CN106316862A - Quaternary ammonium tetrafluoroborate preparation method - Google Patents
Quaternary ammonium tetrafluoroborate preparation method Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/12—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of quaternary ammonium compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
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Abstract
The invention relates to the field of preparation of supercapacitor electrolytes, in particular to a quaternary ammonium tetrafluoroborate preparation method. The preparation method includes steps: 1) subjecting tertiary amine, fluoborate and haloalkane to reaction in existence of a reaction solvent, performing solid-liquid separation after reaction is finished, and removing the solvent from a liquid phase to obtain crude products; 2) adding a solvent into the crude products obtained at the step 1), and recrystallizing to obtain quaternary ammonium tetrafluoroborate. The quaternary ammonium tetrafluoroborate preparation method has advantages that by one-pot reaction from most basic raw materials, intermediate separation is avoided, and simplicity in operation is realized; by adoption of a non-aqueous system, waste gas, waste water and industrial residues are less, the solvents and the raw materials are convenient to recycle, and economy is achieved; contents of metal ions in products are controlled to be: Na<10ppm, K<10ppm, Fe<1ppm and Cl<10ppm, and quality and performances of the quaternary ammonium tetrafluoroborate can be improved.
Description
Technical field
The present invention relates to the preparation field of ultracapacitor electrolysis matter, particularly relate to the system of a kind of tetrafluoroborate
Preparation Method.
Background technology
Ultracapacitor owing to power characteristic is good, the feature such as charge/discharge rates is fast, have extended cycle life and environmental pollution is little, be
A kind of model electrochemical energy storage device developed rapidly in recent years, can be widely applied to electrical vehicular power power supply or accessory power supply,
The energy-storage system of the clean energy resource generatings such as solar energy, tide energy and wind-force.Tetrafluoroborate because its have at solvent
The features such as middle dissolubility is big, electrical conductivity is high, electric durability is good, are widely used in ultracapacitor.Currently, use more main
There are tetraethyl ammonium tetrafluoroborate (TEA), triethyl methyl ammonium tetrafluoroborate (TEMA) and dicyclo fourth ammonium tetrafluoroborate
(SBP)。
Having of the open report of the preparation method of tetrafluoroborate is a lot, is summed up, can be divided three classes:
1) quaternary ammonium salt and borofluoride react (WO2004039761, JP2012109539, EP2772495,
WO2014029833)
2) quaternary ammonium salt and fluoboric acid react (EP1642894, JP2013067572, JP2000226361)
3) quaternary ammonium base and fluoboric acid react (JP2001247522)
These preparation methoies all also exist that post processing purge process is complicated, and product quality is the highest, particularly the sun such as Na, K from
Son is difficult to the deficiencies such as removal.Wherein, latter two method, owing to using to fluoboric acid, a large amount of water can be introduced, and Tetrafluoroboric acid quaternary ammonium
Salt often has extraordinary dissolubility in water, and product be separated from aqueous solution very trouble and inefficiency.Separately
Outward, quaternary ammonium base is all to be obtained by ion exchange by quaternary ammonium salt, more expensive on cost.The present invention solves prior art production technology
Complex operation, cost of material are high, product yield is low, of poor quality and the metal ion such as sodium, potassium is difficult to the problem removed, the present invention
The operation preparing tetrafluoroborate is simplified, and product quality and yield are promoted, raw material and running cost fall
Low, and sodium in product, potassium content are effectively controlled.
Summary of the invention
The shortcoming of prior art in view of the above, it is an object of the invention to provide the system of a kind of tetrafluoroborate
Preparation Method, is used for solving the problems of the prior art.
For achieving the above object and other relevant purposes, the present invention provides the preparation method of a kind of tetrafluoroborate,
Described preparation method is one kettle way, comprises the steps:
1) tertiary amine, borofluoride, alkyl halide react under conditions of reaction dissolvent exists, and have reacted rear solid-liquid and have divided
From, obtain crude product after liquid phase desolvation;
2) step 1) gained crude product add solvent recrystallization i.e. obtain described tetrafluoroborate;
The structural formula of described tetrafluoroborate is:
Wherein, R1、R4It is each independently selected from the alkyl of the straight or branched of C1-C20;
R2、R3It is each independently selected from the alkyl of the straight or branched of C1-C20, or R2、R3Together with the nitrogen-atoms of bridge joint
Form C4-C10 cycloalkyl.
In some embodiments of the present invention, described step 1) in, the mol ratio of tertiary amine and borofluoride be 1:0.8~
1:2。
In some embodiments of the present invention, described step 1) in, borofluoride is selected from lithium fluoroborate, Sodium fluoroborate, fluorine
The combination of one or more in ammonium borate or Potassium borofluoride.
In some embodiments of the present invention, described step 1) in, tertiary amine is 1:1~1:3 with the mol ratio of alkyl halide.
In some embodiments of the present invention, described step 1) in, alkyl halide structural formula is:
R1-X;
Wherein, R1Selected from the alkyl of the straight or branched of C1-C20, X is selected from Cl, Br, I.
In some embodiments of the present invention, described step 1) in, the structural formula of tertiary amine is:
Wherein, R4Alkyl selected from the straight or branched of C1-C20;
R2、R3It is each independently selected from the alkyl of the straight or branched of C1-C20, or R2、R3Together with the nitrogen-atoms of bridge joint
Form C4-C10 cycloalkyl.
In some embodiments of the present invention, described step 1) in, the temperature of reaction is 120~180 DEG C.
In some embodiments of the present invention, described step 1) in, temperature during solid-liquid separation is not higher than 60 DEG C.
In some embodiments of the present invention, described step 1) in, reaction dissolvent is organic solvent.
In some embodiments of the present invention, described step 1) in, reaction dissolvent is polar non-solute.
In some embodiments of the present invention, described step 1) in, organic solvent is in nitrile solvents, carbonate-based solvent
The combination of one or more.
In some embodiments of the present invention, described step 1) in, described organic solvent is selected from acetonitrile, propionitrile, butyronitrile, different
Butyronitrile, succinonitrile, glutaronitrile, benzene acetonitrile, dimethyl carbonate, diethyl carbonate, Ethyl methyl carbonate, ethylene carbonate, carbonic acid third
The combination of one or more in alkene ester etc..
In some embodiments of the present invention, described step 2) in, described solvent is selected from alcohols solvent.
In some embodiments of the present invention, described step 2) in, in described solvent selected from methanol, ethanol, isopropanol
The combination of one or more.
In some embodiments of the present invention, described step 2) in, possibly together with crown ether in described solvent.
In some embodiments of the present invention, described step 2) in, described crown ether is 12-crown-4,15-crown-5,18-crown-
6, the combination of one or more in bicyclohexane also-18-crown-6.
Compared with the existing methods, its major advantage is the present invention: the present invention uses one pot reaction, from most basic
Raw material sets out, and is not required to separation of intermediates, simple to operate;And employing non-aqueous system, the three wastes are few, and all solvents and raw material can conveniently return
Receipts are applied mechanically, economical and practical;In product, metal ion content controls at Na < 10ppm, K < 10ppm, Fe < 1ppm, Cl-< 10ppm, can
Improve quality and the performance of tetrafluoroborate.Visible, the invention provides one can obtain high-quality high purity product and
Economical and practical preparation method.
Detailed description of the invention
Inventor, with tertiary amine, borofluoride and alkyl halide as raw material, uses one kettle way to prepare high-quality
Highly purified tetrafluoroborate product, thus provide a kind of simple efficient method to prepare high-quality Tetrafluoroboric acid season
Ammonium salt, completes the present invention on this basis.
One aspect of the present invention provides the preparation method of a kind of tetrafluoroborate, and described preparation method can be one pot
Method, described preparation method may include that tertiary amine, borofluoride, alkyl halide react under conditions of reaction dissolvent exists, reaction
After completing, solid-liquid separation obtains liquid phase, and the structural formula of described tetrafluoroborate can be:
Wherein, R1、R4Can be each independently selected from C1-C20, C1-C12, C1-C10, C1-C8, C1-C6, C1-C4 or
The alkyl of the straight or branched of C1-C3;
R2、R3C1-C20, C1-C12, C1-C10, C1-C8, C1-C6, C1-C4 or C1-C3 can be each independently selected from
The alkyl of straight or branched, or R2、R3Can also with bridge joint nitrogen-atoms together be formed C4-C10 (such as, C4, C5, C6, C7,
C8, C9, C10) cycloalkyl, such as, R2、R3With the nitrogen-atoms of bridge joint can together with form the compound that structural formula is as follows:
Wherein, n is the integer of 4~10.
In the preparation method of described tetrafluoroborate, the structural formula of tertiary amine can be:
Wherein, the R in the structural formula of tertiary amine2、R3、R4R generally and in the structural formula of tetrafluoroborate2、R3、R4
Corresponding;
R4Can be independently selected from the straight chain of C1-C20, C1-C12, C1-C10, C1-C8, C1-C6, C1-C4 or C1-C3
Or the alkyl of side chain;
R2、R3C1-C20, C1-C12, C1-C10, C1-C8, C1-C6, C1-C4 or C1-C3 can be each independently selected from
The alkyl of straight or branched, or R2、R3Can also with bridge joint nitrogen-atoms together be formed C4-C10 (such as, C4, C5, C6, C7,
C8, C9, C10) cycloalkyl.Such as, R2、R3With the nitrogen-atoms of bridge joint can together with form the compound that structural formula is as follows:
Wherein, n is the integer of 4~10.
In the preparation method of described tetrafluoroborate, borofluoride is often referred to fluorine-containing borate (BF4 -) salt, fluorine boron
The object lesson of hydrochlorate includes but not limited to one or more in lithium fluoroborate, Sodium fluoroborate, ammonium fluoroborate or Potassium borofluoride
Combination.Those skilled in the art can adjust the consumption of borofluoride, such as, tertiary amine and fluoboric acid according to real reaction situation
The mol ratio of salt can be 1:0.8~1:2,1:0.85~1:1.5 or 1:0.9~1:1.
In the preparation method of described tetrafluoroborate, the structural formula of alkyl halide can be:
R1-X;
Wherein, R1Straight or branched selected from C1-C20, C1-C12, C1-C10, C1-C8, C1-C6, C1-C4 or C1-C3
Alkyl, X be selected from Cl, Br, I.The consumption of alkyl halide generally can be excessive, and such as, tertiary amine is permissible with the mol ratio of alkyl halide
For 1:1~1:3,1:1~1:2 or 1:1~1:1.2.
In the preparation method of described tetrafluoroborate, the mixing of tertiary amine, borofluoride, alkyl halide and reaction dissolvent
During, generally can carry out under low temperature or normal temperature condition, to reach the mesh preventing the alkyl halide that boiling point is the highest from escaping
, described cryogenic conditions can be not higher than 20 DEG C, not higher than 10 DEG C or not higher than 5 DEG C, in the embodiment of the invention
In, described cryogenic conditions is-5~5 DEG C.
In the preparation method of described tetrafluoroborate, above-mentioned reaction is carried out the most in a heated condition, the temperature of heating
Degree can be 120~180 DEG C or 140-170 DEG C.Those skilled in the art can control response time, example according to reaction process
As, can determine whether reaction completes by the response situation of raw material in monitoring reaction system, be embodied as in the present invention one
In mode, the response time can be 4~12 hours.
In the preparation method of described tetrafluoroborate, generally reaction system can be lowered the temperature before solid-liquid separation, such as,
Temperature during solid-liquid separation can be not higher than 60 DEG C or 20~60 DEG C, in the embodiment of the invention, solid-liquid separation
Time temperature can be room temperature.
In the preparation method of described tetrafluoroborate, described step 1) in, reaction dissolvent can be organic solvent, more
It is specifically as follows polar non-solute, such as, can be to include but not limited in nitrile solvents, carbonate-based solvent etc.
Kind or multiple combination, more such as, the example of reaction dissolvent applicatory includes but not limited to acetonitrile, propionitrile, butyronitrile, isobutyl
Nitrile, succinonitrile, glutaronitrile, benzene acetonitrile, dimethyl carbonate, diethyl carbonate, Ethyl methyl carbonate, ethylene carbonate, propylene carbonate
The combination of one or more in ester etc..In described preparation method, the consumption of reaction dissolvent is not particularly limited, as long as not to this
The goal of the invention of invention produces and limits, in the embodiment of the invention, and tertiary amine and the mol ratio of reaction dissolvent
Can be 1:2~1:10, or 1:3~1:5.In the present invention one preferred implementation, solid-liquid separation obtains liquid phase and also removes molten
Agent, the mode of desolvation does not has particular restriction, as long as the goal of the invention not to the present invention produces limits, the most permissible
For decompression precipitation.
The preparation method of tetrafluoroborate provided by the present invention can also include: by above-mentioned reaction products therefrom weight
Crystallize and i.e. obtain described tetrafluoroborate.
In the preparation method of described tetrafluoroborate, the concrete grammar of recrystallization can be, at above-mentioned reaction gained
Product adds solvent and carries out recrystallization.Described recrystallization solvent is usually organic solvent, and those skilled in the art are optional to close
Suitable recrystallization solvent carries out recrystallization to product, and preferred solvent is alcohols solvent, the example bag of described alcohols solvent
The combination of one or more included but be not limited in methanol, ethanol, isopropanol, the consumption of solvent is not particularly limited, as long as not
Goal of the invention generation to the present invention limits.In some embodiments of the present invention, in described recrystallization solvent possibly together with
Crown ether, the example of concrete spendable crown ether includes but not limited to 12-crown-4,15-crown-5,18-crown-6, bicyclohexane also-18-
The combination of one or more in crown-6 grade.Those skilled in the art can adjust the consumption of crown ether according to recrystallization system, such as
The consumption of crown ether can be the 0.1%~2% of tertiary amine weight.
The invention provides the preparation method of a kind of tetrafluoroborate, tetrafluoroborate provided by the present invention
Preparation method use one pot reaction, from most basic raw material, be not required to separation of intermediates, after simple economy locate
Reason, can purify and obtain high-quality highly purified tetrafluoroborate product, and whole course of reaction is simple to operate, and uses non-
Aqueous systems, the three wastes are few, and all solvents and raw material can facilitate recovery, and economical and practical, in product, metal ion content controls
Na<10ppm,K<10ppm,Fe<1ppm,Cl-< 10ppm can improve quality and the performance of tetrafluoroborate.Visible, this
Bright providing a kind of can obtain high-quality high purity product and economical and practical preparation method, and the method reactions steps is simple, become
This is rationally suitable for extensive industrialization.
Below by way of specific instantiation, embodiments of the present invention being described, those skilled in the art can be by this specification
Disclosed content understands other advantages and effect of the present invention easily.The present invention can also be by the most different concrete realities
The mode of executing is carried out or applies, the every details in this specification can also based on different viewpoints and application, without departing from
Various modification or change is carried out under the spirit of the present invention.
It should be clear that conventional equipment in the concrete process equipment indicated or device all use this area in the following example or
Device.
In addition, it is to be understood that the one or more method steps mentioned in the present invention do not repel before and after described combination step
Additive method step can also be there is or additive method step can also be inserted between these steps specifically mentioned, unless separately
It is described;Should also be understood that the combination annexation between the one or more equipment/devices mentioned in the present invention is not repelled
Can also exist before and after described unit equipment/device other equipment/devices or these two equipment/devices specifically mentioned it
Between can also insert other equipment/devices, except as otherwise noted.And, except as otherwise noted, the numbering of various method steps is only
Differentiate the convenient tool of various method steps, rather than for limiting the ordering of various method steps or limiting the enforceable model of the present invention
Enclose, being altered or modified of its relativeness, in the case of without essence change technology contents, enforceable when being also considered as the present invention
Category.
Embodiment 1
The preparation of tetraethyl ammonium fluoroborate:
In 500mL autoclave, under stirring, it is sequentially added into 140g acetonitrile, 68.9g Potassium borofluoride, 61.0g triethylamine, cooling
To-5~5 DEG C, import 44.7g ethyl chloride.Being heated to 150~160 DEG C of insulation reaction 6 hours, in still, pressure is 0.6MPa.Cooling
To 45~55 DEG C, sucking filtration, filter cake 14g acetonitrile rinses, and merging filtrate obtains the acetonitrile solution of product.Filtrate reduced in volume, adds
Entering 720g ethanol, 0.38g 18-crown-6 carries out recrystallization, filters, and obtains product 110.2g after vacuum drying.1H NMR(300MHz,
D2O): δ=1.13~1.19 (m, 12H, CH3× 4), 3.12~3.19 (q, J=7.2Hz, 8H, CH2×4)。13C NMR
(75MHz,D2O): δ=6.54 (CH3),51.9(CH2)。19F NMR(376MHz,D2O): δ=-150.40.Na<10ppm,K<
10ppm,Fe<1ppm,Cl-<10ppm。
Embodiment 2
Triethyl methyl ammonium fluoroborate:
In 500mL autoclave, under stirring, it is sequentially added into 140g acetonitrile, 75.5g Potassium borofluoride, 61.0g triethylamine, cooling
To-5~5 DEG C, import 34.8g chloromethanes.Being heated to 155~165 DEG C of insulation reaction 8 hours, in still, pressure is 0.3MPa.Cooling
To 20~30 DEG C, sucking filtration, filter cake 14g acetonitrile rinses, and merging filtrate obtains the acetonitrile solution of product.Filtrate reduced in volume, adds
Entering 300g ethanol, 0.4g 18-crown-6 carries out recrystallization, filters, and obtains product 111.4g after vacuum drying.1H NMR(300MHz,
D2O): δ=1.24~1.30 (m, 9H, CH3×3),2.89(s,3H,CH3), 3.24~3.32 (q, J=7.2Hz, 6H, CH2×
3)。13C NMR(75MHz,D2O): δ=6.99 (CH3),46.27(CH3),55.79(CH2)。19F NMR(376MHz,D2O):δ
=-150.46.Na<10ppm,K<10ppm,Fe<1ppm,Cl-<10ppm。
Embodiment 3
4-butyl ammonium fluoroborate:
In 500mL autoclave, it is sequentially added into 150g diethyl carbonate, 66g Sodium fluoroborate, 93g tri-n-butylamine under stirring, adds
96g1-n-butyl bromide.Being heated to 135~145 DEG C of insulation reaction 10 hours, in still, pressure is 0.3MPa.It is cooled to 30~40 DEG C, takes out
Filter, filter cake 20g diethyl carbonate rinses, merging filtrate.Filtrate reduced in volume, adds 300g methanol, and 0.5g 12-crown-4 enters
Row recrystallization, filters, and obtains product 155.7g after vacuum drying.(Na<10ppm,K<10ppm,Fe<1ppm,Cl-<10ppm。)
Embodiment 4
N, N-dimethyl pyrrolidine tetrafluoroborate:
In 500mL autoclave, under stirring, it is sequentially added into 150g Ethyl methyl carbonate, 79g ammonium fluoroborate, 43g1-methylpyrrole
Alkane, is cooled to-5~5 DEG C and imports 53g chloromethanes.Insulation reaction 8 hours at 140~150 DEG C, in still, pressure is 0.4MPa.Cooling
To 40 DEG C, sucking filtration, filter cake 20g Ethyl methyl carbonate rinses, merging filtrate.Filtrate reduced in volume, adds 250g methanol,
0.2g15-crown-5 carries out recrystallization, filters, and obtains product 87.8g after vacuum drying.(Na<10ppm,K<10ppm,Fe<1ppm,
Cl-<10ppm。)
Embodiment 5
N-methyl-N-butyl pyrrolidine tetrafluoroborate:
In 500mL autoclave, it is sequentially added into 140g butyronitrile, 69g Potassium borofluoride, 43g1-crassitude, adds 60g1-
Chlorobutane.Being heated to 140~150 DEG C of insulation reaction 8 hours, in still, pressure is 0.3MPa.It is cooled to 30~40 DEG C, sucking filtration, filter
Cake 15g butyronitrile rinses, merging filtrate.Filtrate reduced in volume, adds 300g ethanol, and 0.25g 18-crown-6 carries out recrystallization, mistake
Filter, obtains product 109.1g after vacuum drying.(Na<10ppm,K<10ppm,Fe<1ppm,Cl-<10ppm。)
In sum, the present invention effectively overcomes various shortcoming of the prior art and has high industrial utilization.
The principle of above-described embodiment only illustrative present invention and effect thereof, not for limiting the present invention.Any ripe
Above-described embodiment all can be modified under the spirit and the scope of the present invention or change by the personage knowing this technology.Cause
This, have usually intellectual such as complete with institute under technological thought without departing from disclosed spirit in art
All equivalences become are modified or change, and must be contained by the claim of the present invention.
Claims (10)
1. a preparation method for tetrafluoroborate, comprises the steps:
1) tertiary amine, borofluoride, alkyl halide react under conditions of reaction dissolvent exists, and have reacted rear solid-liquid separation, liquid
Crude product is obtained after phase desolvation;
2) step 1) gained crude product add solvent recrystallization i.e. obtain described tetrafluoroborate;
The structural formula of described tetrafluoroborate is:
Wherein, R1、R4It is each independently selected from the alkyl of the straight or branched of C1-C20;
R2、R3It is each independently selected from the alkyl of the straight or branched of C1-C20, or R2、R3Formed together with the nitrogen-atoms of bridge joint
C4-C10 cycloalkyl.
The preparation method of a kind of tetrafluoroborate the most as claimed in claim 1, it is characterised in that described step 1) in,
Tertiary amine is 1:0.8~1:2 with the mol ratio of borofluoride;
And/or, described step 1) in, borofluoride is selected from lithium fluoroborate, Sodium fluoroborate, ammonium fluoroborate or Potassium borofluoride
Kind or multiple combination.
The preparation method of a kind of tetrafluoroborate the most as claimed in claim 1, it is characterised in that described step 1) in,
Tertiary amine is 1:1~1:3 with the mol ratio of alkyl halide;
And/or, described step 1) in, alkyl halide structural formula is:
R1-X;
Wherein, X is selected from Cl, Br, I.
The preparation method of a kind of tetrafluoroborate the most as claimed in claim 1, it is characterised in that described step 1) in,
The structural formula of tertiary amine is:
The preparation method of a kind of tetrafluoroborate the most as claimed in claim 1, it is characterised in that described step 1) in,
The temperature of reaction is 120~180 DEG C.
The preparation method of a kind of tetrafluoroborate the most as claimed in claim 1, it is characterised in that described step 1) in,
Temperature during solid-liquid separation is not higher than 60 DEG C.
The preparation method of a kind of tetrafluoroborate the most as claimed in claim 1, it is characterised in that described step 1) in,
Reaction dissolvent is organic solvent.
The preparation method of a kind of tetrafluoroborate the most as claimed in claim 7, it is characterised in that described step 1) in,
Described organic solvent is the combination of one or more in nitrile solvents, carbonate-based solvent.
The preparation method of a kind of tetrafluoroborate the most as claimed in claim 8, it is characterised in that described step 1) in,
Described organic solvent is selected from acetonitrile, propionitrile, butyronitrile, isopropyl cyanide, succinonitrile, glutaronitrile, benzene acetonitrile, dimethyl carbonate, carbonic acid two
The combination of one or more in ethyl ester, Ethyl methyl carbonate, ethylene carbonate, Allyl carbonate.
The preparation method of a kind of tetrafluoroborate the most as claimed in claim 1, it is characterised in that described step 2) in,
Described solvent is selected from alcohols solvent;
And/or, the combination of one or more in methanol, ethanol, isopropanol of the described alcohols solvent;
And/or, possibly together with crown ether in described solvent;
And/or, described crown ether is one or more in 12-crown-4,15-crown-5,18-crown-6, bicyclohexane also-18-crown-6
Combination.
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CN107793442A (en) * | 2017-10-19 | 2018-03-13 | 常州大学 | A kind of preparation method of tetrafluoroborate |
CN112876370A (en) * | 2021-02-24 | 2021-06-01 | 东营市泽澳化工有限责任公司 | Method for improving effective conversion rate of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride |
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