CN104059076B - A kind of preparation method of capacitor electrolyte spiro quaternary ammonium salt - Google Patents
A kind of preparation method of capacitor electrolyte spiro quaternary ammonium salt Download PDFInfo
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- 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
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- 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
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Abstract
The invention discloses the preparation method of a kind of high-purity ultracapacitor electrolysis matter spiro quaternary ammonium salt, the problem that preparation method raw material availability, product yield and the purity of the spiro quaternary ammonium salt solving prior art are low, the invention mainly includes steps: prepared by (one) spiro quaternary ammonium salt crude product, (two) spiro quaternary ammonium salt crude product purifies.After preparing spiro quaternary ammonium salt crude product by two step method, first use silica gel column chromatography spiro quaternary ammonium salt crude product to carry out eluting to remove halogen ion, then carry out recrystallization to go the removal of impurity further, be greatly improved the purity of spiro quaternary ammonium salt by two-step purifying, and processing step is simple, can have strong operability；Silica gel column chromatography deionized water is carried out secondary eluting again and reuses to reclaim unreacted halogenation spiro quaternary ammonium salt, thus to be greatly improved overall reaction yield, reduce production cost.
Description
Technical field
The present invention relates to the synthetic method of a kind of ultracapacitor electrolysis matter, especially relate to the preparation method of a kind of capacitor electrolyte spiro quaternary ammonium salt.
Background technology
Ultracapacitor (double layer capacitor) is the novel energy memory device between secondary cell and conventional electrostatic capacitor; have that power density is high, have extended cycle life, operating temperature range width, good cycling stability, non-maintaining and advantages of environment protection, be widely used in regulex, sensor, the back-up source of crisis memorizer, the starter of motor vehicles, wind-power electricity generation and solar power system etc..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, as a kind of novel electrolytes salt (CHIBA K, 2007, Electrochemistry, 75,664-667), has that dissolubility in conventional organic solvent is big, potential window width, electrical conductivity advantages of higher.Its supporting electrolyte being used as ultracapacitor is provided that higher energy density and power density.
Such as, license notification number CN102093367B, the Chinese patent of authorized announcement date 2013.02.27 discloses the preparation method of a kind of spiro quaternary ammonium salt for organic electrolyte of super capacitor, the method is achieved by following process: with water as reaction medium, by cyclic diamine with glycol disulfonic acid ester at a certain temperature, through condensation reaction, obtain corresponding spiro quaternary ammonium salt；This ammonium salt is obtained corresponding spiro quaternary ammonium salt by ion exchange；Finally it is purified and obtains target product.It is disadvantageous in that, the utilization rate of raw material, product yield and purity are low.
Summary of the invention
The present invention is the problem that preparation method raw material availability, product yield and the purity of the spiro quaternary ammonium salt in order to solve prior art is low, provide a kind of process stabilizing, selectivity is good, the preparation method of the capacitor electrolyte spiro quaternary ammonium salt that the utilization rate of raw material, product yield and purity are high.
To achieve these goals, the present invention is by the following technical solutions:
A kind of preparation method of capacitor electrolyte spiro quaternary ammonium salt, described preparation method comprises the following steps:
(1) prepared by spiro quaternary ammonium salt crude product
(1) with water as reaction medium, in the presence of base, by cyclic secondary amine with saturated dihalide through condensation reaction, halogenation spiro quaternary ammonium salt is obtained.
(2) halogenation spiro quaternary ammonium salt step (1) obtained and ion-exchanger are placed in organic solvent and carry out ion exchange, filter, and distillation filtrate removes organic solvent, dries, obtains spiro quaternary ammonium salt crude product.The present invention prepares spiro quaternary ammonium salt crude product by two-step method, and course of reaction is stablized easily-controllable, and the selectivity in course of reaction is good.
(2) spiro quaternary ammonium salt crude product purifies
The spiro quaternary ammonium salt crude product of step (one) gained is added in silica gel column chromatography and carries out loading, it is subsequently adding eluant and carries out eluting, collect eluent, period takes 0.5 ~ 1ml eluent as sample liquid every 10 ~ 20min, in sample liquid, instill the silver nitrate aqueous solution of 1 ~ 2 1mol/L, if macroscopic muddiness occurs in sample liquid, stop eluting, the eluent solvent evaporated that will collect, the white solid obtained i.e. obtains spiro quaternary ammonium salt sterling after recrystallization, drying.Purification step in the present invention is the inventive point of the present invention, the present invention first uses silica gel column chromatography spiro quaternary ammonium salt crude product to carry out eluting to remove halogen ion, carry out recrystallization again to go the removal of impurity further, the purity (purity reaches more than 99.99%) of spiro quaternary ammonium salt it is greatly improved by two-step purifying, and processing step is simple, can have strong operability, the most important thing is, silica gel column chromatography is used spiro quaternary ammonium salt crude product to carry out eluting to remove halogen ion, unreacted halogenation spiro quaternary ammonium salt can also be reclaimed by the way of secondary eluting reuse, thus to be greatly improved overall reaction yield, reduce cost.
As preferably, in step (1), cyclic secondary amine, saturated dihalide are 1:1 ~ 1.1:1 ~ 1.2 with the mol ratio of alkali, the quality of water is 5 ~ 15 times of cyclic secondary amine and saturated dihalide gross mass, wherein, described cyclic secondary amine is nafoxidine or hexahydro piperidines, and described saturated dihalide is the substituted saturated dihalide of end group, and its structural formula is as follows:
,
Wherein, X, X ' it is independent halogen, n=1,2.
As preferably, described alkali is alkali metal hydroxide, alkaline earth metal hydroxide, alkali 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), halogenation spiro quaternary ammonium salt is 1:1 ~ 1.5 with the mol ratio of ion-exchanger, the quality of organic solvent is 5 ~ 15 times of halogenation spiro quaternary ammonium salt and ion-exchanger gross mass, wherein, described ion-exchanger is alkali metal or the corresponding salt of alkaline-earth metal, the alkali metal of hexafluorophosphoric acid or the corresponding salt of alkaline-earth metal of fluoboric acid, and organic solvent is dichloromethane, chloroform, acetonitrile or acetone.
As preferably, described ion-exchanger is NaBF4Or NaPF6, described organic solvent is dichloromethane or acetonitrile.
As preferably, in step (two), the draw ratio of silica gel column chromatography is 10 ~ 20:1, and during loading, spiro quaternary ammonium salt crude product is 1:10 ~ 30 with the mass ratio of silica gel.
As preferably, in step (two), described eluant is acetonitrile, ethyl acetate, ethanol or methanol.
As preferably, in step (two), the process conditions of drying are: at 80 ~ 90 DEG C, vacuum dries 5 ~ 24h.Using vacuum drying, drying effect is good, and is not likely to produce impurity.
As preferably, silica gel column chromatography deionized water after eluting is carried out secondary eluting, period takes 0.5 ~ 1ml eluent as sample liquid every 10 ~ 20min, the silver nitrate aqueous solution of 1 ~ 2 1mol/L is instilled in sample liquid, if there is not macroscopic muddiness in sample liquid, stop eluting, collect secondary eluent, obtain halo spiro quaternary ammonium saline solution, then the evaporation of halogenation spiro quaternary ammonium saline solution is removed moisture, then at 80 ~ 90 DEG C, dry 5 ~ 6h, obtain flaxen halogenation spiro quaternary ammonium salt, finally the halogenation spiro quaternary ammonium salt obtained is reused in step (2).Silica gel column chromatography deionized water is carried out secondary eluting and reuses to reclaim unreacted halogenation spiro quaternary ammonium salt, thus to be greatly improved overall reaction yield, reduce production cost.
Therefore, there is advantages that
(1) present invention first uses silica gel column chromatography spiro quaternary ammonium salt crude product to carry out eluting to remove halogen ion, carry out recrystallization again to go the removal of impurity further, it is greatly improved the purity (purity reaches more than 99.99%) of spiro quaternary ammonium salt by two-step purifying, and processing step is simple, can have strong operability；
(2) silica gel column chromatography deionized water is carried out secondary eluting and reuses to reclaim unreacted halogenation spiro quaternary ammonium salt, thus to be greatly improved overall reaction yield, reduce production cost.
Detailed description of the invention
Below by detailed description of the invention, the present invention will be further described.
In the present invention, if not refering in particular to, all percentage ratios are unit of weight, all devices and raw material and are all commercially available or the industry is conventional, the method in following embodiment, if no special instructions, are this area conventional method.
Embodiment 1
The preparation method of a kind of capacitor electrolyte spiro quaternary ammonium salt, comprises the following steps:
(1) prepared by spiro quaternary ammonium salt crude product
(1) after saturated dihalide, alkali and water being added in round-bottomed flask, drip cyclic secondary amine with vigorous stirring, control reaction temperature less than 50 DEG C, control cyclic secondary amine and drip complete in 0.5h, it is heated to reflux stirring reaction 1h afterwards, aqueous solvent is distilled off, obtains halogenation spiro quaternary ammonium salt, wherein, cyclic secondary amine is nafoxidine, saturated dihalide is Isosorbide-5-Nitrae-dibromobutane, and alkali is NaOH, nafoxidine, 1,4-dibromobutane is 1:1:1 with the mol ratio of NaOH, and the quality of water is 5 times of nafoxidine and Isosorbide-5-Nitrae-dibromobutane gross mass.
(2) the halogenation spiro quaternary ammonium salt, ion-exchanger and the organic solvent that step (1) are obtained add in round-bottomed flask, are heated to reflux stirring 0.5h, cold filtration, distillation filtrate removes organic solvent, dries, obtains spiro quaternary ammonium salt crude product, wherein, ion-exchanger is NaBF4, organic solvent is acetonitrile, halogenation spiro quaternary ammonium salt and NaBF4Mol ratio be 1:1, the quality of acetonitrile is halogenation spiro quaternary ammonium salt and NaBF45 times of gross mass.
(2) spiro quaternary ammonium salt crude product purifies
nullThe spiro quaternary ammonium salt crude product of step (one) gained is added in silica gel column chromatography and carries out loading，The draw ratio of silica gel column chromatography is 10:1，During loading, spiro quaternary ammonium salt crude product is 1:10 with the mass ratio of silica gel，It is subsequently adding ethanol and carries out eluting as eluant，Collect eluent，Period takes 0.5ml eluent as sample liquid every 10min，The silver nitrate aqueous solution of 1 1mol/L is instilled in sample liquid，If there is macroscopic muddiness in sample liquid，Stop eluting，The eluent solvent evaporated that will collect，The white solid obtained is through recrystallization、At 80 DEG C, vacuum i.e. obtains spiro quaternary ammonium salt sterling after drying 5h，Afterwards，Silica gel column chromatography deionized water after eluting is carried out secondary eluting as eluent，Period takes 0.5ml eluent as sample liquid every 10min，The silver nitrate aqueous solution of 1 1mol/L is instilled in sample liquid，If there is not macroscopic muddiness in sample liquid，Stop eluting，Collect secondary eluent，Obtain halo spiro quaternary ammonium saline solution，Then the evaporation of halogenation spiro quaternary ammonium saline solution is removed moisture，Then at 80 DEG C, dry 5h，Obtain flaxen halogenation spiro quaternary ammonium salt，Finally the halogenation spiro quaternary ammonium salt obtained 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
The preparation method of a kind of capacitor electrolyte spiro quaternary ammonium salt, comprises the following steps:
(1) prepared by spiro quaternary ammonium salt crude product
(1) after saturated dihalide, alkali and water being added in round-bottomed flask, drip cyclic secondary amine with vigorous stirring, control reaction temperature less than 50 DEG C, control cyclic secondary amine and drip complete in 1 h, it is heated to reflux stirring reaction 1h afterwards, aqueous solvent is distilled off, obtains halogenation spiro quaternary ammonium salt, wherein, cyclic secondary amine is hexahydro piperidines, saturated dihalide is Isosorbide-5-Nitrae-dichloroetane, and alkali is KOH, hexahydro piperidines, 1,4-dichloroetane is 1:1.05:1.1 with the mol ratio of KOH, and the quality of water is 10 times of hexahydro piperidines and Isosorbide-5-Nitrae-dichloroetane gross mass.
(2) the halogenation spiro quaternary ammonium salt, ion-exchanger and the organic solvent that step (1) are obtained add in round-bottomed flask, are heated to reflux stirring 1h, cold filtration, distillation filtrate removes organic solvent, dries, obtains spiro quaternary ammonium salt crude product, wherein, ion-exchanger is KBF4, organic solvent is dichloromethane, halogenation spiro quaternary ammonium salt and KBF4Mol ratio be 1:1.2, the quality of dichloromethane is halogenation spiro quaternary ammonium salt and KBF410 times of gross mass.
(2) spiro quaternary ammonium salt crude product purifies
nullThe spiro quaternary ammonium salt crude product of step (one) gained is added in silica gel column chromatography and carries out loading，The draw ratio of silica gel column chromatography is 15:1，During loading, spiro quaternary ammonium salt crude product is 1:20 with the mass ratio of silica gel，It is subsequently adding acetonitrile and carries out eluting as eluant，Collect eluent，Period takes 0.6ml eluent as sample liquid every 15min，The silver nitrate aqueous solution of 1 1mol/L is instilled in sample liquid，If there is macroscopic muddiness in sample liquid，Stop eluting，The eluent solvent evaporated that will collect，The white solid obtained is through recrystallization、At 85 DEG C, vacuum i.e. obtains spiro quaternary ammonium salt sterling after drying 12h，Afterwards，Silica gel column chromatography deionized water after eluting is carried out secondary eluting as eluent，Period takes 0.6ml eluent as sample liquid every 15min，The silver nitrate aqueous solution of 1 1mol/L is instilled in sample liquid，If there is not macroscopic muddiness in sample liquid，Stop eluting，Collect secondary eluent，Obtain halo spiro quaternary ammonium saline solution，Then the evaporation of halogenation spiro quaternary ammonium saline solution is removed moisture，Then at 85 DEG C, dry 5.5h，Obtain flaxen halogenation spiro quaternary ammonium salt，Finally the halogenation spiro quaternary ammonium salt obtained 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
The preparation method of a kind of capacitor electrolyte spiro quaternary ammonium salt, comprises the following steps:
(1) prepared by spiro quaternary ammonium salt crude product
(1) after saturated dihalide, alkali and water being added in round-bottomed flask, drip cyclic secondary amine with vigorous stirring, control reaction temperature and be less than 50 DEG C, control cyclic secondary amine and drip complete in 1.5h, it is heated to reflux stirring reaction 1.5h afterwards, aqueous solvent is distilled off, obtains halogenation spiro quaternary ammonium salt, wherein, cyclic secondary amine is nafoxidine, saturated dihalide is 1,8-bis-bromooctane, and alkali is Ca(OH)2, nafoxidine, 1,8-bis-bromooctane and Ca(OH)2Mol ratio be 1:1.1:1.2, the quality of water is nafoxidine and 1,15 times of 8-bis-bromooctane gross mass.
(2) the halogenation spiro quaternary ammonium salt, ion-exchanger and the organic solvent that step (1) are obtained add in round-bottomed flask, are heated to reflux stirring 1.5h, cold filtration, distillation filtrate removes organic solvent, dries, obtains spiro quaternary ammonium salt crude product, wherein, ion-exchanger is NaPF4, organic solvent is acetone, halogenation spiro quaternary ammonium salt and NaPF4Mol ratio be 1:1.5, the quality of acetone is halogenation spiro quaternary ammonium salt and NaPF415 times of gross mass.
(2) spiro quaternary ammonium salt crude product purifies
nullThe spiro quaternary ammonium salt crude product of step (one) gained is added in silica gel column chromatography and carries out loading，The draw ratio of silica gel column chromatography is 20:1，During loading, spiro quaternary ammonium salt crude product is 1:30 with the mass ratio of silica gel，It is subsequently adding ethyl acetate and carries out eluting as eluant，Collect eluent，Period takes 1ml eluent as sample liquid every 20min，The silver nitrate aqueous solution of 2 1mol/L is instilled in sample liquid，If there is macroscopic muddiness in sample liquid，Stop eluting，The eluent solvent evaporated that will collect，The white solid obtained is through recrystallization、At 90 DEG C, vacuum i.e. obtains spiro quaternary ammonium salt sterling after drying 24h，Afterwards，Silica gel column chromatography deionized water after eluting is carried out secondary eluting as eluent，Period takes 1ml eluent as sample liquid every 20min，The silver nitrate aqueous solution of 2 1mol/L is instilled in sample liquid，If there is not macroscopic muddiness in sample liquid，Stop eluting，Collect secondary eluent，Obtain halo spiro quaternary ammonium saline solution，Then the evaporation of halogenation spiro quaternary ammonium saline solution is removed moisture，Then at 90 DEG C, dry 6h，Obtain flaxen halogenation spiro quaternary ammonium salt，Finally the halogenation spiro quaternary ammonium salt obtained 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 obtained by the present invention more than 90%, purity ＞ 99.99%, content of halide ions ＜ 5ppm, yield is the highest with purity, is therefore highly suitable for organic electrolyte and the ultracapacitor of ultracapacitor.
Embodiment described above is the one preferably scheme of the present invention, and the present invention not makees any pro forma restriction, also has other variant and remodeling on the premise of without departing from the technical scheme described in claim.
Claims (2)
1. the preparation method of a capacitor electrolyte spiro quaternary ammonium salt, it is characterised in that described preparation method comprises the following steps:
(1) prepared by spiro quaternary ammonium salt crude product
(1) with water as reaction medium, in the presence of base, by cyclic secondary amine with saturated dihalide through condensation reaction, obtain halogenation spiro quaternary ammonium salt, cyclic secondary amine, saturated dihalide are 1:1 ~ 1.1:1 ~ 1.2 with the mol ratio of alkali, the quality of water is 5 ~ 15 times of cyclic secondary amine and saturated dihalide gross mass, and wherein, described alkali is NaOH, KOH or Ca (OH)2, described cyclic secondary amine is nafoxidine or hexahydro piperidines, and described saturated dihalide is Isosorbide-5-Nitrae-dibromobutane, Isosorbide-5-Nitrae-dichloroetane or 1,8-bis-bromooctane；
(2) halogenation spiro quaternary ammonium salt step (1) obtained and ion-exchanger are placed in organic solvent and carry out ion exchange, filter, and distillation filtrate removes organic solvent, dries, obtains spiro quaternary ammonium salt crude product, and described ion-exchanger is NaBF4Or NaPF6, described organic solvent is dichloromethane or acetonitrile；
(2) spiro quaternary ammonium salt crude product purifies
The spiro quaternary ammonium salt crude product of step (one) gained is added in silica gel column chromatography and carries out loading, the draw ratio of silica gel column chromatography is 10 ~ 20:1, during loading, spiro quaternary ammonium salt crude product is 1:10 ~ 30 with the mass ratio of silica gel, it is subsequently adding eluant acetonitrile, ethyl acetate, ethanol or methanol carry out eluting, collect eluent, period takes 0.5 ~ 1ml eluent as sample liquid every 10 ~ 20min, the silver nitrate aqueous solution of 1 ~ 2 1mol/L is instilled in sample liquid, if there is macroscopic muddiness in sample liquid, stop eluting, the eluent solvent evaporated that will collect, the white solid obtained is through recrystallization, spiro quaternary ammonium salt sterling is i.e. obtained after drying；Afterwards, silica gel column chromatography deionized water after eluting is carried out secondary eluting, period takes 0.5 ~ 1ml eluent as sample liquid every 10 ~ 20min, the silver nitrate aqueous solution of 1 ~ 2 1mol/L is instilled in sample liquid, if there is not macroscopic muddiness in sample liquid, stop eluting, collect secondary eluent, obtain halogenation spiro quaternary ammonium saline solution, then the evaporation of halogenation spiro quaternary ammonium saline solution is removed moisture, then at 80 ~ 90 DEG C, dry 5 ~ 6h, obtain flaxen halogenation spiro quaternary ammonium salt, finally the halogenation spiro quaternary ammonium salt obtained is reused in step (2).
Preparation method the most according to claim 1, it is characterised in that in step (two), the process conditions of drying are: at 80 ~ 90 DEG C, vacuum dries 5 ~ 24h.
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| CN106117218B (en) * | 2016-06-23 | 2018-09-14 | 东莞东阳光科研发有限公司 | A kind of preparation method of tetrafluoro boric acid spiro quaternary ammonium salt |
| CN106674232A (en) * | 2017-01-04 | 2017-05-17 | 湖南省正源储能材料与器件研究所 | Method for preparing high-purity spiral ammonium salt with ion exchange purification method |
| CN115124454A (en) * | 2022-07-14 | 2022-09-30 | 山东氟能化工材料有限公司 | Synthesis method of spiro quaternary ammonium salt with complex structure, product and application thereof |
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Address after: 315112 Zhejiang city of Ningbo province Yinzhou District five Township Wuxiang No. 552 West Road Applicant after: NINGBO CRRC NEW ENERGY TECHNOLOGY CO., LTD. Address before: 315112 Zhejiang city of Ningbo province Yinzhou District five Township Wuxiang No. 552 West Road Applicant before: Ningbo Nanche New Energy Technology Co., Ltd. |
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Inventor after: Huang Qingfu Inventor after: Ruan Dianbo Inventor after: Fu Guansheng Inventor after: Wu Zhenhuan Inventor before: Zuo Feilong Inventor before: Ruan Dianbo Inventor before: Fu Guansheng Inventor before: Zhang Hongquan Inventor before: Chen Zhaoping Inventor before: Wu Zhenhuan |
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