CN116554224A - Method for preparing difluoro sodium bisoxalate phosphate by using fluorine-containing solvent - Google Patents
Method for preparing difluoro sodium bisoxalate phosphate by using fluorine-containing solvent Download PDFInfo
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- 239000002904 solvent Substances 0.000 title claims abstract description 55
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 51
- 239000011737 fluorine Substances 0.000 title claims abstract description 51
- -1 difluoro sodium bisoxalate phosphate Chemical compound 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 73
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 39
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 39
- 239000010452 phosphate Substances 0.000 claims abstract description 39
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 39
- 239000011734 sodium Substances 0.000 claims abstract description 39
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims abstract description 20
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims abstract description 10
- OGFAWKRXZLGJSK-UHFFFAOYSA-N 1-(2,4-dihydroxyphenyl)-2-(4-nitrophenyl)ethanone Chemical compound OC1=CC(O)=CC=C1C(=O)CC1=CC=C([N+]([O-])=O)C=C1 OGFAWKRXZLGJSK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011775 sodium fluoride Substances 0.000 claims abstract description 10
- 235000013024 sodium fluoride Nutrition 0.000 claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 229920001661 Chitosan Polymers 0.000 claims description 26
- GBPVMEKUJUKTBA-UHFFFAOYSA-N methyl 2,2,2-trifluoroethyl carbonate Chemical group COC(=O)OCC(F)(F)F GBPVMEKUJUKTBA-UHFFFAOYSA-N 0.000 claims description 22
- 238000004821 distillation Methods 0.000 claims description 21
- AFNWOEJOULWFIS-BTJKTKAUSA-N (z)-4-hydroxy-4-oxobut-2-enoate;tris(2-hydroxyethyl)azanium Chemical compound OC(=O)\C=C/C(O)=O.OCCN(CCO)CCO AFNWOEJOULWFIS-BTJKTKAUSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 18
- 230000035484 reaction time Effects 0.000 claims description 18
- 238000001291 vacuum drying Methods 0.000 claims description 18
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 238000010521 absorption reaction Methods 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 9
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical group COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- 238000004062 sedimentation Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- FRDZTMZLPMAUEW-UHFFFAOYSA-N 1-amino-3-prop-1-enylthiourea Chemical compound C(=CC)NC(NN)=S FRDZTMZLPMAUEW-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims 3
- 239000003960 organic solvent Substances 0.000 claims 3
- 239000012300 argon atmosphere Substances 0.000 claims 1
- 239000012299 nitrogen atmosphere Substances 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 8
- 239000000654 additive Substances 0.000 abstract description 8
- 230000000996 additive effect Effects 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 6
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 abstract description 4
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 abstract description 3
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 239000011255 nonaqueous electrolyte Substances 0.000 abstract description 2
- 238000002161 passivation Methods 0.000 abstract description 2
- 235000006408 oxalic acid Nutrition 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- MRDKYAYDMCRFIT-UHFFFAOYSA-N oxalic acid;phosphoric acid Chemical compound OP(O)(O)=O.OC(=O)C(O)=O MRDKYAYDMCRFIT-UHFFFAOYSA-N 0.000 description 11
- 238000001914 filtration Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N aminothiocarboxamide Natural products NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- 239000002000 Electrolyte additive Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 239000002879 Lewis base Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 150000007527 lewis bases Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000005031 thiocyano group Chemical group S(C#N)* 0.000 description 1
- NONOKGVFTBWRLD-UHFFFAOYSA-N thioisocyanate group Chemical group S(N=C=O)N=C=O NONOKGVFTBWRLD-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000004879 turbidimetry Methods 0.000 description 1
- 238000007039 two-step 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
-
- 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
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Molecular Biology (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
Abstract
The invention relates to the field of fine chemical industry, in particular to a method for preparing difluoro sodium bisoxalate phosphate by using a fluorine-containing solvent; the method adopts sodium fluoride, phosphorus pentabromide, sodium hexafluorophosphate, fluorine-containing solvent, oxalic acid and dichloroethane to prepare difluoro sodium bisoxalato phosphate; the method has the advantages of simple process, mild reaction conditions, small investment, low-cost and easily-obtained raw materials, high product purity and high yield; the difluoro bisoxalic acid sodium phosphate prepared by the method has low chloride ion content, and the product is easy to purify; the difluoro sodium bisoxalato phosphate prepared by the invention can be used as an additive of a nonaqueous electrolyte battery, has small addition amount, and can effectively improve the passivation film structure of the positive and negative electrode surfaces of the battery and promote the stability of the battery in low-temperature circulation after the difluoro sodium bisoxalato phosphate is added into the electrolyte.
Description
Technical Field
The invention relates to the field of fine chemical industry, in particular to a method for preparing difluoro sodium bisoxalate phosphate by using a fluorine-containing solvent.
Background
Electrolyte additives refer to small amounts of additives added to the electrolyte to improve the electrochemical performance of the electrolyte and to improve the quality of the cathode deposition. The electrolyte additive is some natural or artificial organic or inorganic compound, which does not participate in the electrode reaction in the electrolysis process, but can replace the electrochemical performance of the electrolyte system to influence the ion discharge condition, so that the electrolysis process is in a better state.
CN202010833746.6: belongs to the technical field of battery materials, and in particular relates to a preparation method of oxalic acid phosphate, oxalic acid phosphate derivatives, a preparation method of oxalic acid phosphate derivatives and electrolyte salts. The preparation method of the oxalic acid phosphate is a two-step reaction method, and can promote the complete reaction of reactants, so that the oxalic acid phosphate product is purer. In the preparation method of the oxalic acid phosphate and the derivative thereof, all reactants are organic matters, the solvent is a nonaqueous solvent, the oxalic acid phosphate and the derivative thereof with high purity can be obtained, the problems of high chloride ion concentration and high free acid content are avoided, the atom economy in the reaction process is high, the impurities are less, the reaction raw materials are not required to be synthesized in advance, the reaction process is simplified, the production cost is saved, the safety of the reaction process is improved, and the method is more environment-friendly. The invention adopts a similar method to prepare the oxalic acid phosphate and the derivatives thereof, reduces equipment investment, labor cost and energy consumption, and has good industrial application prospect.
CN202210663113.4: relates to an electrolyte additive generated in situ, a preparation method and application thereof, wherein the additive is a multifunctional additive of Lewis acid-base complex; the multifunctional additive of the Lewis acid-base complex is prepared by adding Lewis acid and Lewis base into conventional electrolyte and then carrying out Lewis acid-base coordination reaction between the Lewis acid and the Lewis base; the additive can be generated in situ in the electrolyte, and has the functions of widening an electrochemical window of the electrolyte, resisting flame, inhibiting decomposition and hydrolysis of electrolyte salt, removing harmful impurities of the electrolyte, stabilizing electrode materials, electrolyte interfaces and the like. The multifunctional electrolyte containing the additive can be used for improving the working voltage, energy density, power density, cycle life and safety of an electrochemical energy storage device, and is easy to popularize and apply.
Cn202110233620.X: belongs to the technical field of battery materials, and in particular relates to an oxalic acid phosphate derivative, a preparation method thereof, electrolyte and a secondary battery. The structural general formula of the oxalic acid phosphate derivative is shown as the formula (I): wherein M is Li, na or K, R1, R2, R3 and R4 are respectively selected from F, thiocyano or thioisocyanate groups, and R1, R2, R3 and R4 are not F at the same time. The oxalic acid phosphate derivative has good thermal stability and high ionic conductivity, can effectively inhibit the rising of moisture and acidity of electrolyte in the storage process, has important significance for improving the stability and safety of the electrolyte, can ensure that the secondary battery has good cycle performance and storage performance at normal temperature and high temperature, and has longer service life.
The applicant believes that the above-mentioned patents and prior art have significant drawbacks: the cost is high, the three wastes are more, the reaction steps are complex, the reaction time is longer, and the problem that the chlorine ion of the product is higher because chlorine-containing raw materials are not adopted is solved.
Disclosure of Invention
Aiming at the technical problems in the background technology, the invention provides a method for preparing difluoro sodium bisoxalate phosphate by using a fluorine-containing solvent, and the method has the advantages of simple process, mild reaction condition, small investment, low-cost and easily-obtained raw materials, high product purity and high yield; the difluoro bisoxalic acid sodium phosphate prepared by the invention has low chloride ion content, and the product is easy to purify and treat.
In order to achieve the above purpose and achieve the above technical effects, the present invention adopts the following technical scheme:
a method for preparing difluoro sodium bisoxalato phosphate by using a fluorine-containing solvent:
s1: adding 4-10 parts of sodium fluoride, 40-55 parts of phosphorus pentabromide and 10-20 parts of sodium hexafluorophosphate into a reaction kettle according to parts by weight, adding 200-300 parts of fluorine-containing solvent, and slowly heating under the protection of nitrogen for reaction;
s2: slowly dripping 17-30 parts of dry anhydrous oxalic acid, heating, and after the reaction is finished, enabling generated gas to flow into a solution filled with sodium hydroxide for absorption, and distilling under reduced pressure to remove a fluorine-containing solvent;
s3: under the protection of nitrogen, 1000-1300 parts of dichloroethane is added into a reaction kettle, and after stirring and crystal precipitation and sedimentation, the sodium difluorobis (oxalato) phosphate is obtained by filtering and drying in a vacuum drying oven.
As a preferable embodiment of the present invention, the fluorine-containing solvent is methyl trifluoroethyl carbonate.
As a preferable technical scheme of the invention, the preparation method of the methyl trifluoroethyl carbonate comprises the following steps:
s1: according to weight portions, 45-65 portions of chitosan, 20-27 portions of triethanolamine maleate, 0.6-3.5 portions of 4-propenyl thiosemicarbazide and 200-300 portions of DMF are reacted for 2-4 hours at 60-70 ℃, and DMF is removed by reduced pressure distillation to obtain chitosan catalyst;
s2: according to the weight portions, 100 to 127 portions of trifluoroethanol, 5 to 10 portions of chitosan catalyst and 16 to 28 portions of carbonic ester are uniformly mixed, the mixture is reacted for 4 to 7 hours at the temperature of 60 to 70 ℃, after the reaction is finished, the mixture is filtered and distilled to obtain methyl trifluoroethyl carbonic ester, and the carbonic ester is dimethyl carbonate.
Further, the triethanolamine maleate salt, CAS:41397-50-6.
As a preferable technical scheme of the invention, the reaction temperature of S1 is 50-65 ℃ and the reaction time is 20-30h.
As a preferable technical scheme of the invention, the dripping time of the anhydrous oxalic acid is 1-1.5h.
As a preferable technical scheme of the invention, the reaction temperature of S2 is 50-65 ℃ and the reaction time is 2-4h.
As a preferable technical scheme of the invention, the temperature of the reduced pressure distillation is 40-50 ℃ and the pressure is 130-140Pa.
As a preferable technical scheme of the invention, the vacuum degree of vacuum drying is-0.09 to-0.1 MPa, and the drying temperature is 90-105 ℃.
Reaction mechanism:
and respectively carrying out Michael addition reaction on the amino group of the chitosan and triethanolamine maleate and 4-propenyl thiocarbamide to obtain the chitosan catalyst.
The technical effects are as follows:
compared with the prior art, the method for preparing the difluoro sodium bisoxalate phosphate by using the fluorine-containing solvent has the following remarkable effects:
1. the method has the advantages of simple process, mild reaction conditions, small investment, low-cost and easily-obtained raw materials, high product purity and high yield;
2. the difluoro bisoxalic acid sodium phosphate prepared by the method has low chloride ion content, and the product is easy to purify;
3. the difluoro sodium bisoxalato phosphate prepared by the invention can be used as an additive of a nonaqueous electrolyte battery, has small addition amount, and can effectively improve the passivation film structure of the positive and negative electrode surfaces of the battery and promote the stability of the battery in low-temperature circulation after the difluoro sodium bisoxalato phosphate is added into the electrolyte.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
A method for preparing difluoro sodium bisoxalato phosphate by using a fluorine-containing solvent, which is characterized in that the difluoro sodium bisoxalato phosphate is prepared by the following steps:
s1: adding 4g of sodium fluoride, 40g of phosphorus pentabromide and 10g of sodium hexafluorophosphate into a reaction kettle, adding 200g of fluorine-containing solvent, and slowly heating under the protection of nitrogen for reaction;
s2: then slowly dripping 17g of dry anhydrous oxalic acid, heating, and after the reaction is finished, enabling the generated gas to flow into a solution filled with sodium hydroxide for absorption, and removing the fluorine-containing solvent by reduced pressure distillation;
s3: under the protection of nitrogen, 1000g of dichloroethane is added into a reaction kettle, and after stirring and crystal precipitation and sedimentation, the sodium difluorobis (oxalato) phosphate is obtained by filtering and drying in a vacuum drying oven.
The fluorine-containing solvent is methyl trifluoroethyl carbonate.
The preparation method of the methyl trifluoroethyl carbonate comprises the following steps:
s1: 45g of chitosan, 20g of triethanolamine maleate, 0.6g of 4-propenyl thiocarbamide and 200g of DMF are reacted for 2 hours at 60 ℃, and DMF is removed by reduced pressure distillation to obtain a chitosan catalyst;
s2: 100g of trifluoroethanol, 5g of chitosan catalyst and 16g of dimethyl carbonate are uniformly mixed, reacted for 4 hours at 60 ℃, filtered and distilled to obtain methyl trifluoroethyl carbonate after the reaction is finished.
The triethanolamine maleate salt, CAS:41397-50-6
The reaction temperature of S1 is 50 ℃ and the reaction time is 20h.
The dripping time of the anhydrous oxalic acid is 1h.
The reaction temperature of S2 is 50 ℃ and the reaction time is 2h.
The temperature of the reduced pressure distillation is 40 ℃ and the pressure is 130Pa.
The vacuum degree of vacuum drying is-0.09 MPa, and the drying temperature is 90 ℃.
Example 2
A method for preparing difluoro sodium bisoxalato phosphate by using a fluorine-containing solvent, which is characterized in that the difluoro sodium bisoxalato phosphate is prepared by the following steps:
s1: adding 6g of sodium fluoride, 45g of phosphorus pentabromide and 14g of sodium hexafluorophosphate into a reaction kettle, adding 240g of fluorine-containing solvent, and slowly heating under the protection of nitrogen for reaction;
s2: slowly dripping 20g of dry anhydrous oxalic acid, heating, and after the reaction is finished, enabling the generated gas to flow into a solution filled with sodium hydroxide for absorption, and distilling under reduced pressure to remove the fluorine-containing solvent;
s3: under the protection of nitrogen, 1100g of dichloroethane is added into a reaction kettle, and after the crystals are precipitated and settled, the mixture is filtered and dried in a vacuum drying oven, thus obtaining difluoro sodium bisoxalate phosphate.
The fluorine-containing solvent is methyl trifluoroethyl carbonate.
The preparation method of the methyl trifluoroethyl carbonate comprises the following steps:
s1: 50g of chitosan, 22g of triethanolamine maleate, 1g of 4-propenyl thiosemicarbazide and 240g of DMF are reacted for 3 hours at 6,5 ℃, and DMF is removed by reduced pressure distillation to obtain a chitosan catalyst;
s2: 110g of trifluoroethanol, 7g of chitosan catalyst and 20g of dimethyl carbonate are uniformly mixed, reacted for 5 hours at 65 ℃, filtered and distilled to obtain methyl trifluoroethyl carbonate after the reaction is finished.
The triethanolamine maleate salt, CAS:41397-50-6
The reaction temperature of S1 is 55 ℃ and the reaction time is 24 hours.
The dripping time of the anhydrous oxalic acid is 1h.
The reaction temperature of S2 is 55 ℃ and the reaction time is 3h.
The temperature of the reduced pressure distillation is 45 ℃ and the pressure is 135Pa.
The vacuum degree of vacuum drying is-0.095 MPa, and the drying temperature is 95 ℃.
Example 3
A method for preparing difluoro sodium bisoxalato phosphate by using a fluorine-containing solvent, which is characterized in that the difluoro sodium bisoxalato phosphate is prepared by the following steps:
s1: adding 8g of sodium fluoride, 50g of phosphorus pentabromide and 18g of sodium hexafluorophosphate into a reaction kettle, adding 280g of fluorine-containing solvent, and slowly heating under the protection of nitrogen for reaction;
s2: slowly dripping 25g of dry anhydrous oxalic acid, heating, and after the reaction is finished, enabling the generated gas to flow into a solution filled with sodium hydroxide for absorption, and distilling under reduced pressure to remove the fluorine-containing solvent;
s3: under the protection of nitrogen, 1200g of dichloroethane is added into a reaction kettle, and after stirring and crystal precipitation and sedimentation, the sodium difluorobis (oxalato) phosphate is obtained by filtering and drying in a vacuum drying oven.
The fluorine-containing solvent is methyl trifluoroethyl carbonate.
The preparation method of the methyl trifluoroethyl carbonate comprises the following steps:
s1: 60g of chitosan, 26g of triethanolamine maleate, 2g of 4-propenyl thiosemicarbazide and 280g of DMF are reacted for 3 hours at 65 ℃, and DMF is removed by reduced pressure distillation to obtain a chitosan catalyst;
s2: 1,20g of trifluoroethanol, 9g of chitosan catalyst and 24g of dimethyl carbonate are uniformly mixed, reacted for 6 hours at 65 ℃, filtered and distilled to obtain methyl trifluoroethyl carbonate after the reaction is finished.
The triethanolamine maleate salt, CAS:41397-50-6
The reaction temperature of S1 is 60 ℃ and the time is 280-30h.
The dripping time of the anhydrous oxalic acid is 1.5h.
The reaction temperature of S2 is 60 ℃ and the reaction time is 3h.
The temperature of the reduced pressure distillation is 45 ℃ and the pressure is 135Pa.
The vacuum degree of vacuum drying is-0.095 MPa, and the drying temperature is 100 ℃.
Example 4
A method for preparing difluoro sodium bisoxalato phosphate by using a fluorine-containing solvent, which is characterized in that the difluoro sodium bisoxalato phosphate is prepared by the following steps:
s1: adding 10g of sodium fluoride, 55g of phosphorus pentabromide and 20g of sodium hexafluorophosphate into a reaction kettle, adding 300g of fluorine-containing solvent, and slowly heating under the protection of nitrogen for reaction;
s2: slowly dripping 30g of dry anhydrous oxalic acid, heating, and after the reaction is finished, enabling the generated gas to flow into a solution filled with sodium hydroxide for absorption, and distilling under reduced pressure to remove the fluorine-containing solvent;
s3: 1300g of dichloroethane is added into a reaction kettle under the protection of nitrogen, and after stirring and crystal precipitation and sedimentation, the sodium difluorobis (oxalato) phosphate is obtained by filtering and drying in a vacuum drying oven.
The fluorine-containing solvent is methyl trifluoroethyl carbonate.
The preparation method of the methyl trifluoroethyl carbonate comprises the following steps:
s1: 65g of chitosan, 27g of triethanolamine maleate, 3.5g of 4-propenyl thiocarbamide and 300g of DMF are reacted for 4 hours at 70 ℃, and DMF is removed by reduced pressure distillation to obtain a chitosan catalyst;
s2: 127g of trifluoroethanol, 10g of chitosan catalyst and 28g of dimethyl carbonate are uniformly mixed, reacted for 7 hours at 70 ℃, filtered and distilled to obtain methyl trifluoroethyl carbonate after the reaction is finished.
The triethanolamine maleate salt, CAS:41397-50-6
The reaction temperature of S1 is 65 ℃ and the reaction time is 30h.
The dripping time of the anhydrous oxalic acid is 1.5h.
The reaction temperature of S2 is 65 ℃ and the reaction time is 4 hours.
The temperature of the reduced pressure distillation is 50 ℃ and the pressure is 140Pa.
The vacuum degree of vacuum drying is-0.1 MPa, and the drying temperature is 105 ℃.
Comparative example 1
A method for preparing difluoro sodium bisoxalato phosphate by using a fluorine-containing solvent, which is characterized in that the difluoro sodium bisoxalato phosphate is prepared by the following steps:
s1: adding 4g of sodium fluoride, 40g of phosphorus pentabromide and 10g of sodium hexafluorophosphate into a reaction kettle, adding 200g of solvent, and slowly heating under the protection of nitrogen for reaction;
s2: then slowly dripping 17g of dry anhydrous oxalic acid, heating, and after the reaction is finished, enabling the generated gas to flow into a solution filled with sodium hydroxide for absorption, and removing the fluorine-containing solvent by reduced pressure distillation;
s3: under the protection of nitrogen, 1000g of dichloroethane is added into a reaction kettle, and after stirring and crystal precipitation and sedimentation, the sodium difluorobis (oxalato) phosphate is obtained by filtering and drying in a vacuum drying oven.
The fluorine-containing solvent is dimethyl carbonate.
The reaction temperature of S1 is 50 ℃ and the reaction time is 20h.
The dripping time of the anhydrous oxalic acid is 1h.
The reaction temperature of S2 is 50 ℃ and the reaction time is 2h.
The temperature of the reduced pressure distillation is 40 ℃ and the pressure is 130Pa.
The vacuum degree of vacuum drying is-0.09 MPa, and the drying temperature is 90 ℃.
Comparative example 2
A method for preparing difluoro sodium bisoxalato phosphate by using a fluorine-containing solvent, which is characterized in that the difluoro sodium bisoxalato phosphate is prepared by the following steps:
s1: adding 4g of sodium fluoride, 40g of phosphorus pentabromide and 10g of sodium hexafluorophosphate into a reaction kettle, adding 200g of fluorine-containing solvent, and slowly heating under the protection of nitrogen for reaction;
s2: then slowly dripping 17g of dry anhydrous oxalic acid, heating, and after the reaction is finished, enabling the generated gas to flow into a solution filled with sodium hydroxide for absorption, and removing the fluorine-containing solvent by reduced pressure distillation;
s3: under the protection of nitrogen, 1000g of dichloroethane is added into a reaction kettle, and after stirring and crystal precipitation and sedimentation, the sodium difluorobis (oxalato) phosphate is obtained by filtering and drying in a vacuum drying oven.
The fluorine-containing solvent is methyl trifluoroethyl carbonate.
The preparation method of the methyl trifluoroethyl carbonate comprises the following steps:
s1: 45g of chitosan, 0.6g of 4-propenyl thiocarbamide and 200g of DMF are reacted for 2 hours at 60 ℃, and DMF is removed by reduced pressure distillation to obtain a chitosan catalyst;
s2: 100g of trifluoroethanol, 5g of chitosan catalyst and 16g of dimethyl carbonate are uniformly mixed, reacted for 4 hours at 60 ℃, filtered and distilled to obtain methyl trifluoroethyl carbonate after the reaction is finished.
The reaction temperature of S1 is 50 ℃ and the reaction time is 20h.
The dripping time of the anhydrous oxalic acid is 1h.
The reaction temperature of S2 is 50 ℃ and the reaction time is 2h.
The temperature of the reduced pressure distillation is 40 ℃ and the pressure is 130Pa.
The vacuum degree of vacuum drying is-0.09 MPa, and the drying temperature is 90 ℃.
Comparative example 3
A method for preparing difluoro sodium bisoxalato phosphate by using a fluorine-containing solvent, which is characterized in that the difluoro sodium bisoxalato phosphate is prepared by the following steps:
s1: adding 4g of sodium fluoride, 40g of phosphorus pentabromide and 10g of sodium hexafluorophosphate into a reaction kettle, adding 200g of fluorine-containing solvent, and slowly heating under the protection of nitrogen for reaction;
s2: then slowly dripping 17g of dry anhydrous oxalic acid, heating, and after the reaction is finished, enabling the generated gas to flow into a solution filled with sodium hydroxide for absorption, and removing the fluorine-containing solvent by reduced pressure distillation;
s3: under the protection of nitrogen, 1000g of dichloroethane is added into a reaction kettle, and after stirring and crystal precipitation and sedimentation, the sodium difluorobis (oxalato) phosphate is obtained by filtering and drying in a vacuum drying oven.
The fluorine-containing solvent is methyl trifluoroethyl carbonate.
The preparation method of the methyl trifluoroethyl carbonate comprises the following steps:
s1: 45g of chitosan and 20g of triethanolamine maleate, 200g of DMF are reacted for 2 hours at 60 ℃, and DMF is removed by reduced pressure distillation to obtain a chitosan catalyst;
s2: 100g of trifluoroethanol, 5g of chitosan catalyst and 16g of dimethyl carbonate are uniformly mixed, reacted for 4 hours at 60 ℃, filtered and distilled to obtain methyl trifluoroethyl carbonate after the reaction is finished.
The triethanolamine maleate salt, CAS:41397-50-6
The reaction temperature of S1 is 50 ℃ and the reaction time is 20h.
The dripping time of the anhydrous oxalic acid is 1h.
The reaction temperature of S2 is 50 ℃ and the reaction time is 2h.
The temperature of the reduced pressure distillation is 40 ℃ and the pressure is 130Pa.
The vacuum degree of vacuum drying is-0.09 MPa, and the drying temperature is 90 ℃.
The difluoro bisoxalato sodium phosphate prepared in the above specific embodiment was subjected to test analysis by the following method, and the test results are shown in the following table:
1. sodium difluorobis (oxalato) phosphate purity by 31 P-NMR 19 F-NMR was analyzed and identified, and NMR was performed using deuterated DMSO as a solvent and TMS as a reference.
2. The content of chloride ions is analyzed by a turbidimetry method, and the specific method comprises the following steps: taking 0.5g of solid sample, dissolving in 8mL of deionized water, adding 1mLAgNO after bubbles completely disappear 3 /HNO 3 Solution (AgNO) 3 ：HNO 3 ：H 2 O=1: 65:34, mass ratio), and then the resulting solution was diluted to 25mL with distilled water, and the chloride ion range was determined by comparing with the turbidity of the standard sample.
| Product purity/% | Product yield/% | Chloride ion content/ppm | |
| Example 1 | 99.3 | 73 | 5 |
| Example 2 | 99.5 | 74 | 4 |
| Example 3 | 99.6 | 76 | 3 |
| Example 4 | 99.6 | 75 | 3 |
| Comparative example 1 | 89.5 | 61 | 18 |
| Comparative example 2 | 94.7 | 63 | 13 |
| Comparative example 3 | 96.3 | 65 | 12 |
The applicant states that the process of the invention is illustrated by the above examples, but the invention is not limited to, i.e. does not mean that the invention must be carried out in dependence on the above process steps. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of selected raw materials, addition of auxiliary components, selection of specific modes, etc. fall within the scope of the present invention and the scope of disclosure.
Claims (10)
1. A method for preparing difluoro sodium bisoxalato phosphate by using a fluorine-containing solvent, which is characterized in that the difluoro sodium bisoxalato phosphate is prepared by the following steps:
s1: adding 4-10 parts of sodium fluoride, 40-55 parts of phosphorus pentabromide and 10-20 parts of sodium hexafluorophosphate into a reaction kettle according to parts by weight, adding 200-300 parts of fluorine-containing solvent, and slowly heating under the protection of inert atmosphere for reaction;
s2: slowly dripping 17-30 parts of dry anhydrous oxalic acid, heating, and after the reaction is finished, enabling generated gas to flow into a solution filled with sodium hydroxide for absorption, and distilling under reduced pressure to remove a fluorine-containing solvent;
s3: under the protection of inert atmosphere, 1000-1300 parts of dichloroethane is added into a reaction kettle, and after stirring and crystal precipitation and sedimentation, the mixture is filtered and dried in a vacuum drying oven, so as to obtain difluoro sodium bisoxalate phosphate.
2. A process for preparing sodium difluorobis-oxalato phosphate from a fluorine-containing solvent as claimed in claim 1, wherein: the fluorine-containing solvent is methyl trifluoroethyl carbonate.
3. A process for preparing sodium difluorobis-oxalato phosphate from a fluorine-containing solvent as claimed in claim 2, wherein: the preparation method of the methyl trifluoroethyl carbonate comprises the following steps:
s1: according to weight portions, 45-65 portions of chitosan, 20-27 portions of triethanolamine maleate, 0.6-3.5 portions of 4-propenyl thiosemicarbazide and 200-300 portions of organic solvent are reacted for 2-4 hours at 60-70 ℃, and the organic solvent is removed by reduced pressure distillation to obtain the chitosan catalyst;
s2: according to the weight portions, 100 to 127 portions of trifluoroethanol, 5 to 10 portions of chitosan catalyst and 16 to 28 portions of carbonic ester are uniformly mixed, the mixture is reacted for 4 to 7 hours at the temperature of 60 to 70 ℃, after the reaction is finished, the mixture is filtered and distilled to obtain methyl trifluoroethyl carbonic ester, and the carbonic ester is dimethyl carbonate.
4. A process for preparing sodium difluorobis-oxalato phosphate from a fluorine-containing solvent as claimed in claim 3, wherein: the organic solvent is DMF.
5. A process for preparing sodium difluorobis-oxalato phosphate from a fluorine-containing solvent as claimed in claim 1, wherein: the reaction temperature of the S1 is 50-65 ℃ and the reaction time is 20-30h.
6. A process for preparing sodium difluorobis-oxalato phosphate from a fluorine-containing solvent as claimed in claim 1, wherein: the dripping time of the anhydrous oxalic acid is 1-1.5h.
7. A process for preparing sodium difluorobis-oxalato phosphate from a fluorine-containing solvent as claimed in claim 1, wherein: the reaction temperature of the S2 is 50-65 ℃ and the reaction time is 2-4h.
8. A process for preparing sodium difluorobis-oxalato phosphate from a fluorine-containing solvent as claimed in claim 1, wherein: the reduced pressure distillation temperature is 40-50 ℃ and the pressure is 130-140Pa.
9. A process for preparing sodium difluorobis-oxalato phosphate from a fluorine-containing solvent as claimed in claim 1, wherein: the vacuum degree of vacuum drying is-0.09 to-0.1 MPa, and the drying temperature is 90-105 ℃.
10. A process for preparing sodium difluorobis-oxalato phosphate from a fluorine-containing solvent as claimed in claim 1, wherein: the inert atmosphere is nitrogen atmosphere or argon atmosphere.
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