CN1762979B - Tetraethyl tetrafluo ammonium fluoroborate preparation method - Google Patents
Tetraethyl tetrafluo ammonium fluoroborate preparation method Download PDFInfo
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- CN1762979B CN1762979B CN 200510086517 CN200510086517A CN1762979B CN 1762979 B CN1762979 B CN 1762979B CN 200510086517 CN200510086517 CN 200510086517 CN 200510086517 A CN200510086517 A CN 200510086517A CN 1762979 B CN1762979 B CN 1762979B
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- tetraethyl
- ammonium
- acid
- preparation
- boric acid
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Abstract
The present invention relates to the preparation process of tetraethyl ammonium tetrafluoroborate as electronic level reagent in producing electronic elements. The preparation process includes recrystallization to obtain refined boric acid, preparing fluoroboric acid with hydrofluoric acid and boric acid in the equal molar ratio, exchange reaction of tetraethyl ammonium halide and fluoroboric acid at 10-50 deg.c and alcohol in the presence of organic solvent, eliminating hydrogen halide at 30-90 deg.c and reduced pressure condition, recrystallization and low temperature decompression drying to obtain ultimate product tetraethyl ammonium tetrafluoroborate. The ultimate product reaches the quality requirement of: purity not lower than 99.5 %, water content not more than 10 ppm, Fe not more than 1.0 ppm, Si not more than 3.0 ppm, Na not more than 3.0 ppm, and K not more than 3.0 ppm.
Description
Technical field
The present invention relates to a kind of preparation method who is used to prepare the electronic-grade reagent-tetraethyl-ammonium tetrafluoroborate of electronic component, tetraethyl-ammonium tetrafluoroborate molecular formula is (C2H5) 4N+BF4-.
Background technology
Product (C
2H
5)
4N
+BF
4 -Can make by quaternary ammonium hydroxide or quaternary ammonium salt and fluoroboric acid reaction.Many documents once had report, as: JP2001-247522A mentions and uses quaternary ammonium hydroxide can obtain highly purified (C as raw material and fluoroboric acid reaction
2H
5)
4N
+BF
4 -The JP2000-226361 report uses quaternary ammonium salt to carry out (C as raw material
2H
5)
4N
+BF
4 -Synthetic.JP2000-226360 then carries out haloalkane and low-carbon (LC) reactive tertiary amine earlier, carries out generating final product (C with the fluoroboric acid reaction again
2H
5)
4N
+BF
4 -In addition, (C
2H
5)
4N
+BF
4 -Can also be by the haloalkane of tetraethyl-amine and hydrofluoric acid reaction, and then react under hot conditions with boron trifluoride methanol solution and to obtain purpose product (C
2H
5)
4N
+BF
4 -
Make a general survey of above-mentioned (C
2H
5)
4N
+BF
4 -The preparation method, quaternary ammonium hydroxide is that the preparation method of raw material is relatively gentle, technical process is corresponding also shorter; But because the source of quaternary ammonium hydroxide mostly is to adopt the IX of quaternary ammonium salt to obtain; Therefore, when adopting quaternary ammonium hydroxide to be raw material, keep away and unavoidably have some such as metals ions such as potassium, sodium; To obtaining high purity, the purpose product (C of metal ion not basically
2H
5)
4N
+BF
4 -Production process result in hand cramps and the difficulty.Second method and the third method are actual to be that a kind of method is that quaternary ammonium salt is the preparation method of raw material, and the 4th kind of method be because temperature of reaction is higher, and boron trifluoride methanol solution toxicity belongs to hazardous substance more greatly, should not adopt.Relevant employing quaternary ammonium salt is the bibliographical information of the operational path of raw material, all adopts the low-carbon (LC) quaternary ammonium salt in the presence of organic solvent, to react with fluoroboric acid, through concentrated, crystallization process, can obtain high purity purpose product.The document introduction that has concentrates, the crystallization process introduction uses multiple organic solvent to carry out crystallization and washing, the trouble that causes organic solvent to reclaim like this.
Summary of the invention:
The objective of the invention is to study a kind of synthetic and process for refining of this product; Utilize tetraethyl-ammonium halide salt and fluoroboric acid in the presence of alcohol organic solvent, to carry out permutoid reaction; Obtain product behind the decompression dehydrohalogenation; Dry through recrystallization and low-temperature reduced-pressure, finally obtain high-purity qualified tetraethyl-ammonium tetrafluoroborate.
The industriallization that this invention is looked ahead, therefore, starting material that this invention is used are industrial raw material; The fluoroboric acid of the fluoroboric acid of one of them, particularly domestic production is by the reaction of boric acid and hydrofluoric acid and get, and often contains higher metals ion; Bring unnecessary trouble for the production process that obtains high purity purpose product; Therefore, this invention is carried out the preparation of fluoroboric acid then from the treating process of basic raw materials-boric acid; The tetraethyl-ammonium halide reaction for preparing certain density fluoroboric acid and industrial first grade; Obtain the purpose product through concentrated, crystallization process, carry out the treating process of the recrystallization of product then, finally obtain the high-quality product that conforms with this technical indicator.
The present invention mainly is the synthetic and treating process of this product, and its reaction equation is:
(C
2H
5)
4N
+X
-+HBF
4→(C
2H
5)
4N
+BF
4 -+HX↑
In the formula: X-is a haloid element, can be: fluorine (F), chlorine (CL), bromine (Br).
That is: tetraethyl-ammonium halide salt and fluoroboric acid carry out permutoid reaction in 10～50 ℃ under existing with alcohol organic solvent; Obtain product in 30～90 ℃, decompression behind the dehydrohalogenation; Dry through recrystallization and low-temperature reduced-pressure, finally obtain high-purity qualified tetraethyl-ammonium tetrafluoroborate.
The concrete operations of the relevant electronic-grade title product of this invention are following:
(1), boric acid is refining:
Concrete operations are following:
Industrial boric acid is dissolved in the deionized water that boils, filters then, filtrating is reduced to room temperature; Crystallization is filtered, and washs with deionized water; Then filter cake is dissolved in the deionized water that boils again cooling, crystallization, triplicate recrystallization process; Can obtain purity and be 99.8% refining boric acid, yield is 42～50%.
(2), the preparation of fluoroboric acid:
Fluoroboric acid synthetic reaction equation is: 4HF+H
3BO
3=HBF
4+ 4H
2O
Concrete operations are following:
Taking by weighing concentration and be 40% industrial top grade hydrofluoric acid adds in the reactor that gathers tetrafluoro material or band corrosion-proof lining that has stirring, condensation reflux unit and cooling coil; Add boric acid while stirring in batches; Reaction temperature is 30～40 ℃; Finish after the boric acid; Continue to stir half an hour, at room temperature left standstill then 2 hours, filter, remove insoluble matter impurity; Promptly get the fluoborate aqueous solution of 33% ± 1 concentration, hydrofluoric acid and boric acid consumption are 1: 1 in molar ratio;
(3), the preparation of tetraethyl-ammonium tetrafluoroborate:
The preparation of tetraethyl-ammonium tetrafluoroborate is in gathering tetrafluoro material reactor drum, to carry out.1: 2 ratio adds tetraethyl-ammonium halide crystal and alcohol organic solvent at first by weight, in 10～50 ℃, slowly drips fluoborate aqueous solution, and fluoborate aqueous solution and tetraethyl-ammonium halide crystalline consumption are by weight being 1: 1; After finishing fluoroboric acid, continue reaction 2 hours, then; Concentrating under reduced pressure, 30～90 ℃ of temperature controls are after reaction finishes; Add alcohol organic solvent with tetraethyl-ammonium halide crystal equal weight again and stir and carried out crystallization in 2 hours, crystallization liquid is through filtering, and uses the alcohol organic solvent washing leaching cake; Removal has the mother liquor of impurity, the wet-milling that obtains---and tetraethyl-ammonium borofluoride crystal (bullion), alcohol organic solvent are isopropylcarbinol, butanols or octanol.；
(4), the tetraethyl-ammonium borofluoride is refining:
Treating process is to adopt the method for recrystallization, and concrete operations are following:
In having the container of condensation reflux unit, add ethanolic soln; Add the tetraethyl-fluoroboric acid ammonium salt wet-milling through alcohol solvent washing simultaneously, intensification is boiled, and treats that solid is all after the dissolving; Be cooled to room temperature while stirring; And at room temperature carry out crystallization, filtration, and with the washing of the ethanolic soln under the room temperature, twice of repeated recrystallization process.The crystal that obtains carries out drying in 40～80 ℃ under vacuum condition, promptly get purified tetraethyl-ammonium borofluoride, wherein purified tetraethyl-ammonium tetrafluoroborate purity:>=99.5%; Water-content≤10ppm; Fe≤1.0ppm; Si≤3.0ppm; Na≤3.0ppm; K≤3.0ppm.
The quality of final product reaches requirement: purity:>=99.5%; Water-content≤10ppm; Fe≤1.0ppm; Si≤3.0ppm; Na≤3.0ppm; K≤3.0ppm.Therefore, the present invention includes the building-up process of feed hydrogen fluoric acid.
Embodiment
Embodiment 1
(1), boric acid is refining:
Concrete operations are following:
Industrial boric acid is dissolved in the deionized water that boils, filters then, filtrating is reduced to room temperature, crystallization; Filter, and wash, then filter cake is dissolved in the deionized water that boils again, cooling, crystallization with deionized water; The triplicate recrystallization process can be made with extra care boric acid, and yield is 42～50%; Table 1 is the refining influence to product of industrial boric acid.
The refining influence of table 1 boric acid to product
(2) preparation of fluoroboric acid:
Take by weighing the adding of 100ml40% (wt) hydrofluoric acid and have gathering in the tetrafluoro material reactor drum of stirring, condensation reflux unit and spiral coil cooling tube; In 1 hour, add boric acid 34.5 grams while stirring, temperature of reaction is 35 ℃ in batches, finishes boric acid and continues to stir half a hour; Stop then stirring and at room temperature left standstill 2 hours; Filter, remove not tolerant impurity, promptly get the fluoborate aqueous solution of 33% ± concentration; The fluoroboric acid of self-control fluoroboric acid and market sale sees the following form to the influence of final product quality:
The commercially available comparison that product is influenced with the self-control fluoroboric acid of table 2
(3) the tetraethyl-ammonium borofluoride is synthetic and refining:
Take by weighing 25g etamon chloride and 50g butanols and add and to gather in the reactor drum of tetrafluoro material,, slowly drip fluoborate aqueous solution in 2 hours in 30 ℃; Be warming up to 40 ℃ then and continue reaction 2 hours, after reaction finishes, concentrating under reduced pressure; And at room temperature add butanols 25g, and stir and carried out crystallization in 2 hours, filter; And, remove the mother liquor that has impurity, the wet-milling that obtains---tetraethyl-ammonium tetrafluoroborate 40g with the butanols washing; Tetraethyl-ammonium tetrafluoroborate wet-milling is put into the container that has condensation reflux unit that the 150ml ethanolic soln is housed, and intensification is boiled, and treats that solid is all after the dissolving; Cooling is cooled to room temperature, and at room temperature carries out crystallization, filtration while stirring; And with the washing of the ethanolic soln under the room temperature, repeated recrystallization process twice is through vacuum-drying; Obtain the qualified tetraethyl-ammonium tetrafluoroborate of 21g product, yield is 64.2% (mol).
Embodiment 2
The preparation of refining, the fluoroboric acid of boric acid is with embodiment 1,
Take by weighing 30g tetraethylammonium bromide and 60g isopropylcarbinol, other processes obtain the qualified tetraethyl-ammonium tetrafluoroborate of 23g product with instance 1, and yield is 69.53% (mol).
Embodiment 3
The preparation of refining, the fluoroboric acid of boric acid takes by weighing 30g tetraethyl ammonium fluoride and 60g octanol with embodiment 1, and other processes obtain the qualified tetraethyl-ammonium tetrafluoroborate of 23g product with instance 1, and yield is 69.53% (mol).
Claims (3)
1. the preparation method of a tetraethyl-ammonium tetrafluoroborate is characterized in that:
(1) boric acid is refining:
Industrial boric acid is dissolved in the deionized water that boils, filters then, filtrating is reduced to room temperature, crystallization; Filter, and wash, then filter cake is dissolved in the deionized water that boils again with deionized water; Cooling, crystallization, the triplicate recrystallization process obtains purity and is 99.8% refining boric acid;
(2) preparation of fluoroboric acid:
Take by weighing concentration and be 40% hydrofluoric acid and add in the reactor drum that gathers tetrafluoro material or band corrosion-proof lining that has stirring, condensation reflux unit and spiral coil cooling tube, add boric acid while stirring in batches, temperature of reaction is 30～40 ℃; Finish after the boric acid; Continue to stir half a hour, at room temperature left standstill then 2 hours, filter, remove insolubles impurity; Promptly get the fluoborate aqueous solution of 33% ± 1 concentration, hydrofluoric acid, boric acid consumption are 1: 1 in molar ratio;
(3) preparation of tetraethyl-ammonium tetrafluoroborate:
The preparation of tetraethyl-ammonium tetrafluoroborate is in gathering tetrafluoro material reactor drum, to carry out, and 1: 2 ratio adds tetraethyl-ammonium halide crystal and alcohol organic solvent at first by weight, in 10～50 ℃; Slowly drip fluoborate aqueous solution, fluoborate aqueous solution and tetraethyl-ammonium halide crystalline consumption be by weight being 1: 1, finish fluoroboric acid after; Continue reaction 2 hours, then, concentrating under reduced pressure; 30～90 ℃ of temperature controls, after reaction finished, the alcohol organic solvent of adding and tetraethyl-ammonium halide crystal equal weight stirred and carried out crystallization in 2 hours again; Crystallization liquid is through filtering; And use the alcohol organic solvent washing leaching cake, remove the mother liquor that has impurity, the wet-milling that obtains-tetraethyl-ammonium tetrafluoroborate crystal bullion;
(4) the tetraethyl-ammonium tetrafluoroborate is refining:
In having the container of condensation reflux unit, add ethanolic soln, add the tetraethyl-Tetrafluoroboric acid ammonium salt wet-milling through the alcohol solvent washing simultaneously, intensification is boiled; After treating that solid all dissolves; Be cooled to room temperature while stirring, and at room temperature carry out crystallization, filtration, and wash with the ethanolic soln under the room temperature; Twice of repeated recrystallization process; The crystal that obtains carries out drying in 40～80 ℃ under vacuum condition, promptly get purified tetraethyl-ammonium tetrafluoroborate, wherein purified tetraethyl-ammonium tetrafluoroborate purity:>=99.5%; Water-content≤10ppm; Fe≤1.0ppm; Si≤3.0ppm; Na≤3.0ppm; K≤3.0ppm.
2. the preparation method of a kind of tetraethyl-ammonium tetrafluoroborate according to claim 1 is characterized in that: described tetraethyl-ammonium halide is etamon chloride, tetraethylammonium bromide or tetraethyl ammonium fluoride.
3. the preparation method of a kind of tetraethyl-ammonium tetrafluoroborate according to claim 1 is characterized in that: described alcohol organic solvent is ethanol, butanols or octanol.
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|---|---|---|---|
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|---|---|---|---|
| CN 200510086517 CN1762979B (en) | 2005-09-26 | 2005-09-26 | Tetraethyl tetrafluo ammonium fluoroborate preparation method |
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| CN1762979B true CN1762979B (en) | 2012-10-10 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101987824B (en) * | 2009-07-31 | 2013-07-03 | 岳阳凯门科技有限公司 | Preparation method of high-purity conductive salt for super capacitor |
| CN103159223A (en) * | 2011-12-14 | 2013-06-19 | 常熟市新华化工有限公司 | Method for producing fluoroboric acid |
| CN105819463A (en) * | 2016-04-27 | 2016-08-03 | 云南铁坦新材料科技股份有限公司 | Synthesis method of ferrous tetrafluoroborate |
| CN108586263B (en) * | 2018-05-23 | 2019-09-10 | 武汉大学 | A kind of simple and convenient process for preparing of tetraethyl ammonium tetrafluoroborate |
| CN110922333B (en) * | 2019-10-10 | 2022-11-25 | 浙江工业大学 | Method for preparing tetraethyl ammonium tetrafluoroborate by electrodialysis technology |
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Non-Patent Citations (2)
| Title |
|---|
| [作者] 安建国.由硼砂生产硼酸 [机构] 淄博市山东冶金工业学校.[刊名] 化学教学 8.1995,(8),第40-41页. * |
| 【作者】 安建国.由硼砂生产硼酸 【机构】 淄博市山东冶金工业学校.【刊名】 化学教学 8.1995,(8),第40-41页. |
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