CN104059076A - Preparation method of high-purity supercapacitor electrolyte spiro quaternary ammonium salt - Google Patents
Preparation method of high-purity supercapacitor electrolyte spiro quaternary ammonium salt Download PDFInfo
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- C07—ORGANIC CHEMISTRY
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- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/10—Spiro-condensed systems
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/10—Spiro-condensed systems
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Abstract
The invention discloses a preparation method of a high-purity supercapacitor electrolyte spiro quaternary ammonium salt, and solves the problems of low raw material utilization ratio, low product yield and low purity in the spiro quaternary ammonium salt preparation method in the prior art. The method mainly comprises the following steps: (1) preparing a spiro quaternary ammonium salt crude product; and (2) purifying the spiro quaternary ammonium salt crude product. The spiro quaternary ammonium salt crude product prepared by the two-step process is eluted by a silica gel chromatographic column to remove halogen ions, and recrystallized to further remove impurities; and the two-step purification can greatly enhance the purity of the spiro quaternary ammonium salt, and has the advantages of simple technical steps and high controllability. The silica gel chromatographic column is subjected to secondary elution with deionized water to recover the unreacted halogenated spiro quaternary ammonium salt for reutilization, thereby greatly enhancing the overall reaction yield and lowering the production cost.
Description
Technical field
The present invention relates to a kind of synthetic method of ultracapacitor electrolysis matter, especially relate to a kind of preparation method of high purity ultracapacitor electrolysis matter spiro quaternary ammonium salt.
Background technology
Ultracapacitor (double layer capacitor) is the novel energy memory device between secondary cell and conventional electrostatic electrical condenser; have power density high, have extended cycle life, operating temperature range is wide, good cycling stability, non-maintaining and advantages of environment protection, is widely used in the backup power source of regulex, sensor, crisis storer, starter gear, wind-power electricity generation and the solar power system etc. of Motor vehicles.Quaternary ammonium salt, as the nonaqueous electrolyte of ultracapacitor, can be used as the chemical cell of energy storage device or the supporting electrolyte of ultracapacitor.
Spiro quaternary ammonium salt is as a kind of novel electrolytes salt (CHIBA K, 2007, Electrochemistry, 75,664-667), has that solubleness is large in conventional organic solvent, electromotive force window is wide, specific conductivity advantages of higher.Its supporting electrolyte as ultracapacitor can provide higher energy density and power density.
For example, license notification number CN102093367B, the Chinese patent of Granted publication day 2013.02.27 discloses a kind of preparation method of spiro quaternary ammonium salt for organic electrolyte of super capacitor, the method is achieved by following process: taking water as reaction medium, by cyclic diamine and glycol disulfonic acid ester at a certain temperature, through condensation reaction, obtain corresponding spiro quaternary ammonium salt; This ammonium salt is obtained to corresponding spiro quaternary ammonium salt by ion-exchange; Finally it is carried out to purifying and obtain target product.Its weak point is, utilization ratio, product yield and the purity of raw material are low.
Summary of the invention
The present invention is the low problem of preparation method's raw material availability, product yield and purity of the spiro quaternary ammonium salt in order to solve prior art, a kind of process stabilizing is provided, selectivity is good, the preparation method of the high purity ultracapacitor electrolysis matter spiro quaternary ammonium salt that utilization ratio, product yield and the purity of raw material are high.
To achieve these goals, the present invention is by the following technical solutions:
A preparation method for high purity ultracapacitor electrolysis matter spiro quaternary ammonium salt, described preparation method comprises the following steps:
(1) spiro quaternary ammonium salt crude product preparation
(1), taking water as reaction medium, under the existence of alkali, cyclic secondary amine and saturated dihalide, through condensation reaction, are obtained to halogenation spiro quaternary ammonium salt.
(2) halogenation spiro quaternary ammonium salt step (1) being obtained and ion-exchanger are placed in organic solvent and carry out ion-exchange, filter, and distillation filtrate is removed organic solvent, dries, and obtains spiro quaternary ammonium salt crude product.The present invention prepares spiro quaternary ammonium salt crude product by two-step approach, the stable easily control of reaction process, and selectivity in reaction process is good.
(2) spiro quaternary ammonium salt crude product is purified
The spiro quaternary ammonium salt crude product of step () gained is added and in silica gel column chromatography, carries out loading, then add eluent to carry out wash-out, collect elutriant, get 0.5 ~ 1ml elutriant as sample liquid every 10 ~ 20min during this time, in sample liquid, splash into the silver nitrate aqueous solution of 1 ~ 2 1mol/L, if macroscopic muddiness appears in sample liquid, stop wash-out, by the elutriant solvent evaporated of collecting, the white solid obtaining obtains spiro quaternary ammonium salt sterling after recrystallization, oven dry.Purification step in the present invention is inventive point of the present invention, the present invention first adopts silica gel column chromatography to carry out wash-out to remove halogen ion to spiro quaternary ammonium salt crude product, carry out again recrystallization further to remove impurity, can greatly improve the purity (purity reaches more than 99.99%) of spiro quaternary ammonium salt by two-step purifying, and processing step is simple, the property grasped is strong, the most important thing is, adopt silica gel column chromatography to carry out wash-out to remove halogen ion to spiro quaternary ammonium salt crude product, can also reclaim unreacted halogenation spiro quaternary ammonium salt by the mode of secondary wash-out reuses, thereby greatly to improve total reaction yield, reduce costs.
As preferably, in step (1), the mol ratio of cyclic secondary amine, saturated dihalide and alkali is 1:1 ~ 1.1:1 ~ 1.2, the quality of water is cyclic secondary amine and saturated dihalide total mass 5 ~ 15 times, wherein, described cyclic secondary amine is Pyrrolidine or six hydrogen piperidines, and described saturated dihalide is the saturated dihalide that end group replaces, and its structural formula is as follows:
, wherein, X, X ' is halogen independently, n=1,2.
As preferably, described alkali is alkali metal hydroxide, alkaline earth metal hydroxides, alkaline carbonate or alkaline earth metal carbonate, and described saturated dihalide is Isosorbide-5-Nitrae-dibromobutane.
As preferably, described alkali is NaOH, KOH or Ca (OH)
2.
As preferably, in step (2), the mol ratio of halogenation spiro quaternary ammonium salt and ion-exchanger is 1:1 ~ 1.5, the quality of organic solvent is halogenation spiro quaternary ammonium salt and ion-exchanger total mass 5 ~ 15 times, wherein, described ion-exchanger is basic metal or the corresponding salt of alkaline-earth metal of the basic metal of fluoroboric acid or the corresponding salt of alkaline-earth metal, phosphofluoric acid, and organic solvent is methylene dichloride, trichloromethane, acetonitrile or acetone.
As preferably, described ion-exchanger is NaBF
4or NaPF
6, described organic solvent is methylene dichloride or acetonitrile.
As preferably, in step (two), the length-to-diameter ratio of silica gel column chromatography is 10 ~ 20:1, and when loading, the mass ratio of spiro quaternary ammonium salt crude product and silica gel is 1:10 ~ 30.
As preferably, in step (two), described eluent is acetonitrile, ethyl acetate, ethanol or methyl alcohol.
As preferably, in step (two), the processing condition of oven dry are: at 80 ~ 90 DEG C, vacuum is dried 5 ~ 24h.Adopt vacuum drying, drying effect is good, and is difficult for producing impurity.
As preferably, silica gel column chromatography after wash-out is carried out to secondary wash-out with deionized water, get 0.5 ~ 1ml elutriant as sample liquid every 10 ~ 20min during this time, in sample liquid, splash into the silver nitrate aqueous solution of 1 ~ 2 1mol/L, if there is not macroscopic muddiness in sample liquid, stop wash-out, collect secondary elutriant, obtain halo spiro quaternary ammonium salt brine solution, then the evaporation of halogenation spiro quaternary ammonium salt brine solution is removed to moisture, then at 80 ~ 90 DEG C, dry 5 ~ 6h, obtain flaxen halogenation spiro quaternary ammonium salt, finally the halogenation spiro quaternary ammonium salt obtaining is reused in step (2).Silica gel column chromatography is carried out to secondary wash-out with deionized water and reuse to reclaim unreacted halogenation spiro quaternary ammonium salt, thereby greatly to improve total reaction yield, reduce production costs.
Therefore, the present invention has following beneficial effect:
(1) the present invention first adopts silica gel column chromatography to carry out wash-out to remove halogen ion to spiro quaternary ammonium salt crude product, carry out again recrystallization further to remove impurity, can greatly improve the purity (purity reaches more than 99.99%) of spiro quaternary ammonium salt by two-step purifying, and processing step is simple, the property grasped is strong;
(2) silica gel column chromatography is carried out to secondary wash-out with deionized water and reuse to reclaim unreacted halogenation spiro quaternary ammonium salt, thereby greatly to improve total reaction yield, reduce production costs.
Embodiment
Below by embodiment, the present invention will be further described.
In the present invention, if not refer in particular to, all per-cent is weight unit, and all devices and raw material all can be buied from market or the industry is conventional, and the method in following embodiment, if no special instructions, is this area ordinary method.
Embodiment 1
A preparation method for high purity ultracapacitor electrolysis matter spiro quaternary ammonium salt, comprises the following steps:
(1) spiro quaternary ammonium salt crude product preparation
(1) after saturated dihalide, alkali and water are added in round-bottomed flask, under vigorous stirring, drip cyclic secondary amine, control temperature of reaction and be less than 50 DEG C, control cyclic secondary amine dropwises in 0.5h, reflux stirring reaction 1h afterwards, distill out desolventizing water, obtain halogenation spiro quaternary ammonium salt, wherein, cyclic secondary amine is Pyrrolidine, saturated dihalide is Isosorbide-5-Nitrae-dibromobutane, and alkali is NaOH, Pyrrolidine, 1, the mol ratio of 4-dibromobutane and NaOH is 1:1:1, and the quality of water is Pyrrolidine and Isosorbide-5-Nitrae-dibromobutane total mass 5 times.
(2) the halogenation spiro quaternary ammonium salt, ion-exchanger and the organic solvent that step (1) are obtained add in round-bottomed flask, and reflux stirs 0.5h, cold filtration, distillation filtrate is removed organic solvent, dries, and obtains spiro quaternary ammonium salt crude product, wherein, ion-exchanger is NaBF
4, organic solvent is acetonitrile, halogenation spiro quaternary ammonium salt and NaBF
4mol ratio be 1:1, the quality of acetonitrile is halogenation spiro quaternary ammonium salt and NaBF
45 times of total mass.
(2) spiro quaternary ammonium salt crude product is purified
The spiro quaternary ammonium salt crude product of step () gained is added and in silica gel column chromatography, carries out loading, the length-to-diameter ratio of silica gel column chromatography is 10:1, when loading, the mass ratio of spiro quaternary ammonium salt crude product and silica gel is 1:10, then add ethanol to carry out wash-out as eluent, collect elutriant, get 0.5ml elutriant as sample liquid every 10min during this time, in sample liquid, splash into the silver nitrate aqueous solution of 1 1mol/L, if there is macroscopic muddiness in sample liquid, stop wash-out, by the elutriant solvent evaporated of collecting, the white solid obtaining is through recrystallization, at 80 DEG C, vacuum obtains spiro quaternary ammonium salt sterling after drying 5h, afterwards, silica gel column chromatography after wash-out is carried out to secondary wash-out with deionized water as elutriant, get 0.5ml elutriant as sample liquid every 10min during this time, in sample liquid, splash into the silver nitrate aqueous solution of 1 1mol/L, if there is not macroscopic muddiness in sample liquid, stop wash-out, collect secondary elutriant, obtain halo spiro quaternary ammonium salt brine solution, then the evaporation of halogenation spiro quaternary ammonium salt brine solution is removed to moisture, then at 80 DEG C, dry 5h, obtain flaxen halogenation spiro quaternary ammonium salt, finally the halogenation spiro quaternary ammonium salt obtaining is reused in step (2).
The spiro quaternary ammonium salt sterling that the present embodiment obtains is white crystal, purity > 99.99%, content of halide ions < 5ppm, yield 90%.
Embodiment 2
A preparation method for high purity ultracapacitor electrolysis matter spiro quaternary ammonium salt, comprises the following steps:
(1) spiro quaternary ammonium salt crude product preparation
(1) after saturated dihalide, alkali and water are added in round-bottomed flask, under vigorous stirring, drip cyclic secondary amine, control temperature of reaction and be less than 50 DEG C, control cyclic secondary amine dropwises in 1 h, reflux stirring reaction 1h afterwards, distill out desolventizing water, obtain halogenation spiro quaternary ammonium salt, wherein, cyclic secondary amine is six hydrogen piperidines, saturated dihalide is Isosorbide-5-Nitrae-dichlorobutane, and alkali is KOH, six hydrogen piperidines, 1, the mol ratio of 4-dichlorobutane and KOH is 1:1.05:1.1, and the quality of water is six hydrogen piperidines and Isosorbide-5-Nitrae-dichlorobutane total mass 10 times.
(2) the halogenation spiro quaternary ammonium salt, ion-exchanger and the organic solvent that step (1) are obtained add in round-bottomed flask, and reflux stirs 1h, cold filtration, distillation filtrate is removed organic solvent, dries, and obtains spiro quaternary ammonium salt crude product, wherein, ion-exchanger is KBF
4, organic solvent is methylene dichloride, halogenation spiro quaternary ammonium salt and KBF
4mol ratio be 1:1.2, the quality of methylene dichloride is halogenation spiro quaternary ammonium salt and KBF
410 times of total mass.
(2) spiro quaternary ammonium salt crude product is purified
The spiro quaternary ammonium salt crude product of step () gained is added and in silica gel column chromatography, carries out loading, the length-to-diameter ratio of silica gel column chromatography is 15:1, when loading, the mass ratio of spiro quaternary ammonium salt crude product and silica gel is 1:20, then add acetonitrile to carry out wash-out as eluent, collect elutriant, get 0.6ml elutriant as sample liquid every 15min during this time, in sample liquid, splash into the silver nitrate aqueous solution of 1 1mol/L, if there is macroscopic muddiness in sample liquid, stop wash-out, by the elutriant solvent evaporated of collecting, the white solid obtaining is through recrystallization, at 85 DEG C, vacuum obtains spiro quaternary ammonium salt sterling after drying 12h, afterwards, silica gel column chromatography after wash-out is carried out to secondary wash-out with deionized water as elutriant, get 0.6ml elutriant as sample liquid every 15min during this time, in sample liquid, splash into the silver nitrate aqueous solution of 1 1mol/L, if there is not macroscopic muddiness in sample liquid, stop wash-out, collect secondary elutriant, obtain halo spiro quaternary ammonium salt brine solution, then the evaporation of halogenation spiro quaternary ammonium salt brine solution is removed to moisture, then at 85 DEG C, dry 5.5h, obtain flaxen halogenation spiro quaternary ammonium salt, finally the halogenation spiro quaternary ammonium salt obtaining is reused in step (2).
The spiro quaternary ammonium salt sterling that the present embodiment obtains is white crystal, purity > 99.99%, content of halide ions < 5ppm, yield 93%.
Embodiment 3
A preparation method for high purity ultracapacitor electrolysis matter spiro quaternary ammonium salt, comprises the following steps:
(1) spiro quaternary ammonium salt crude product preparation
(1) after saturated dihalide, alkali and water are added in round-bottomed flask, under vigorous stirring, drip cyclic secondary amine, control temperature of reaction and be less than 50 DEG C, control cyclic secondary amine and dropwise in 1.5h, reflux stirring reaction 1.5h afterwards, distill out desolventizing water, obtain halogenation spiro quaternary ammonium salt, wherein, cyclic secondary amine is Pyrrolidine, saturated dihalide is 1,8-, bis-bromooctanes, and alkali is Ca(OH)
2, Pyrrolidine, 1,8-bis-bromooctanes and Ca(OH)
2mol ratio be 1:1.1:1.2, the quality of water is Pyrrolidine and 1,8-, bis-bromooctane total masses 15 times.
(2) the halogenation spiro quaternary ammonium salt, ion-exchanger and the organic solvent that step (1) are obtained add in round-bottomed flask, and reflux stirs 1.5h, cold filtration, distillation filtrate is removed organic solvent, dries, and obtains spiro quaternary ammonium salt crude product, wherein, ion-exchanger is NaPF
4, organic solvent is acetone, halogenation spiro quaternary ammonium salt and NaPF
4mol ratio be 1:1.5, the quality of acetone is halogenation spiro quaternary ammonium salt and NaPF
415 times of total mass.
(2) spiro quaternary ammonium salt crude product is purified
The spiro quaternary ammonium salt crude product of step () gained is added and in silica gel column chromatography, carries out loading, the length-to-diameter ratio of silica gel column chromatography is 20:1, when loading, the mass ratio of spiro quaternary ammonium salt crude product and silica gel is 1:30, then add ethyl acetate to carry out wash-out as eluent, collect elutriant, get 1ml elutriant as sample liquid every 20min during this time, in sample liquid, splash into the silver nitrate aqueous solution of 2 1mol/L, if there is macroscopic muddiness in sample liquid, stop wash-out, by the elutriant solvent evaporated of collecting, the white solid obtaining is through recrystallization, at 90 DEG C, vacuum obtains spiro quaternary ammonium salt sterling after drying 24h, afterwards, silica gel column chromatography after wash-out is carried out to secondary wash-out with deionized water as elutriant, get 1ml elutriant as sample liquid every 20min during this time, in sample liquid, splash into the silver nitrate aqueous solution of 2 1mol/L, if there is not macroscopic muddiness in sample liquid, stop wash-out, collect secondary elutriant, obtain halo spiro quaternary ammonium salt brine solution, then the evaporation of halogenation spiro quaternary ammonium salt brine solution is removed to moisture, then at 90 DEG C, dry 6h, obtain flaxen halogenation spiro quaternary ammonium salt, finally the halogenation spiro quaternary ammonium salt obtaining is reused in step (2).
The spiro quaternary ammonium salt sterling that the present embodiment obtains is white crystal, purity > 99.99%, content of halide ions < 5ppm, yield 95%.
As can be seen from the above-described embodiment, the spiro quaternary ammonium salt sterling yield obtaining by the present invention is more than 90%, purity > 99.99%, content of halide ions < 5ppm, yield and purity are very high, are therefore highly suitable for organic electrolyte and the ultracapacitor of ultracapacitor.
Above-described embodiment is preferably scheme of one of the present invention, not the present invention is done to any pro forma restriction, also has other variant and remodeling under the prerequisite that does not exceed the technical scheme that claim records.
Claims (10)
1. a preparation method for high purity ultracapacitor electrolysis matter spiro quaternary ammonium salt, is characterized in that, described preparation method comprises the following steps:
(1) spiro quaternary ammonium salt crude product preparation
(1), taking water as reaction medium, under the existence of alkali, cyclic secondary amine and saturated dihalide, through condensation reaction, are obtained to halogenation spiro quaternary ammonium salt;
(2) halogenation spiro quaternary ammonium salt step (1) being obtained and ion-exchanger are placed in organic solvent and carry out ion-exchange, filter, and distillation filtrate is removed organic solvent, dries, and obtains spiro quaternary ammonium salt crude product;
(2) spiro quaternary ammonium salt crude product is purified
The spiro quaternary ammonium salt crude product of step () gained is added and in silica gel column chromatography, carries out loading, then add eluent to carry out wash-out, collect elutriant, get 0.5 ~ 1ml elutriant as sample liquid every 10 ~ 20min during this time, in sample liquid, splash into the silver nitrate aqueous solution of 1 ~ 2 1mol/L, if macroscopic muddiness appears in sample liquid, stop wash-out, by the elutriant solvent evaporated of collecting, the white solid obtaining obtains spiro quaternary ammonium salt sterling after recrystallization, oven dry.
2. preparation method according to claim 1, it is characterized in that, in step (1), the mol ratio of cyclic secondary amine, saturated dihalide and alkali is 1:1 ~ 1.1:1 ~ 1.2, the quality of water is cyclic secondary amine and saturated dihalide total mass 5 ~ 15 times, and wherein, described cyclic secondary amine is Pyrrolidine or six hydrogen piperidines, described saturated dihalide is the saturated dihalide that end group replaces, and its structural formula is as follows:
, wherein, X, X ' is halogen independently, n=1,2.
3. preparation method according to claim 2, is characterized in that, described alkali is alkali metal hydroxide, alkaline earth metal hydroxides, alkaline carbonate or alkaline earth metal carbonate, and described saturated dihalide is Isosorbide-5-Nitrae-dibromobutane.
4. preparation method according to claim 3, is characterized in that, described alkali is NaOH, KOH or Ca (OH)
2.
5. preparation method according to claim 1, it is characterized in that, in step (2), the mol ratio of halogenation spiro quaternary ammonium salt and ion-exchanger is 1:1 ~ 1.5, the quality of organic solvent is halogenation spiro quaternary ammonium salt and ion-exchanger total mass 5 ~ 15 times, wherein, the basic metal of the corresponding salt of the basic metal that described ion-exchanger is fluoroboric acid or alkaline-earth metal, phosphofluoric acid or the corresponding salt of alkaline-earth metal, organic solvent is methylene dichloride, trichloromethane, acetonitrile or acetone.
6. preparation method according to claim 5, is characterized in that, described ion-exchanger is NaBF
4or NaPF
6, described organic solvent is methylene dichloride or acetonitrile.
7. preparation method according to claim 1, is characterized in that, in step (two), the length-to-diameter ratio of silica gel column chromatography is 10 ~ 20:1, and when loading, the mass ratio of spiro quaternary ammonium salt crude product and silica gel is 1:10 ~ 30.
8. preparation method according to claim 1, is characterized in that, in step (two), described eluent is acetonitrile, ethyl acetate, ethanol or methyl alcohol.
9. preparation method according to claim 1, is characterized in that, in step (two), the processing condition of oven dry are: at 80 ~ 90 DEG C, vacuum is dried 5 ~ 24h.
10. preparation method according to claim 1, it is characterized in that, in step (two), silica gel column chromatography after wash-out is carried out to secondary wash-out with deionized water, get 0.5 ~ 1ml elutriant as sample liquid every 10 ~ 20min during this time, in sample liquid, splash into the Silver Nitrate water of 1 ~ 2 1mol/L, if there is not macroscopic muddiness in sample liquid, stop wash-out, collect secondary elutriant, obtain halo spiro quaternary ammonium salt brine solution, then the evaporation of halogenation spiro quaternary ammonium salt brine solution is removed to moisture, then at 80 ~ 90 DEG C, dry 5 ~ 6h, obtain flaxen halogenation spiro quaternary ammonium salt, finally the halogenation spiro quaternary ammonium salt obtaining is reused in step (2).
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