CN110117297A - A kind of preparation method of 2- phosphate base sulfuric acid acrylic ester - Google Patents
A kind of preparation method of 2- phosphate base sulfuric acid acrylic ester Download PDFInfo
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- CN110117297A CN110117297A CN201910284210.0A CN201910284210A CN110117297A CN 110117297 A CN110117297 A CN 110117297A CN 201910284210 A CN201910284210 A CN 201910284210A CN 110117297 A CN110117297 A CN 110117297A
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- Prior art keywords
- sulfuric acid
- acrylic ester
- phosphate
- phosphate base
- preparation
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- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 33
- 239000010452 phosphate Substances 0.000 title claims abstract description 32
- -1 sulfuric acid acrylic ester Chemical class 0.000 title claims abstract description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 claims abstract description 20
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 16
- DHCLVCXQIBBOPH-UHFFFAOYSA-N Glycerol 2-phosphate Chemical compound OCC(CO)OP(O)(O)=O DHCLVCXQIBBOPH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 56
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 48
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 21
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052792 caesium Inorganic materials 0.000 claims description 6
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 6
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- LULAYUGMBFYYEX-UHFFFAOYSA-N metachloroperbenzoic acid Natural products OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 239000003125 aqueous solvent Substances 0.000 claims description 2
- 235000009508 confectionery Nutrition 0.000 claims description 2
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- RWRDJVNMSZYMDV-UHFFFAOYSA-L radium chloride Chemical compound [Cl-].[Cl-].[Ra+2] RWRDJVNMSZYMDV-UHFFFAOYSA-L 0.000 claims description 2
- 229910001630 radium chloride Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229940045872 sodium percarbonate Drugs 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 14
- 239000003513 alkali Substances 0.000 claims 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims 1
- 239000000654 additive Substances 0.000 abstract description 9
- 230000000996 additive effect Effects 0.000 abstract description 9
- 239000003792 electrolyte Substances 0.000 abstract description 9
- 238000005292 vacuum distillation Methods 0.000 abstract description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 5
- 150000001875 compounds Chemical group 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- 230000001588 bifunctional effect Effects 0.000 abstract description 2
- 238000006467 substitution reaction Methods 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 229910001386 lithium phosphate Inorganic materials 0.000 description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 4
- 229910000160 potassium phosphate Inorganic materials 0.000 description 4
- 235000011009 potassium phosphates Nutrition 0.000 description 4
- 230000006837 decompression Effects 0.000 description 3
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 description 3
- 239000001488 sodium phosphate Substances 0.000 description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 description 3
- 238000010025 steaming Methods 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- 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 description 1
- 229910012265 LiPO2F2 Inorganic materials 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical class C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 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
- C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
- C07F9/6552—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a six-membered ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
The present invention relates to a kind of preparation methods of 2- phosphate base sulfuric acid acrylic ester, the following steps are included: glycerol -2- phosphate is added into the reaction kettle for fill nonaqueous solvents and stirs evenly, temperature of reaction kettle is dropped to and starts gradually to be added dropwise thionyl chloride progress substitution reaction afterwards to a certain degree, de-chlorine hydride is removed by vacuum distillation, reaction solution is washed to neutrality with saturated sodium bicarbonate solution again, it stands, liquid separation obtains 2- phosphate base propylene sulfite solution；Poor solvent is added after concentration to be recrystallized, 2- phosphate base propylene sulfite intermediate is obtained after filtering, which can further aoxidize to obtain 2- phosphate base sulfuric acid acrylic ester.Above-mentioned preparation method, product purification are easy, and the compound structure is novel, and product acidity is low, and moisture is low, and purity is high, product is expected to as a kind of bifunctional lithium-ion battery electrolytes additive.
Description
[technical field]
The invention belongs to battery electrolyte additive technology fields more particularly to a kind of 2- phosphate base sulfuric acid acrylic ester to add
Add the preparation method of agent.
[background technique]
Lithium ion battery has high quality and volume energy density, therefore mesh relative to lead-acid battery, nickel-metal hydride battery etc.
Before be new energy power vehicle preferred power resources.But lithium ion battery is also faced with a series of ask in the specific use process
Topic, as battery holds when high temperature cyclic performance is poor, battery is easy to produce low gas, low temperature discharge capacity, low temperature charging when high temperature is placed
Analysis lithium easily occurs, thus brings a series of security risk, affects the use and large-scale promotion of lithium-ion-power cell.
Recently as the demand that automobile course continuation mileage is promoted, battery producer releases nickelic battery system successively, such as
The energy density of NCM811/ graphite cell can achieve 280Wh/kg, and the energy density of NCM811/SiO- graphite cell system can
To reach 300Wh/kg.The presence of nickelic positive electrode proposes higher challenge to the matching of corresponding electrolyte: needing to be electrolysed
Liquid can either reduce positive electrode to the catalysis oxidation of electrolyte, improve the cyclical stability of battery in protection positive electrode；Again
The SEI impedance to be formed in cathode is smaller, guarantees the cryogenic property of battery.Phosphate material be a kind of common positive electrode and
Electrolyte clad or additive, as used Li in Chinese patent CN108666526A3PO4As clad, main body can be prevented
Material directly and electrolyte contacts, to improve battery capacity conservation rate, improve high rate performance, enhancing thermal stability, to change
The high-temperature behavior of kind battery.Addition LiPO2F2 additive, the additive into electrolyte are disclosed in Japan Patent 3439085
Protective film can be formed on electrode interface, to improve the high temperature cyclic performance of battery.Sulfuric acid ester series compound is a kind of
Very effective low temperature electrolytic solution additive, such as sulfuric acid vinyl ester, sulfuric acid acrylic ester, double sulfuric acid vinyl esters.Patent
Use sulfuric acid vinyl ester as electrolysis additive in CN105633465A, additive reduction potential with higher is being changed
One layer of densification, stable SEI film can be formed in negative terminal surface at the stage, optimize negative terminal surface film, reduce cathode and electrolyte
Between resistance, to promote the cryogenic property of battery.
[summary of the invention]
In view of this, 2- phosphate base sulfuric acid acrylic ester is as a kind of compatible addition of lithium-ion battery electrolytes high/low temperature
Agent, the additive combine phosphate structure with sulfuric acid ester structure, and wherein the high temperatures of battery can be improved in phosphate structure
Can, sulfate group structure can participate in the cryogenic property that cathode SEI forms a film and improves battery.
The purpose of the present invention is to provide a kind of purifications to be easy, the preparation 2- phosphate base sulfuric acid acrylic ester of high production efficiency
Preparation method.
In order to achieve the above object, the present invention adopts the following technical scheme:
A kind of 2- phosphate base sulfuric acid acrylic ester, structural formula are shown in formula I:
A kind of 2- phosphate base sulfuric acid acrylic ester and preparation method thereof, comprising the following steps: be added into reaction kettle non-aqueous
Solvent and glycerol -2- phosphate, stir and dissolve it sufficiently, and thionyl chloride is added dropwise after reaction kettle is fallen to a certain temperature and opens
Begin to react；After completion of the reaction, be evaporated under reduced pressure, remove de-chlorine hydride, add alkaline aqueous solution wash solution to pH be 7-8；Liquid separation
2- phosphate base propylene sulfite solution is obtained after extraction, and poor solvent is added after reduced pressure and is recrystallized, after filtering
Obtain the 2- phosphate base propylene sulfite intermediate of high-purity.The intermediate is continuously added and fills the anti-of nonaqueous solvents
It answers in kettle, a certain amount of oxidant and catalyst is added, further oxidation obtains 2- phosphate base sulfuric acid acrylic ester.
Preferably, in the above preparation method, the glycerol -2- phosphate is glycerol -2- phosphoric acid-disodium, sweet
- two lithium of oil -2- phosphoric acid, glycerol -2- phosphoric acid-dipotassium, glycerol -2- phosphoric acid-magnesium, any one in-two caesium of glycerol -2- phosphoric acid,
Preferably glycerol -2- phosphoric acid-disodium,-two lithium of glycerol -2- phosphoric acid.
Preferably, in the above preparation method, the nonaqueous solvents is methylene chloride, acetonitrile, tetrahydrofuran, 1,
2- dichloroethanes, one of chloroform or carbon tetrachloride or multiple combinations, preferably methylene chloride, dichloroethanes.
Preferably, the poor solvent is ether, n-hexane, benzene, pentane, one of toluene or a variety of groups
It closes, preferably ether, n-hexane.
Preferably, in the above preparation method, the mass ratio of glycerol -2- phosphate and halogenated alkane solvents is 1:
0.3-1:2, preferably 1:1-1:1.5；The molar ratio of glycerol -2- phosphate and thionyl chloride be 1:0.8-1:1.5, preferably 1:
1-1:1.2.
Preferably, in the above preparation method, the reaction temperature is -10-10 DEG C, reaction time 2-8h,
Preferably -5-5 DEG C and 4-6h.
Preferably, in the above preparation method, the alkaline aqueous solution stated be sodium bicarbonate solution, sodium carbonate liquor,
Solution of potassium carbonate, preferably sodium bicarbonate solution, sodium carbonate liquor.
Preferably, the catalyst is ruthenium trichloride, ruthenic oxide, four (triphenylphosphines) in above-mentioned preparation method
Palladium, radium chloride, ferric sulfate, dosage are the 0.01%-1% of substrate；Preferably ruthenium trichloride, ruthenic oxide, dosage are substrate
0.04-0.06%.
Preferably, in the above preparation method, the oxidant is hydrogen peroxide, ozone, metachloroperbenzoic acid, tungsten
One of sour sodium, sodium hypochlorite, SODIUM PERCARBONATE, potassium permanganate are a variety of, preferably hydrogen peroxide, sodium hypochlorite；2- phosphate
The molar ratio of base propylene sulfite and oxidant is 1:1.2~1:3, preferably 1:1.5-1:2.
Preferably, in the above preparation method, vacuum distillation gained solvent can be recycled and carry out rectifying separation, repeat
It utilizes.
Above-mentioned preparation method, product purification are easy, and the compound structure is novel, and product acidity is low, and moisture is low, purity is high,
Product is expected to as a kind of bifunctional lithium-ion battery electrolytes additive.
[specific embodiment]
It is as follows that the present invention enumerates embodiment, and illustrated embodiment is used only for helping to understand the present invention, is not intended to limit this
The range of invention.
Embodiment 1:
Glycerol -2- disodic alkaliine 216g, methylene chloride 300g are added into reaction kettle, and temperature of reaction kettle is adjusted to
5 DEG C, it is added dropwise 120g thionyl chloride, time for adding 30min, after being added dropwise, the reaction was continued 4h.End of reaction carries out decompression steaming
It evaporates, removes the HCl and complete SOCl of unreacted2, it adds saturated sodium bicarbonate aqueous solution and is washed, until solution ph >=
7, liquid separation is carried out, the dichloromethane solution of 2- sodium phosphate base propylene sulfite is obtained.It is white that it is concentrated under reduced pressure into appearance at room temperature
Color solid is added 200g n-hexane and is recrystallized, 2- phosphate base propylene sulfite 175.6g, yield is obtained by filtration
67%, purity 99.91%.
175.6g 2- sodium phosphate base propylene sulfite obtained above is added to the reaction for filling 300g methylene chloride
In kettle, while 0.08g ruthenium trichloride is added, opens and stir and be stirred at 5 DEG C.Then it is gradually added dropwise into reaction kettle
The sodium hypochlorite that 598g concentration is 10% stops reaction after the reaction was continued after completion of dropwise addition 4h.It is layered after standing, last time is water
Layer, lower layer are dichloromethane solution, and liquid separation simultaneously takes subnatant to carry out obtaining white solid after vacuum distillation removes solvent.Then it uses
Distilled water wash and obtains 118g 2- sodium phosphate base sulfuric acid acrylic ester, yield after being recrystallized and dried with n-hexane
It is 60%, moisture 29ppm, acid value 22ppm.
Embodiment 2:
Glycerol -2- phosphoric acid dilithium salt 184g, methylene chloride 200g are added into reaction kettle, and temperature of reaction kettle is adjusted to
0 DEG C, it is added dropwise 120g thionyl chloride, time for adding 30min, after being added dropwise, the reaction was continued 4h.End of reaction carries out decompression steaming
It evaporates, removes the HCl and complete SOCl of unreacted2, it adds saturated sodium bicarbonate aqueous solution and is washed, until solution ph >=
7, liquid separation is carried out, the dichloromethane solution of 2- lithium phosphate base propylene sulfite is obtained.It is white that it is concentrated under reduced pressure into appearance at room temperature
Color solid is added 200g n-hexane and is recrystallized, 2- lithium phosphate base propylene sulfite 167.9g, yield is obtained by filtration
73%, purity 99.5%.
167.9g 2- lithium phosphate base propylene sulfite obtained above is added to the reaction for filling 200g methylene chloride
In kettle, while 0.09g ruthenium trichloride is added, opens and stir and be stirred at 0 DEG C.Then it is gradually added dropwise into reaction kettle
The sodium hypochlorite that 652g concentration is 10% stops reaction after the reaction was continued after completion of dropwise addition 5h.It is layered after standing, last time is water
Layer, lower layer are dichloromethane solution, and liquid separation simultaneously takes subnatant to carry out obtaining white solid after vacuum distillation removes solvent.Then it uses
Distilled water wash and obtains 107g 2- lithium phosphate base sulfuric acid acrylic ester, yield after being recrystallized and dried with n-hexane
It is 60%, moisture 43ppm, acid value 35ppm.
Embodiment 3:
Glycerol -2- di(2-ethylhexyl)phosphate sylvite 248g, methylene chloride 300g are added into reaction kettle, and temperature of reaction kettle is adjusted
To -5 DEG C, it is added dropwise 120g thionyl chloride, time for adding 30min, after being added dropwise, the reaction was continued 5h.End of reaction is depressurized
Distillation removes the HCl and complete SOCl of unreacted2, add saturated sodium bicarbonate aqueous solution and washed, until solution ph
>=7, liquid separation is carried out, the dichloromethane solution of 2- potassium phosphate base propylene sulfite is obtained.It is concentrated under reduced pressure into appearance at room temperature
White solid is added 200g n-hexane and is recrystallized, 2- potassium phosphate base propylene sulfite 235.4g, yield is obtained by filtration
80%, purity 99.5%.
235.4g 2- potassium phosphate base propylene sulfite obtained above is added to the reaction for filling 300g methylene chloride
In kettle, while 0.12g ruthenium-oxide is added, opens and stir and be stirred at -5 DEG C.Then it is gradually added into reaction kettle
165.6g metachloroperbenzoic acid stops reaction after the reaction was continued 5h.It is layered after standing, last time is water layer, lower layer is dichloromethane
Alkane solution, liquid separation simultaneously take subnatant to carry out obtaining white solid after vacuum distillation removes solvent.Then it is washed with distilled water
And 186g 2- potassium phosphate base sulfuric acid acrylic ester, yield 75%, moisture are obtained after being recrystallized and dried with n-hexane
25ppm, acid value 59ppm.
Embodiment 4:
Glycerol -2- di(2-ethylhexyl)phosphate cesium salt 454g, methylene chloride 500g are added into reaction kettle, and temperature of reaction kettle is adjusted to
0 DEG C, it is added dropwise 120g thionyl chloride, time for adding 30min, after being added dropwise, the reaction was continued 6h.End of reaction carries out decompression steaming
It evaporates, removes the HCl and complete SOCl of unreacted2, it adds saturated sodium bicarbonate aqueous solution and is washed, until solution ph >=
7, liquid separation is carried out, the dichloromethane solution of 2- phosphoric acid caesium base propylene sulfite is obtained.It is white that it is concentrated under reduced pressure into appearance at room temperature
Color solid is added 200g n-hexane and is recrystallized, 2- phosphoric acid caesium base propylene sulfite 305.5g, yield is obtained by filtration
63%, purity 99.5%.
305.5g 2- phosphoric acid caesium base propylene sulfite obtained above is added to the reaction for filling 400g methylene chloride
In kettle, while 0.15g ruthenium trichloride is added, opens and stir and be stirred at 0 DEG C.Then it is gradually added dropwise into reaction kettle
The sodium hypochlorite that 566g concentration is 10% stops reaction after the reaction was continued after completion of dropwise addition 4h.It is layered after standing, last time is water
Layer, lower layer are dichloromethane solution, and liquid separation simultaneously takes subnatant to carry out obtaining white solid after vacuum distillation removes solvent.Then it uses
Distilled water wash and obtains 173.6g 2- phosphoric acid caesium base sulfuric acid acrylic ester after being recrystallized and dried with n-hexane, produces
Rate is 55%, moisture 49ppm, acid value 76ppm.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of preparation method of 2- phosphate base sulfuric acid acrylic ester, which is characterized in that its preparation process comprises the steps of:
Nonaqueous solvents and glycerol -2- phosphate are added into reaction kettle, stirs and dissolves it sufficiently, reaction kettle is dropped to centainly
Thionyl chloride is added dropwise after temperature and starts to react；After completion of the reaction, it is evaporated under reduced pressure, removes de-chlorine hydride, add alkaline aqueous solution
Wash solution to pH be 7-8；2- phosphate base propylene sulfite solution is obtained after liquid separation extraction, is added after reduced pressure bad
Solvent is recrystallized, and the 2- phosphate base propylene sulfite intermediate of high-purity is obtained after filtering；The intermediate is continued
It is added in the reaction kettle for filling nonaqueous solvents, a certain amount of oxidant and catalyst is added, further oxidation obtains 2- phosphoric acid
Alkali sulfuric acid acrylic ester；
The structural formula of 2- phosphate base sulfuric acid acrylic ester obtained is shown in formula I:
2. the preparation method of 2- phosphate base sulfuric acid acrylic ester according to claim 1, which is characterized in that described is sweet
Oil -2- phosphate is glycerol -2- phosphoric acid-disodium,-two lithium of glycerol -2- phosphoric acid, glycerol -2- phosphoric acid-dipotassium, glycerol -2- phosphoric acid -
Magnesium, any one in-two caesium of glycerol -2- phosphoric acid.
3. the preparation method of 2- phosphate base sulfuric acid acrylic ester according to claim 1, which is characterized in that described is non-aqueous
Solvent is methylene chloride, acetonitrile, tetrahydrofuran, 1,2- dichloroethanes, one of chloroform or carbon tetrachloride or multiple combinations.
4. the preparation method of 2- phosphate base sulfuric acid acrylic ester according to claim 1, which is characterized in that described bad molten
Agent is ether, n-hexane, benzene, pentane, one of toluene or multiple combinations.
5. the preparation method of 2- phosphate base sulfuric acid acrylic ester according to claim 1, which is characterized in that glycerol -2- phosphorus
The mass ratio of hydrochlorate and halogenated alkane solvents is 1:0.3-1:2；The molar ratio of glycerol -2- phosphate and thionyl chloride is 1:0.8-
1:1.5。
6. the preparation method of 2- phosphate base sulfuric acid acrylic ester according to claim 1, which is characterized in that the reaction
Temperature is -10-10 DEG C, reaction time 2-8h.
7. the preparation method of 2- phosphate base sulfuric acid acrylic ester according to claim 1, which is characterized in that the alkalinity
Aqueous solution is sodium bicarbonate solution, sodium carbonate liquor, solution of potassium carbonate.
8. the preparation method of 2- phosphate base sulfuric acid acrylic ester according to claim 1, which is characterized in that the catalyst
For ruthenium trichloride, ruthenic oxide, tetrakis triphenylphosphine palladium, radium chloride, ferric sulfate, dosage is the 0.01%-1% of substrate.
9. the preparation method of 2- phosphate base sulfuric acid acrylic ester according to claim 1, which is characterized in that the oxidant
For one of hydrogen peroxide, ozone, metachloroperbenzoic acid, sodium tungstate, sodium hypochlorite, SODIUM PERCARBONATE, potassium permanganate or a variety of.
10. the preparation method of 2- phosphate base sulfuric acid acrylic ester according to claim 1, which is characterized in that 2- phosphate
The molar ratio of base propylene sulfite and oxidant is 1:1.2~1:3.
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