CN110627824A - Preparation method of bisoxalato borate - Google Patents

Preparation method of bisoxalato borate Download PDF

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Publication number
CN110627824A
CN110627824A CN201911013549.3A CN201911013549A CN110627824A CN 110627824 A CN110627824 A CN 110627824A CN 201911013549 A CN201911013549 A CN 201911013549A CN 110627824 A CN110627824 A CN 110627824A
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oxalate
borate
oxalato
ether
bisoxalato
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王广强
张�杰
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Shanghai Kun New Material Co Ltd
Shanghai Rukun New Material Co Ltd
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Shanghai Kun New Material Co Ltd
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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
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/022—Boron compounds without C-boron linkages

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Abstract

The invention relates to the technical field of preparation of lithium battery electrolyte additives, and particularly relates to a preparation method of bisoxalatoborate. The preparation raw materials at least comprise dialkyl silicon oxalate and MBF4And M is selected from any one of Li, Na, K, Rb and Cs. The method for preparing the bisoxalatoborate has the advantages that the conversion rate of the target product is high, the reaction product is single, and almost no by-product is generated; water and oxalic acid are not introduced in the process, the reaction and purification processes are simple and convenient, and the product quality is easy to control; the process has no three wastes, and the produced recovered solvent and filtered mother liquor can be reused after distillation.

Description

Preparation method of bisoxalato borate
Technical Field
The invention relates to the technical field of preparation of lithium battery electrolyte additives, in particular to a simple, convenient and economic preparation method of bisoxalato borate, which is easy to industrialize.
Background
With the rapid development of global economy, the demand of people for energy is increasing day by day, and the limitation of the traditional fossil fuel and the brought ecological environment problem are prominent day by day, so that people are prompted to turn to some clean renewable new energy sources. Among them, lithium ion batteries are receiving much attention because of a series of advantages such as relatively high discharge voltage and specific energy, long cycle life and long storage life.
In order to obtain a lithium ion battery with high energy density, a functional additive can be added into the electrolyte of the lithium ion battery, and under a normal condition, the energy density and the cycle performance of the lithium ion battery can be obviously improved by adding a small amount of the electrolyte additive. Among a series of electrolyte additives, bis (oxalato) borate electrolyte additives exhibit good performance.
At present, the manufacturing methods of the double oxalate borate electrolyte additive are more, and the following parts are listed:
german patent DE19829030C1 proposes compounds containing lithium as starting material, such as LiOH or Li2CO3A method for preparing LiBOB from oxalic acid or oxalate, boric acid or boron oxide. The preparation method is simple and feasible, and the raw materials are cheap and easy to obtain. However, since the whole reaction process is accompanied by the existence of a large amount of water, and the water has great negative influence on the LiBOB used as the electrolyte of the lithium ion battery, how to ensure that the product is anhydrous becomes the key for preparing the LiBOB by the method. In addition, the LiBOB product prepared by the method easily contains unreacted raw material substances such as oxalic acid and the like, and the product purity is low.
U.S. Pat. No. 4, 0034235, 1 uses Li [ B (OCH)3)4]And (CH)3)3SiOOCCSi(CH3) And (3) reacting in an acetonitrile solvent to prepare LiBOB. The preparation method does not generate water in the reaction process, and the obtained product has high purity. The disadvantages are that the raw materials of the synthetic route are difficult to obtain, the cost is high, and the synthetic route is not suitable for industrialized production.
In patent CN 104447828B, a lithium source compound, a boron compound and an oxalic acid compound are used as main raw materials, and a solid-liquid phase combination method is adopted to prepare a crude lithium bis (oxalato) borate product through reaction, suction filtration and vacuum drying. The reaction and purification processes of the method are complex, the product quality is not easy to control in the preparation process, and more waste liquid is generated in the whole implementation process, which is not beneficial to environmental protection.
In summary, in the current process for preparing the bis (oxalato) borate, the problems of low yield and purity, more water and oxalic acid residues, more wastes generated in the process and the like caused by high reaction temperature exist, and the development of the bis (oxalato) borate electrolyte additive is not facilitated.
Therefore, in combination with the above problems, it is an urgent need to provide a method for preparing bisoxalato borate, which is a problem to be solved by those skilled in the art.
Disclosure of Invention
The invention provides a bisoxalic acidBorate, which is prepared from dialkyl silicon oxalate and MBF4And M is selected from any one of Li, Na, K, Rb and Cs.
In a preferred embodiment of the present invention, the dialkyl silicon oxalate is reacted with MBF4The molar ratio of (2-4): 1.
in a preferred embodiment of the present invention, the dialkyl silicon oxalate has a structural formula shown in formula i:
in the formula I, R1、R2Independently selected from any one of C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl and C6-C12 aryl.
In a preferred embodiment of the present invention, the dialkyl silicon oxalate comprises one or more of dimethyl silicon oxalate, diethyl silicon oxalate, 1-dichloro-1-silacyclopentane, dipropyl silicon oxalate, methyl ethyl silicon oxalate and methyl allyl silicon oxalate.
In a second aspect, the present invention provides a method for preparing a bisoxalatoborate, comprising the steps of:
dialkyl silicon oxalate and MBF4Mixing, reacting to obtain a bisoxalato borate solution and/or a bisoxalato borate solid-liquid mixture, and performing post-treatment to obtain the bisoxalato borate.
As a preferable scheme of the invention, the reaction temperature is 0-120 ℃, and the reaction time is 0.1-48 h.
As a preferable aspect of the present invention, the post-treatment process of the bis (oxalato) borate solution comprises: filtering, concentrating under reduced pressure, and recrystallizing with the first poor solvent.
As a preferable mode of the present invention, the post-treatment process of the bisoxalatoborate solid-liquid mixture includes: the second poor solvent recrystallizes.
As a preferable mode of the present invention, the preparation raw material further includes a non-aqueous solvent, and the non-aqueous solvent includes one or a combination of more of acetonitrile, propionitrile, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 4-dioxane, acetone, butanone, methyl isobutyl ketone, N-dimethylformamide, N-dimethylacetamide, ethyl acetate, methyl acetate, butyl acetate, isopropyl acetate, γ -butyrolactone, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether.
In a preferred embodiment of the present invention, the first poor solvent and the second poor solvent independently comprise one or more of dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, ethyl methyl carbonate, diethyl ether, isopropyl ether, tert-butyl methyl ether, benzene, toluene, o-xylene, m-xylene, p-xylene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, hexane, heptane, octane, dichloromethane, trichloromethane, carbon tetrachloride, 1, 2-dichloroethane, 1,1, 2-trichloroethane, tetrachloroethane, tetrachloroethylene, 1,2, 3-trichloropropane, n-butyl ether and isopropyl ether.
Advantageous effects
The method for preparing the bisoxalatoborate provided by the invention has the advantages that the reaction temperature of the target product is low, the conversion rate is higher, the reaction product is single, and almost no by-product is generated; the process does not introduce water and oxalic acid, the reaction and purification process is simple and convenient, and the product quality is easy to control; the process has no three wastes, and the produced recovered solvent and filtered mother liquor can be reused after distillation.
Detailed Description
For purposes of the following detailed description, it is to be understood that the invention may assume various alternative variations and step sequences, except where expressly specified to the contrary. Moreover, other than in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.
When a range of values is disclosed herein, the range is considered to be continuous and includes both the minimum and maximum values of the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range-describing features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein. For example, a stated range from "1 to 10" should be considered to include any and all subranges between the minimum value of 1 and the maximum value of 10. Exemplary subranges of the range 1 to 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8, 5.5 to 10, and the like.
In a first aspect, the present invention provides a bisoxalato borate salt having a general formula of M [ B (C)2O4)2]The preparation raw materials at least comprise dialkyl silicon oxalate and MBF4And M is selected from any one of Li, Na, K, Rb and Cs.
In one embodiment, when M is Li, M [ B (C)2O4)2]Is lithium bis (oxalato) borate, MBF4Is lithium tetrafluoroborate.
In one embodiment, when M is Na, M [ B (C)2O4)2]Is sodium bisoxalato, MBF4Is sodium tetrafluoroborate.
In one embodiment, when M is K, M [ B (C)2O4)2]Is potassium bis (oxalato) borate, MBF4Is potassium tetrafluoroborate.
In one embodiment, when M is Rb, M [ B (C)2O4)2]Is rubidium bisoxalato borate, MBF4Is rubidium tetrafluoroborate.
In one embodiment, when M is Cs, M [ B (C)2O4)2]Is cesium bisoxalato borate, MBF4Is cesium tetrafluoroborate.
In one embodiment, the dialkyl silicon oxalate is of the formula I:
in the formula I, R1、R2Independently selected from any one of C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl and C6-C12 aryl.
In one embodiment, the dialkyl silicon oxalate includes a combination of one or more of dimethyl silicon oxalate, diethyl silicon oxalate, 1-dichloro-1-silacyclopentane, dipropyl silicon oxalate, methyl ethyl silicon oxalate, methyl allyl silicon oxalate.
In one embodiment, the method for preparing the bisoxalato borate salt comprises the steps of:
dialkyl silicon oxalate and MBF4Mixing, reacting to obtain a bisoxalato borate solution and/or a bisoxalato borate solid-liquid mixture, and performing post-treatment to obtain the bisoxalato borate.
In one embodiment, the preparation of the bisoxalato borate salt is carried out under a dry inert gas atmosphere.
In one embodiment, the dry inert gas comprises one or more combinations of nitrogen, argon, or helium.
Preferably, the dry inert gas is nitrogen.
In one embodiment, the reaction temperature is 0-120 ℃, and the reaction temperature is preferably 20-90 ℃ by comprehensively considering the stability of materials, the safety and controllability of the reaction and the like.
In one embodiment, the reaction time is 0.1-48 hours, and factors such as stability of materials and safety and controllability of the reaction are comprehensively considered, and the reaction time is preferably 1-20 hours.
In one embodiment, the preparation feedstock further comprises a non-aqueous solvent.
In one embodiment, the non-aqueous solvent comprises one or a combination of more of acetonitrile, propionitrile, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 4-dioxane, acetone, butanone, methyl isobutyl ketone, N-dimethylformamide, N-dimethylacetamide, ethyl acetate, methyl acetate, butyl acetate, isopropyl acetate, γ -butyrolactone, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether.
In one embodiment, the moisture content of the non-aqueous solvent is not more than 0.1 wt%, preferably not more than 0.05 wt%.
In one embodiment, the amount of the non-aqueous solvent is 2 to 50 times of the theoretical weight of the bisoxalato borate salt product, and preferably 2 to 30 times of the theoretical weight of the bisoxalato borate salt product in consideration of the yield and purity of the product.
In one embodiment, the dialkyl silicon oxalate is reacted with MBF4The molar ratio of (2-4): 1.
the dialkyl silicon oxalate and MBF4(in the formula, M is selected from any one of Li, Na, K, Rb and Cs) and the reaction solvent, but the mixing method is not limited, and the mixing method is within the scope of the present invention, and generally, the mixing method is suitable for industrial production operation.
In one embodiment, the post-treatment process of the bis (oxalato) borate solution comprises: filtering, concentrating under reduced pressure, and recrystallizing with the first poor solvent.
The purpose of filtering in the post-treatment process of the bisoxalato borate solution is to remove insoluble impurities in the bisoxalato borate solution.
In one embodiment, the post-treatment process of the bis (oxalato) borate solution further comprises re-filtering and drying after the recrystallization of the first poor solvent.
The purpose of the refiltering is to remove the filtrate and obtain the bisoxalatoborate.
In one embodiment, the post-treatment process of the bisoxalato borate solid-liquid mixture comprises: the second poor solvent recrystallizes.
In one embodiment, the post-treatment process of the bisoxalatoborate solid-liquid mixture further comprises filtration and drying after recrystallization of the second poor solvent.
And filtering in the post-treatment process of the bisoxalatoborate solid-liquid mixture to remove filtrate to obtain the bisoxalatoborate.
In one embodiment, in the post-treatment process of the bisoxalato borate solution and/or the bisoxalato borate solid-liquid mixture, the pore diameters of the media for filtering and re-filtering are 0.1 to 10 μm, and the pore diameters of the media for filtering and re-filtering are preferably 0.1 to 3 μm, and further preferably 0.1 to 1 μm in comprehensive consideration of the filtering efficiency and the filtering effect.
In one embodiment, the filter media is selected from the group consisting of a filter membrane, a filter paper, a ceramic membrane, and combinations of one or more thereof.
Preferably, the filtration medium is a filtration membrane.
The filter medium is not particularly limited, and a filter medium that meets the pore size requirement can be used in the present invention.
In one embodiment, the non-aqueous solvent is removed by concentration under reduced pressure, i.e., distillation under reduced pressure.
In one embodiment, the amount of the non-aqueous solvent remaining after the concentration under reduced pressure is 0.2 to 0.4 times the weight of the theoretical bisoxalatoborate product, and the yield and purity of the bisoxalatoborate product are considered together, and preferably, the amount of the non-aqueous solvent remaining after the concentration under reduced pressure is 0.3 times the weight of the theoretical bisoxalatoborate product.
In one embodiment, the vacuum degree of the reduced pressure concentration is 10 to 10kPa, and the temperature range is 30 to 100 ℃.
In one embodiment, the first poor solvent and the second poor solvent independently comprise one or more of dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, ethyl methyl carbonate, diethyl ether, isopropyl ether, tert-butyl methyl ether, benzene, toluene, o-xylene, m-xylene, p-xylene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, hexane, heptane, octane, dichloromethane, trichloromethane, carbon tetrachloride, 1, 2-dichloroethane, 1,1, 2-trichloroethane, tetrachloroethane, tetrachloroethylene, 1,2, 3-trichloropropane, n-butyl ether and isopropyl ether.
In one embodiment, the amount of the first poor solvent or the second poor solvent is 2 to 150 times the weight of the theoretical bis (oxalato) borate product, and preferably 2 to 130 times the weight of the theoretical bis (oxalato) borate product in consideration of the yield and purity of the bis (oxalato) borate product. The specific embodiments are not intended to be limiting, but are within the scope of the invention, which is generally convenient for commercial operations.
In one embodiment, the vacuum degree of the drying is 10-10 kPa, and the temperature range is 60-100 ℃. The specific embodiments are not intended to be limiting, but are within the scope of the invention, which is generally convenient for commercial operations.
The principle of the invention is as follows:
MBF4+2R1R2Si(C2O4)→M[B(C2O4)2]+2R1R2SiF2，
and M is one of Li, Na, K, Rb and Cs.
The applicant researches and discovers that after a dialkyl silicon oxalate solid and a tetrafluoroborate salt in a specific ratio react in a non-aqueous solvent, a high-quality and high-yield bis-oxalato borate salt can be obtained through a series of purification methods such as filtration, reduced pressure concentration and poor solvent crystallization, and presumably, under appropriate reaction conditions, the bond energy of B-O is greater than that of Si-O, the corresponding coordination capacity B-O is greater than that of Si-O, and the dialkyl silicon oxalate solid and the tetrafluoroborate salt undergo a normalization reaction to obtain the high-quality and high-yield bis-oxalato borate salt.
The applicant found that the selection of the non-aqueous solvent, the remaining amount of the non-aqueous solvent after concentration under reduced pressure, and the amount of the poor solvent have a large influence on the yield and purity of the product. The non-aqueous solvent with larger polarity is selected, and the raw material has better solubility in the non-aqueous solvent, thus being beneficial to forward reaction. The used non-aqueous solvent determines the post-treatment mode, when the residual non-aqueous solvent is too much after the reduced pressure concentration, the acting force between the bisoxalato borate and the non-aqueous solvent is larger, and after the poor solvent is added, the bisoxalato borate is not beneficial to crystallization and precipitation, so that the yield and the purity are influenced.
The research of the applicant finds that the yield and the purity of the product can be improved by slightly excessive dialkyl silicon oxalate. It is presumed that the reason is probably that a slight excess of the dialkylsilicon oxalate can promote the completion of the conversion of the reaction, while the residual dialkylsilicon oxalate is easily removed by crystallization, beating, etc. without affecting the quality of the product. When dialkyl silicon oxalate reacts with MBF4The molar ratio of (2-4): 1, the yield and the purity of the bisoxalatoborate are good, and improper control can result in that a target product cannot be obtained, so that higher difficulty is caused to the discovery of the application.
In addition, the solvents and reagents used were purchased from Shanghai Allantin Biotechnology Ltd, unless otherwise stated.
The present invention will be specifically described below by way of examples.
Preparation example 1
Preparation of dimethyl silicon oxalate
Adding 756g (8.40mol) of anhydrous oxalic acid and 1290g (10mol) of dimethyl silicon dichloride into a reaction bottle at room temperature, and heating to 70-75 ℃ for reflux reaction for 24 hours. Then, the temperature is reduced to 25 ℃, 1000g of dichloromethane is added, the mixture is filtered and washed by 300g of dichloromethane to obtain a solid, and the solid is dried under the conditions of 60 ℃ and 200mBar to obtain 1104g of dimethyl silicon oxalate. The yield thereof was found to be 90%, the chloride ion content thereof was found to be 2ppm, the water content thereof was found to be 14ppm, and the acid value thereof was found to be 15 ppm.
Preparation example 2
Preparation of diethyl silicon oxalate
Adding 360g (4.00mol) of anhydrous oxalic acid and 785g (5.00mol) of diethyl silicon dichloride into a reaction bottle at room temperature, and heating to 120-125 ℃ for reflux reaction for 8 hours. Then, the temperature was decreased to 25 ℃ and 500g of methylene chloride was added, and the mixture was filtered and washed with 200g of methylene chloride to obtain a solid, which was dried at 80 ℃ under 200mBar conditions to obtain 592g of diethyl oxalatosilyl ester. The yield thereof was 85%, the chloride ion content thereof was 3ppm, the water content thereof was 18ppm, and the acid value thereof was 25 ppm.
The detection method of the dimethyl silicon oxalate and the diethyl silicon oxalate comprises the following steps: measuring the purity of the bisoxalato borate by selecting ion chromatography; yield (%) — actual product mass/theoretical product mass × 100%; the chloride ion detection method comprises the following steps: detecting by an ion chromatograph; the water content detection method comprises the following steps: the water content was measured by using Karl Fischer moisture meter of Mettler-Tollido corporation; the acid value detection method comprises the following steps: the test is carried out according to the national standard GB/T4954-2002 petroleum products and lubricant neutralization value determination method.
Example 1
The embodiment 1 of the invention provides lithium bis (oxalato) borate, and the preparation raw materials comprise dimethyl silicon oxalate, lithium tetrafluoroborate and non-aqueous solvent acetonitrile;
the dimethyl silicon oxalate is the self-made dimethyl silicon oxalate;
the preparation method of the lithium bis (oxalato) borate comprises the following steps:
at room temperature, 1000g of non-aqueous solvent acetonitrile and 322g (2.2mol) of self-made dimethyl silicon oxalate solid are respectively added into a reaction bottle in a nitrogen atmosphere, and the mixture is heated to 43-47 ℃ while being stirred. A solution prepared from 94g (1.0mol) of lithium tetrafluoroborate solid and 500g of acetonitrile which is a nonaqueous solvent was added dropwise to the reaction flask with stirring for 5 hours. And then stirring for 6 hours at the temperature of 53-57 ℃ to obtain the lithium bis (oxalato) borate solution.19F-NMR analysis shows that lithium tetrafluoroborate in the reaction solution has completely reacted.
And cooling the lithium bis (oxalato) borate solution to normal temperature, and filtering to remove trace insoluble substances. Concentrating the filtrate at 63-67 ℃ under reduced pressure to obtain a viscous and semitransparent solid-liquid mixture, adding 800g of dichloroethane as a first poor solvent, cooling to 0 ℃ in a cold water bath, crystallizing to separate out a large amount of white solid, transferring the white solid into a glove box, filtering, and drying for 6 hours at 73-77 ℃ under reduced pressure to obtain 191.5g of white powdery lithium bis (oxalato) borate.
The residual amount of the non-aqueous solvent acetonitrile after the decompression concentration is 0.3 time of the weight of the theoretical lithium bis (oxalato) borate product;
the filter medium is a filter membrane;
the pore size of the filter medium is 0.22 μm;
the vacuum degree of the reduced pressure concentration is 2 kPa;
the vacuum degree of the reduced pressure drying is 3 kPa.
Example 2
The embodiment 2 of the invention provides sodium bisoxalato, which is prepared from diethyl silicon oxalate, sodium tetrafluoroborate and a non-aqueous solvent N, N-dimethylformamide as raw materials;
the dimethyl silicon oxalate is the self-made diethyl silicon oxalate;
the preparation method of the sodium bisoxalato borate comprises the following steps:
at room temperature, in a nitrogen atmosphere, respectively adding 1000g of a non-aqueous solvent N, N-dimethylformamide and self-made diethyl oxalate solid (383g and 2.20mol) into a reaction bottle, heating to 83-87 ℃ while stirring, uniformly dividing sodium tetrafluoroborate solid (168g and 1.00mol) into six times, adding into the reaction bottle, and stirring at 83-87 ℃ for 4 hours to obtain a sodium bisoxalato solid-liquid mixture.19F-NMR analysis shows that sodium tetrafluoroborate in the reaction solution completely reacts.
Cooling the sodium bisoxalato solid-liquid mixture to 25 ℃, adding 1000g of dichloroethane as a second poor solvent, cooling to 0 ℃ in a cold water bath, crystallizing to separate out a large amount of white solids, transferring the white solids into a glove box, filtering, and drying at 73-77 ℃ for 10 hours under reduced pressure to obtain 200.9g of white powdery sodium bisoxalato.
The residual amount of the non-aqueous solvent N, N-dimethylformamide after the decompression concentration is 0.3 time of the weight of a theoretical sodium bisoxalateproduct;
the filter medium is a filter membrane;
the pore diameter of the filter medium in the filtration is 0.22 μm;
the vacuum degree of the reduced pressure drying is 3 kPa.
Example 3
The embodiment 3 of the invention provides potassium bis (oxalato) borate, which is prepared from dimethyl silicon oxalate, potassium tetrafluoroborate and a non-aqueous solvent tetrahydrofuran as raw materials;
the dimethyl silicon oxalate is the self-made dimethyl silicon oxalate;
the preparation method of the potassium bis (oxalate) borate comprises the following steps:
at room temperature, in a nitrogen atmosphere, 100g of non-aqueous solvent tetrahydrofuran and 41.8g (0.24mol) of self-made dimethyl silicon oxalate solid are respectively added into a reaction bottle and stirred, the mixture is heated to 68-72 ℃, 12.6g (0.1mol) of potassium tetrafluoroborate solid is equally divided into four times and added into the reaction bottle, and then the mixture is stirred for 12 hours at the temperature of 68-72 ℃ to obtain the potassium bisoxalato borate solid-liquid mixture.19F-NMR analysis showed the reaction to be complete.
And cooling the potassium bis (oxalato) borate solid-liquid mixture to 25 ℃, adding 100g of a second poor solvent toluene, cooling to 0 ℃ in a cold water bath, crystallizing to separate out a large amount of white solids, transferring the white solids into a glove box, filtering, and drying under reduced pressure at 108-112 ℃ for 12 hours to obtain 21.0g of white powdery potassium bis (oxalato) borate.
The residual amount of the non-aqueous solvent tetrahydrofuran after the decompression concentration is 0.3 time of the weight of a theoretical potassium bis (oxalato) borate product;
the filter medium is a filter membrane;
the pore diameter of the filter medium in the filtration is 0.22 μm;
the vacuum degree of the reduced pressure drying is 3 kPa.
Example 4
Embodiment 4 of the present invention provides rubidium bis (oxalate) borate, wherein the raw materials for preparation are dimethyl silicon oxalate, rubidium tetrafluoroborate and a non-aqueous solvent N, N-dimethylacetamide;
the dimethyl silicon oxalate is the self-made dimethyl silicon oxalate;
the preparation method of the rubidium bisoxalateborate comprises the following steps:
at room temperature, in a nitrogen atmosphere, respectively adding 20g of non-aqueous solvent N, N-dimethylacetamide and 1.5g (0.01mol) of self-made solid dimethyl silicon oxalate into a reaction bottle, stirring, heating to 35-38 ℃, equally dividing 0.52g (0.003mol) of solid rubidium tetrafluoroborate into three times, adding into the reaction bottle, and stirring at 38-42 ℃ for 12 hours to obtain a rubidium bisoxalato borate solid-liquid mixture.19F-NMR analysis showed the reaction to be complete.
And cooling the solid-liquid mixture of rubidium bisoxalateborate to 25 ℃, adding 100g of dichloroethane as a second poor solvent, cooling to 0 ℃ in a cold water bath, crystallizing to separate out a white solid, transferring the white solid into a glove box, filtering, and drying for 24 hours at 73-77 ℃ under reduced pressure to obtain 0.72g of white powdery rubidium bisoxalateborate.
The residual amount of the non-aqueous solvent N, N-dimethylacetamide after the reduced pressure concentration is 0.3 times of the weight of a theoretical rubidium bisoxalato borate product;
the filter medium is a filter membrane;
the pore diameter of the filter medium in the filtration is 0.22 μm;
the vacuum degree of the reduced pressure drying is 3 kPa.
Example 5
Embodiment 5 of the present invention provides cesium bis (oxalate) borate, which is prepared from dimethyl silicon oxalate, cesium tetrafluoroborate and a non-aqueous solvent acetonitrile;
the dimethyl silicon oxalate is the self-made dimethyl silicon oxalate;
the preparation method of the cesium bis (oxalate) borate comprises the following steps:
at room temperature, in a nitrogen atmosphere, respectively adding 100g of non-aqueous solvent acetonitrile and 14.6g (0.1mol) of self-made dimethyl silicon oxalate solid into a reaction bottle, stirring, heating to 25-30 ℃, uniformly dividing 6.6g (0.03mol) of cesium tetrafluoroborate solid into three times, adding into the reaction bottle, and then carrying out heat preservation and stirring at 25-30 ℃ for 16 hours to obtain the cesium bisoxalato borate solid-liquid mixture.19F-NMR analysis showed the reaction to be complete.
And cooling the solid-liquid mixture of cesium bis (oxalato) borate to 25 ℃, adding 100g of a second poor solvent n-butyl ether, cooling to 0 ℃ in a cold water bath, crystallizing to separate out a large amount of white solids, transferring the white solids into a glove box, filtering, and drying at 73-77 ℃ under reduced pressure for 12 hours to obtain 8.1g of white powdery cesium bis (oxalato) borate.
The residual amount of the non-aqueous solvent acetonitrile after the decompression concentration is 0.3 time of the weight of a theoretical cesium bisoxalato borate product;
the filter medium is a filter membrane;
the pore diameter of the filter medium in the filtration is 0.22 μm;
the vacuum degree of the reduced pressure drying is 3 kPa.
Comparative example 1
The invention provides a lithium bis (oxalato) borate, which is prepared from dimethyl silicon oxalate, lithium tetrafluoroborate and non-aqueous solvent acetonitrile;
the dimethyl silicon oxalate is the self-made dimethyl silicon oxalate;
the preparation method of the lithium bis (oxalato) borate comprises the following steps:
at room temperature, 1000g of non-aqueous solvent acetonitrile and dimethyl silicon oxalate solid (292.7g and 2.00mol) are respectively added into a reaction bottle and stirred in a nitrogen atmosphere, and the mixture is heated to 43-47 ℃. Dropwise adding a mixed solvent of lithium tetrafluoroborate (94g and 1.00mol) and 500g of non-aqueous solvent acetonitrile into a reaction bottle, dropwise adding for 5 hours, and stirring at the temperature of 43-47 ℃ for 6 hours to obtain a lithium bis (oxalato) borate solution.19F-NMR analysis shows that a small amount of lithium difluoro (oxalato) borate remains in the reaction solution.
Cooling the lithium bis (oxalato) borate solution to normal temperature, filtering to remove trace insoluble substances, concentrating the filtrate at 63-67 ℃ under reduced pressure under vacuum degree to form a viscous and semitransparent solid-liquid mixture, adding 800g of a first poor solvent dichloroethane, cooling to 0 ℃ in a cold water bath, crystallizing to separate out a large amount of white solids, transferring the white solids into a glove box for filtering, and drying under reduced pressure at 73-77 ℃ for 6 hours to obtain 185.1g of white powdery lithium bis (oxalato) borate.
The residual amount of the non-aqueous solvent acetonitrile after the decompression concentration is 0.3 time of the weight of the theoretical lithium bis (oxalato) borate product;
the filter medium is a filter membrane;
the pore diameter of the filter medium in the filtration is 0.22 μm;
the vacuum degree of the reduced pressure concentration is 2 kPa;
the vacuum degree of the reduced pressure drying is 3 kPa.
Comparative example 2
Comparative example 2 of the present invention provides a method for preparing lithium bis (oxalato) borate, which is the same as example 1 except that the residual amount of acetonitrile as a non-aqueous solvent after the reduced pressure concentration is 1 time of the theoretical weight of the lithium bis (oxalato) borate.
Comparative example 3
Comparative example 3 of the present invention provides a method for preparing lithium bis (oxalato) borate, which is the same as example 1 except that the residual amount of acetonitrile as a non-aqueous solvent after the concentration under reduced pressure is 0.05 times of the theoretical weight of the lithium bis (oxalato) borate.
Comparative example 4
Comparative example 4 of the present invention provides a method for preparing lithium bis (oxalato) borate, which is the same as in example 1 except that the non-aqueous solvent acetonitrile is replaced with acetone.
Performance testing
Measuring the purity of the bisoxalato borate by selecting ion chromatography; yield (%) — actual product mass/theoretical product mass × 100%; the detection method of the fluorine ions and the chloride ions comprises the following steps: detecting by an ion chromatograph; the water content detection method comprises the following steps: the water content was measured by using Karl Fischer moisture meter of Mettler-Tollido corporation; the acid value detection method comprises the following steps: the test is carried out according to the national standard GB/T4954-2002 petroleum products and lubricant neutralization value determination method; the nuclear magnetic test method comprises the following steps: testing using a nuclear magnetic resonance spectrometer. The test results are shown in table 1.
TABLE 1
The "-" in Table 1 indicates that no corresponding performance test was performed on this example.
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.

Claims (10)

1. The preparation method of the bis (oxalato) borate is characterized in that the preparation raw materials at least comprise dialkyl silicon oxalate and MBF4And M is selected from any one of Li, Na, K, Rb and Cs.
2. The method for producing the bisoxalatoborate according to claim 1, wherein the dialkyloxalatosilicate is reacted with MBF4The molar ratio of (2-4): 1.
3. the method of preparing the bis (oxalato) borate according to claim 1, wherein the dialkyl (oxalato) silicate has a structural formula shown in formula I:
in the formula I, R1、R2Independently selected from any one of C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl and C6-C12 aryl.
4. The method according to claim 3, wherein the dialkylsilicon oxalate comprises a combination of one or more selected from the group consisting of dimethylsilyl oxalate, diethylsilicon oxalate, 1-dichloro-1-silacyclopentane, dipropylsilicyl oxalate, methylethyl silicon oxalate, and methallyl silicon oxalate.
5. The method for producing a bisoxalatoborate according to any one of claims 1 to 4, which comprises the steps of:
dialkyl silicon oxalate and MBF4Mixing, reacting to obtain a bisoxalato borate solution and/or a bisoxalato borate solid-liquid mixture, and performing post-treatment to obtain the bisoxalato borate.
6. The method for producing a bisoxalatoborate according to claim 5, wherein the reaction temperature is 0 to 120 ℃ and the reaction time is 0.1 to 48 hours.
7. The method for producing the bisoxalato borate salt of claim 5, wherein the post-treatment process of the bisoxalato borate solution comprises: filtering, concentrating under reduced pressure, and recrystallizing with the first poor solvent.
8. The method for preparing the bisoxalato borate salt as claimed in claim 5, wherein the post-treatment process of the bisoxalato borate salt solid-liquid mixture comprises: the second poor solvent recrystallizes.
9. The method for preparing the bisoxalatoborate according to any one of claims 6 to 8, wherein the raw material for preparation further comprises a non-aqueous solvent, and the non-aqueous solvent comprises one or more of acetonitrile, propionitrile, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 4-dioxane, acetone, butanone, methyl isobutyl ketone, N-dimethylformamide, N-dimethylacetamide, ethyl acetate, methyl acetate, butyl acetate, isopropyl acetate, gamma-butyrolactone, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether.
10. The method according to claim 9, wherein the first poor solvent and the second poor solvent independently comprise one or more selected from the group consisting of dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, ethyl methyl carbonate, diethyl ether, isopropyl ether, t-butyl methyl ether, benzene, toluene, o-xylene, m-xylene, p-xylene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, hexane, heptane, octane, dichloromethane, trichloromethane, carbon tetrachloride, 1, 2-dichloroethane, 1,1, 2-trichloroethane, tetrachloroethane, tetrachloroethylene, 1,2, 3-trichloropropane, n-butyl ether and isopropyl ether.
CN201911013549.3A 2019-10-23 2019-10-23 Preparation method of bisoxalato borate Pending CN110627824A (en)

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