CN113549100A - Method for synthesizing fluorinated silane containing low-polymer epoxy ethane - Google Patents
Method for synthesizing fluorinated silane containing low-polymer epoxy ethane Download PDFInfo
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- CN113549100A CN113549100A CN202111013137.7A CN202111013137A CN113549100A CN 113549100 A CN113549100 A CN 113549100A CN 202111013137 A CN202111013137 A CN 202111013137A CN 113549100 A CN113549100 A CN 113549100A
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- 150000004756 silanes Chemical class 0.000 title claims abstract description 30
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 17
- 230000002194 synthesizing effect Effects 0.000 title claims description 15
- 229920000642 polymer Polymers 0.000 title description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 99
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 229910052708 sodium Inorganic materials 0.000 claims description 19
- 239000011734 sodium Substances 0.000 claims description 19
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 229920000570 polyether Polymers 0.000 claims description 16
- -1 sodium alkoxide Chemical class 0.000 claims description 16
- 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 15
- AWQTZFCYSLRFJO-UHFFFAOYSA-N diethoxy(methoxy)silane Chemical compound CCO[SiH](OC)OCC AWQTZFCYSLRFJO-UHFFFAOYSA-N 0.000 claims description 14
- 239000012025 fluorinating agent Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 10
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 8
- KEZMLECYELSZDC-UHFFFAOYSA-N 3-chloropropyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(OCC)CCCCl KEZMLECYELSZDC-UHFFFAOYSA-N 0.000 claims description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 8
- 239000006227 byproduct Substances 0.000 claims description 8
- 238000003682 fluorination reaction Methods 0.000 claims description 8
- 229910000077 silane Inorganic materials 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 238000001308 synthesis method Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000006266 etherification reaction Methods 0.000 claims description 6
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical group FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000006384 oligomerization reaction Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 230000006837 decompression Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 3
- 238000010189 synthetic method Methods 0.000 abstract description 3
- 239000002000 Electrolyte additive Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 26
- 239000007788 liquid Substances 0.000 description 13
- 239000000706 filtrate Substances 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 6
- 229910015900 BF3 Inorganic materials 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910010941 LiFSI Inorganic materials 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 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
- 239000003960 organic solvent Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011888 foil 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
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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
- 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
- C07F7/12—Organo silicon halides
- C07F7/121—Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20
- C07F7/123—Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20 by reactions involving the formation of Si-halogen linkages
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The invention discloses a synthetic method of fluorinated silane containing oligoethylene oxide, which relates to the technical field of battery electrolyte additives. The synthetic method of the fluorinated silane containing the oligomeric ethylene oxide improves various parameters in the reaction process and a post-treatment method, and achieves the effect of improving the yield and the purity of the fluorinated silane containing the oligomeric ethylene oxide.
Description
Technical Field
The invention relates to the technical field of battery electrolyte additives, in particular to a method for synthesizing fluorinated silane containing low-polymer epoxy ethane.
Background
The electrolyte of the lithium battery is usually prepared by using an organic solvent, generally a high-purity organic solvent, electrolyte lithium salt, necessary additives and other raw materials according to a certain proportion under a certain condition, fluorinated silane containing oligomeric ethylene oxide is often added in the production process of the electrolyte, and the adaptability of electrolysis is improved by the stability of the oligomeric ethylene oxide.
The fluorinated silanes containing oligomeric ethylene oxide are synthesized in low yields and purity due to the harsh reaction conditions.
Disclosure of Invention
The present invention has been made to solve the above-mentioned problems occurring in the prior art, and an object of the present invention is to provide a method for synthesizing a fluorinated silane containing an oligoethylene oxide.
In order to achieve the purpose, the invention provides the following technical scheme:
a method for synthesizing fluorinated silane containing oligomeric ethylene oxide comprises the following steps:
1) under the protection of nitrogen, reacting alcohol containing polyether chains with metal sodium to generate sodium alkoxide, and then carrying out etherification reaction with halogenated silane compounds to obtain polyether chain-containing silane compounds;
2) under the protection of nitrogen, the silane compound containing polyether chains is subjected to fluorination reaction under the action of a fluorinating agent to obtain the fluorinated silane of the oligomeric ethylene oxide.
Further, in the step 1), the alcohol containing the polyether chain is diethylene glycol monomethyl ether;
the halogenated silane compound is 3-chloropropyldiethoxymethylsilane;
the polyether chain-containing silane compound is 3- (methoxy diethoxy) propyl methyl bis (methoxy diethoxy) silane;
the specific chemical reaction formula is as follows:
in the step 2), the fluorinated silane for oligomerization of ethylene oxide is 3- (methoxy diethoxy) propyl-methyl-difluorosilane;
the specific chemical reaction formula is as follows:
further, in the step 1), the molar ratio of the alcohol containing a polyether chain, the sodium metal and the halogenated silane compound is 1: 0.2-0.5: 1-1.05.
Further, in the step 2), the molar ratio of the polyether chain-containing silane compound to the fluorinating agent is 1: 2-3.
Further, in the step 2), the fluorinating agent is boron trifluoride ethyl ether.
Further, in step 2), the solvent for the fluorination reaction is toluene.
Further, in the step 1), the reaction temperature for producing sodium alkoxide is 60-80 ℃; the temperature of the etherification reaction is 80-120 ℃, and the time is 22-26 h.
Further, in the step 2), the temperature of the fluorination reaction is 80-90 ℃ and the time is 22-26 h.
Further, in the step 1), after the etherification reaction is completed, filtering is further needed, toluene is added for dissolution, and then washing, drying with anhydrous magnesium sulfate and concentration are carried out to obtain the polyether chain-containing silane compound.
Further, in the step 2), after the fluorination reaction is completed, the solvent, the residual fluorinating agent and the by-products are directly removed by concentration under reduced pressure.
Compared with the prior art, the invention has the beneficial effects that:
the synthetic method of the fluorinated silane containing the oligomeric ethylene oxide improves various parameters in the reaction process and a post-treatment method, and achieves the effect of improving the yield and the purity of the fluorinated silane containing the oligomeric ethylene oxide.
Drawings
FIG. 1 is a hydrogen nuclear magnetic spectrum of 3- (methoxydiethoxy) propyl-methyl-difluorosilane prepared in the first example of the present invention;
fig. 2 is a carbon nuclear magnetic spectrum of 3- (methoxydiethoxy) propyl-methyl-difluorosilane prepared in the first example 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 3- (methoxy diethoxy) propyl-methyl-difluorosilane (F) comprises the following steps:
1) under the protection of nitrogen, 60g (0.5mol) of diethylene glycol monomethyl ether is added into a 250mL three-neck flask, 3.45g (0.15mol) of metallic sodium is added in five batches, the mixture is heated to 80 ℃ to react until the metallic sodium disappears, then 105.4g (0.5mol) of 3-chloropropyldiethoxymethylsilane is added, the mixture is heated to 120 ℃ and maintained at 120 ℃ for reaction for 24 hours, after the reaction is finished, the temperature is reduced to room temperature, the mixture is filtered, a small amount of toluene is washed (10mL multiplied by 2), 200mL of toluene is added into the obtained filtrate to be stirred and dissolved, 50mL of water is added to be washed twice, the phases are separated, anhydrous magnesium sulfate is added into the obtained toluene to be dried, the mixture is filtered and is concentrated under reduced pressure, 101.25g of colorless liquid 3- (methoxydiethoxy) propyl methyl bis (methoxydiethoxy) silane is obtained, the yield is 68.77%, and the specific chemical reaction formula is as follows:
2) under the protection of nitrogen, 88.34g (0.3mol) of 3- (methoxy diethoxy) propyl methyl bis (methoxy diethoxy) silane was dissolved in 200mL of toluene, 177.41g (0.6mol) of 48% boron trifluoride ethyl ether was slowly added dropwise thereto, the mixture was heated to 80 ℃ with stirring, and the temperature was maintained at 80 ℃ for 24 hours, after the reaction was completed, the solvent, the remaining fluorinating agent and by-products were removed by concentration under reduced pressure to obtain 45.15g of colorless transparent liquid 3- (methoxy diethoxy) propyl-methyl-difluorosilane, the yield was 62.10%, the purity was 99.6%, and the specific chemical reaction formula was as follows:
the total yield of 3- (methoxydiethoxy) propyl-methyl-difluorosilane was 42.71%.
The hydrogen nuclear magnetic spectrum of 3- (methoxy diethoxy) propyl-methyl-difluorosilane is shown in figure 1, and the carbon nuclear magnetic spectrum is shown in figure 2.
Example two:
the synthesis method of 3- (methoxy diethoxy) propyl-methyl-difluorosilane (F) comprises the following steps:
1) under the protection of nitrogen, 60g (0.5mol) of diethylene glycol monomethyl ether is added into a 250mL three-neck flask, 2.3g (0.1mol) of metallic sodium is added in five batches, the mixture is heated to 70 ℃ to react until the metallic sodium disappears, then 105.4g (0.5mol) of 3-chloropropyldiethoxymethylsilane is added, the mixture is heated to 80 ℃ and maintained at 80 ℃ for reaction for 26 hours, after the reaction is finished, the temperature is reduced to room temperature, the mixture is filtered, a small amount of toluene is washed (10mL multiplied by 2), 200mL of toluene is added into the obtained filtrate to be stirred and dissolved, 50mL of toluene is added into the obtained filtrate to be washed twice, the phases are separated, anhydrous magnesium sulfate is added into the obtained toluene to be dried, the filtration and the concentration under reduced pressure are carried out, and 102.45g of colorless liquid 3- (methoxydiethoxy) propyl methyl bis (methoxydiethoxy) silane is obtained, wherein the yield is 69.59%.
2) Under nitrogen protection, 88.34g (0.3mol) of 3- (methoxydiethoxy) propylmethylbis (methoxydiethoxy) silane was dissolved in 200mL of toluene, 266.12g (0.9mol) of 48% boron trifluoride ether was slowly added dropwise thereto, the mixture was heated to 80 ℃ with stirring, and the temperature was maintained at 80 ℃ for 26 hours to effect reaction, after which the reaction was completed, the solvent, the remaining fluorinating agent and by-products were removed by concentration under reduced pressure to obtain 45.25g of colorless transparent liquid 3- (methoxydiethoxy) propyl-methyl-difluorosilane, the yield was 62.24% and the purity was 99.7%.
The total yield of 3- (methoxydiethoxy) propyl-methyl-difluorosilane was 43.31%.
Example three:
the synthesis method of 3- (methoxy diethoxy) propyl-methyl-difluorosilane (F) comprises the following steps:
1) under the protection of nitrogen, 60g (0.5mol) of diethylene glycol monomethyl ether is added into a 250mL three-neck flask, 5.75g (0.25mol) of metallic sodium is added in five batches, the mixture is heated to 60 ℃ to react until the metallic sodium disappears, 110.65g (0.525mol) of 3-chloropropyldiethoxymethylsilane is added, the mixture is heated to 120 ℃ and maintained at 120 ℃ to react for 24 hours, after the reaction is finished, the temperature is reduced to room temperature, the mixture is filtered, a small amount of toluene is washed (10mL multiplied by 2), 200mL of toluene is added into the obtained filtrate to be stirred and dissolved, 50mL of toluene is added into the obtained filtrate to be washed twice, the phases are separated, anhydrous magnesium sulfate is added into the obtained toluene to be dried, the filtration is carried out, the reduced pressure concentration is carried out, and 101.38g of colorless liquid 3- (methoxydiethoxy) propyl methyl bis (methoxydiethoxy) silane is obtained, and the yield is 68.86%.
2) Under nitrogen protection, 88.34g (0.3mol) of 3- (methoxydiethoxy) propylmethylbis (methoxydiethoxy) silane was dissolved in 200mL of toluene, 236.55g (0.8mol) of 48% boron trifluoride ether was slowly added dropwise thereto, the mixture was heated to 90 ℃ with stirring and maintained at 90 ℃ for 22 hours, and after completion of the reaction, the solvent, the remaining fluorinating agent and by-products were removed by concentration under reduced pressure to obtain 46.12g of colorless transparent liquid 3- (methoxydiethoxy) propyl-methyl-difluorosilane, with a yield of 63.44% and a purity of 99.6%.
The total yield of 3- (methoxydiethoxy) propyl-methyl-difluorosilane was 43.68%.
Example four:
the synthesis method of 3- (methoxy diethoxy) propyl-methyl-difluorosilane (F) comprises the following steps:
1) under the protection of nitrogen, 60g (0.5mol) of diethylene glycol monomethyl ether is added into a 250mL three-neck flask, 4.6g (0.2mol) of metallic sodium is added in five batches, the mixture is heated to 80 ℃ to react until the metallic sodium disappears, then 109.6g (0.52mol) of 3-chloropropyldiethoxymethylsilane is added, the mixture is heated to 90 ℃ and maintained at 90 ℃ for reaction for 22 hours, after the reaction is finished, the temperature is reduced to room temperature, the mixture is filtered, a small amount of toluene is washed (10mL multiplied by 2), 200mL of toluene is added into the obtained filtrate to be stirred and dissolved, 50mL of toluene is added into the obtained filtrate to be washed twice, the phases are separated, anhydrous magnesium sulfate is added into the obtained toluene to be dried, the filtration is carried out, and the reduced pressure concentration is carried out, so that 101.92g of colorless liquid 3- (methoxydiethoxy) propyl methyl bis (methoxydiethoxy) silane is obtained, and the yield is 69.23%.
2) Under nitrogen protection, 88.34g (0.3mol) of 3- (methoxydiethoxy) propylmethylbis (methoxydiethoxy) silane was dissolved in 200mL of toluene, 177.41g (0.6mol) of 48% boron trifluoride ether was slowly added dropwise thereto, the mixture was heated to 85 ℃ with stirring, and the temperature was maintained at 85 ℃ for 23 hours to carry out a reaction, after which the reaction was completed, the solvent, the remaining fluorinating agent and by-products were removed by concentration under reduced pressure to obtain 45.72g of colorless transparent liquid 3- (methoxydiethoxy) propyl-methyl-difluorosilane, the yield was 62.89%, and the purity was 99.5%.
The total yield of 3- (methoxydiethoxy) propyl-methyl-difluorosilane was 43.54%.
Example five:
the synthesis method of 3- (methoxy diethoxy) propyl-methyl-difluorosilane (F) comprises the following steps:
1) under the protection of nitrogen, 60g (0.5mol) of diethylene glycol monomethyl ether is added into a 250mL three-neck flask, 3.45g (0.15mol) of metallic sodium is added in five batches, the mixture is heated to 75 ℃ to react until the metallic sodium disappears, then 107.5g (0.51mol) of 3-chloropropyldiethoxymethylsilane is added, the mixture is heated to 110 ℃ and maintained at 110 ℃ for reaction for 23 hours, after the reaction is finished, the temperature is reduced to room temperature, the mixture is filtered, a small amount of toluene is washed (10mL multiplied by 2), 200mL of toluene is added into the obtained filtrate to be stirred and dissolved, 50mL of toluene is added into the obtained filtrate to be washed twice, the phases are separated, anhydrous magnesium sulfate is added into the obtained toluene to be dried, the filtration is carried out, and the reduced pressure is concentrated, 100.68g of colorless liquid 3- (methoxy diethoxy) propyl methyl bis (methoxy diethoxy) silane is obtained, and the yield is 68.38%.
2) Under nitrogen protection, 88.34g (0.3mol) of 3- (methoxydiethoxy) propylmethylbis (methoxydiethoxy) silane was dissolved in 200mL of toluene, 221.77g (0.75mol) of 48% boron trifluoride ether was slowly added dropwise thereto, the mixture was heated to 83 ℃ with stirring and maintained at 83 ℃ for 24 hours, after completion of the reaction, the solvent, the remaining fluorinating agent and by-products were removed by concentration under reduced pressure to obtain 46.01g of colorless transparent liquid 3- (methoxydiethoxy) propyl-methyl-difluorosilane, the yield was 63.29%, and the purity was 99.6%.
The total yield of 3- (methoxydiethoxy) propyl-methyl-difluorosilane was 43.28%.
Example six:
the synthesis method of 3- (methoxy diethoxy) propyl-methyl-difluorosilane (F) comprises the following steps:
1) under the protection of nitrogen, 60g (0.5mol) of diethylene glycol monomethyl ether is added into a 250mL three-neck flask, 4.6g (0.2mol) of metallic sodium is added in five batches, the mixture is heated to 65 ℃ to react until the metallic sodium disappears, then 106.4g (0.505mol) of 3-chloropropyldiethoxymethylsilane is added, the mixture is heated to 100 ℃ and maintained at 100 ℃ for reaction for 25 hours, after the reaction is finished, the temperature is reduced to room temperature, the mixture is filtered, a small amount of toluene is washed (10mL multiplied by 2), 200mL of toluene is added into the obtained filtrate to be stirred and dissolved, 50mL of toluene is added into the obtained filtrate to be washed twice, the phases are separated, anhydrous magnesium sulfate is added into the obtained toluene to be dried, the filtration is carried out, the reduced pressure is carried out, and 101.36g of colorless liquid 3- (methoxy diethoxy) propyl methyl bis (methoxy diethoxy) silane is obtained, wherein the yield is 68.84%.
2) Under nitrogen protection, 88.34g (0.3mol) of 3- (methoxydiethoxy) propylmethylbis (methoxydiethoxy) silane was dissolved in 200mL of toluene, 206.98g (0.7mol) of 48% boron trifluoride diethyl ether was slowly added dropwise thereto, the mixture was heated to 88 ℃ with stirring, and the temperature was maintained at 88 ℃ for 25 hours to carry out a reaction, after which the reaction was completed, the solvent, the remaining fluorinating agent and by-products were removed by concentration under reduced pressure to obtain 45.56g of colorless transparent liquid 3- (methoxydiethoxy) propyl-methyl-difluorosilane, the yield was 62.57%, and the purity was 99.5%.
The total yield of 3- (methoxydiethoxy) propyl-methyl-difluorosilane was 43.14%.
Comparative example one:
purchasing a finished product of customized 3- (methoxy diethoxy) propyl-methyl-difluorosilane on the market, selecting 5 components in a random sampling mode, performing purity detection by using a high performance liquid chromatograph, and recording the average purity value of 89% of 5 groups of samples.
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
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% 3- (methoxydiethoxy) propyl-methyl-difluorosilane (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
Claims (10)
1. The method for synthesizing fluorinated silane containing oligomeric ethylene oxide is characterized by comprising the following steps: the synthesis method comprises the following steps:
1) under the protection of nitrogen, reacting alcohol containing polyether chains with metal sodium to generate sodium alkoxide, and then carrying out etherification reaction with halogenated silane compounds to obtain polyether chain-containing silane compounds;
2) under the protection of nitrogen, the silane compound containing polyether chains is subjected to fluorination reaction under the action of a fluorinating agent to obtain the fluorinated silane of the oligomeric ethylene oxide.
2. The method of synthesizing fluorinated oligomeric ethylene oxide-containing silanes of claim 1, wherein:
in the step 1), the alcohol containing the polyether chain is diethylene glycol monomethyl ether;
the halogenated silane compound is 3-chloropropyldiethoxymethylsilane;
the polyether chain-containing silane compound is 3- (methoxy diethoxy) propyl methyl bis (methoxy diethoxy) silane;
the specific chemical reaction formula is as follows:
in the step 2), the fluorinated silane for oligomerization of ethylene oxide is 3- (methoxy diethoxy) propyl-methyl-difluorosilane;
the specific chemical reaction formula is as follows:
3. the method of synthesizing fluorinated silanes containing oligoethylene oxides as claimed in claim 1 or 2, wherein: in the step 1), the molar ratio of the alcohol containing a polyether chain, the metal sodium and the halogenated silane compound is 1: 0.2-0.5: 1-1.05.
4. The method of synthesizing fluorinated silanes containing oligoethylene oxides as claimed in claim 1 or 2, wherein: in the step 2), the molar ratio of the polyether chain-containing silane compound to the fluorinating agent is 1: 2-3.
5. The method of synthesizing fluorinated silanes containing oligoethylene oxides as claimed in claim 1 or 2, wherein: in the step 2), the fluorinating agent is boron trifluoride ethyl ether.
6. The method of synthesizing fluorinated silanes containing oligoethylene oxides as claimed in claim 1 or 2, wherein: in the step 2), the solvent for the fluorination reaction is toluene.
7. The method of synthesizing fluorinated silanes containing oligoethylene oxides as claimed in claim 1 or 2, wherein: in the step 1), the reaction temperature for producing the sodium alkoxide is 60-80 ℃; the temperature of the etherification reaction is 80-120 ℃, and the time is 22-26 h.
8. The method of synthesizing fluorinated silanes containing oligoethylene oxides as claimed in claim 1 or 2, wherein: in the step 2), the temperature of the fluorination reaction is 80-90 ℃ and the time is 22-26 h.
9. The method of synthesizing fluorinated silanes containing oligoethylene oxides as claimed in claim 1 or 2, wherein: in the step 1), after the etherification reaction is completed, filtering is further needed, toluene is added for dissolution, and the polyether chain-containing silane compound is obtained after water washing, anhydrous magnesium sulfate drying and concentration.
10. The method of synthesizing fluorinated silanes containing oligoethylene oxides as claimed in claim 1 or 2, wherein: in the step 2), after the fluorination reaction is finished, the solvent, the residual fluorinating agent and the by-product are directly removed by decompression and concentration.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924495A (en) * | 2012-10-15 | 2013-02-13 | 中国科学院广州能源研究所 | Organic halogenosilane containing polyether chain and application of organic halogenosilane to non-aqueous lithium ion battery electrolyte |
| CN107868098A (en) * | 2016-09-27 | 2018-04-03 | 中央硝子株式会社 | The process for purification and manufacture method of silane compound containing unsaturated bond |
| CN109072005A (en) * | 2016-03-08 | 2018-12-21 | 科慕埃弗西有限公司 | Polysilane compound comprising perfluor (poly-) ether group |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924495A (en) * | 2012-10-15 | 2013-02-13 | 中国科学院广州能源研究所 | Organic halogenosilane containing polyether chain and application of organic halogenosilane to non-aqueous lithium ion battery electrolyte |
| CN109072005A (en) * | 2016-03-08 | 2018-12-21 | 科慕埃弗西有限公司 | Polysilane compound comprising perfluor (poly-) ether group |
| CN107868098A (en) * | 2016-09-27 | 2018-04-03 | 中央硝子株式会社 | The process for purification and manufacture method of silane compound containing unsaturated bond |
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