CN102584602A - Quaternary ammonium salt and preparation method thereof - Google Patents
Quaternary ammonium salt and preparation method thereof Download PDFInfo
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Abstract
The invention provides a preparation method for a quaternary ammonium salt. The preparation method comprises the following steps: a) causing amine to react with dimethyl carbonate in an organic solvent, thereby generating a quaternary ammonium alkaline compound, and b) performing neutralization reaction on the quaternary ammonium alkaline compound and inorganic complexing acid, and purifying a reaction product, thereby obtaining the quaternary ammonium salt. The invention also provides three quaternary ammonium salts, of which the structures are respectively expressed as (VII), (X) and (XI), according to the preparation method. The quaternary ammonium salt prepared according to the method contains no organic halide residual, so that no halogen ion is ionized by an electrolyte solution prepared from electrolyte and the electrochemical property is excellent. A potential window test proves that the quaternary ammonium salt prepared according to the method provided by the invention has a wider potential window scope, a potential window curve is smooth in the potential window scope, no obvious oxidoreduction peak appears, and the quaternary ammonium salt is suitable for the electrolyte solution of a power storage device.
Description
Technical field
The present invention relates to ammonium compounds synthetic field, particularly quaternary ammonium salt and preparation method thereof.
Background technology
Quaternary ammonium salt is claimed quarternary ammonium salt again, is four compounds that Wasserstoffatoms is all formed by hydrocarbyl substituted in the ammonium radical ion, and English name is quaternary-N, and general formula is R
4NX, R is an alkyl in the general formula, X is halogen anion such as F
-, Cl
-, Br
-Or I
-, or acid group such as HSO
4 -, RCOO
-Or BF
4 -Deng.Quaternary ammonium salt is soluble in water, has better electrochemical performance, and the solution behind the water-soluble or organic solvent has electroconductibility, is a kind of good ionogen.In addition, quaternary ammonium salt is in chemical industry, medicine, mining, weaving and energy field extensive application.
In recent years; People have carried out big quantity research to quaternary ammonium salt and compound method thereof; And obtain a series of achievements, existing quaternary ammonium salt is mainly according to following prepared in one of two ways: a kind of is the halides that earlier amine is converted into quaternary ammonium salt, converts the halides of quaternary ammonium salt to quaternary ammonium hydroxide through methods such as exchange resins again; Make quaternary ammonium hydroxide and acid that neutralization reaction takes place at last, obtain title product.Like application number is the compound method that 200580013312.5 Chinese patent discloses a kind of quaternary ammonium compound and compsn thereof; It is that trialkylamine and alkyl bromide reaction are generated tetraalkyl bromination quaternary ammonium salt; Through the example exchange resin tetraalkyl bromination quaternary ammonium salt is converted into the tetraalkyl quaternary ammonium hydroxide again, at last quaternary ammonium hydroxide is converted into the anionic tetraalkyl ammonium salt of selection of selection.And for example application number is the preparation method that 200810234142.9 Chinese patent document discloses the salt of a kind of pair of fluoroform sulfimide metal; This method is to be raw material with fluoroform halo sulphonyl, liquefied ammonia and organic amine alkali; Adopt nonpolar inert solvent; Generation contains the mixture solution of two fluoroform sulfimide quaternary ammonium salts; Distillation is reclaimed mixture solution and is obtained two fluoroform sulfimide quaternary ammonium salt solids; Two fluoroform sulfimide quaternary ammonium salt solids that make and alkalimetal oxide are reacted the mixture that generates bis trifluoromethyl sulfimide metal-salt in the aqueous solution, the mixture with the bis trifluoromethyl sulfimide metal-salt that makes obtains title product after operations such as decompression dehydration, drying at last.
Aforesaid method Organohalogen compounds in the building-up process of quaternary ammonium hydroxide are participated in; Organohalogen compounds are prone to take place residual and difficult removal; Therefore it is residual that the quaternary ammonium salt that obtains certainly will have Organohalogen compounds, this quaternary ammonium salt is configured to electrolytic solution after, Organohalogen compounds ionization goes out halide-ions; The halide-ions that ionization goes out can reduce influences the electrolyte electrochemical performance, thereby reduces the lithium cell that ionogen thus processes or the capacity and the cycle performance of ultracapacitor.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of quaternary ammonium salt electrolyte preparation method, and it is residual not have Organohalogen compounds by this method synthetic quaternary ammonium salt product, and chemical property is better.
In view of this, the present invention provides a kind of preparation method of quaternary ammonium salt, comprising:
A), amine and methylcarbonate react in organic solvent and generate the quaternary ammonium basic cpd;
B), said quaternary ammonium basic cpd and inorganic complex acid generation neutralization reaction, reaction product is purified, obtain quaternary ammonium salt.
Preferably, said inorganic complex acid is fluoroboric acid or phosphofluoric acid.
Preferably, among the step a, said temperature of reaction is 50 ℃～200 ℃.
Preferably; Said reaction product is purified is specially: use the recrystallisation solvent recrystallization to purify reaction product; Said recrystallisation solvent is one or more in methyl alcohol, ethanol, Virahol, methylcarbonate, diethyl carbonate, acetone and the 2-butanone, and the Tc of said recrystallization is-50 ℃～5 ℃.
Preferably, said amine is Tri-n-Propylamine, and said inorganic complex acid is a fluoroboric acid.
Preferably, said amine is piperazine, and said inorganic complex acid is a fluoroboric acid.
Preferably, said amine is quadrol, and said inorganic complex acid is a fluoroboric acid.
The present invention also provides a kind of quaternary ammonium salt of structure shown in (VII) of preparation according to the method described above:
The present invention also provides a kind of quaternary ammonium salt of structure shown in (X) of preparation according to the method described above:
The present invention also provides a kind of quaternary ammonium salt of structure shown in (XI) of preparation according to the method described above:
The present invention provides a kind of preparation method of quaternary ammonium salt, and the present invention is with the synthetic quaternary ammonium salt of two-step approach, and the first step uses methylcarbonate that amine is converted into the quaternary ammonium basic cpd, and second step was with in the inorganic complex acid and the quaternary ammonium basic cpd, obtained quaternary ammonium salt.Preparing method provided by the invention does not have Organohalogen compounds and participates in, so no Organohalogen compounds are residual in the reaction product, and the electrolytic solution that is mixed with of ionogen can ionization not go out halide-ions thus, and chemical property is good.Through electrochemical window test proof, the quaternary ammonium salt for preparing according to method provided by the invention has higher electrochemical window scope, and in the above-mentioned electrochemical window scope, the electrochemical window curve is all smooth, does not have obvious redox peak and occurs, and is suitable in the energy storage device electrolytic solution.
The present invention also provide three kinds according to the method described above the structures of preparation respectively like (VII), (X) with quaternary ammonium salt (XI); Above-mentioned three kinds of quaternary ammonium salts have the electrochemical window scope of broad; And in above-mentioned electrochemical window scope, the electrochemical window curve is all smooth, does not have obvious redox peak and occurs; Chemical property is better, is suitable in the energy storage device electrolytic solution.
Description of drawings
Fig. 1 is the electrochemical window curve of the electrolytic solution of the quaternary ammonium salt configuration that made by embodiment 1;
Fig. 2 is the electrochemical window curve of the electrolytic solution of the quaternary ammonium salt configuration that made by embodiment 2;
Fig. 3 is the electrochemical window curve of the electrolytic solution of the quaternary ammonium salt configuration that made by embodiment 3;
Fig. 4 is the electrochemical window curve of the electrolytic solution of the quaternary ammonium salt configuration that made by embodiment 4;
Fig. 5 is the electrochemical window curve of the electrolytic solution of the quaternary ammonium salt configuration that made by embodiment 5;
Fig. 6 is the electrochemical window curve of the electrolytic solution of the quaternary ammonium salt configuration that made by embodiment 6;
Fig. 7 is the electrochemical window curve of the electrolytic solution of the quaternary ammonium salt configuration that made by embodiment 7;
Fig. 8 is the electrochemical window curve of the electrolytic solution of the quaternary ammonium salt configuration that made by embodiment 8;
Fig. 9 is the electrochemical window curve of the electrolytic solution of the quaternary ammonium salt configuration that made by embodiment 9;
Figure 10 is the electrochemical window curve of the electrolytic solution of the quaternary ammonium salt configuration that made by embodiment 10;
Figure 11 is the electrochemical window curve of the electrolytic solution of the quaternary ammonium salt configuration that made by embodiment 11.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described, describe just to further specifying feature and advantage of the present invention but should be appreciated that these, rather than to the restriction of claim of the present invention.
The embodiment of the invention discloses a kind of preparation method of quaternary ammonium salt, comprise the steps:
A), amine and methylcarbonate react in organic solvent and generate the quaternary ammonium basic cpd;
B), said quaternary ammonium basic cpd and inorganic complex acid generation neutralization reaction, reaction product is purified, obtain quaternary ammonium salt.
The present invention is with the synthetic quaternary ammonium salt of two-step approach, and the first step is that amine is converted into the quaternary ammonium basic cpd, and second step was with in the acid and the quaternary ammonium basic cpd, obtained quaternary ammonium salt.
Among the above-mentioned preparation method; Step a is the process that amine is converted into the quaternary ammonium basic cpd; The present invention preferably selects primary amine, secondary amine, tertiary amine or polyamine for use, and above-mentioned amine can be branched structure, like Tri N-Propyl Amine, diethylamine, Tri-n-Propylamine or quadrol etc.; Also can be and contain the N heterocycle structure, like tetramethyleneimine, hexahydropyridine or piperazine etc.Those skilled in the art can confirm the mol ratio of amine and methylcarbonate according to the quantity of the substituted hydrogen of needs in the amine.
With the Tri N-Propyl Amine is example, and following reaction takes place for Tri N-Propyl Amine and methylcarbonate among the step a:
Temperature of reaction preferably is made as 50 ℃～200 ℃, after the reaction unreacted amine, methylcarbonate and organic solvent is removed in the mixture heating up evaporation that obtains, and generates the quaternary ammonium basic cpd.
Because the compound that step a makes is alkalescence, perishable electrode is not suitable in the battery, therefore needs to use acid that it is neutralized into neutral compound.Step b is that the quaternary ammonium basic cpd with acid the process that the acid-base neutralisation reaction generates neutral quaternary ammonium salt takes place; The inorganic complex acid that uses in this step preferably uses fluoroboric acid or phosphofluoric acid; Fluoroboric acid ion and phosphofluoric acid ionic ionic radius are less; Mobility of ions is high, and stable chemical performance, can give electrolyte system higher specific conductivity as ionogen.Fluorine atom and boron atom, fluorine atom and phosphorus atom all are with covalent bonds in above-mentioned two kinds of ions, and structure is comparatively stable, can ionization not produce halide-ions, therefore can not influence the electrolyte electrochemical performance.
Continuation is example with the Tri N-Propyl Amine, uses fluoroboric acid, and the reaction formula of step b is following:
To obtain product after reaction finishes and carry out obtaining quaternary ammonium salt after the purification processes, in order to obtain high-purity product, the present invention preferably carries out purification processes according to following mode:
C), reaction product is purified with recrystallisation solvent dissolving back recrystallization, obtain quaternary ammonium salt.
In the above-mentioned purification process; Tc is preferably-50 ℃～5 ℃; During the recrystallisation solvent that uses is preferably in methyl alcohol, ethanol, Virahol, methylcarbonate, diethyl carbonate, acetone and the 2-butanone one or more, above-mentioned recrystallisation solvent has suitable solubleness to title product, separates out in-50 ℃～5 ℃ temperature in order to guarantee title product; And impurity is not separated out, and improves product purity.
The molar mass of the also preferred control quaternary ammonium salt cationic of the present invention is 74g/mol～300g/mol; Small molecules quaternary ammonium salt cationic in the above-mentioned scope has higher mobility of ions; Help improving electrolytical specific conductivity; Widen the electrolyte decomposition voltage range, make ionogen have better chemical property.
The present invention also provides three kinds of quaternary ammonium salts of preparation according to the method described above, and its structure is respectively like (VII), (X) with (XI).
In above-mentioned three kinds of compounds, the quaternary ammonium salt of structure shown in (VII) is to be that raw material makes with Tri-n-Propylamine, methylcarbonate and fluoroboric acid; The quaternary ammonium salt of structure shown in (X) is to be that raw material makes with piperazine, methylcarbonate and fluoroboric acid; The quaternary ammonium salt of structure shown in (XI) is to be that raw material makes with quadrol, methylcarbonate and fluoroboric acid.
In order further to understand the present invention, below in conjunction with embodiment quaternary ammonium salt preparation method provided by the invention to be described, protection scope of the present invention is not limited by the following examples.
1, with in the reaction kettle of packing into after 0.1mol ethamine, 0.3mol methylcarbonate and the 100ml methanol mixed, it is 120 ℃ that temperature of reaction kettle is set, and finishes reaction after 12 hours, the mixing solutions that reaction is obtained put into petridish at 60 ℃ of heating evaporations to generating solid.
2, the solid that step 1 is obtained is dissolved in the zero(ppm) water, and the adding fluoroboric acid is neutralized to and no longer produces bubble in the solution, then mixing solutions heating evaporation to solid is separated out fully.
3, the solid that step 2 is obtained is in methanol mixed and be heated to solid and all dissolve; Rapidly solution is placed-20 ℃～-10 ℃ environment crystallization 12 hours then; Take out after the crystallization and carry out suction filtration, obtain the trimethylammonium of structure shown in (I) of white, a fluoroethane boric acid ammonium salt crystal.Product is advanced nucleus magnetic hydrogen spectrum test and test result is resolved, analysis result is following:
1, with the reaction kettle of packing into after 0.1mol Tri N-Propyl Amine, 0.3mol methylcarbonate and the 100ml methanol mixed, it is 130 ℃ that temperature of reaction kettle is set, and finishes reaction after 12 hours, the mixing solutions that reaction is obtained put into petridish at 50 ℃ of heating evaporations to generating solid.
2, the solid that step 1 is obtained is dissolved in the zero(ppm) water, and the adding fluoroboric acid is neutralized to and no longer produces bubble in the solution, then mixing solutions heating evaporation to solid is separated out fully.
3, the solid that step 2 is obtained and volume ratio are that 2: 1 ethanol mixes with isopropyl alcohol mixture; And be heated to solid and all dissolve; Rapidly solution is placed-50 ℃～-40 ℃ environment crystallization 12 hours then; Take out after the crystallization and carry out suction filtration, obtain the trimethylammonium of structure shown in (II) of white, a PrF boric acid ammonium salt crystal.Product is advanced nucleus magnetic hydrogen spectrum test and test result is resolved, analysis result is following:
1, with the reaction kettle of packing into after 0.1mol n-Butyl Amine 99,0.3mol methylcarbonate and the 100ml methanol mixed, it is 180 ℃ that temperature of reaction kettle is set, and finishes reaction after 16 hours, the mixing solutions that reaction is obtained put into petridish at 70 ℃ of heating evaporations to generating solid.
2, with what step 1 obtained solid is dissolved in the zero(ppm) water, the adding fluoroboric acid is neutralized to and no longer produces bubble in the solution, then mixing solutions heating evaporation to solid is separated out fully.
3, solid and the methanol mixed that step 2 is obtained also is heated to solid and all dissolves; Rapidly solution is placed-20 ℃～0 ℃ environment crystallization 12 hours then; Take out after the crystallization and carry out suction filtration, obtain structure trimethylammonium shown in (III) of white, monobutyl fluoroboric acid ammonium salt crystal.Product is advanced nucleus magnetic hydrogen spectrum test and test result is resolved, analysis result is following:
1, with the reaction kettle of packing into after 0.1mol diethylamine, 0.2mol methylcarbonate and the 100ml methanol mixed, it is 140 ℃ that temperature of reaction kettle is set, and finishes reaction after 12 hours, the mixing solutions that reaction is obtained put into petridish at 60 ℃ of heating evaporations to generating solid.
2, with what step 1 obtained solid is dissolved in the zero(ppm) water, the adding fluoroboric acid is neutralized to and no longer produces bubble in the solution, then mixing solutions heating evaporation to solid is separated out fully.
3, the solid that step 2 is obtained mixes with Virahol and is heated to solid and all dissolves; Rapidly solution is placed-30 ℃～-20 ℃ environment crystallization 12 hours then; Take out after the crystallization and carry out suction filtration, obtain the dimethyl-of structure shown in (IV) of white, diethylammonium fluoroboric acid ammonium salt crystal.Product is advanced nucleus magnetic hydrogen spectrum test and test result is resolved, analysis result is following:
1, with in the reaction kettle of packing into after 0.1mol di-n-propylamine, 0.2mol methylcarbonate and the 100ml methanol mixed; It is 180 ℃ that temperature of reaction kettle is set; Finish reaction after 12 hours, the mixing solutions that reaction is obtained put into petridish at 60 ℃ of heating evaporations to generating solid.
2, the solid that step 1 is obtained is dissolved in the zero(ppm) water, and the adding fluoroboric acid is neutralized to solution and no longer produces bubble, and mixing solutions thermal evaporation to solid is separated out fully.
3, the solid that step 2 is obtained and volume ratio are that 1: 1 methylcarbonate mixes with the 2-butanone mixing solutions; And be heated to solid and dissolve fully; Rapidly solution is placed-30 ℃～-40 ℃ environment crystallization 12 hours then; Take out after the crystallization and carry out suction filtration, obtain the dimethyl-of structure shown in (V) of white, dipropyl fluoroboric acid ammonium salt crystal.Product is advanced nucleus magnetic hydrogen spectrum test and test result is resolved, analysis result is following:
1, with the reaction kettle of packing into after 0.1mol Di-n-Butyl Amine, 0.2mol methylcarbonate and the 100ml methanol mixed; It is 180 ℃ that temperature of reaction kettle is set; Finish reaction after 12 hours, the mixing solutions that reaction is obtained put into petridish at 60 ℃ of heating evaporations to generating solid.
2, the solid that step 1 is obtained is dissolved in the zero(ppm) water, adds fluoroboric acid and is neutralized to and no longer produces bubble in the solution, leaves standstill and treats the solution layering in 10 minutes, separates with separating funnel, keeps upper strata liquid, is heated to be evaporated to solid and to separate out fully.
3, the solid that step 2 is obtained and volume ratio are that 1: 1 methyl alcohol mixes with the acetone mixing solutions; And be heated to solid and dissolve fully; Rapidly solution is placed-40 ℃～-30 ℃ environment crystallization 12 hours then; Take out after the crystallization and carry out suction filtration, obtain the dimethyl-of structure shown in (VI) of white, dibutyl fluoroboric acid ammonium salt crystal.Product is advanced nucleus magnetic hydrogen spectrum test and test result is resolved, analysis result is following:
Embodiment 7
1, with the reaction kettle of packing into after 0.1mol Tri-n-Propylamine, 0.1mol methylcarbonate and the 100ml methanol mixed; It is 170 ℃ that temperature of reaction kettle is set; Finish reaction after 12 hours, the mixing solutions that reaction is obtained put into petridish at 60 ℃ of heating evaporations to generating solid.
2, the solid that step 1 is obtained is dissolved in the zero(ppm) water, and the adding fluoroboric acid is neutralized to solution and no longer produces bubble, and underpressure distillation mixing solutions to solid is separated out fully again.
3, the solid that step 2 is obtained and volume ratio are that 3: 1 methyl alcohol mixes with the diethyl carbonate mixing solutions; And be heated to solid and dissolve fully; Rapidly solution is placed-30 ℃～-40 ℃ environment crystallization 12 hours then; Take out after the crystallization and carry out suction filtration, obtain the monomethyl of structure shown in (VII) of white, tripropyl Tetrafluoroboric acid ammonium salt crystal.Product is advanced nucleus magnetic hydrogen spectrum test and test result is resolved, analysis result is following:
Embodiment 8
1, with the reaction kettle of packing into after 0.11mol tetramethyleneimine, 0.21mol methylcarbonate and the 100ml methanol mixed, it is 80 ℃ that temperature of reaction kettle is set, and finishes reaction after 10 hours, the mixing solutions that reaction is obtained put into petridish at 60 ℃ of heating evaporations to generating solid.
2, the solid that step 1 is obtained is dissolved in the zero(ppm) water, and the adding fluoroboric acid is neutralized to solution and no longer produces bubble, and underpressure distillation mixing solutions to solid is separated out fully again.
3, the solid that step 2 is obtained and volume ratio are that 1: 1 ethanol mixes with the propyl carbinol mixing solutions; And be heated to solid and dissolve fully; Rapidly solution is placed-40 ℃～-50 ℃ environment crystallization 12 hours then, takes out after the crystallization and carry out suction filtration, the structure that obtains white shown in (VIII) 1; 1 (N, N)-dimethyl tetrahydro pyrroles's fluoroboric acid ammonium salt crystal.Product is advanced nucleus magnetic hydrogen spectrum test and test result is resolved, analysis result is following:
Embodiment 9
1, with the reaction kettle of packing into after 0.1mol hexahydropyridine, 0.21mol methylcarbonate and the 100ml methanol mixed; It is 140 ℃ that temperature of reaction kettle is set; Finish reaction after 12 hours, the mixing solutions that reaction is obtained put into petridish at 60 ℃ of heating evaporations to generating solid.
2, the solid that step 1 is obtained is dissolved in the zero(ppm) water, and the adding fluoroboric acid is neutralized to solution and no longer produces bubble, and underpressure distillation mixing solutions to solid is separated out fully again.
3, the solid that step 2 is obtained and volume are that 1: 1 methyl alcohol and alcohol mixed solution mixes; And be heated to solid and all dissolve; Rapidly solution is placed-10 ℃～5 ℃ environment crystallization 12 hours then, takes out after the crystallization and carry out suction filtration, the structure that obtains white shown in (IX) 1; 1 (N, N)-dimethyl-pentahydro-pyridine ammonium borofluoride crystal.Product is advanced nucleus magnetic hydrogen spectrum test and test result is resolved, analysis result is following:
Embodiment 10
1, with the reaction kettle of packing into after 0.1mol piperazine, 0.4mol methylcarbonate and the 100ml methanol mixed, it is 190 ℃ that temperature of reaction kettle is set, and finishes reaction after 12 hours, the mixing solutions that reaction is obtained put into petridish at 60 ℃ of heating evaporations to generating solid.
2, the solid that step 1 is obtained is dissolved in the zero(ppm) water, and the adding fluoroboric acid is neutralized to solution and no longer produces bubble, and underpressure distillation mixing solutions to solid is separated out fully again.
3, the solid that step 2 is obtained mixes with acetone and is heated to solid and all dissolves; Rapidly solution is placed-30 ℃～-20 ℃ environment crystallization 12 hours then; Take out after the crystallization and carry out suction filtration, the structure that obtains white shown in (X) (1,1; 4,4)-tetramethyl-tetrahydrochysene piperazine fluoroboric acid ammonium salt crystal.Product is advanced nucleus magnetic hydrogen spectrum test and test result is resolved, analysis result is following:
Embodiment 11
1, with the reaction kettle of packing into after 0.1mol quadrol, 0.6mol methylcarbonate and the 100ml methanol mixed, it is 180 ℃ that temperature of reaction kettle is set, and finishes reaction after 12 hours, the mixing solutions that reaction is obtained put into petridish at 60 ℃ of heating evaporations to generating solid.
2, the solid that step 1 is obtained is dissolved in the zero(ppm) water, and the adding fluoroboric acid is neutralized to solution and no longer produces bubble, and underpressure distillation mixing solutions to solid is separated out fully again.
3, solid and the methanol mixed that step 2 is obtained also is heated to solid and all dissolves, and rapidly solution placed-15 ℃～5 ℃ environment crystallization 12 hours then, takes out after the crystallization and carries out suction filtration; Obtain white structure shown in (XI) (1; 1,1,4; 4,4)-hexamethyl second boron difluoride acid ammonium salt crystal.Product is advanced nucleus magnetic hydrogen spectrum test and test result is resolved, analysis result is following:
Quaternary ammonium salt and 1 with difference embodiment 1～11 preparation; 2-Ucar 35 carbonic ether is made into electrolytic solution; Above-mentioned electrolytic solution is carried out the test of electrochemical potential window respectively on electrochemical workstation; Be respectively electrochemical window curve referring to Fig. 1～Figure 11, can know by above-mentioned curve by the electrolytic solution of embodiment 1～11 configuration:
The quaternary ammonium salt electrochemical window scope of embodiment 1 preparation is-2.8～3.2V;
The quaternary ammonium salt electrochemical window scope of embodiment 2 preparations is-4～3.6V;
The quaternary ammonium salt electrochemical window scope of embodiment 3 preparations is-4.3～3.9V;
The quaternary ammonium salt electrochemical window scope of embodiment 4 preparations is-5.1～3V;
The quaternary ammonium salt electrochemical window scope of embodiment 5 preparations is-5.6～3V;
The quaternary ammonium salt electrochemical window scope of embodiment 6 preparations is-4.7～4.2V;
The quaternary ammonium salt electrochemical window scope of embodiment 7 preparations is-3.8～3.3V;
The quaternary ammonium salt electrochemical window scope of embodiment 8 preparations is-4～3.3V;
The quaternary ammonium salt electrochemical window scope of embodiment 9 preparations is-3.4～2V;
The quaternary ammonium salt electrochemical window scope of embodiment 10 preparations is-3.7～2V;
The quaternary ammonium salt electrochemical window scope of embodiment 11 preparations is-5.1～3.5V;
Above-mentioned quaternary ammonium salt electrochemical window a wider range, and in above-mentioned electrochemical window scope, above-mentioned curve is all smooth, does not have obvious redox peak and occurs, and explains that thus material purity is high, is suitable in the energy storage device electrolytic solution.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be conspicuous concerning those skilled in the art, and defined General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments among this paper.Therefore, the present invention will can not be restricted to these embodiment shown in this paper, but will meet and principle disclosed herein and features of novelty the wideest corresponding to scope.
Claims (10)
1. the preparation method of a quaternary ammonium salt is characterized in that, comprising:
A), amine and methylcarbonate react in organic solvent and generate the quaternary ammonium basic cpd;
B), said quaternary ammonium basic cpd and inorganic complex acid generation neutralization reaction, reaction product is purified, obtain quaternary ammonium salt.
2. preparation method according to claim 1 is characterized in that, said inorganic complex acid is fluoroboric acid or phosphofluoric acid.
3. preparation method according to claim 1 is characterized in that, among the step a, said temperature of reaction is 50 ℃～200 ℃.
4. preparation method according to claim 1; It is characterized in that; Said reaction product is purified is specially: use the recrystallisation solvent recrystallization to purify reaction product; Said recrystallisation solvent is one or more in methyl alcohol, ethanol, Virahol, methylcarbonate, diethyl carbonate, acetone and the 2-butanone, and the Tc of said recrystallization is-50 ℃～5 ℃.
5. preparation method according to claim 1 is characterized in that, said amine is Tri-n-Propylamine, and said inorganic complex acid is a fluoroboric acid.
6. preparation method according to claim 1 is characterized in that, said amine is piperazine, and said inorganic complex acid is a fluoroboric acid.
7. preparation method according to claim 1 is characterized in that, said amine is quadrol, and said inorganic complex acid is a fluoroboric acid.
8. the quaternary ammonium salt of structure shown in (VII) for preparing according to the said method of claim 5:
9. the quaternary ammonium salt of structure shown in (X) for preparing according to the said method of claim 7:
10. the quaternary ammonium salt of structure shown in (XI) for preparing according to the said method of claim 9:
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| CN111606810A (en) * | 2020-06-23 | 2020-09-01 | 江苏康爱特环境工程集团有限公司 | Preparation method of 6-bromohexyltrimethylammonium bromide |
| CN114308122A (en) * | 2022-01-12 | 2022-04-12 | 万华化学集团股份有限公司 | Quaternary ammonia base phase transfer catalyst, preparation method and application thereof in preparation of 1, 3-di (2-hydroxy isopropyl) benzene |
| CN116162045A (en) * | 2023-03-07 | 2023-05-26 | 衢州市九洲化工有限公司 | Preparation method of tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt |
| KR20240022779A (en) | 2022-08-12 | 2024-02-20 | 삼화페인트공업주식회사 | Method for preparing high purity quaternary ammonium salt |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4762629A (en) * | 1986-03-20 | 1988-08-09 | Nippon Chemi-Con Corporation | Electrolyte for electrolytic capacitor |
| US4892944A (en) * | 1987-05-13 | 1990-01-09 | Mitsubishi Petrochemical Co., Ltd. | Process for producing quaternary salts |
| JP2002151360A (en) * | 2000-11-08 | 2002-05-24 | Kuraray Co Ltd | Electric double-layer capacitor |
| WO2003095414A1 (en) * | 2002-05-14 | 2003-11-20 | Stella Chemifa Kabushiki Kaisha | Method of purifying quaternary alkylammonium salt and quaternary alkylammonium salt |
| EP1165486B1 (en) * | 1999-03-24 | 2005-06-22 | University Of Leicester | Ionic liquids |
-
2011
- 2011-01-05 CN CN2011100013169A patent/CN102584602A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4762629A (en) * | 1986-03-20 | 1988-08-09 | Nippon Chemi-Con Corporation | Electrolyte for electrolytic capacitor |
| US4892944A (en) * | 1987-05-13 | 1990-01-09 | Mitsubishi Petrochemical Co., Ltd. | Process for producing quaternary salts |
| EP1165486B1 (en) * | 1999-03-24 | 2005-06-22 | University Of Leicester | Ionic liquids |
| JP2002151360A (en) * | 2000-11-08 | 2002-05-24 | Kuraray Co Ltd | Electric double-layer capacitor |
| WO2003095414A1 (en) * | 2002-05-14 | 2003-11-20 | Stella Chemifa Kabushiki Kaisha | Method of purifying quaternary alkylammonium salt and quaternary alkylammonium salt |
Non-Patent Citations (1)
| Title |
|---|
| KARIV-MILLER, ESSIE等: "An electrochemical study of a tetraalkylammonium amalgam", 《JOURNAL OF ELECTROANALYTICAL CHEMISTRY AND INTERFACIAL ELECTROCHEMISTRY》, vol. 147, 31 December 1983 (1983-12-31), pages 319 - 22 * |
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| CN114308122A (en) * | 2022-01-12 | 2022-04-12 | 万华化学集团股份有限公司 | Quaternary ammonia base phase transfer catalyst, preparation method and application thereof in preparation of 1, 3-di (2-hydroxy isopropyl) benzene |
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