CN112759611B - Preparation method of battery electrolyte additive - Google Patents
Preparation method of battery electrolyte additive Download PDFInfo
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- CN112759611B CN112759611B CN202110109115.4A CN202110109115A CN112759611B CN 112759611 B CN112759611 B CN 112759611B CN 202110109115 A CN202110109115 A CN 202110109115A CN 112759611 B CN112759611 B CN 112759611B
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- solvent
- alkenyl
- phosphate
- alcohol
- methyl
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- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000002000 Electrolyte additive Substances 0.000 title description 8
- -1 alkenyl phosphate Chemical compound 0.000 claims abstract description 51
- 239000007788 liquid Substances 0.000 claims abstract description 47
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 44
- 239000010452 phosphate Substances 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 239000002904 solvent Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000005406 washing Methods 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012074 organic phase Substances 0.000 claims abstract description 20
- 238000000605 extraction Methods 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 16
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims abstract description 16
- 239000000047 product Substances 0.000 claims abstract description 16
- 239000011230 binding agent Substances 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 11
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 10
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000000706 filtrate Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 150000002460 imidazoles Chemical class 0.000 claims abstract description 7
- 150000004693 imidazolium salts Chemical class 0.000 claims abstract description 7
- 239000011261 inert gas Substances 0.000 claims abstract description 7
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 42
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 42
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 33
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- GSYBSZRLMHKNIH-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;hydrogen carbonate Chemical compound OC([O-])=O.CCCC[NH+]1CN(C)C=C1 GSYBSZRLMHKNIH-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000012071 phase Substances 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 239000008096 xylene Substances 0.000 claims description 6
- HCGMDEACZUKNDY-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;acetate Chemical compound CC(O)=O.CCCCN1CN(C)C=C1 HCGMDEACZUKNDY-UHFFFAOYSA-N 0.000 claims description 4
- MQULENUFIVJNPK-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;formate Chemical compound [O-]C=O.CCCC[NH+]1CN(C)C=C1 MQULENUFIVJNPK-UHFFFAOYSA-N 0.000 claims description 4
- GKCVFQNAFQNNQE-UHFFFAOYSA-N C(CCC)N1CN(C=C1)C.C(CC)(=O)O Chemical compound C(CCC)N1CN(C=C1)C.C(CC)(=O)O GKCVFQNAFQNNQE-UHFFFAOYSA-N 0.000 claims description 4
- SQPFPKSOPRMSDP-UHFFFAOYSA-N C(CCC)N1CN(C=C1)C.O Chemical compound C(CCC)N1CN(C=C1)C.O SQPFPKSOPRMSDP-UHFFFAOYSA-N 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000002516 radical scavenger Substances 0.000 claims 1
- 239000008346 aqueous phase Substances 0.000 abstract description 4
- 239000002608 ionic liquid Substances 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 19
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 4
- NGFFLHMFSINFGB-UHFFFAOYSA-N [chloro(methoxy)phosphoryl]oxymethane Chemical compound COP(Cl)(=O)OC NGFFLHMFSINFGB-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
- 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 3
- 230000007547 defect Effects 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- MQCJHQBRIPSIKA-UHFFFAOYSA-N prenyl phosphate Chemical compound CC(C)=CCOP(O)(O)=O MQCJHQBRIPSIKA-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- LGTLXDJOAJDFLR-UHFFFAOYSA-N diethyl chlorophosphate Chemical compound CCOP(Cl)(=O)OCC LGTLXDJOAJDFLR-UHFFFAOYSA-N 0.000 description 1
- GZNJJEODYYLYSA-UHFFFAOYSA-N diethyl prop-2-enyl phosphate Chemical compound CCOP(=O)(OCC)OCC=C GZNJJEODYYLYSA-UHFFFAOYSA-N 0.000 description 1
- QVKQJEWZVQFGIY-UHFFFAOYSA-N dipropyl hydrogen phosphate Chemical class CCCOP(O)(=O)OCCC QVKQJEWZVQFGIY-UHFFFAOYSA-N 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 229940021013 electrolyte solution Drugs 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/113—Esters of phosphoric acids with unsaturated acyclic alcohols
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- 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
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
Abstract
The invention provides a preparation method of alkenyl phosphate, which is characterized by comprising the following steps: the method comprises the following steps: under the protection of inert gas, adding an alcohol containing alkenyl, an imidazole salt catalyst, a first solvent and an acid-binding agent into a reaction vessel, uniformly stirring, dropwise adding a halogenated phosphate solution dissolved in a second solvent into the reaction vessel at 0-50 ℃, reacting for 0.5-2 h, returning to room temperature after the reaction is finished, filtering, removing solid salt, washing the salt for 3-5 times, collecting washing liquid, adding a saturated sodium bicarbonate solution into the filtrate, stirring for 5-10 min, standing, collecting an organic phase, extracting the aqueous phase for 3-5 times, collecting an extraction liquid, combining the washing liquid, the organic phase and the extraction liquid, drying by anhydrous magnesium sulfate, decoloring by activated carbon, and carrying out reduced pressure rectification to obtain the product alkenyl phosphate. Compared with the prior art, the method has the advantages that the imidazolium salt ionic liquid is used for preparing the alkenyl phosphate, the reaction conditions are milder, the reaction time is shorter, and high yield and purity can be achieved.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a preparation method of a battery electrolyte additive, and more particularly relates to a preparation method of alkenyl phosphate.
Background
Lithium batteries are a class of batteries that use lithium metal or lithium alloys as the negative electrode material, using non-hydrolyzing electrolyte solutions. The chemical characteristics of lithium metal are very active, and in addition, the flash point of an organic solvent used by a lithium ion battery is relatively low, when the lithium battery is charged or heated, irreversible oxidative decomposition or thermal decomposition of electrolyte is easy to occur inside the battery, a large amount of combustible gas is generated, the internal pressure of the battery can rapidly rise, and once the shell of the battery is burst, the combustion is easy to occur, and explosion and the like are initiated. Therefore, the flame retardant is added into the lithium ion battery electrolyte, so that the flammability of the lithium ion battery electrolyte can be effectively reduced
Because the combustion event of the charging and discharging process occurs in the existing electric automobile, the safety problem of the electric automobile draws attention to people. Therefore, it is urgently needed to develop and popularize a flame retardant additive which does not reduce the original electrolyte performance. The unsaturated phosphate is a novel nonaqueous lithium ion battery electrolyte additive, and is beneficial to forming a stable and compact passivation film on the surface of an electrode, preventing further decomposition of solvent molecules, and effectively improving the high-temperature storage and high-temperature cycle performance of the lithium ion battery, so that the potential safety hazards of sudden fire and the like caused by high temperature in the charging and discharging process of the lithium ion battery of the electric automobile can be effectively prevented. In addition, the unsaturated phosphate ester is a phosphorus-containing high polymer material with good transparency, wear resistance, heat resistance and flame retardance, so that the unsaturated phosphate ester has excellent application prospect and industrial value, and can be used as a key high-performance electrolyte flame retardant material in novel power batteries such as lithium ion batteries and super capacitors.
At present, the preparation methods of unsaturated phosphate mainly comprise the following steps:
(1) the method for preparing the unsaturated phosphate ester by using phosphorus oxychloride, triethylamine and unsaturated alcohol as raw materials to react in an aprotic solvent has the advantages of low reaction steps, low yield, more byproducts and higher three-waste materials in the post-treatment process due to low activity of the phosphorus oxychloride, large intermediate position and the like in the reaction process, so the method is not suitable for large-scale production.
(2) The method takes phosphate and unsaturated alcohol as substrates, unsaturated phosphate is synthesized through ester exchange reaction, partial products are subjected to condensation reaction, and the boiling points of intermediates and products in the reaction process are very close to each other, so that the difficulty of rectification and purification in the later period is high, the yield is low, the waste is more, the content of final products cannot meet the high-quality requirement, and the method is not suitable for industrial requirements.
(3) The method for preparing the unsaturated phosphate ester by using the phosphite ester and the unsaturated alcohol as substrates, iodine as a catalyst and hydrogen peroxide as an oxidant has the defects of complex reaction, long reaction time, increased by-products, low yield, low purity, difficult product separation and the like because unsaturated bonds (such as alkenyl, alkynyl and the like) are easily oxidized due to the use of the strong oxidant of the hydrogen peroxide.
(4) Halogenated phosphate and corresponding alcohol are used as raw materials, pyridine, triethylamine, sodium carbonate, potassium carbonate and the like are used as acid-binding agents in an organic solvent, and after the reaction is finished, solid salt and a product are separated by a filtration mode, so that unsaturated phosphate is obtained. However, the method has the defects that the solvent is volatile during filtration, the operating environment of workers is poor, and the halogenated phosphate is hydrolyzed in advance when meeting alkaline conditions, so that the yield is influenced, and the like.
(5) The preparation method comprises the steps of taking halogenated phosphate and corresponding alcohol as raw materials, taking water or an organic solvent as a solvent, taking crown ether or quaternary ammonium salt as a catalyst, taking an inorganic alkali solution as an acid-binding agent, and adding a polymerization inhibitor to prepare the unsaturated phosphate.
Disclosure of Invention
The invention aims to overcome a series of defects existing in the preparation of unsaturated phosphate in the prior art, and provides a preparation method of alkenyl phosphate, which is characterized by comprising the following steps: the method comprises the following steps: under the protection of inert gas, adding alcohol, an imidazole salt catalyst, a first solvent and an acid-binding agent into a reaction vessel, stirring uniformly, dropwise adding a halogenated phosphate solution dissolved in a second solvent into the reaction vessel at 0-50 ℃, reacting for 0.5-2 h, returning to room temperature after the reaction is finished, filtering, removing solid salt, washing salt for 3-5 times, collecting washing liquid, adding a saturated sodium bicarbonate solution into filtrate, stirring for 5-10 min, standing for liquid separation, collecting an organic phase, extracting a water phase for 3-5 times, collecting an extraction liquid, combining the washing liquid, the organic phase and the extraction liquid, drying by anhydrous magnesium sulfate, decoloring by activated carbon, and carrying out reduced pressure rectification to obtain the product alkenyl phosphate.
The invention relates to a preparation method of alkenyl phosphate. Wherein the alcohol is an alcohol containing an alkenyl group.
According to the preparation method of the alkenyl phosphate, the imidazole salt catalyst is one or more of 1-methyl-3-butyl imidazole formate, 1-methyl-3-butyl imidazole acetate, 1-methyl-3-butyl imidazole propionate, 1-methyl-3-butyl imidazole hydroxide, 1-butyl-3-methyl-imidazole bicarbonate or 1-butyl-3-methyl-imidazole carbonate.
According to the preparation method of the alkenyl phosphate, the inert gas is selected from nitrogen or argon.
According to the preparation method of the alkenyl phosphate, the first solvent is selected from one or more of dichloromethane, chloroform, tetrahydrofuran, toluene, n-hexane, cyclohexane, xylene, benzene, DMF or DMSO.
According to the preparation method of the alkenyl phosphate, the second solvent is selected from one or more of dichloromethane, chloroform, tetrahydrofuran, toluene, n-hexane, cyclohexane, xylene, benzene, dioxane, DMF or DMSO.
According to the preparation method of the alkenyl phosphate, the acid-binding agent is selected from organic amine.
According to the preparation method of alkenyl phosphate, the acid-binding agent is selected from triethylamine, diethylamine, pyridine or aniline.
According to the preparation method of the alkenyl phosphate, the alcohol is preferably allyl alcohol.
The preparation method of alkenyl phosphate is characterized in that the molar ratio of the number of hydroxyl groups in alcohol to the number of halogen atoms in halogenated phosphate to the acid-binding agent is 1:1: 1-1.5.
The preparation method of the alkenyl phosphate is characterized by comprising the following steps: the molar ratio of the alcohol to the imidazolium salt catalyst is 1: 0.01-0.1.
The preparation method of the alkenyl phosphate is characterized by comprising the following steps: the first solvent and the second solvent may be the same or different.
The preparation method of the alkenyl phosphate is characterized by comprising the following steps: preferably, the first solvent and the second solvent are the same.
The invention further provides an application of the imidazolium salt ionic liquid catalyst in preparation of a battery electrolyte additive, and the battery electrolyte additive is an alkenyl phosphate compound.
The main contributions of the present invention with respect to the prior art are the following:
(1) according to the invention, unsaturated alcohol and halogenated phosphate ester are used as reaction substrates, imidazolium salt ionic liquid is used as a catalyst, and alkenyl phosphate ester is prepared under the condition of an acid-binding agent.
(2) The catalyst used in the method is simple and easy to obtain, low in price and good in catalytic activity, and can obtain satisfactory yield and yield under the condition of using a small amount of catalyst, and compared with other prior art, the method has the unexpected technical effect.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present disclosure more apparent, the technical solutions of the embodiments of the present disclosure are clearly and completely described. It is to be understood that the described embodiments are only a few embodiments of the present disclosure, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the disclosure without any inventive step, are within the scope of protection of the disclosure.
Provided is a method for preparing alkenyl phosphate, which is characterized in that: the method comprises the following steps: under the protection of inert gas, adding alcohol, an imidazole salt catalyst, a first solvent and an acid-binding agent into a reaction vessel, stirring uniformly, dropwise adding a halogenated phosphate solution dissolved in a second solvent into the reaction vessel at 0-50 ℃, reacting for 0.5-2 h, returning to room temperature after the reaction is finished, filtering, removing solid salt, washing salt for 3-5 times, collecting washing liquid, adding a saturated sodium bicarbonate solution into filtrate, stirring for 5-10 min, standing for liquid separation, collecting an organic phase, extracting a water phase for 3-5 times, collecting an extraction liquid, combining the washing liquid, the organic phase and the extraction liquid, drying by anhydrous magnesium sulfate, decoloring by activated carbon, and carrying out reduced pressure rectification to obtain the product alkenyl phosphate.
The invention relates to a preparation method of alkenyl phosphate. Wherein the alcohol is an alcohol containing an alkenyl group.
According to the preparation method of the alkenyl phosphate, the imidazole salt catalyst is one or more of 1-methyl-3-butyl imidazole formate, 1-methyl-3-butyl imidazole acetate, 1-methyl-3-butyl imidazole propionate, 1-methyl-3-butyl imidazole hydroxide, 1-butyl-3-methyl-imidazole bicarbonate or 1-butyl-3-methyl-imidazole carbonate.
According to the preparation method of the alkenyl phosphate, the inert gas is selected from nitrogen or argon.
According to the preparation method of the alkenyl phosphate, the first solvent is selected from one or more of dichloromethane, chloroform, tetrahydrofuran, toluene, n-hexane, cyclohexane, xylene, benzene, DMF or DMSO.
According to the preparation method of the alkenyl phosphate, the second solvent is selected from one or more of dichloromethane, chloroform, tetrahydrofuran, toluene, n-hexane, cyclohexane, xylene, benzene, dioxane, DMF or DMSO.
According to the preparation method of the alkenyl phosphate, the acid-binding agent is selected from organic amine.
According to the preparation method of alkenyl phosphate, the acid-binding agent is selected from triethylamine, diethylamine, pyridine or aniline.
According to the preparation method of the alkenyl phosphate, the alcohol is preferably allyl alcohol.
The preparation method of the alkenyl phosphate is characterized in that the molar ratio of hydroxyl number in alcohol, halogen atom number of halogenated phosphate and acid-binding agent is 1:1: 1-1.5.
The preparation method of the alkenyl phosphate is characterized by comprising the following steps: the molar ratio of the alcohol to the imidazolium salt catalyst is 1: 0.01-0.1.
The preparation method of the alkenyl phosphate is characterized by comprising the following steps: the first solvent and the second solvent may be the same or different.
The preparation method of the alkenyl phosphate is characterized by comprising the following steps: preferably, the first solvent and the second solvent are the same.
The invention further provides an application of the imidazolium salt ionic liquid catalyst in preparation of a battery electrolyte additive, and the battery electrolyte additive is an alkenyl phosphate compound.
Example 1
Under the protection of nitrogen, 100mmol of allyl alcohol, 5mmol of 1-methyl-3-butylimidazole formate, 30ml of dichloromethane and 100mmol of triethylamine are added into a reaction vessel and uniformly stirred, a solution of dimethyl chlorophosphate (100mmol) dissolved in 30ml of dichloromethane is dropwise added into the reaction vessel at room temperature to react for 1h, after the reaction is finished, the system is filtered to remove solid triethylamine hydrochloride, the triethylamine hydrochloride is washed for 3 times by dichloromethane, washing liquid is collected, saturated sodium bicarbonate solution is added into the filtrate, the mixture is stirred for 10min, standing and liquid separation are carried out, an organic phase is collected, a water phase is extracted for 3 times by dichloromethane, extraction liquid is collected, the washing liquid, the organic phase and the extraction liquid are combined, dried by anhydrous magnesium sulfate, decolored by activated carbon and rectified under reduced pressure to obtain a product of dimethyl allylphosphate, the yield is 90.8 percent by calculation, the purity was 99.1%.
Example 2
Under the protection of nitrogen, 100mmol of allyl alcohol, 1mmol of 1-methyl-3-butyl imidazole acetate, 30ml of toluene and 100mmol of triethylamine are added into a reaction vessel and stirred evenly, at room temperature, a solution of dimethyl chlorophosphate (100mmol) dissolved in 30ml of toluene was added dropwise to the reaction vessel, and (2) reacting for 1h, after the reaction is finished, filtering the system, removing solid triethylamine hydrochloride, washing the triethylamine hydrochloride for 3 times by using toluene, collecting washing liquid, adding a saturated sodium bicarbonate solution into the filtrate, stirring for 10min, standing for liquid separation, collecting an organic phase, extracting a water phase by using toluene for 3 times, collecting extract liquor, combining the washing liquid, the organic phase and the extract liquor, drying by using anhydrous magnesium sulfate, decoloring by using activated carbon, and performing reduced pressure rectification to obtain a product, namely allyl dimethyl phosphate, wherein the yield is 93.3% and the purity is 99.3%.
Example 3
Under the protection of nitrogen, 100mmol of allyl alcohol, 10mmol of 1-methyl-3-butylimidazole propionate, 30ml of toluene and 100mmol of triethylamine are added into a reaction vessel and uniformly stirred, a solution of dimethyl chlorophosphate (100mmol) dissolved in 30ml of toluene is dropwise added into the reaction vessel at 0 ℃, the reaction is carried out for 2 hours, after the reaction is finished, the system is recovered to room temperature, the system is filtered to remove solid triethylamine hydrochloride, the triethylamine hydrochloride is washed with toluene for 5 times, washing liquid is collected, saturated sodium bicarbonate solution is added into the filtrate, the mixture is stirred for 10 minutes, standing and liquid separation are carried out, an organic phase is collected, an aqueous phase is extracted with toluene for 5 times, extraction liquid is collected, the washing liquid, the organic phase and the extraction liquid are combined, the drying is carried out through anhydrous magnesium sulfate, activated carbon is decolored, the product is reduced pressure and rectified, the product of allyl dimethyl phosphate is obtained, the yield is 92.7 percent by calculation, the purity was 99.0%.
Example 4
Under the protection of nitrogen, 100mmol of allyl alcohol, 10mmol of 1-methyl-3-butylimidazole hydroxide, 30ml of n-hexane and 100mmol of triethylamine are added into a reaction vessel and uniformly stirred, a solution of diethyl chlorophosphate (100mmol) dissolved in 30ml of n-hexane is dropwise added into the reaction vessel at 50 ℃, the reaction is carried out for 0.5h, after the reaction is finished, the system is recovered to room temperature, the system is filtered to remove solid triethylamine hydrochloride, the triethylamine hydrochloride is washed by n-hexane for 5 times, washing liquid is collected, saturated sodium bicarbonate solution is added into the filtrate, the stirring is carried out for 10min, standing and liquid separation are carried out, an organic phase is collected, an aqueous phase is extracted by n-hexane for 5 times, extraction liquid is collected, the washing liquid, the organic phase and the extraction liquid are combined, dried by anhydrous magnesium sulfate, decolored by activated carbon, the product of allyl diethyl phosphate is obtained by decompression rectification, the calculation is carried out, the yield was 95.0% and the purity was 99.5%.
Example 5
Under the protection of nitrogen, 100mmol of allyl alcohol, 10mmol of 1-butyl-3-methyl-imidazole carbonate, 30ml of cyclohexane and 150mmol of triethylamine are added into a reaction vessel and uniformly stirred, a solution of chlorinated di-n-propyl phosphate (100mmol) dissolved in 30ml of cyclohexane is dripped into the reaction vessel under the condition of room temperature to react for 2 hours, after the reaction is finished, the system is filtered to remove solid triethylamine hydrochloride, the triethylamine hydrochloride is washed by cyclohexane for 3 times, washing liquid is collected, saturated sodium bicarbonate solution is added into the filtrate to be stirred for 10 minutes, standing and liquid separation are carried out, an organic phase is collected, an aqueous phase is extracted by cyclohexane for 3 times, extraction liquid is collected, the washing liquid, the organic phase and the extraction liquid are combined, dried by anhydrous magnesium sulfate, decolored by activated carbon, and rectified under reduced pressure to obtain the product of allyl di-n-propyl phosphate, the yield is 94.2 percent by calculation, the purity was 99.4%.
Comparative example 1
Under the protection of nitrogen, 100mmol of allyl alcohol, 5mmol of benzyltrimethylammonium chloride, 30ml of dichloromethane and 100mmol of triethylamine are added into a reaction vessel and uniformly stirred, at room temperature, a solution of dimethyl chlorophosphate (100mmol) dissolved in 30ml of dichloromethane is dropwise added into the reaction vessel to react for 1h, after the reaction is finished, the system is filtered to remove solid triethylamine hydrochloride, the triethylamine hydrochloride is washed for 3 times by dichloromethane, washing liquid is collected, a saturated sodium bicarbonate solution is added into the filtrate and stirred for 10min, standing and liquid separation are carried out, an organic phase is collected, a water phase is extracted for 3 times by dichloromethane, extraction liquid is collected, the washing liquid, the organic phase and the extraction liquid are combined, the drying is carried out by anhydrous magnesium sulfate, activated carbon is used for decolorization, reduced pressure rectification is carried out to obtain a product of dimethyl allylphosphate, and the yield is only 76.9% and the purity is 83.6% by calculation.
Finally, it should be noted that: it should be understood that the above examples are only for clearly illustrating the present invention and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the scope of the invention.
Claims (9)
1. A preparation method of alkenyl phosphate is characterized in that: the method comprises the following steps: under the protection of inert gas, adding alcohol, an imidazole salt catalyst, a first solvent and an acid-binding agent into a reaction container, uniformly stirring, dropwise adding a halogenated phosphate solution dissolved in a second solvent into the reaction container at 0-50 ℃, reacting for 0.5-2 h, returning to room temperature after the reaction is finished, filtering, removing solid salt, washing salt for 3-5 times, collecting washing liquid, adding a saturated sodium bicarbonate solution into filtrate, stirring for 5-10 min, standing for liquid separation, collecting an organic phase, extracting a water phase for 3-5 times, collecting an extraction liquid, combining the washing liquid, the organic phase and the extraction liquid, drying by anhydrous magnesium sulfate, decoloring by activated carbon, and carrying out reduced pressure rectification to obtain a product of alkenyl phosphate, wherein the alcohol is alcohol containing alkenyl; the imidazole salt catalyst is one or more of 1-methyl-3-butylimidazole formate, 1-methyl-3-butylimidazole acetate, 1-methyl-3-butylimidazole propionate, 1-methyl-3-butylimidazole hydroxide, 1-butyl-3-methyl-imidazole bicarbonate or 1-butyl-3-methyl-imidazole carbonate; the acid-binding agent is selected from organic amine.
2. The method according to claim 1, wherein the inert gas is selected from nitrogen and argon.
3. The method for preparing an alkenyl phosphate according to claim 1 or 2, wherein the first solvent is one or more selected from the group consisting of dichloromethane, chloroform, tetrahydrofuran, toluene, n-hexane, cyclohexane, xylene, benzene, DMF and DMSO.
4. The method for preparing an alkenyl phosphate according to claim 1 or 2, wherein the second solvent is one or more selected from the group consisting of dichloromethane, chloroform, tetrahydrofuran, toluene, n-hexane, cyclohexane, xylene, benzene, dioxane, DMF and DMSO.
5. The method of claim 1 or 2, wherein the acid scavenger is triethylamine, diethylamine, pyridine or aniline.
6. The process for producing an alkenyl phosphate according to claim 1 or 2, wherein the alcohol is allyl alcohol.
7. The method for preparing alkenyl phosphate according to claim 1 or 2, wherein the molar ratio of the number of hydroxyl groups in the alcohol to the number of halogen atoms in the halogenated phosphate to the acid-binding agent is 1:1:1 to 1.5.
8. The method for preparing an alkenyl phosphate according to claim 1 or 2, wherein: the molar ratio of the alcohol to the imidazolium salt catalyst is 1: 0.01-0.1.
9. The method for preparing an alkenyl phosphate according to claim 1 or 2, wherein: the first solvent and the second solvent are the same.
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