CN102070651B - Method for preparing organic electrolyte oxaspiro quatemary ammonium salt of super capacitor - Google Patents
Method for preparing organic electrolyte oxaspiro quatemary ammonium salt of super capacitor Download PDFInfo
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- CN102070651B CN102070651B CN2010105947141A CN201010594714A CN102070651B CN 102070651 B CN102070651 B CN 102070651B CN 2010105947141 A CN2010105947141 A CN 2010105947141A CN 201010594714 A CN201010594714 A CN 201010594714A CN 102070651 B CN102070651 B CN 102070651B
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- 0 CC(CC1)CC[N+]11CO*CC1 Chemical compound CC(CC1)CC[N+]11CO*CC1 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N C1NCCOC1 Chemical compound C1NCCOC1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a method for preparing the organic electrolyte oxaspiro quatemary ammonium salt of a super capacitor, which is implemented by the following steps of: performing condensation reaction on cyclic diamine and oxa alkyl dihalide or oxa glycol disulfonate ester at a certain temperature to obtain a corresponding spiro quatemary ammonium salt; performing ion exchange on the spiro quatemary ammonium salt to obtain the corresponding spiro quatemary ammonium salt; and finally purifying the spiro quatemary ammonium salt to obtain a target product. The method ensures high selectivity, high target product yield and impurity content of the electrolyte of less than 5ppm, and can meet the requirements of the organic electrolyte of the super capacitor.
Description
Technical field
The present invention relates to a kind of compound method of ultracapacitor organic electrolyte, specifically a kind of method for preparing oxa-volution quaternary ammonium salt.
Technical background
Ultracapacitor (double layer capacitor) is a kind of high-energy power storage element that development in recent years is got up; Have high power density, high cycle life, advantage such as impulse electricity and environmentally safe fast; Be widely used in the backup power source of regulex, transmitter, computer memory, the clear energy sources systems such as starter gear, wind-power electricity generation and solar power system of Motor vehicles, thereby receive publicity.Quaternary amine can be used as the chemical cell of energy storages device or the supporting electrolyte of high-energy electrical condenser as the nonaqueous electrolyte of ultracapacitor.
Up to now, as the quaternary amine ion, comprise that aliphatics quaternary amine ion (CN:1503778) and aromatic series quaternary amine ion (CN:1361716 and CN:1524853) are by broad research and be applied to ultracapacitor (US:5086374; JP:2004-146592; Kobayashi et al, Synthetic Metals, 1987,18,619～624).Spiro quaternary ammonium salt is as one type of new compound; At patent documentation (US:2007-201185, WO:2005-022571, JP:2006-186052; JP2006-49447; JP:2005-294332, JP:2005-260030, etc.) in narrated the ultracapacitor organic electrolyte that contains such quaternary ammonium salt.This electrolytic solution can satisfy the requirement of the electrochemistry and the chemicalstability of ultracapacitor, and higher capacity is provided, and improves energy density and power density.
As spiro quaternary ammonium salt compound method, patent (US:2007-49750, JP2005-294332, US:3055171) and journal article (ARKIVOC, 2002 (iii), 63-70; Chem.Ber., 1924,57,187; Chem.Ber., 1916,49; Cyclic amine has been described 970) and the dihalo hydrocarbon carries out nucleophilic substitution reaction; Synthesize corresponding halogeno salt earlier, prepare the building-up process of spiro quaternary ammonium salt again through IX, this method yield is lower; And in the preparation process, used a large amount of organic solvents, therefore existed obviously not enough as large-scale method for producing.Especially in product, contain a large amount of halogen ions, be difficult to satisfy the requirement of electrochemical product.
Summary of the invention
The present invention is intended to overcome the weak point of prior art and provides a kind of easy and simple to handle, and selectivity is good, and yield is high, is suitable for the preparation method of the ultracapacitor organic electrolyte oxa-volution quaternary ammonium salt of large-scale production.
For achieving the above object, the present invention is achieved in that
A kind of preparation method of ultracapacitor organic electrolyte oxa-volution quaternary ammonium salt, can implement as follows successively:
(1) is reaction medium with water, under the effect of alkali,,, makes sulfonic acid oxa-volution quaternary ammonium salt through condensation reaction with the mixing solutions of cyclic diamine and oxa-saturated dihalide or oxa-glycol disulfonic acid ester;
(2) the said sulfonic acid oxa-of step (1) volution quaternary ammonium salt is obtained corresponding spiro quaternary ammonium salt through IX;
(3) the said spiro quaternary ammonium salt of step (2) is carried out purifying, promptly get title product ultracapacitor organic electrolyte oxa-volution quaternary ammonium salt.
The structure of oxa-volution quaternary ammonium salt is following:
Wherein: n, m, p=1,2,3; X=Ms
-, Ts
-, p-Ts
-, BF
4 -, PF
6 -, N (SO
2CF
3)
2 -
As a kind of preferred version, cyclic diamine according to the invention is Pyrrolidine, six hydrogen piperidines, six methylene imines or luxuriant and rich with fragrance quinoline.
Corresponding construction is following:
n＝1，2，3
As another kind of preferred version, oxa-saturated dihalide according to the invention is oxa-dichloro-alkane, oxa-dibrominated alkane or oxa-diiodo alkane.
The structure of oxa-saturated dihalide is following:
Wherein: m=1,2,3; P=1,2; X=Cl, Br, I.
Further, oxa-glycol disulfonic acid ester according to the invention is an oxa-1,4-butyleneglycol or oxa-1,5-pentanediol or oxa-1, corresponding methanesulfonate ester of 6-pinakon or benzene sulfonate.
The structure of oxa-glycol is following:
The structure of methanesulfonate ester is following:
The structure of benzene sulfonate is following:
Wherein: R is a hydrogen, alkyl, alkoxyl group, functional groups such as nitro.
Further, the used alkali of condensation reaction is sodium hydroxide in the step according to the invention (1), basic metal or alkaline earth metal hydroxidess such as Pottasium Hydroxide, yellow soda ash, basic metal or alkaline earth metal carbonates such as salt of wormwood.
In addition, the used alkali of condensation reaction is basic metal or alkaline earth metal carbonate in the step according to the invention (1).
Secondly, the reaction times of condensation reaction according to the invention is 0.1～24 hour, is preferably 2～16 hours.
Once more, the mol ratio of cyclic diamine according to the invention, oxa-saturated dihalide and alkali is followed successively by 1: 1～2: 1～4; Be preferably 1: 1～1.5: 1～2.
The mol ratio of said cyclic diamine, oxa-glycol disulfonic acid ester and alkali is followed successively by 1: 1～2: 1～4; Be preferably 1: 1～1.5: 1～2.
The required ionite of ion exchange reaction according to the invention is the basic metal of fluoroboric acid or the basic metal or the corresponding salt of earth alkali metal of corresponding salt of earth alkali metal or phosphofluoric acid.Definitely, ionite of the present invention is a fluoroboric acid, the corresponding salt of the basic metal of fluoroboric acid such as Sodium tetrafluoroborate, lithium-fluoroborate or earth alkali metal, phosphofluoric acid.
Purge process in the step according to the invention (3) is in alcohol, ketone, nitrile organic solvent, and adding activated carbon, molecular sieve carry out recrystallization.
The chemical principle that the present invention relates to is following:
The present invention is reaction medium with water, and cyclic amine and oxa-saturated dihalide or oxa-glycol sulphonate are the compound method of the oxa-volution quaternary ammonium salt of reaction raw materials.High yield, highly selective make oxa-volution quaternary ammonium salt; And obtain corresponding Tetrafluoroboric acid spiro quaternary ammonium salt, phosphofluoric acid spiro quaternary ammonium salt through carrying out IX with fluoroboric acid, phosphofluoric acid or its corresponding salt; Target product yield is high; Quality is good, can make the foreign matter content in the ionogen be less than 5ppm, can satisfy the requirement of ultracapacitor organic electrolyte.
The present invention is a reaction medium with water, has avoided the use of a large amount of organic solvents.This method selectivity is good, and target product yield is high, can make the foreign matter content in the ionogen be less than 5ppm, can satisfy the requirement of ultracapacitor organic electrolyte.
Embodiment
Following examples will be described further the present invention, but content of the present invention does not receive the restriction of this embodiment.
Embodiment 1
The preparation of 8-oxa--spiral shell [4,5] quaternary ammonium salt
1.1 the preparation of p-methyl benzenesulfonic acid 8-oxa--spiral shell [4,5] quaternary ammonium salt
In 2 liters of three mouthfuls of reaction flasks; Under agitation luxuriant and rich with fragrance quinoline (43.5 grams, 0.5 mole) is splashed into and contains 1,4-butyleneglycol two p-toluenesulfonic esters (238.8 grams; 0.6 mole) and salt of wormwood (103.5 grams; 0.75 in the deionized water (800 milliliters) mole), 25 ℃ were reacted 5 hours down, reflux is 8 hours then.Concentrating under reduced pressure will obtain resistates and add ethanol, filter.Filtrating concentrates, and obtains p-methyl benzenesulfonic acid 8-oxa--spiral shell [4,5] quaternary ammonium salt 133.1 grams through ethyl alcohol recrystallization, and yield is 85%.
Structural analysis is following:
The nuclear magnetic resonance spectroscopy result is:
1H NMR (400MHz, D
2O): δ=2.32-2.38 (m, 4H, 2xCH
2), 2.45 (s, 3H, CH
3), 3.51-3.56 (m, 4H, 2xCH
2), 3.68-3.70 (m, 4H, 2xCH
2), 4.08-4.10 (m, 4H, 2xCH
2), 7.55 (d, 2H), 7.84 (d, 2H).
1.2 the preparation of Tetrafluoroboric acid 8-oxa--spiral shell [4,5] quaternary ammonium salt
With above-mentioned p-methyl benzenesulfonic acid 8-oxa--spiral shell [4, the 5] quaternary ammonium salt that obtains (62.7 grams, 0.2 mole), sodium tetrafluoroborate (27.4 grams, 0.25 mole) and 300 milliliters of acetonitriles join in 500 milliliters of reaction flasks reflux 6 hours.Cooling is filtered, and filtrating concentrating obtains Tetrafluoroboric acid 8-oxa--spiral shell [4,5] quaternary ammonium salt 40.7 grams, and yield is 89%.
With Tetrafluoroboric acid 8-oxa--spiral shell [4,5] the quaternary ammonium salt bullion that obtains, with the Virahol dissolving, add activated carbon, reflux filter 23 0 minute filters, and the filtrating cooling obtains the white crystals of Tetrafluoroboric acid 8-oxa--spiral shell [4,5] quaternary ammonium salt.
Drying is after high pressure liquid chromatographic analysis purity is 99.9%.
Detect through chromatography of ions: Na:2.0ppm, K:4.5ppm, Fe:2.4ppm, Mg:3.0ppm, Ca:4.0ppm, halide-ions is not seen.
The nuclear magnetic resonance spectroscopy result is:
1H NMR (400MHz, D
2O): δ=2.35-2.39 (m, 4H, 2xCH
2), 3.54-3.57 (m, 4H, 2xCH
2), 3.66-3.69 (m, 4H, 2xCH
2), 4.11-4.14 (m, 4H, 2xCH
2).
Results of elemental analyses is: theoretical value (C
8H
16NO
4BF
4): C, 41.95; H, 7.04; N, 6.12% observed value: C, 42.13; H, 7.21; N, 6.35%.
Embodiment 2
The preparation of 8-oxa--spiral shell [4,5] quaternary ammonium salt
2.1 the preparation of methylsulphonic acid 8-oxa--spiral shell [4,5] quaternary ammonium salt
In 500 milliliters of three mouthfuls of reaction flasks; Under agitation luxuriant and rich with fragrance quinoline (43.5 grams, 0.5 mole) is splashed into and contains 1,4-butyleneglycol dimethyl methyl acid esters (128.4 grams; 0.6 mole) and yellow soda ash (91.5 grams; 0.75 in the deionized water (750 milliliters) mole), 25 ℃ were reacted 6 hours down, reflux is 8 hours then.Concentrating under reduced pressure will obtain resistates and add ethanol, filter.Filtrating concentrates, and behind ethyl alcohol recrystallization, obtains methylsulphonic acid 8-oxa--spiral shell [4,5] quaternary ammonium salt 103.1 grams, and yield is 87%.
Structural analysis is following:
The nuclear magnetic resonance spectroscopy result is:
1H NMR (400MHz, D
2O): δ=2.34-2.38 (m, 4H, 2xCH
2), 2.88 (s, 3H, CH
3), 3.53-3.57 (m, 4H, 2xCH
2), 3.66-3.69 (m, 4H, 2xCH
2), 4.02-4.05 (m, 4H, 2xCH
2).
2.2 the preparation of phosphofluoric acid 8-oxa--spiral shell [4,5] quaternary ammonium salt
With above-mentioned methylsulphonic acid 8-oxa--spiral shell [4, the 5] quaternary ammonium salt that obtains (47.5 grams, 0.2 mole), lithium hexafluoro phosphate (38 grams, 0.25 mole) and 150 milliliters of ethanol join in 500 milliliters of reaction flasks reflux 4 hours.Cooling is filtered, and obtains phosphofluoric acid 8-oxa--spiral shell [4,5] quaternary ammonium salt 52.2 grams, and yield is 91%.
With phosphofluoric acid 8-oxa--spiral shell [4,5] the quaternary ammonium salt bullion that obtains, obtain the white crystals of phosphofluoric acid 8-oxa--spiral shell [4,5] quaternary ammonium salt through the Virahol recrystallization.
Dry post analysis purity is 99.9%.
Detect through chromatography of ions: Na:4.5ppm, K:2.5ppm, Fe:2.6ppm, Mg:3.0ppm, Ca:4.0ppm, halide-ions is not seen.
Embodiment 3
The preparation of 8-oxa--spiral shell [4,5] quaternary ammonium salt
1.1 the preparation of p-methyl benzenesulfonic acid 8-oxa--spiral shell [4,5] quaternary ammonium salt
In 2 liters of three mouthfuls of reaction flasks, under agitation luxuriant and rich with fragrance quinoline (43.5 grams, 0.5 mole) is splashed into and contains 1; In the deionized water (700 milliliters) of 4-dibromobutane (129.6 grams, 0.6 mole) and salt of wormwood (96.6 grams, 0.75 mole); 25 ℃ were reacted 8 hours down, and reflux is 5 hours then.Concentrating under reduced pressure will obtain resistates and add ethanol, filter.Obtain 8-oxa--spiral shell [4,5] quaternary ammonium salt bromo-derivative 84.4 grams after filtrating concentrates, yield is 76%.
1.2 the preparation of Tetrafluoroboric acid 8-oxa--spiral shell [4,5] quaternary ammonium salt
With above-mentioned 8-oxa--spiral shell [4,5] the quaternary ammonium salt bromo-derivative that makes (44.4 grams, 0.2 mole), sodium tetrafluoroborate (27.4 grams, 0.25 mole) and 200 milliliters of acetone join in 500 milliliters of reaction flasks reflux 7 hours.Cooling is filtered, and filtrating concentrating obtains Tetrafluoroboric acid 8-oxa--spiral shell [4,5] quaternary ammonium salt 38.9 grams, and yield is 89%.
With Tetrafluoroboric acid 8-oxa--spiral shell [4,5] the quaternary ammonium salt bullion that obtains,, obtain the white crystals of Tetrafluoroboric acid 8-oxa--spiral shell [4,5] quaternary ammonium salt with the Virahol dissolving.
Drying is after high pressure liquid chromatographic analysis purity is 99.9%.
Detect through chromatography of ions: Na＜2.0ppm, K＜2.0ppm, Fe＜2.0ppm, Mg＜3.0ppm, Ca＜3.0ppm, Br
-: 4.0ppm.
Embodiment 4
The preparation of 9-oxa--spiral shell [5,5] quaternary ammonium salt
3.1 the preparation of p-methyl benzenesulfonic acid 9-oxa--spiral shell [5,5] quaternary ammonium salt
In 2 liters of three mouthfuls of reaction flasks, under agitation luxuriant and rich with fragrance quinoline (43.5 grams, 0.5 mole) is splashed into and contains 1; 5-pentanediol dimethyl methyl acid esters (136.8 grams; 0.6 mole) with the deionized water (800 milliliters, volume ratio 8: 2) of yellow soda ash (91.5 restrain, 0.75 mole) in; 25 ℃ were reacted 4 hours down, and reflux is 8 hours then.Concentrating under reduced pressure will obtain resistates and add ethanol, filter.Filtrating concentrates, and behind ethyl alcohol recrystallization, obtains p-methyl benzenesulfonic acid 9-oxa--spiral shell [5,5] quaternary ammonium salt 105.4 grams, and yield is 84%.
Structural analysis is following:
The nuclear magnetic resonance spectroscopy result is:
1H NMR (400MHz, D
2O): δ=1.75-1.79 (m, 2H), 2.30-2.35 (m, 4H, 2xCH
2), 2.90 (s, 3H, CH
3), 3.57-3.60 (m, 4H, 2xCH
2), 3.67-3.70 (m, 4H, 2xCH
2), 4.05-4.08 (m, 4H, 2xCH
2).
3.2 the preparation of phosphofluoric acid 9-oxa--spiral shell [5,5] quaternary ammonium salt
With above-mentioned obtain to methylsulphonic acid 9-oxa--spiral shell [5,5] quaternary ammonium salt (37.7 gram, 0.15 mole), lithium hexafluoro phosphate (22.8 grams, 0.15 mole) and 150 milliliters of ethanol join in 500 milliliters of reaction flasks reflux 4 hours.Cooling is filtered, and obtains phosphofluoric acid 9-oxa--spiral shell [5,5] quaternary ammonium salt 40.6 grams, and yield is 90%.
With phosphofluoric acid 9-oxa--spiral shell [5,5] the quaternary ammonium salt bullion that obtains, obtain the white crystals of phosphofluoric acid 9-oxa--spiral shell [5,5] quaternary ammonium salt through the Virahol recrystallization.
Dry post analysis purity is 99.9%.
Detect through chromatography of ions: Na:4.0ppm, K:3.6ppm, Fe:2.2ppm, Mg:3.0ppm, Ca:4.0ppm, halide-ions is not seen.
Embodiment 5
The preparation of 7-oxa--spiral shell [4,4] quaternary ammonium salt
4.1 the preparation of methylsulphonic acid 7-oxa--spiral shell [4,4] quaternary ammonium salt
In 2 liters of three mouthfuls of reaction flasks; Under agitation pyrroles's (42.6 grams, 0.6 mole) is splashed into and contains 2-oxa--1,4-butyleneglycol dimethyl methyl acid esters (129.6 grams; 0.6 mole) and yellow soda ash (91.5 grams; 0.75 in the deionized water (800 milliliters) mole), 25 ℃ were reacted 5 hours down, reflux is 10 hours then.Concentrating under reduced pressure will obtain resistates and add ethanol, filter.Filtrating concentrates, and behind ethyl alcohol recrystallization, obtains methylsulphonic acid 7-oxa--spiral shell [4,5] quaternary ammonium salt 133.8 grams, and yield is 86%.
Structural analysis is following:
The nuclear magnetic resonance spectroscopy result is:
1H NMR (400MHz, D
2O): δ=2.38-2.40 (m, 4H, 2xCH
2), 2.90 (s, 3H, CH
3), 3.61-3.63 (m, 2H, CH
2), 3.70-3.73 (m, 4H, 2xCH
2), 4.05-4.08 (m, 4H, 2xCH
2), 4.24-4.27 (m, 2H, CH
2).
4.2 the preparation of Tetrafluoroboric acid 7-oxa--spiral shell [4,4] quaternary ammonium salt
With above-mentioned methylsulphonic acid 7-oxa--spiral shell [4, the 4] quaternary ammonium salt that obtains (22.3 grams, 0.1 mole), LiBF4 (9.4 grams, 0.1 mole) and 100 ml methanol join in 250 milliliters of reaction flasks reflux 3 hours.Cooling is filtered, and obtains Tetrafluoroboric acid 7-oxa--spiral shell [4,4] quaternary ammonium salt 19.8 grams, and yield is 92%.
With Tetrafluoroboric acid 7-oxa--spiral shell [4,4] the quaternary ammonium salt bullion that obtains, obtain the white crystals of Tetrafluoroboric acid 7-oxa--spiral shell [4,4] quaternary ammonium salt through twice ethyl alcohol recrystallization.
Dry post analysis purity is 99.9%.
Detect through chromatography of ions: Na:3.5ppm, K:3.0ppm, Fe:2.5ppm, Mg:3.5ppm, Ca:4.0ppm, halide-ions is not seen.
Embodiment 6
The preparation of 8-oxa--spiral shell [4,5] quaternary ammonium salt
5.1 the preparation of methylsulphonic acid 7-oxa--spiral shell [4,5] quaternary ammonium salt
In 2 liters of three mouthfuls of reaction flasks; Under agitation six hydrogen piperidines (51.0 grams, 0.6 mole) are splashed into and contain 2-oxa--1,4-butyleneglycol dimethyl methyl acid esters (129.6 grams; 0.6 mole) and yellow soda ash (91.5 grams; 0.75 in the deionized water (700 milliliters) mole), 25 ℃ were reacted 4 hours down, reflux is 10 hours then.Concentrating under reduced pressure will obtain resistates and add ethanol, filter.Filtrating concentrates, and behind ethyl alcohol recrystallization, obtains methylsulphonic acid 8-oxa--spiral shell [4,5] quaternary ammonium salt 128 grams, and yield is 90%.
Structural analysis is following:
The nuclear magnetic resonance spectroscopy result is:
1H NMR (400MHz, D
2O): δ=1.72-1.74 (m, 2H), 2.33-2.36 (m, 4H, 2xCH
2), 2.92 (s, 3H, CH
3), 3.60-3.62 (m, 2H, CH
2), 3.65-3.68 (m, 4H, 2xCH
2), 4.07-4.10 (m, 4H, 2xCH
2), 4.21-4.25 (m, 2H, CH
2).
5.2 the preparation of Tetrafluoroboric acid 8-oxa--spiral shell [4,5] quaternary ammonium salt
With above-mentioned methylsulphonic acid 8-oxa--spiral shell [4, the 5] quaternary ammonium salt that obtains (23.7 grams, 0.1 mole), LiBF4 (9.4 grams, 0.1 mole) and 100 ml methanol join in 250 milliliters of reaction flasks reflux 3 hours.Cooling is filtered, and obtains Tetrafluoroboric acid 8-oxa--spiral shell [4,5] quaternary ammonium salt 21.5 grams, and yield is 94%.
With Tetrafluoroboric acid 8-oxa--spiral shell [4,5] the quaternary ammonium salt bullion that obtains, obtain the white crystals of Tetrafluoroboric acid 8-oxa--spiral shell [4,5] quaternary ammonium salt through twice ethyl alcohol recrystallization.
Dry post analysis purity is 99.9%.
Detect through chromatography of ions: Na:4.6ppm, K:3.4ppm, Fe:2.6ppm, Mg:3.0ppm, Ca:4.5ppm, halide-ions is not seen.
The above is merely the preferred embodiments of the present invention, is not limited to the present invention, and for a person skilled in the art, the present invention can have various changes and variation.All within spirit of the present invention and principle, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (1)
1. the preparation method of a ultracapacitor organic electrolyte oxa-volution quaternary ammonium salt is characterized in that, implements successively as follows:
(1) preparation of methylsulphonic acid 8-oxa--spiral shell [4,5] quaternary ammonium salt
In 2 liters of three mouthfuls of reaction flasks; Under agitation with 51.0 grams; Contain 129.6 grams 0.6 six hydrogen piperidines of mole splash into, 0.6 mole 2-oxa--1 is in 700 ml deionized water of the yellow soda ash of 4-butyleneglycol dimethyl methyl acid esters and 91.5 grams; 25 ℃ were reacted 4 hours down, and reflux is 10 hours then; Concentrating under reduced pressure will obtain resistates and add ethanol, filter; Filtrating concentrates, and behind ethyl alcohol recrystallization, obtains methylsulphonic acid 8-oxa--spiral shell [4,5] quaternary ammonium salt 128 grams, and yield is 90%;
(2) preparation of Tetrafluoroboric acid 8-oxa--spiral shell [4,5] quaternary ammonium salt
With above-mentioned 23.7 grams that obtain, methylsulphonic acid 8-oxa--spiral shell [4,5] quaternary ammonium salt of 0.1 mole; 9.4 gram, 0.1 mole LiBF4 and 100 ml methanol join in 250 milliliters of reaction flasks, reflux 3 hours; Cooling is filtered, and obtains the Tetrafluoroboric acid 8-oxa--spiral shell [4 of 21.5 grams; 5] quaternary ammonium salt, yield are 94%;
With Tetrafluoroboric acid 8-oxa--spiral shell [4,5] the quaternary ammonium salt bullion that obtains, obtain the white crystals of Tetrafluoroboric acid 8-oxa--spiral shell [4,5] quaternary ammonium salt through twice ethyl alcohol recrystallization; Dry post analysis purity is 99.9%.
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| CN102942581B (en) * | 2012-11-21 | 2015-11-18 | 渤海大学 | Ultracapacitor spiro quaternary ammonium salt and preparation method thereof |
| CN104059076B (en) * | 2014-04-29 | 2016-11-02 | 宁波中车新能源科技有限公司 | A kind of preparation method of capacitor electrolyte spiro quaternary ammonium salt |
| CN106463277A (en) * | 2014-05-21 | 2017-02-22 | 大金工业株式会社 | Electrolyte and electrochemical device |
| CN104650095B (en) * | 2015-02-16 | 2017-06-06 | 衢州康鹏化学有限公司 | A kind of preparation method of tetrafluoro boric acid spiro quaternary ammonium salt |
| KR101830636B1 (en) * | 2017-01-04 | 2018-02-21 | 삼화페인트공업주식회사 | Method For Preparing spiro quarternary ammonium salt |
| CN108470643A (en) * | 2018-03-29 | 2018-08-31 | 渤海大学 | A kind of preparation method of adamantane amine electrolytic solution for super capacitor |
| CN113045512B (en) * | 2021-03-17 | 2023-03-21 | 重庆中科超容科技有限公司 | One-step preparation method of N, N-dimethylpyrrolidinium salt |
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