effects on the symmetric and asymmetric S_N2 reactions in the acetonitrile solution: a reaction density functional theory study[J]. The Journal of Physical Chemistry. B, 2020, 124(15): 3114-3122.
28	杜治平, 姚洁, 曾毅, 等. 碳酸乙烯酯的酯交换反应研究进展[J]. 天然气化工, 2003, 28(4): 22-29.
	Du Z P, Yao J, Zeng Y, et al. Progress in study of transesterification of ethylene carbonate[J]. Natural Gas Chemical Industry, 2003, 28(4): 22-29.
29	Laloo J Z A, Rhyman L, Ramasami P, et al. Ion-pair S_N2 substitution: activation strain analyses of counter-ion and solvent effects[J]. Chemistry-A European Journal, 2016, 22(13): 4431-4439.
30	Kim D W, Song C E, Chi D Y. New method of fluorination using potassium fluoride in ionic liquid: significantly enhanced reactivity of fluoride and improved selectivity[J]. Journal of the American Chemical Society, 2002, 124(35): 10278-10279.
31	Oh Y H, Choi H, Park C, et al. Harnessing ionic interactions and hydrogen bonding for nucleophilic fluorination[J]. Molecules, 2020, 25(3): 721.
32	Carvalho N F, Pliego J R. Theoretical design and calculation of a crown ether phase-transfer-catalyst scaffold for nucleophilic fluorination merging two catalytic concepts[J]. The Journal of Organic Chemistry, 2016, 81(18): 8455-8463.
33	NIST chemistry webbook, NIST standard reference database number 69 [DB/OL]. Gaithersburg MD, 20899: National Institute of Standards and Technology, 2024. .

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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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