CN115772150A - Preparation method of ethylene carbonate fluoro derivative - Google Patents
Preparation method of ethylene carbonate fluoro derivative Download PDFInfo
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- CN115772150A CN115772150A CN202211406702.0A CN202211406702A CN115772150A CN 115772150 A CN115772150 A CN 115772150A CN 202211406702 A CN202211406702 A CN 202211406702A CN 115772150 A CN115772150 A CN 115772150A
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- ethylene carbonate
- carbonate
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 239000012043 crude product Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 23
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 21
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 17
- 239000000047 product Substances 0.000 claims abstract description 16
- KQDOUXAQOUQPQW-UHFFFAOYSA-N 4-bromo-1,3-dioxolan-2-one Chemical compound BrC1COC(=O)O1 KQDOUXAQOUQPQW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012025 fluorinating agent Substances 0.000 claims abstract description 9
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 9
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 8
- 238000005893 bromination reaction Methods 0.000 claims abstract description 7
- 230000001276 controlling effect Effects 0.000 claims abstract description 7
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 7
- 230000001105 regulatory effect Effects 0.000 claims abstract description 7
- 238000005286 illumination Methods 0.000 claims abstract description 6
- 230000031709 bromination Effects 0.000 claims abstract description 4
- WMNPLXMHVCFDKJ-UHFFFAOYSA-N bromoethene;carbonic acid Chemical compound BrC=C.OC(O)=O WMNPLXMHVCFDKJ-UHFFFAOYSA-N 0.000 claims abstract description 3
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 11
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 8
- 235000003270 potassium fluoride Nutrition 0.000 claims description 8
- 239000011698 potassium fluoride Substances 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 4
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 claims description 4
- RGKCBZXUQPAWOY-UHFFFAOYSA-N 1-bromopyrrole-2,5-dione Chemical compound BrN1C(=O)C=CC1=O RGKCBZXUQPAWOY-UHFFFAOYSA-N 0.000 claims description 2
- QRADPXNAURXMSB-UHFFFAOYSA-N 2-bromo-1,1-dioxo-1,2-benzothiazol-3-one Chemical compound C1=CC=C2S(=O)(=O)N(Br)C(=O)C2=C1 QRADPXNAURXMSB-UHFFFAOYSA-N 0.000 claims description 2
- MARXMDRWROUXMD-UHFFFAOYSA-N 2-bromoisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(Br)C(=O)C2=C1 MARXMDRWROUXMD-UHFFFAOYSA-N 0.000 claims description 2
- MENYRYNFSIBDQN-UHFFFAOYSA-N 5,5-dibromoimidazolidine-2,4-dione Chemical compound BrC1(Br)NC(=O)NC1=O MENYRYNFSIBDQN-UHFFFAOYSA-N 0.000 claims description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- GUNJVIDCYZYFGV-UHFFFAOYSA-K antimony trifluoride Chemical compound F[Sb](F)F GUNJVIDCYZYFGV-UHFFFAOYSA-K 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 2
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000009776 industrial production Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 229910052731 fluorine Inorganic materials 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 13
- 239000011737 fluorine Substances 0.000 description 13
- 238000001914 filtration Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 5
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- ZTGBMKXOOBTYPT-UHFFFAOYSA-N BrC(=O)O.C=C Chemical compound BrC(=O)O.C=C ZTGBMKXOOBTYPT-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- VNAQNRVIJHCIFS-UHFFFAOYSA-N difluoro carbonate Chemical compound FOC(=O)OF VNAQNRVIJHCIFS-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- DSMUTQTWFHVVGQ-UHFFFAOYSA-N 4,5-difluoro-1,3-dioxolan-2-one Chemical compound FC1OC(=O)OC1F DSMUTQTWFHVVGQ-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- DPYHWBDMHWWBCQ-UHFFFAOYSA-N dibromo carbonate Chemical compound BrOC(=O)OBr DPYHWBDMHWWBCQ-UHFFFAOYSA-N 0.000 description 2
- YCGZNZYMKQRQRS-UHFFFAOYSA-N ethenyl carbonobromidate Chemical compound BrC(=O)OC=C YCGZNZYMKQRQRS-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Inorganic materials Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- HIGQQEOWQNDHJD-UHFFFAOYSA-N 4,4-dichloro-1,3-dioxolan-2-one Chemical compound ClC1(Cl)COC(=O)O1 HIGQQEOWQNDHJD-UHFFFAOYSA-N 0.000 description 1
- OYOKPDLAMOMTEE-UHFFFAOYSA-N 4-chloro-1,3-dioxolan-2-one Chemical compound ClC1COC(=O)O1 OYOKPDLAMOMTEE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of a fluoro derivative of ethylene carbonate, which comprises the following steps: reacting the ethylene carbonate with a bromination reagent under the action of an initiator, and regulating and controlling reaction conditions and the reagent dosage to obtain a crude product of the bromo ethylene carbonate or a crude product of 4, 5-dibromo ethylene carbonate; dissolving the crude product of bromo-ethylene carbonate or 4, 5-dibromo-ethylene carbonate, adding a fluorinating agent, carrying out fluorination reaction under the action of a phase transfer catalyst at the reaction temperature of 50-120 ℃ for 4-6 h, and purifying to obtain the target product of fluoro-ethylene carbonate or 4, 5-difluoro-ethylene carbonate. The method has the advantages of mild reaction conditions, high product yield, high purity, low raw material cost, simple process and environmental protection, and realizes the industrial production of fluoroethylene carbonate and 4, 5-difluoroethylene carbonate on the same production line only by regulating and controlling the reaction temperature, the illumination conditions and the reagent dosage.
Description
The technical field is as follows:
the invention relates to a preparation method of a fluoro derivative of ethylene carbonate.
Background art:
fluoroethylene carbonate is an important electrolyte additive for lithium ion batteries. The safety and stability performance of the lithium battery is obviously improved while the decomposition of the electrolyte is inhibited, such as: cyclic charging efficiency, high and low temperature resistance, stability and the like.
Compared with fluoroethylene carbonate, the 4, 5-difluoroethylene carbonate has higher dielectric constant, higher oxidation resistance and symmetrical structure stability and has outstanding advantage in improving the negative electrode of silica ink, so that the 4, 5-difluoroethylene carbonate is mainly applied to lithium ion electrolyte of a lithium battery, and the difluoroethylene carbonate can effectively improve the high and low temperature resistance of the lithium ion electrolyte and can improve the flame retardant property of the lithium ion electrolyte.
In the prior art, the production and preparation methods of fluoroethylene carbonate can be classified into the following methods: (1) Electrochemical fluorination, currently limited to the laboratory development stage; (2) The addition method adopts addition preparation of hydrogen fluoride and vinylene carbonate, such as high-pressure addition preparation of vinyl fluoride, carbon dioxide and oxygen, is limited to a laboratory development stage at present, and has the defects of poor selectivity, high cost, difficult control of reaction and the like; (3) A fluorine source replacing fluorination by a fluorine atom, i.e., replacing a hydrogen atom or a chlorine atom with a fluorine atom, the fluorine source comprising: fluorine gas, hydrogen fluoride, potassium fluoride, fluosilicic acid, organic amine hydrofluoride and the like, and in the existing fluorine source replacement patent technology: the fluorine gas is used as a fluorine source for preparation, so that side reactions are more, and the purity of the product is difficult to reach the standard; the acid value content in the product obtained by using the hydrogen fluoride as the fluorine source can not meet the requirements of electronic-grade products, the subsequent treatment is needed, the production cost is increased, the requirements on equipment and personnel are high due to the high toxicity and strong corrosivity of the hydrogen fluoride, and the adoption of the fluosilicic acid or the organic amine hydrofluoride as the fluorine source is only limited to laboratory research and development.
In the prior art, the preparation methods of 4, 5-difluoroethylene carbonate mainly comprise the following steps: (1) The defect of the method that the ethylene carbonate is taken as the raw material and fluorine gas is taken as the fluorine source for the addition reaction to prepare the difluoroethylene carbonate is that: the raw material cost is high, the equipment is easy to corrode, the equipment requirement is high, and the method is not suitable for industrial production; (2) The method has the defects that the simple substance fluorine is very active, so that the fluoro position and the fluoro quantity are difficult to control in the fluoro process, the reaction liquid prepared by the method is a mixture, the physicochemical properties of byproducts are similar to those of products, the separation and purification efficiency is influenced, and the fluorine simple substance has strong corrosivity and extremely high requirements on equipment; (3) The method for preparing the 4, 5-difluoroethylene carbonate by using the potassium fluoride and the dichloroethylene carbonate has the defects of long reaction time, low yield and difficult separation of impurities to obtain a high-purity product.
The invention content is as follows:
the invention aims to provide a preparation method of a fluoroethylene carbonate fluoro derivative, which has the advantages of mild reaction conditions, high product yield, high purity, low raw material cost, simple and environment-friendly process, and realizes industrial production of fluoroethylene carbonate and 4, 5-difluoroethylene carbonate only by regulating and controlling reaction temperature, illumination conditions and reagent dosage in the same production line.
The invention is realized by the following technical scheme:
a preparation method of ethylene carbonate fluoro-derivative comprises the following steps:
1. bromination reaction: dissolving ethylene carbonate in a first organic solvent, reacting with a bromination reagent under the action of an initiator, and regulating and controlling reaction conditions and reagent dosage to obtain a crude product of the bromo-ethylene carbonate or a crude product of 4, 5-dibromo-ethylene carbonate; the brominating agent is selected from one or more of N-bromosuccinimide, N-bromophthalimide, N-bromomaleimide, N-bromosaccharin and dibromohydantoin; when the crude product of the bromoethylene carbonate is synthesized, the mol ratio of the ethylene carbonate to the bromination reagent is as follows: 1.05-1.1, reacting under natural light conditions, wherein the reaction temperature is 20-60 ℃, and the reaction time is 2-6 h; when the crude product of the 4, 5-dibromo ethylene carbonate is synthesized, the molar ratio of the ethylene carbonate to the bromization reagent is as follows: 1.05 to 1.1; the reaction is carried out under the illumination condition of an incandescent lamp, the power of the incandescent lamp is 40-100W, the reaction temperature is 40-80 ℃, and the reaction time is 4-8 h;
2. and (3) fluoro reaction: dissolving a bromo-ethylene carbonate crude product or a 4, 5-dibromo-ethylene carbonate crude product in a second organic solvent, adding a fluorinating agent, carrying out fluorination reaction under the action of a phase transfer catalyst at the reaction temperature of 50-120 ℃ for 4-6 h, and purifying to obtain a target product, namely fluoro-ethylene carbonate or 4, 5-difluoro-ethylene carbonate; the phase transfer catalyst is one or two of benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide and dodecyl trimethyl ammonium chloride, and the dosage of the phase transfer catalyst is 0.005-0.01 time of the molar weight of the bromoethylene carbonate or the crude product of the 4, 5-dibromo ethylene carbonate.
In the first step, the initiator is one or two of azodiisobutyronitrile and dibenzoyl peroxide; the molar ratio of the ethylene carbonate to the initiator is as follows: 1, 0.03-0.05.
The first organic solvent is one or more of benzene, toluene, normal hexane, cyclohexane and carbon tetrachloride, and the moisture content of the first organic solvent is less than 50ppm.
In the second step, the second organic solvent is one or more of sulfolane, dimethyl carbonate and acetonitrile, and the moisture content of the second organic solvent is less than 50ppm.
The fluorinating agent is selected from one or two of potassium fluoride, sodium fluoride, ammonium fluoride, calcium fluoride, zinc fluoride, magnesium fluoride and antimony fluoride, and when synthesizing fluoroethylene carbonate, the usage amount of the fluorinating agent is 1.5 to 3 times of the molar weight of a crude product of bromoethylene carbonate; when synthesizing 4, 5-difluoro ethylene carbonate, the usage amount of the fluorinating agent is 3-5 times of the molar weight of the crude product of bromo ethylene carbonate.
The invention has the following beneficial effects:
1. the method has the advantages of mild reaction conditions, high product yield, high purity, low raw material cost and simple process, and realizes the industrial production of fluoroethylene carbonate and 4, 5-difluoroethylene carbonate on the same production line only by regulating and controlling the reaction temperature, the illumination conditions and the reagent dosage.
2. The bromization reagent selected by the invention is safer than bromine water, is easier to store and is easier to control the reaction.
3. Firstly, compared with the chloro-substitution, the bromo-substitution has higher reaction conversion rate, the chloro-substitution conversion rate of the ethylene carbonate is generally between 80 and 85 percent, and the bromo-substitution conversion rate of the ethylene carbonate is generally more than 90 percent; secondly, in the fluorination, bromoethylene carbonate and 4, 5-dibromo ethylene carbonate are easier to fluorinate than chloroethylene carbonate and 4, 5-dichloro ethylene carbonate, the fluorination reaction conditions are milder, and the fluorination time is shorter; thirdly, when synthesizing 4, 5-dibromo ethylene carbonate, because the radius of bromine atom is larger than that of chlorine atom, after one hydrogen atom in the ethylene carbonate is replaced by bromine, the hydrogen on the same carbon is not easy to be replaced, so that the bromination reaction only generates the 4, 5-dibromo ethylene carbonate and does not generate the 4, 4-dibromo ethylene carbonate, thus not only improving the reaction yield, but also being easier to purify.
4. The invention selects the brominating reagent and the fluorinating reagent which are easy to obtain and store, and avoids the problems that the reaction process is difficult to control and a lot of waste gas is generated in the production process of selecting chlorine, fluorine, bromine water, hydrogen fluoride and other raw materials.
In a word, the method has the advantages of mild reaction conditions, high product yield, high purity, low raw material cost, simple process and environmental protection, and realizes the industrial production of fluoroethylene carbonate and 4, 5-difluoroethylene carbonate on the same production line only by regulating and controlling the reaction temperature, the illumination conditions and the reagent dosage.
The specific implementation mode is as follows:
the following is a further description of the invention and is not intended to be limiting.
Example 1:
preparation of vinyl bromocarbonate:
under natural light, under the protection of nitrogen, ethylene carbonate (92.4 g, 1.05mol) and n-hexane (700 g) with the moisture content of 45ppm are sequentially added into a round-bottom four-neck flask provided with a condenser, a stirrer and a thermometer, the temperature is raised to 40 ℃ under stirring, the mixture of azodiisobutyronitrile (5.3 g) and bromosuccinimide (178 g) is evenly added in 4 batches, the reaction is continued for 4 hours at 40 ℃, the heating is stopped, insoluble substances are removed by filtration, the n-hexane is removed under reduced pressure, and 280g of crude product of the ethylene bromocarbonate is obtained, wherein the content of the ethylene bromocarbonate is 53%.
Preparation of fluoroethylene carbonate:
adding the above bromoethylene carbonate (280 g), potassium fluoride (103 g), sulfolane (400 g) and tetrabutylammonium bromide (2.5 g) into a round-bottom three-neck flask with a condenser, a stirrer and a thermometer, heating to 100 ℃ under stirring, reacting for 5 hours, filtering the reaction solution, concentrating the filtrate under reduced pressure to remove the solvent, obtaining a crude product of fluoroethylene carbonate, carrying out reduced pressure rectification on the crude product, and carrying out nitrogen protection in the whole process to obtain 87g of target product fluoroethylene carbonate, wherein the purity is more than or equal to 99.5%, the yield is 82%, and the moisture is 42ppm.
Example 2
4, 5-ethylene dibromocarbonate:
under a 60W incandescent lamp, ethylene carbonate (92.4 g, 1.05mol) and n-hexane (1000 g) with a moisture content of 45ppm were sequentially added to a round-bottom four-necked flask equipped with a condenser, a stirrer and a thermometer under the protection of nitrogen, the temperature was raised to 80 ℃ with stirring, a mixture of azobisisobutyronitrile (6.0 g) and bromosuccinimide (356 g, 2mol) was added in 4 portions, the reaction was continued at 80 ℃ for 7 hours, heating was stopped, insoluble matter was removed by filtration, and n-hexane was removed under reduced pressure to obtain 470g of crude 4, 5-dibromoethylene carbonate with a bromoethylene carbonate content of 44%.
Preparation of 4, 5-difluoroethylene carbonate:
adding the 4, 5-ethylene dibromide carbonate (470 g), potassium fluoride (215 g), sulfolane (600 g) and tetrabutylammonium bromide (2.3 g) into a round-bottom three-necked flask with a condenser, a stirrer and a thermometer, heating to 110 ℃ under stirring for reacting for 6 hours, filtering the reaction liquid, decompressing and concentrating the filtrate to remove the solvent to obtain a crude product of the 4, 5-ethylene difluorocarbonate, decompressing and rectifying the crude product, and performing nitrogen protection in the whole process to obtain 96g of the target product of the 4, 5-ethylene difluorocarbonate, wherein the purity is more than or equal to 99.5%, the yield is 77.4% and the moisture is 40ppm.
Example 3
Preparation of vinyl bromocarbonate:
under natural light, under the protection of nitrogen, ethylene carbonate (96.8g, 1.1mol) and carbon tetrachloride (650 g) with the moisture content of 40ppm are sequentially added into a round-bottom four-neck flask provided with a condenser, a stirrer and a thermometer, the temperature is raised to 60 ℃ under stirring, a mixture of azobisisobutyronitrile (7.3 g) and bromosuccinimide (178 g) is uniformly added in 4 batches, the reaction is continued for 4 hours at 60 ℃, the heating is stopped, insoluble substances are removed by filtration, and the carbon tetrachloride is removed under reduced pressure, so that 290g of crude product of the ethylene bromocarbonate is obtained, wherein the content of the ethylene bromocarbonate is 52.5%.
Preparation of fluoroethylene carbonate:
adding the above bromoethylene carbonate (290 g), potassium fluoride (132 g), acetonitrile (450 g) and tetrabutylammonium bromide (2.6 g) into a round-bottom three-neck flask with a condenser, a stirrer and a thermometer, heating to 100 ℃ under stirring for reaction for 5 hours, filtering the reaction solution, concentrating the filtrate under reduced pressure to remove the solvent to obtain a crude product of the fluoroethylene carbonate, performing reduced pressure rectification on the crude product, and performing nitrogen protection in the whole process to obtain 89g of the target product fluoroethylene carbonate, wherein the purity is more than or equal to 99.5%, the yield is 84%, and the water content is 37ppm.
Example 4
4, 5-ethylene dibromocarbonate:
ethylene carbonate (96.8g, 1.1 mol) and carbon tetrachloride (900 g) having a moisture content of 40ppm were sequentially fed under a 60W incandescent lamp to a round-bottom four-necked flask equipped with a condenser, a stirrer and a thermometer under nitrogen atmosphere, the temperature was raised to 80 ℃ under stirring, a mixture of azobisisobutyronitrile (8.5 g) and bromosuccinimide (356g, 2mol) was added in 4 portions, the reaction was continued at 80 ℃ for 7 hours, the heating was stopped, insoluble matter was removed by filtration, and carbon tetrachloride was removed under reduced pressure to obtain 475g of crude 4, 5-dibromoethylene carbonate having a bromoethylene carbonate content of 44.6%.
Preparation of 4, 5-difluoroethylene carbonate:
adding the 4, 5-ethylene dibromide carbonate (475 g), potassium fluoride (240 g), acetonitrile (700 g) and tetrabutylammonium bromide (2.5 g) into a round-bottom three-necked flask with a condenser, a stirrer and a thermometer, heating to 120 ℃ under stirring for reaction for 5.5h, filtering the reaction solution, concentrating the filtrate under reduced pressure to remove the solvent to obtain a crude product of the 4, 5-ethylene difluorocarbonate, carrying out reduced pressure rectification on the crude product, and carrying out nitrogen protection in the whole process to obtain 98g of the target product of the 4, 5-ethylene difluorocarbonate, wherein the purity is more than or equal to 99.5 percent, the yield is 79 percent, and the moisture is 35ppm.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (7)
1. A preparation method of fluorinated derivatives of ethylene carbonate is characterized by comprising the following steps:
1. bromination reaction: dissolving ethylene carbonate in a first organic solvent, reacting with a bromization reagent under the action of an initiator, and regulating and controlling reaction conditions and reagent dosage to obtain a crude product of the bromization ethylene carbonate or a crude product of 4, 5-dibromo ethylene carbonate; the brominating agent is selected from one or more of N-bromosuccinimide, N-bromophthalimide, N-bromomaleimide, N-bromosaccharin and dibromohydantoin; when the crude product of the brominated ethylene carbonate is synthesized, the molar ratio of the ethylene carbonate to the bromination reagent is as follows: 1.05-1.1, reacting under natural light conditions, wherein the reaction temperature is 20-60 ℃, and the reaction time is 2-6 h; when the crude product of the 4, 5-dibromo ethylene carbonate is synthesized, the molar ratio of the ethylene carbonate to the bromization reagent is as follows: 1.05-1.1; the reaction is carried out under the illumination condition of an incandescent lamp, the power of the incandescent lamp is 40-100W, the reaction temperature is 40-80 ℃, and the reaction time is 4-8 h;
2. and (3) fluoro reaction: dissolving a bromoethylene carbonate crude product or a 4, 5-dibromo ethylene carbonate crude product in a second organic solvent, then adding a fluorinating agent, carrying out a fluorination reaction under the action of a phase transfer catalyst, wherein the reaction temperature is 50-120 ℃, the reaction time is 4-6 h, and purifying to obtain a target product fluoroethylene carbonate or 4, 5-difluoro ethylene carbonate; the phase transfer catalyst is one or two of benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide and dodecyl trimethyl ammonium chloride, and the dosage of the phase transfer catalyst is 0.005-0.01 time of the molar weight of the bromoethylene carbonate or the crude product of the 4, 5-dibromo ethylene carbonate.
2. The preparation method according to claim 1, wherein in the first step, the initiator is one or two selected from azobisisobutyronitrile and dibenzoyl peroxide.
3. The method according to claim 1, wherein the molar ratio of ethylene carbonate to initiator is: 1, 0.03-0.05.
4. The method according to claim 1, wherein the first organic solvent is one or more of benzene, toluene, n-hexane, cyclohexane and carbon tetrachloride, and the moisture content of the first organic solvent is less than 50ppm.
5. The method of claim 1, wherein in step two, the second organic solvent is one or more of sulfolane, dimethyl carbonate and acetonitrile, and the moisture content of the second organic solvent is less than 50ppm.
6. The method according to claim 1, wherein the fluorinating agent is one or two selected from potassium fluoride, sodium fluoride, ammonium fluoride, calcium fluoride, zinc fluoride, magnesium fluoride and antimony fluoride.
7. The preparation method according to claim 1, characterized in that, when synthesizing fluoroethylene carbonate, the amount of fluorinating agent is 1.5-3 times of the molar weight of crude bromoethylene carbonate; when synthesizing 4, 5-difluoro ethylene carbonate, the usage amount of the fluorinating agent is 3-5 times of the molar weight of the crude product of bromo ethylene carbonate.
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