CN108314623A - A kind of preparation method of adamantane amine quaternary ammonium salt suitable for electrolytic solution for super capacitor - Google Patents
A kind of preparation method of adamantane amine quaternary ammonium salt suitable for electrolytic solution for super capacitor Download PDFInfo
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- 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
- C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
- C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
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- C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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- H—ELECTRICITY
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Abstract
The preparation method of a kind of adamantane amine quaternary ammonium salt suitable for electrolytic solution for super capacitor, by 1 amantadine and C1~C8Alkylating reagent is placed in reaction dissolvent, return stirring reaction, and temperature is down to room temperature after the completion of reaction, and separation obtains intermediate；Gained intermediate is added in reaction dissolvent, and C is added1~C8Alkylating reagent and inorganic base, the intermediate and enter C1~C8Alkylating reagent, inorganic base molar ratio be 1:1.2:1.2, under the conditions of 20 DEG C~120 DEG C, return stirring reaction cools down after the completion of reaction, suitable acid is added, back flow reaction obtains adamantane amine quaternary ammonium salt crude product after 12 hours；Three times with solvent recrystallization, amantadine quaternary ammonium salt is obtained.Advantage is：Simple for process, easy to operate, the electrochemical window mouth width of product, solubility is preferable, can be used as electrolytic solution for super capacitor.
Description
Technical field
The invention belongs to the preparation field that ultracapacitor is electrolysed matter, more particularly to a kind of ultracapacitor that is suitable for is electrolysed
The preparation method of the adamantane amine quaternary ammonium salt of liquid.
Background technology
The used organic system electrolyte of organic system ultracapacitor is mainly quaternary ammonium salt organic electrolyte, the gold being prepared
Rigid alkanamine class quaternary ammonium salt has electrochemical window more broader than the tetrafluoro boric acid spiro quaternary ammonium salt of traditional commerce change, and solubility is compared with four
Ethyl ammonium tetrafluoroborate is more preferable (tetraethyl ammonium tetrafluoroborate concentration in PC is up to 1mol/L), can further increase
The operating voltage of ultracapacitor.
The method that tradition prepares quaternary ammonium salt is typically directly to be alkylated to react with alkyl halide using amine.Although this method
Have the advantages that easy to operate.But a large amount of alkyl halide must be used using this method, it just can guarantee that product is quaternary ammonium salt.
Cause the waste of alkyl halide.In addition, three identical alkyl substitutions may only be made using primary amine as raw material by this method
Quaternary ammonium salt, different alkyl-substituted quaternary ammonium salts can not be prepared, the solubility property of product is undesirable.
Invention content
The technical problem to be solved in the present invention is to provide a kind of adamantane amine seasons suitable for electrolytic solution for super capacitor
The preparation method of ammonium salt, simple for process, easy to operate, the electrochemical window mouth width of product, solubility is preferable, can be used as super electricity
Container electrolyte uses.
A kind of preparation method of adamantane amine quaternary ammonium salt suitable for electrolytic solution for super capacitor, includes the following steps:
(1) by 1- amantadines and C1~C8Alkylating reagent is according to molar ratio 1:10 are placed in reaction dissolvent, 20 DEG C~120
Under the conditions of DEG C, return stirring reaction, temperature is down to room temperature after the completion of reaction, and separation obtains intermediate；
(2) gained intermediate in step (1) is added in reaction dissolvent, and C is added1~C8Alkylating reagent and inorganic base,
The intermediate and enter C1~C8Alkylating reagent, inorganic base molar ratio be 1:1.2:1.2, under the conditions of 20 DEG C~120 DEG C,
Return stirring reacts, and cools down after the completion of reaction, suitable acid is added, pH to 5, back flow reaction is adjusted to obtain amantadine after 12 hours
Class quaternary ammonium salt crude product；
(3) by the product in step (2) with solvent recrystallization three times, obtain amantadine quaternary ammonium salt, structural formula is
Wherein, R1、R2、R3For (C1~C8) in one or more combinations, A be formic acid, acetic acid, propionic acid, oxalic acid, phosphoric acid, salt
Acid, hydrobromic acid, sulfuric acid, nitric acid, perchloric acid, thiocyanic acid, cdicynanmide, bis-trifluoromethylsulfoandimide, double fluorine sulfimides, trifluoro second
One kind in sour, double fluorine oxalic acid phosphoric acid, tetrafluoro boric acid, hexafluorophosphoric acid acid group.
Further, in step (1) and step (2), the alkylating reagent be bromomethane, bromic ether, bromo just
Propane, bromo propane, bromination of n-butane, isobutane bromide, bromo pentane, bromo isopentane, bromo neopentane, bromo ring
Pentane, bromo n-hexane, bromocyclohexane, bromo heptane, bromo cycloheptane, n-octane bromide, dimethyl suflfate, sulfuric acid two
Ethyl ester, diazomethane, triethyl orthoformate, methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, the tert-butyl alcohol, positive penta
At least one of alcohol, n-hexyl alcohol, formic acid, formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde.
Further, in step (1), the reaction dissolvent is deionized water, methanol, ethyl alcohol, normal propyl alcohol, isopropanol, just
Butanol, isobutanol, the tert-butyl alcohol, ether, tetrahydrofuran, N,N-dimethylformamide, N, N- diethyl acetamides, acetone, benzene, first
Benzene, ethylbenzene, petroleum ether, pentane, pentamethylene, n-hexane, hexamethylene, dichloromethane, chloroform, carbon tetrachloride, curing
In carbon, -3 methyl imidazolium tetrafluoroborate ionic liquid of 1- ethyls, 1,2- methyl -3- ethyl imidazol(e) tetrafluoroborate ion liquids
At least one.
Further, in step (2), the inorganic base is sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, carbonic acid
One kind in calcium, potassium carbonate, ammonium carbonate, lithium carbonate, sodium bicarbonate, ammonium hydrogen carbonate.
Further, the acid is formic acid, acetic acid, propionic acid, oxalic acid, phosphoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, high chlorine
Acid, thiocyanic acid, cdicynanmide, bis-trifluoromethylsulfoandimide, double fluorine sulfimides, trifluoroacetic acid, double fluorine oxalic acid phosphoric acid, tetrafluoro boron
One kind in acid, hexafluorophosphoric acid.
Further, in step (3), the solvent be deionized water, methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol,
Isobutanol, the tert-butyl alcohol, ether, tetrahydrofuran, N,N-dimethylformamide, N, N- diethyl acetamides, acetone, benzene, toluene, second
In benzene, petroleum ether, pentane, pentamethylene, n-hexane, hexamethylene, dichloromethane, chloroform, carbon tetrachloride, carbon disulfide
It is at least one.
Further, step (1) and step (2) back flow reaction temperature are 80 DEG C~100 DEG C.
Further, the reaction dissolvent in step (1) and step (2) is isopropanol, the C of step (1)1~C8Alkylation examination
Agent is molar ratio 1:1 formic acid and formaldehyde, back flow reaction temperature are 80 DEG C~90 DEG C, and step (2) back flow reaction temperature is 90 DEG C
~100 DEG C.
Further, the organic solvent used in step (1) and step (2) is isopropanol, can obtain higher yields
Target product.
Further, the alkylating reagent described in step (2) is dithyl sulfate, and the inorganic base is barium hydroxide, institute
It is tetrafluoro boric acid to state acid.
Further, the organic solvent used in step (1) and step (2) is isopropanol.
Beneficial effects of the present invention：
It is reacted with amantadine with chemical reagent simple and easy to get and the novel adamantine alkane with different substituent group has been prepared
Amine quaternary ammonium salt.Since quaternary ammonium salt has different substituent groups, the symmetry of its cation is destroyed, therefore in organic solvent
In solubility it is bigger than the tetraethyl ammonium tetrafluoroborate with symmetrical structure, the amantadine quaternary ammonium salt of preparation is in PC
Concentration maximum in (propene carbonate) is up to 2mol/L.
Further, since the rigid structure in amantadine parent is remained in quaternary ammonium salt, so that the electrification of cation
Stability is learned to be promoted.The electrolyte prepared with the quaternary ammonium salt obtained in the present invention by propene carbonate has than conventional quaternary ammonium
The broader electrochemical window of salt.
Electrochemical window is the key factor for determining ultracapacitor operating voltage, therefore, has broader electrochemical window
The quaternary ammonium salt of mouth can improve the operating voltage of ultracapacitor simultaneously.And then energy density for promoting ultracapacitor etc. is important
Performance.
Description of the drawings
Fig. 1 is the N of (corresponding embodiment 1) of the invention, the infrared light of N- dimethyl-N-ethyl amantadine tetrafluoroborates
Spectrogram；
Fig. 2 is the N of (corresponding embodiment 1) of the invention, the hydrogen nuclear magnetic resonance of N- dimethyl-N-ethyl amantadine tetrafluoroborates
Spectrogram；
Fig. 3 is the N, N- dimethyl-N-ethyl amantadine tetrafluoroborate 1.5mol/L PC of (corresponding embodiment 1) of the invention
Three electrode cycle voltammograms of electrolyte；
Fig. 4 is with N, the super capacitor of N- dimethyl-N-ethyl amantadine tetrafluoroborate 1.5mol/L PC electrolyte assembling
The cyclic voltammetry curve of device；
Fig. 5 is with N, the super capacitor of N- dimethyl-N-ethyl amantadine tetrafluoroborate 1.5mol/L PC electrolyte assembling
The impedance spectrum curve of device；
Fig. 6 is with N, the super capacitor of N- dimethyl-N-ethyl amantadine tetrafluoroborate 1.5mol/L PC electrolyte assembling
The constant current charge-discharge curve of device.
Specific implementation mode
The higher adamantane of purity is prepared using 1- amantadines as raw material, in the method simply to flow back in inventor
Amine quaternary ammonium salt provides one kind and simply preparing adamantane amine quaternary ammonium salt method.The present invention is completed on this basis.
Embodiment 1
The preparation of 1.1N, N- dimethyladamantane amine intermediate
In 500mL there-necked flasks, 200mL isopropanols, 0.2mol 1- amantadines, 1mol formic acid, 1mol are sequentially added under stirring
Formaldehyde；80 DEG C of return stirrings are heated to react 48 hours；PH value is adjusted to 12 with sodium hydrate aqueous solution；150mL n-hexanes point
Supernatant liquid is extracted three times；Light yellow transparent liquid N, N- dimethyladamantane amine intermediate is obtained after vacuum drying
0.184mol；1H NMR (300MHz, CDCl3)：δ=1.35~1.46 (m, 12H), 1.85 (s, 3H), 2.04 (s, 6H)；
The preparation of 1.2N, N-dimethyl-N-ethyl adamantane ammonium tetrafluoroborate
In 500mL there-necked flasks, 100mL absolute ethyl alcohols are sequentially added under stirring, 0.1mol N, N- dimethyladamantane amine,
After the completion of reaction, 0.12mol hydrogen-oxygens are added in 0.12mol dithyl sulfates insulation reaction 48 hours at a temperature of 70 DEG C
Change barium dust, the reaction was continued 24 hours at identical temperature；Reaction finish, be cooled to room temperature, with 50% tetrafluoro boric acid adjust pH values to
5；It is separated by filtration, is extracted with 150mL dichloromethane；Filtrate decompression concentrates, and 200mL absolute ethyl alcohols are added and are recrystallized；Vacuum
N, N- dimethyl-N-ethyl amantadine tetrafluoroborates 0.077mol are obtained after drying；It is dense in PC (propene carbonate)
Degree is maximum up to 2mol/L；Fig. 1 is the infrared spectrogram of the quaternary ammonium salt of (corresponding embodiment 1) of the invention；Fig. 2 is that the present invention is (right
Answer embodiment 1) hydrogen nuclear magnetic resonance spectrogram；It can determine that the substance synthesized is target product by Fig. 1 and Fig. 2.Fusing point：246-
248 DEG C,1H NMR (300MHz, DMSO-d6) δ=1.03~1.06 (t, 3H),
1.44~1.56 (dd, 6H), 1.67 (s, 6H), 1.98 (s, 3H), 2.83~2.88 (m, 2H), 4.63 (s, 6H).
Embodiment 2
The preparation of 1.1N, N- dimethyladamantane amine intermediate
In 500mL there-necked flasks, 200mL isopropanols, 0.2mol 1- amantadines, 1mol formic acid, 1mol are sequentially added under stirring
Formaldehyde；90 DEG C of return stirrings are heated to react 48 hours；PH value is adjusted to 12 with sodium hydrate aqueous solution；150mL n-hexanes point
Supernatant liquid is extracted three times；Light yellow transparent liquid N, N- dimethyladamantane amine intermediate is obtained after vacuum drying
0.184mol；
The preparation of 1.2N, N-dimethyl-N-ethyl adamantane ammonium tetrafluoroborate
In 500mL there-necked flasks, 100mL absolute ethyl alcohols are sequentially added under stirring, 0.1mol N, N- dimethyladamantane amine,
After the completion of reaction, 0.12mol barium hydroxides are added in 0.12mol dithyl sulfates insulation reaction 48 hours at a temperature of 80 DEG C
Powder, the reaction was continued 24 hours at identical temperature；Reaction is finished, and is cooled to room temperature, and pH value is adjusted to 5 with 50% tetrafluoro boric acid；It crosses
Filter separation, filtrate remove solvent and are filtered to remove insoluble matter with 150mL dichloromethane dissolved solids；Filtrate decompression concentrates, and is added
200mL absolute ethyl alcohols are recrystallized；Filtering, obtains N, N- dimethyl-N-ethyl amantadine tetrafluoro boric acids after vacuum drying
Salt 0.085mol.
Embodiment 3
The preparation of 1.1N, N- dimethyladamantane amine intermediate
In 500mL there-necked flasks, 200mL isopropanols, 0.2mol 1- amantadines, 1mol formic acid, 1mol are sequentially added under stirring
Formaldehyde；100 DEG C of return stirrings are heated to react 48 hours；PH value is adjusted to 12 with sodium hydrate aqueous solution；150mL n-hexanes point
Supernatant liquid is extracted three times；Light yellow transparent liquid N, N- dimethyladamantane amine intermediate is obtained after vacuum drying
0.180mol；
The preparation of 1.2N, N-dimethyl-N-ethyl adamantane ammonium tetrafluoroborate
In 500mL there-necked flasks, 100mL absolute ethyl alcohols are sequentially added under stirring, 0.1mol N, N- dimethyladamantane amine,
After the completion of reaction, 0.12mol barium hydroxides are added in 0.12mol dithyl sulfates insulation reaction 48 hours at a temperature of 90 DEG C
Powder, the reaction was continued 24 hours at identical temperature；Reaction is finished, and is cooled to room temperature, and pH value is adjusted to 5 with 50% tetrafluoro boric acid；It crosses
Filter separation, filtrate remove solvent and are filtered to remove insoluble matter with 150mL dichloromethane dissolved solids；Filtrate decompression concentrates, and is added
200mL absolute ethyl alcohols are recrystallized；Filtering, obtains N, N- dimethyl-N-ethyl amantadine tetrafluoro boric acids after vacuum drying
Salt 0.084mol.
Embodiment 4
The preparation of 1.1N, N- dimethyladamantane amine intermediate
In 500mL there-necked flasks, 200mL deionized waters, 0.2mol 1- amantadines, 1mol formic acid, 1mol are sequentially added under stirring
Formaldehyde；80 DEG C of return stirrings are heated to react 48 hours；PH value is adjusted to 12 with sodium hydrate aqueous solution；150mL n-hexanes point
Supernatant liquid is extracted three times；Light yellow transparent liquid N, N- dimethyladamantane amine intermediate is obtained after vacuum drying
0.136mol；
The preparation of 1.2N, N-dimethyl-N-ethyl adamantane ammonium tetrafluoroborate
In 500mL there-necked flasks, 100mL isopropanols are sequentially added under stirring, 0.1mol N, N- dimethyladamantane amine,
After the completion of reaction, 0.12mol barium hydroxides are added in 0.12mol dithyl sulfates insulation reaction 48 hours at a temperature of 70 DEG C
Powder, the reaction was continued 24 hours at identical temperature；Reaction is finished, and is cooled to room temperature, and pH value is adjusted to 5 with 50% tetrafluoro boric acid；It crosses
Filter separation, filtrate remove solvent and are filtered to remove insoluble matter with 150mL dichloromethane dissolved solids；Filtrate decompression concentrates, and is added
200mL absolute ethyl alcohols are recrystallized；Filtering, obtains N, N- dimethyl-N-ethyl amantadine tetrafluoro boric acids after vacuum drying
Salt 0.080mol.
Embodiment 5
The preparation of 1.1N, N- dimethyladamantane amine intermediate
In 500mL there-necked flasks, 200mL deionized waters, 0.2mol 1- amantadines, 1mol formic acid, 1mol are sequentially added under stirring
Formaldehyde；90 DEG C of return stirrings are heated to react 48 hours；PH value is adjusted to 12 with sodium hydrate aqueous solution；150mL n-hexanes point
Supernatant liquid is extracted three times；Light yellow transparent liquid N, N- dimethyladamantane amine intermediate is obtained after vacuum drying
0.146mol；
The preparation of 1.2N, N-dimethyl-N-ethyl adamantane ammonium tetrafluoroborate
In 500mL there-necked flasks, 100mL isopropanols are sequentially added under stirring, 0.1mol N, N- dimethyladamantane amine,
After the completion of reaction, 0.12mol barium hydroxides are added in 0.12mol dithyl sulfates insulation reaction 48 hours at a temperature of 80 DEG C
Powder, the reaction was continued 24 hours at identical temperature；Reaction is finished, and is cooled to room temperature, and pH value is adjusted to 5 with 50% tetrafluoro boric acid；It crosses
Filter separation, filtrate remove solvent and are filtered to remove insoluble matter with 150mL dichloromethane dissolved solids；Filtrate decompression concentrates, and is added
200mL absolute ethyl alcohols are recrystallized；Filtering, obtains N, N- dimethyl-N-ethyl amantadine tetrafluoro boric acids after vacuum drying
Salt 0.086mol.
Embodiment 6
The preparation of 1.1N, N- dimethyladamantane amine intermediate
In 500mL there-necked flasks, 200mL deionized waters, 0.2mol 1- amantadines, 1mol formic acid, 1mol are sequentially added under stirring
Formaldehyde；100 DEG C of return stirrings are heated to react 48 hours；PH value is adjusted to 12 with sodium hydrate aqueous solution；150mL n-hexanes point
Supernatant liquid is extracted three times；Light yellow transparent liquid N, N- dimethyladamantane amine intermediate is obtained after vacuum drying
0.140mol；
The preparation of 1.2N, N-dimethyl-N-ethyl adamantane ammonium tetrafluoroborate
In 500mL there-necked flasks, 100mL isopropanols are sequentially added under stirring, 0.1mol N, N- dimethyladamantane amine,
After the completion of reaction, 0.12mol barium hydroxides are added in 0.12mol dithyl sulfates insulation reaction 48 hours at a temperature of 90 DEG C
Powder, the reaction was continued 24 hours at identical temperature；Reaction is finished, and is cooled to room temperature, and pH value is adjusted to 5 with 50% tetrafluoro boric acid；It crosses
Filter separation, filtrate remove solvent and are filtered to remove insoluble matter with 150mL dichloromethane dissolved solids；Filtrate decompression concentrates, and is added
200mL absolute ethyl alcohols are recrystallized；Filtering, obtains N, N- dimethyl-N-ethyl amantadine tetrafluoro boric acids after vacuum drying
Salt 0.083mol.
The yield table of the intermediate product and final products of 1 1- of embodiment of the present invention embodiments 6 of table
The assembling super capacitor prepared with 1N of the embodiment of the present invention, N- dimethyl-N-ethyl adamantane ammonium tetrafluoroborates
Device performance test：
(1) preparation of electrolyte
Under the conditions of drying nitrogen protection, N, N- dimethyl-N-ethyls adamantane ammonium tetrafluoroborate is taken to be prepared with propene carbonate
At the solution of a concentration of 1.5mol/L, electrolyte water content is less than 0.01%；
(2) assembling and performance test of ultracapacitor
Under the conditions of drying nitrogen protection, with 1.5mol/L electrolyte and activated carbon base substrate (activated carbon：Carbon black：Polytetrafluoroethylene (PTFE)
=8:1:1 mass ratio) and polypropylene diaphragm be assembled into button-shaped ultracapacitor, and test performance.Individually pole piece quality is
50mg, dropping liquid amount (dosage of electrolyte in single ultracapacitor) are 0.4g.
The present invention answers the N of embodiment 1, N- dimethyl-N-ethyl amantadine tetrafluoroborate 1.5mol/L PC electrolyte
Three electrode cycle voltammograms it is as shown in Figure 3.The electrochemical window of the quaternary ammonium salt can reach 5.5V ratios as seen from Figure 3
The electrochemical window of 1.5mol/L spiro quaternary ammoniums salt+PC electrolyte reported in the literature wants wide.With N, N- dimethyl-N -s
The cyclic voltammetry curve of the ultracapacitor of ethyl amantadine tetrafluoroborate 1.5mol/L PC electrolyte assembling is as schemed
Shown in 4.The ultracapacitor being assembled into as can be seen from Figure 4 using the electrolyte in the present invention is had in 0-3.0V voltage ranges
There is good cycle characteristics.With N, the assembling of N- dimethyl-N-ethyl amantadine tetrafluoroborate 1.5mol/L PC electrolyte
The impedance spectrum curve of ultracapacitor is as shown in Figure 5.By Fig. 5 it is recognised that the device shows typical ultracapacitor row
To illustrate that the electrolyte in the present invention is suitable for ultracapacitor field.With N, N- dimethyl-N-ethyl amantadine tetrafluoro boron
The constant current charge-discharge curve of the ultracapacitor of hydrochlorate 1.5mol/L PC electrolyte assembling is as shown in Figure 6.As seen from Figure 6
Curve shows the charging and discharging state of the ideal hyper capacitor of approximate isosceles triangle, voltage drop very little.Illustrate the electrolyte
Suitable for ultracapacitor field.
Chemical property parameter of 2 electrolyte of table in charge and discharge
It these are only specific embodiments of the present invention, be not intended to restrict the invention, for those skilled in the art
For member, the invention may be variously modified and varied.Any modification made by all within the spirits and principles of the present invention,
Equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of adamantane amine quaternary ammonium salt suitable for electrolytic solution for super capacitor, it is characterized in that：
Include the following steps:
(1) by appropriate 1- amantadines and C1~C8Alkylating reagent is according to molar ratio 1:10 are placed in reaction dissolvent, 20 DEG C~
Under the conditions of 120 DEG C, return stirring reaction, temperature is down to room temperature after the completion of reaction, and separation obtains intermediate；
(2) gained intermediate in step (1) is added in reaction dissolvent, and C is added1~C8Alkylating reagent and inorganic base, institute
It states intermediate and enters C1~C8Alkylating reagent, inorganic base molar ratio be 1:1.2:1.2, under the conditions of 20 DEG C~120 DEG C, return
Stream is stirred to react, and is cooled down after the completion of reaction, suitable acid is added, pH to 5, back flow reaction is adjusted to obtain product adamantane after 12 hours
Amine quaternary ammonium salt；
(3) by the product in step (2) with solvent recrystallization three times, obtain amantadine quaternary ammonium salt.
2. the preparation method of the adamantane amine quaternary ammonium salt according to claim 1 suitable for electrolytic solution for super capacitor,
It is characterized in that：
In step (1) and step (2), the alkylating reagent is bromomethane, bromic ether, n-propyl bromide, bromo isopropyl
Alkane, bromination of n-butane, isobutane bromide, bromo pentane, bromo isopentane, bromo neopentane, bromocyclopentane, bromo just oneself
Alkane, bromocyclohexane, bromo heptane, bromo cycloheptane, n-octane bromide, dimethyl suflfate, dithyl sulfate, diazonium first
Alkane, triethyl orthoformate, methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, the tert-butyl alcohol, n-amyl alcohol, n-hexyl alcohol, first
At least one of acid, formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde.
3. the preparation method of the adamantane amine quaternary ammonium salt according to claim 1 suitable for electrolytic solution for super capacitor,
It is characterized in that：In step (1) and step (2), the reaction dissolvent is deionized water, methanol, ethyl alcohol, normal propyl alcohol, isopropanol, just
Butanol, isobutanol, the tert-butyl alcohol, ether, tetrahydrofuran, N,N-dimethylformamide, N, N- diethyl acetamides, acetone, benzene, first
Benzene, ethylbenzene, petroleum ether, pentane, pentamethylene, n-hexane, hexamethylene, dichloromethane, chloroform, carbon tetrachloride, curing
In carbon, -3 methyl imidazolium tetrafluoroborate ionic liquid of 1- ethyls, 1,2- methyl -3- ethyl imidazol(e) tetrafluoroborate ion liquids
At least one.
4. the preparation method of the adamantane amine quaternary ammonium salt according to claim 1 suitable for electrolytic solution for super capacitor,
It is characterized in that：In step (2), the inorganic base is sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, calcium carbonate, carbonic acid
One kind in potassium, ammonium carbonate, lithium carbonate, sodium bicarbonate, ammonium hydrogen carbonate.
5. the preparation method of the adamantane amine quaternary ammonium salt according to claim 1 suitable for electrolytic solution for super capacitor,
It is characterized in that：The acid is formic acid, acetic acid, propionic acid, oxalic acid, phosphoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, perchloric acid, sulphur cyanogen
Acid, cdicynanmide, bis-trifluoromethylsulfoandimide, double fluorine sulfimides, trifluoroacetic acid, double fluorine oxalic acid phosphoric acid, tetrafluoro boric acid, hexafluoro phosphorus
One kind in acid.
6. the preparation method of the adamantane amine quaternary ammonium salt according to claim 1 suitable for electrolytic solution for super capacitor,
It is characterized in that：In step (3), the solvent be deionized water, methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutanol,
The tert-butyl alcohol, ether, tetrahydrofuran, N,N-dimethylformamide, N, N- diethyl acetamides, acetone, benzene, toluene, ethylbenzene, oil
At least one in ether, pentane, pentamethylene, n-hexane, hexamethylene, dichloromethane, chloroform, carbon tetrachloride, carbon disulfide
Kind.
7. the preparation method of the adamantane amine quaternary ammonium salt according to claim 1 suitable for electrolytic solution for super capacitor,
It is characterized in that：Step (1) and step (2) back flow reaction temperature are 80 DEG C~100 DEG C.
8. the preparation method of the adamantane amine quaternary ammonium salt according to claim 1 suitable for electrolytic solution for super capacitor,
It is characterized in that：Reaction dissolvent in step (1) and step (2) is isopropanol, the C of step (1)1~C8Alkylating reagent is mole
Than 1:1 formic acid and formaldehyde, back flow reaction temperature are 80 DEG C~90 DEG C, and step (2) back flow reaction temperature is 90 DEG C~100 DEG C.
9. the preparation method of the adamantane amine quaternary ammonium salt according to claim 1 suitable for electrolytic solution for super capacitor,
It is characterized in that：Alkylating reagent described in step (2) is dithyl sulfate, and the inorganic base is barium hydroxide, and the acid is four
Fluoboric acid.
10. the preparation method of the adamantane amine quaternary ammonium salt according to claim 1 suitable for electrolytic solution for super capacitor,
It is characterized in that：The organic solvent used in step (1) and step (2) is isopropanol.
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