CN113698428A - Method for synthesizing carbonic ester functionalized silane - Google Patents
Method for synthesizing carbonic ester functionalized silane Download PDFInfo
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- CN113698428A CN113698428A CN202111011218.3A CN202111011218A CN113698428A CN 113698428 A CN113698428 A CN 113698428A CN 202111011218 A CN202111011218 A CN 202111011218A CN 113698428 A CN113698428 A CN 113698428A
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- 229910000077 silane Inorganic materials 0.000 title claims abstract description 35
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 150000002148 esters Chemical class 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 20
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 21
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims abstract description 12
- 238000001308 synthesis method Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims description 43
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- 238000006462 rearrangement reaction Methods 0.000 claims description 18
- MICBKZBCSXKCMF-UHFFFAOYSA-N 4-(3-trimethoxysilylpropoxymethyl)-1,3-dioxolan-2-one Chemical group CO[Si](OC)(OC)CCCOCC1COC(=O)O1 MICBKZBCSXKCMF-UHFFFAOYSA-N 0.000 claims description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000005417 glycidoxyalkyl group Chemical group 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- -1 propoxy alkyl silane compound Chemical class 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000002000 Electrolyte additive Substances 0.000 abstract description 2
- 239000012467 final product Substances 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 7
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- BIGOJJYDFLNSGB-UHFFFAOYSA-N 3-isocyanopropyl(trimethoxy)silane Chemical group CO[Si](OC)(OC)CCC[N+]#[C-] BIGOJJYDFLNSGB-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910010941 LiFSI Inorganic materials 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 2
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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- 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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Abstract
The invention discloses a synthesis method of carbonic ester functionalized silane, which relates to the technical field of battery electrolyte additives. According to the method for synthesizing the carbonic ester functionalized silane, the method for synthesizing the carbonic ester functionalized silane is improved by changing the consumption of raw materials and the pressure parameter of carbon dioxide, and the yield and the purity of a final product are improved by increasing the pressure of the carbon dioxide in a reaction kettle and changing the consumption of tetrabutylammonium bromide.
Description
Technical Field
The invention relates to the technical field of battery electrolyte additives, in particular to a synthesis method of carbonic ester functionalized silane.
Background
The electrolyte of the lithium battery is a carrier for ion transmission in the battery, generally consists of lithium salt and an organic solvent, plays a role of conducting ions between a positive electrode and a negative electrode of the lithium battery, and guarantees the advantages of high voltage, high specific energy and the like of the lithium battery.
In the preparation process of the carbonic ester functionalized silane, the reaction is carried out in a reaction kettle with higher pressure, and 3- (2, 3-epoxypropoxy) propyl trimethoxy silane and carbon dioxide which are used as raw materials are promoted to carry out organic reaction by a catalyst and a high-pressure environment.
Disclosure of Invention
The present invention aims to provide a method for synthesizing a carbonate functionalized silane, so as to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme:
the synthesis method of the carbonic ester functionalized silane comprises the step of taking an epoxy propoxy alkyl silane compound and carbon dioxide, and carrying out rearrangement reaction under the action of tetrabutylammonium bromide to obtain the carbonic ester functionalized silane.
Further, the glycidoxy alkyl silane compound is 3- (2, 3-glycidoxy) propyl trimethoxy silane;
the carbonic ester functionalized silane is 4- [ [3- (trimethoxysilyl) propoxy ] methyl ] -1, 3-dioxolane-2-one;
the specific chemical reaction formula is as follows:
further, the weight ratio of the glycidoxy alkyl silane compound to the tetrabutylammonium bromide is 1: 0.05 to 0.10.
Further, in the rearrangement reaction process, the pressure of the carbon dioxide is 1.5-2.0 MPa.
Further, the solvent for the rearrangement reaction is ethyl acetate.
Further, the temperature of the rearrangement reaction is 70-90 ℃, and the time is 45-50 h.
Furthermore, stirring is needed in the rearrangement reaction process; the stirring direction during stirring adopts a mode of alternately performing clockwise stirring and anticlockwise stirring; the time of single clockwise stirring or single anticlockwise stirring is 2-3 h.
Further, after the rearrangement reaction is finished, washing and concentrating are carried out to prepare the carbonate functionalized silane.
Further, the washing is performed with a saturated saline solution.
Compared with the prior art, the invention has the beneficial effects that:
according to the method for synthesizing the carbonic ester functionalized silane, the method for synthesizing the carbonic ester functionalized silane is improved by changing the consumption of raw materials and the pressure parameter of carbon dioxide, and the yield and the purity of a final product are improved by increasing the pressure of the carbon dioxide in a reaction kettle and changing the consumption of tetrabutylammonium bromide. Particularly, in the stirring process, the reaction can be fully carried out by a clockwise and anticlockwise combined stirring mode, and the yield and the purity of the product are effectively improved.
Drawings
FIG. 1 is a hydrogen nuclear magnetic spectrum of 4- [ [3- (trimethoxysilyl) propoxy ] methyl ] -1, 3-dioxolan-2-one prepared in the first example of the present invention;
FIG. 2 is a carbon nuclear magnetic spectrum of 4- [ [3- (trimethoxysilyl) propoxy ] methyl ] -1, 3-dioxolan-2-one prepared in the first embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows:
the synthesis method of the carbonic ester functionalized silane comprises the following steps:
adding 23.6g (0.1mol) of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane and 2.00g of tetrabutylammonium bromide into 100mL of ethyl acetate, stirring and dissolving, introducing carbon dioxide to discharge air until the pressure of the carbon dioxide is 1.5MPa, simultaneously heating to 80 ℃, maintaining the temperature at 80 ℃, starting stirring at 1.5MPa, stirring for 2h clockwise stirring and 2h anticlockwise stirring alternately, stirring for rearrangement reaction for 48h, cooling to room temperature and normal pressure after the reaction is finished, taking out the obtained system, cooling to 0 ℃ again, adding saturated salt water to wash (50mL multiplied by 2), carrying out phase separation, drying the obtained organic phase by anhydrous magnesium sulfate, concentrating under reduced pressure to obtain 26.89g of 4- [ [3- (trimethoxysilyl) propoxy ] methyl ] -1, 3-dioxolan-2-one with the yield of 95.92% and the purity of 99.6%, the specific chemical reaction formula is as follows:
4- [ [3- (trimethoxysilyl) propoxy group]Methyl radical]Hydrogen nuclear magnetic spectrum diagram of-1, 3-dioxolan-2-one referring to fig. 1, the hydrogen nuclear magnetic characteristic data is:1HNMR(400MHz,CDCl3)δ0.60-0.70(m,2H),1.61-1.74(m,2H),3.48(t,2H,J＝6.5Hz),3.56(s,9H),3.60(dd,1H,J＝3.6Hz and 10.8Hz),3.67(dd,1H,J＝4.0and 11.0Hz),4.38(dd,1H,J＝5.8and 8.3Hz),4.48(dd,1H,J＝8.3and 8.3Hz),4.74-4.82(m,1H)；
the carbon nuclear magnetic spectrum of 4- [ [3- (trimethoxysilyl) propoxy ] methyl ] -1, 3-dioxolan-2-one is shown in FIG. 2.
Example two:
the synthesis method of the carbonic ester functionalized silane comprises the following steps:
23.6g (0.1mol) of 3- (2, 3-epoxypropoxy) propyltrimethoxysilane and 1.18g of tetrabutylammonium bromide are added into 80mL of ethyl acetate to be stirred and dissolved, carbon dioxide is introduced to discharge air until the pressure of the carbon dioxide is 2.0MPa, simultaneously heating to 70 ℃, maintaining the temperature at 70 ℃ and stirring at 2MPa, starting stirring, stirring clockwise for 2.5h and anticlockwise for 2.5h alternately during stirring, stirring for rearrangement reaction for 50h, after the reaction is finished, cooling to room temperature and normal pressure, taking out the obtained system, cooling to 5 deg.C again, adding saturated saline solution for washing (40mL × 2), separating phases, drying the obtained organic phase with anhydrous magnesium sulfate, concentrating under reduced pressure, 26.46g of 4- [ [3- (trimethoxysilyl) propoxy ] methyl ] -1, 3-dioxolane-2-one are obtained, the yield is 94.38%, and the purity is 99.7%.
Example three:
the synthesis method of the carbonic ester functionalized silane comprises the following steps:
23.6g (0.1mol) of 3- (2, 3-epoxypropoxy) propyltrimethoxysilane and 1.6g of tetrabutylammonium bromide are added into 110mL of ethyl acetate to be stirred and dissolved, carbon dioxide is introduced to discharge air until the pressure of the carbon dioxide is 1.8MPa, simultaneously heating to 80 ℃, maintaining the temperature at 80 ℃ and stirring at 1.8MPa, starting stirring, stirring clockwise for 3 hours and anticlockwise for 3 hours alternately during stirring, stirring for rearrangement reaction for 47 hours, after the reaction is finished, cooling to room temperature and normal pressure, taking out the obtained system, cooling to 3 deg.C again, adding saturated saline solution for washing (50mL × 2), separating phases, drying the obtained organic phase with anhydrous magnesium sulfate, concentrating under reduced pressure, 26.73g of 4- [ [3- (trimethoxysilyl) propoxy ] methyl ] -1, 3-dioxolane-2-one are obtained, the yield is 95.35%, and the purity is 99.5%.
Example four:
the synthesis method of the carbonic ester functionalized silane comprises the following steps:
23.6g (0.1mol) of 3- (2, 3-epoxypropoxy) propyltrimethoxysilane and 2.36g of tetrabutylammonium bromide are added into 120mL of ethyl acetate to be stirred and dissolved, carbon dioxide is introduced to discharge air until the pressure of the carbon dioxide is 1.7MPa, simultaneously heating to 90 deg.C, maintaining 90 deg.C and 1.7MPa, starting stirring, stirring clockwise for 2 hr and counterclockwise for 2 hr alternately, stirring for rearrangement reaction for 45 hr, after the reaction is completed, cooling to room temperature and normal pressure, taking out the obtained system, cooling to 3 deg.C again, adding saturated saline solution for washing (60mL × 2), separating phases, drying the obtained organic phase with anhydrous magnesium sulfate, concentrating under reduced pressure, 26.91g of 4- [ [3- (trimethoxysilyl) propoxy ] methyl ] -1, 3-dioxolane-2-one is obtained, the yield is 95.99%, and the purity is 99.6%.
Example five:
the synthesis method of the carbonic ester functionalized silane comprises the following steps:
23.6g (0.1mol) of 3- (2, 3-epoxypropoxy) propyltrimethoxysilane and 1.5g of tetrabutylammonium bromide are added into 100mL of ethyl acetate to be stirred and dissolved, carbon dioxide is introduced to discharge air until the pressure of the carbon dioxide is 1.9MPa, simultaneously heating to 75 ℃, maintaining the temperature at 75 ℃ and stirring at 1.9MPa, starting stirring, stirring clockwise for 3 hours and anticlockwise for 3 hours alternately during stirring, stirring for rearrangement reaction for 49 hours, after the reaction is finished, cooling to room temperature and normal pressure, taking out the obtained system, cooling to 4 deg.C again, adding saturated saline solution for washing (50mL × 2), separating phases, drying the obtained organic phase with anhydrous magnesium sulfate, concentrating under reduced pressure, 26.59g of 4- [ [3- (trimethoxysilyl) propoxy ] methyl ] -1, 3-dioxolane-2-one is obtained, the yield is 94.85 percent, and the purity is 99.7 percent.
Example six:
the synthesis method of the carbonic ester functionalized silane comprises the following steps:
23.6g (0.1mol) of 3- (2, 3-epoxypropoxy) propyltrimethoxysilane and 1.7g of tetrabutylammonium bromide are added into 110mL of ethyl acetate to be stirred and dissolved, carbon dioxide is introduced to discharge air until the pressure of the carbon dioxide is 1.6MPa, simultaneously heating to 85 deg.C, maintaining at 85 deg.C and 1.6MPa, starting stirring, stirring clockwise for 2.5 hr and counterclockwise for 2.5 hr alternately, stirring for rearrangement reaction for 48 hr, after the reaction is completed, cooling to room temperature and normal pressure, taking out the obtained system, cooling to 3 deg.C again, adding saturated saline solution for washing (55mL × 2), separating phases, drying the obtained organic phase with anhydrous magnesium sulfate, concentrating under reduced pressure, 26.76g of 4- [ [3- (trimethoxysilyl) propoxy ] methyl ] -1, 3-dioxolane-2-one is obtained, the yield is 95.45%, and the purity is 99.6%.
Comparative example one: the common finished product of 4- [ [3- (trimethoxysilyl) propoxy ] methyl ] -1, 3-dioxolane-2-one in the market is purchased, 5 components are selected in a random sampling mode, and the purity of the 5 components is measured by using a high performance liquid chromatograph, wherein the average value of the purity is 98.1%.
The purity of the finished products of examples one to six was compared with the product yield and purity of comparative example one, and the comparison results are shown in table 1.
TABLE 1
| Item | Yield (%) | Purity (%) |
| Example one | 95.92 | 99.6 |
| Example two | 94.38 | 99.7 |
| EXAMPLE III | 95.35 | 99.5 |
| Example four | 95.99 | 99.6 |
| EXAMPLE five | 94.85 | 99.7 |
| EXAMPLE six | 95.45 | 99.6 |
| Comparative example 1 | / | 98.1 |
Application experiments:
ternary material NCM (622) lithium is used as a positive electrode material, a negative electrode adopts mesocarbon microbeads, current collectors of the positive electrode and the negative electrode are distributed into aluminum foils and copper foils, a diaphragm adopts a ceramic diaphragm to form a soft package battery, after electrolyte is injected, the soft package battery is assembled in a glove box, and the test is carried out after the soft package battery is kept stand for 8 hours. And respectively carrying out charging and discharging at the constant temperature of 25 ℃ and at the temperature of 1/10C 3.0V to 4.2V to activate the battery, thus obtaining the battery to be tested. The electrolytes tested included base electrolyte E1 and electrolyte E2, the compositions of which are as follows:
1. basic electrolyte E1
EC：Solution-1：DEC＝3：3：4(v:v:v)，LiPF6：1.0M，0.5％LiFSI，1％VC
2. Electrolyte E2
EC：Solution-1：DEC＝3：3：4(v:v:v)，LiPF6: 1.0M, 0.5% LiFSI, 1% VC, 1% 4- [ [3- (trimethoxysilyl) propoxy%]Methyl radical]-1, 3-dioxolan-2-one additive
And (3) testing results:
1. the test results after 60 ℃ cycling were as follows:
TABLE 2
2. The batteries were placed in a low temperature cabinet, the temperature was controlled at-30 ℃ or-40 ℃ respectively, the resting time was 240min, and then the capacity retention rate of the batteries was measured.
TABLE 3
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. The synthesis method of the carbonic ester functionalized silane is characterized by comprising the following steps: the synthesis method comprises the step of taking an epoxy propoxy alkyl silane compound and carbon dioxide, and carrying out rearrangement reaction under the action of tetrabutylammonium bromide to obtain the carbonic ester functionalized silane.
2. The method of synthesizing a carbonate functionalized silane according to claim 1, wherein:
the glycidoxy alkyl silane compound is 3- (2, 3-glycidoxy) propyl trimethoxy silane;
the carbonic ester functionalized silane is 4- [ [3- (trimethoxysilyl) propoxy ] methyl ] -1, 3-dioxolane-2-one;
the specific chemical reaction formula is as follows:
3. the method of synthesizing a carbonate functionalized silane according to claim 1 or 2, wherein: the weight ratio of the glycidoxyalkylsilane compound to the tetrabutylammonium bromide is 1: 0.05 to 0.10.
4. The method of synthesizing a carbonate functionalized silane according to claim 1 or 2, wherein: in the rearrangement reaction process, the pressure of the carbon dioxide is 1.5-2.0 MPa.
5. The method of synthesizing a carbonate functionalized silane according to claim 1 or 2, wherein: the solvent for the rearrangement reaction is ethyl acetate.
6. The method of synthesizing a carbonate functionalized silane according to claim 1 or 2, wherein: the temperature of the rearrangement reaction is 70-90 ℃, and the time is 45-50 h.
7. The method of synthesizing a carbonate functionalized silane according to claim 1 or 2, wherein: in the rearrangement reaction process, stirring is also needed; the stirring direction during stirring adopts a mode of alternately performing clockwise stirring and anticlockwise stirring; the time of single clockwise stirring or single anticlockwise stirring is 2-3 h.
8. The method of synthesizing a carbonate functionalized silane according to claim 1 or 2, wherein: and after the rearrangement reaction is finished, washing and concentrating are carried out to prepare the carbonic ester functionalized silane.
9. The method of synthesizing a carbonate functionalized silane according to claim 8, wherein: the washing was performed with saturated saline.
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| MÉLANIE DECOSTANZI ET AL.: "Synthesis of sol-gel hybrid polyhydroxyurethanes", 《EUROPEAN POLYMER JOURNAL》 * |
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