CN104387397A - Preparation method of spiro-quaternary ammonium salt electrolyte - Google Patents
Preparation method of spiro-quaternary ammonium salt electrolyte Download PDFInfo
- Publication number
- CN104387397A CN104387397A CN201410596816.5A CN201410596816A CN104387397A CN 104387397 A CN104387397 A CN 104387397A CN 201410596816 A CN201410596816 A CN 201410596816A CN 104387397 A CN104387397 A CN 104387397A
- Authority
- CN
- China
- Prior art keywords
- quaternary ammonium
- ammonium salt
- preparation
- salt electrolyte
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000003792 electrolyte Substances 0.000 title claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 50
- -1 cyclic amine Chemical class 0.000 claims abstract description 49
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims abstract description 10
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims abstract description 10
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003495 polar organic solvent Substances 0.000 claims abstract description 6
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006482 condensation reaction Methods 0.000 claims abstract description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 15
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000004793 Polystyrene Substances 0.000 claims description 11
- 239000003729 cation exchange resin Substances 0.000 claims description 11
- 239000012043 crude product Substances 0.000 claims description 11
- 229910052763 palladium Inorganic materials 0.000 claims description 11
- 229920002223 polystyrene Polymers 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001953 recrystallisation Methods 0.000 claims description 7
- 150000002576 ketones Chemical class 0.000 claims description 4
- 150000002825 nitriles Chemical group 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- 229910052736 halogen Inorganic materials 0.000 abstract description 11
- 150000002367 halogens Chemical class 0.000 abstract description 11
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 abstract description 7
- 150000002009 diols Chemical class 0.000 abstract description 4
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000000376 reactant Substances 0.000 abstract 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 30
- 239000000243 solution Substances 0.000 description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000013078 crystal Substances 0.000 description 7
- 230000003292 diminished effect Effects 0.000 description 7
- 239000012442 inert solvent Substances 0.000 description 7
- 238000004255 ion exchange chromatography Methods 0.000 description 7
- 238000003918 potentiometric titration Methods 0.000 description 7
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 5
- UREZNYTWGJKWBI-UHFFFAOYSA-M benzethonium chloride Chemical compound [Cl-].C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 UREZNYTWGJKWBI-UHFFFAOYSA-M 0.000 description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000012093 Myrtus ugni Nutrition 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 244000061461 Tema Species 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D498/10—Spiro-condensed systems
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention relates to a preparation method of a spiro-quaternary ammonium salt electrolyte. The preparation method is characterized by subjecting a cyclic amine, diol and a strong acid to condensation reaction at 120-180 DEG C for 8-16 hours in a polar organic solvent in the presence of a catalyst, and then purifying the reactant, thus obtaining the spiro-quaternary ammonium salt electrolyte, wherein the cyclic amine is any one of pyrrolidone, piperidine and morpholine; diol is 1,4-butanediol or 1,5-pentanediol; the strong acid is any one of tetrafluoroboric acid, trifluoromethanesulfonic acid and bis(trifluoromethanesulfonyl)imidic acid; the feed mole ratio of the cyclic amine to diol to the strong acid is 1 to (0.7-0.9) to (0.8-1). The preparation method has the advantages that the raw materials are cheap; the whole synthetic reaction is good in selectivity; the product has high yield and high purity; no halide ions are introduced in the reaction process, and the content of halogen in the obtained target product is less than 1ppm, so that the preparation method can meet the requirements of electrochemical energy storage electrolytes and is suitable for industrial production.
Description
Technical field
The invention belongs to the field of chemical synthesis, be specifically related to a kind of preparation method of spiro quaternary ammonium salt electrolyte.
Background technology
Due to electrochemical energy storing device particularly ultracapacitor there is the Large Copacity energy-storage property that excellent pulse charge-discharge performance and conventional physical electric capacity do not have, the application in high energy pulse laser has caused the extensive attention of people.Meanwhile, because its stored energy is large, quality is light, can repeatedly discharge and recharge and be used as department of computer science by people and unify the standby power supply of wireless telecommunications system.Along with the rise of environmental-protecting type electric automotive research; electrochemical capacitor and lead-acid cell and other batteries are with the use of forming composite battery; be applied to the power initiation system of electromobile; protection store battery and energy-conservation effect is played in the starting of vehicle, acceleration, braking procedure, or directly as the power supply of power truck.Also big current instantaneously can be provided for the start up system of oil engine and other engine of heavy-duty cars.Due to electrochemical capacitor, there is above advantage and apply widely, since the sixties, just having started the extensive research to using various use gac as the double electric layer electrochemical electric capacity of electrode materials.At present, the organic electrolyte that commercial widely used ultracapacitor is is electrolytic salt with TEA (tetraethyl ammonium a tetrafluoro borate) and TEMA (triethyl first ammonium a tetrafluoro borate), but under severe conditions and need the field that uses under big current, there is the shortcomings such as specific conductivity is low, capacity is low, poor performance at low temperatures, energy density are low, therefore develop high conductance, Large Copacity, the electrolytic salt of high temperature performance excellence becomes the breach that ultracapacitor develops to extensive energy storage device.
Be widely studied relative to non-cyclic quaternary ammonium salts positively charged ion (CN200610111648, CN201210552334 and CN201110278474) and be applied in ultracapacitor.In this case, in order to improve its low-temperature performance, specific conductivity and capacity, there will be a known and use spiro quaternary ammonium salt as the new ionogen of a class, for in electrolytic solution, at patent documentation (CN201010594705, CN201210475201, CN200680040555, US6469888) cyclic amine is described in and dihalo hydrocarbon carries out nucleophilic substitution reaction, first synthesize corresponding halogeno salt or glycol disulfonic acid ester, the building-up process of spiro quaternary ammonium salt is prepared again by ion-exchange, the method synthesis yield is lower, and halide-ions is there is in preparation process, in recrystallization process, halide-ions residual quantity is large, have a strong impact on its use in electrochemical energy storage element, be difficult to the requirement meeting electrochemical product.
Summary of the invention
Technical problem to be solved by this invention is to provide the preparation method of the spiro quaternary ammonium salt electrolyte that halogen ion-free in a kind of product remains.
For achieving the above object, the technical solution used in the present invention is:
A preparation method for spiro quaternary ammonium salt electrolyte, in polar organic solvent, by cyclic amine, glycol and strong acid under the effect of catalyzer, carries out condensation reaction 8 ~ 16h at 120 DEG C ~ 180 DEG C, and then purifying obtains described spiro quaternary ammonium salt electrolyte;
Wherein, described cyclic amine is any one in Pyrrolidine, hexahydropyridine, morpholine;
Described glycol is Isosorbide-5-Nitrae butyleneglycol or 1,5 pentanediols;
Described strong acid is any one in Tetrafluoroboric acid, trifluoromethanesulfonic acid, two (trimethyl fluoride sulfonyl) imidic acid;
The molar ratio of described cyclic amine, described glycol, described strong acid is 1:0.7 ~ 0.9:0.8 ~ 1.
The structure of described spiro quaternary ammonium salt electrolyte is as follows:
Wherein, n, m are 1,2 or 3 independently; P, q are 1,2 or 3 independently; Y
-for SO
3cF
3 -, BF
4 -, PF
6 -, N (SO
2f)
-, N (SO
2cF
3)
-in any one.
Preferably, described Tetrafluoroboric acid feeds intake with the aqueous solution form that massfraction is 30 ~ 50%.
Preferably, the molar ratio of described cyclic amine, described glycol, described strong acid is 1:0.8 ~ 0.85:0.9 ~ 0.95.
Preferably, described catalyzer is polystyrene storng-acid cation exchange resin and deoxidation type palladium catalyst is the composite catalyst that 20 ~ 50:1 is mixed to get in mass ratio.
Further preferably, the mass ratio of described polystyrene storng-acid cation exchange resin and described deoxidation type palladium catalyst is 28 ~ 35:1.
Preferably, the charging capacity of described catalyzer is 1% ~ 5% of described cyclic amine quality.
Further preferably, the charging capacity of described catalyzer is 1.5% ~ 2.5% of described cyclic amine quality.
Preferably, described polar organic solvent is nitrile organic solvent or organic solvent of ketone.
Further preferably, described polar organic solvent is acetonitrile or acetone.
Preferably, the concrete steps of described purification are: after reacting liquid filtering condensation reaction obtained, vacuum concentration at 115 DEG C ~ 125 DEG C, then carry out crystallization in ethanol and obtain spiro quaternary ammonium salt crude product, then described spiro quaternary ammonium salt crude product is with an organic solvent carried out recrystallization and obtain described spiro quaternary ammonium salt electrolyte.
Further preferably, the organic solvent that described recrystallization uses is nitrile organic solvent, alcohol organic solvent or organic solvent of ketone.
Still more preferably, described organic solvent is methyl alcohol, acetonitrile or acetone.
Because technique scheme is used, the present invention compared with prior art has following advantages:
Cost of material of the present invention is cheap, and the selectivity of whole building-up reactions is good, and product yield is high, purity is high, and in reaction process, halogen ion-free is introduced, and obtains content of halogen in target product and is less than 1ppm, the requirement of electrochemical energy storage electrolytic solution can be met, be applicable to suitability for industrialized production.
Accompanying drawing explanation
Accompanying drawing 1 is the hydrogen nuclear magnetic resonance spectrogram of Tetrafluoroboric acid spiral shell 1,1 '-bis-pyrroles's quaternary ammonium salt;
Accompanying drawing 2 is reaction equation of the present invention.
Embodiment
Below in conjunction with specific embodiment, the present invention is elaborated:
Embodiment 1: the preparation of Tetrafluoroboric acid spiral shell 1,1 '-bis-pyrroles's quaternary ammonium salt
In 2L tetrafluoro autoclave, under whipped state, add inert solvent acetonitrile (328g, 8mol) successively, Pyrrolidine (71g, 1mol), 1,4 butyleneglycols (75g, 0.83mol), composite catalyst (0.046g deoxidation type palladium catalyst; 1.375g polystyrene storng-acid cation exchange resin), then slowly add the tetrafluoroborate solution (179g, containing Tetrafluoroboric acid 81g) of 45% concentration, be warming up to 150 DEG C of reactions 8 hours.Above-mentioned reaction solution is down to room temperature, filtration under diminished pressure, under vacuum 120 DEG C of conditions, is concentrated into semi-solid.Concentrated solution adds ethanol in proper amount after being cooled to 60 DEG C, namely produces a large amount of white crystal, filters and obtains Tetrafluoroboric acid spiral shell 1,1 '-bis-pyrroles's quaternary ammonium salt crude product, and then use recrystallizing methanol dry, yield is 88%.
Proton nmr spectra result: 1H NMR (400MHz, D
2o): δ=2.17 (8*H, 4*CH
2), δ=3.49 (8*H, 4*CH
2), δ=4.8 (D
2o)
Ion chromatography product purity is 99.8%
Detect through ICP: Na:2ppm, K:1ppm, Fe:1ppm, Ca:1.0ppm.
Through potentiometric titration: halogen does not detect.
Embodiment 2: the preparation of Tetrafluoroboric acid spiral shell pyrroles-1,1 '-piperidines quaternary ammonium salt
In 2L tetrafluoro autoclave, under whipped state, add inert solvent acetonitrile (328g, 8mol) successively, hexahydropyridine (85g, 1mol), 1,4 butyleneglycols (75g, 0.83mol), composite catalyst (0.055g deoxidation type palladium catalyst; 1.65g polystyrene storng-acid cation exchange resin), then slowly add the tetrafluoroborate solution (179g, containing Tetrafluoroboric acid 81g) of 45% concentration, be warming up to 150 DEG C of reactions 8 hours.Above-mentioned reaction solution is down to room temperature, filtration under diminished pressure, under vacuum 120 DEG C of conditions, is concentrated into semi-solid.Concentrated solution adds ethanol in proper amount after being cooled to 60 DEG C, namely produces a large amount of white crystal, filters and obtains Tetrafluoroboric acid spiral shell pyrroles-1,1 '-piperidines quaternary ammonium salt crude product, and then use recrystallizing methanol dry, yield is 82%.
Ion chromatography product purity is 99.2%
Detect through ICP: Na:3ppm, K:1.5ppm, Fe:0.8ppm, Ca:0.9ppm.
Through potentiometric titration: halogen does not detect.
Embodiment 3: the preparation of Tetrafluoroboric acid spiral shell 1,1 '-bis-piperidines quaternary ammonium salt
In 2L tetrafluoro autoclave, under whipped state, add inert solvent acetonitrile (328g, 8mol) successively, hexahydropyridine (85g, 1mol), 1,5 pentanediols (86.5g, 0.83mol), composite catalyst (0.055g deoxidation type palladium catalyst; 1.65g polystyrene storng-acid cation exchange resin), then slowly add the tetrafluoroborate solution (179g, containing Tetrafluoroboric acid 81g) of 45% concentration, be warming up to 155 DEG C of reactions 8 hours.Above-mentioned reaction solution is down to room temperature, filtration under diminished pressure, under vacuum 120 DEG C of conditions, is concentrated into semi-solid.Concentrated solution adds ethanol in proper amount after being cooled to 60 DEG C, namely produces a large amount of white crystal, filters and obtains Tetrafluoroboric acid spiral shell 1,1 '-bis-piperidines quaternary ammonium salt crude product, and then use acetone recrystallization dry, yield is 78%.
Ion chromatography product purity is 99.4%
Detect through ICP: Na:2.5ppm, K:0.77ppm, Fe:0.98ppm, Ca:1.2ppm.
Through potentiometric titration: halogen does not detect.
Embodiment 4: the preparation of Tetrafluoroboric acid spiral shell pyrroles-1,1 '-morpholine hyamine
In 2L tetrafluoro autoclave, under whipped state, add inert solvent acetonitrile (328g, 8mol) successively, morpholine (87g, 1mol), 1,4 butyleneglycols (75g, 0.83mol), composite catalyst (0.055g deoxidation type palladium catalyst; 1.65g polystyrene storng-acid cation exchange resin), then slowly add the tetrafluoroborate solution (179g, containing Tetrafluoroboric acid 81g) of 45% concentration, be warming up to 160 DEG C of reactions 8 hours.Above-mentioned reaction solution is down to room temperature, filtration under diminished pressure, under vacuum 120 DEG C of conditions, is concentrated into semi-solid.Concentrated solution adds ethanol in proper amount after being cooled to 60 DEG C, namely produces a large amount of white crystal, filters and obtains Tetrafluoroboric acid spiral shell pyrroles-1,1 '-morpholine hyamine crude product, and then use acetone recrystallization dry, yield is 75%.
Ion chromatography product purity is 99.0%
Detect through ICP: Na:0.88ppm, K:0.58ppm, Fe:0.44ppm, Ca:0.31ppm.
Through potentiometric titration: halogen does not detect.
Embodiment 5: the preparation of Tetrafluoroboric acid spiroperidol-1,1 '-morpholine hyamine
In 2L tetrafluoro autoclave, under whipped state, add inert solvent acetonitrile (328g, 8mol) successively, morpholine (87g, 1mol), 1,5 pentanediols (86.5g, 0.83mol), composite catalyst (0.055g deoxidation type palladium catalyst; 1.65g polystyrene storng-acid cation exchange resin), then slowly add the tetrafluoroborate solution (179g, containing Tetrafluoroboric acid 81g) of 45% concentration, be warming up to 160 DEG C of reactions 8 hours.Above-mentioned reaction solution is down to room temperature, filtration under diminished pressure, under vacuum 120 DEG C of conditions, is concentrated into semi-solid.Concentrated solution adds ethanol in proper amount after being cooled to 60 DEG C, namely produces a large amount of white crystal, filters and obtains Tetrafluoroboric acid spiroperidol-1,1 '-morpholine hyamine crude product, and then use recrystallized from acetonitrile dry, yield is 75%.
Ion chromatography product purity is 88.4%
Detect through ICP: Na:0.67ppm, K:0.36ppm, Fe:0.34ppm, Ca:0.13ppm.
Through potentiometric titration: halogen does not detect.
Embodiment 6: the preparation of trifluoromethanesulfonic acid spiral shell 1,1 '-bis-pyrroles's quaternary ammonium salt
In 2L tetrafluoro autoclave, under whipped state, add inert solvent acetone (464g, 8mol) successively, Pyrrolidine (71g, 1mol), 1,4 butyleneglycols (75g, 0.83mol), composite catalyst (0.046g deoxidation type palladium catalyst; 1.375g polystyrene storng-acid cation exchange resin), then slowly add trifluoromethanesulfonic acid (137g), be warming up to 150 DEG C of reactions 8 hours.Above-mentioned reaction solution is down to room temperature, filtration under diminished pressure, under vacuum 120 DEG C of conditions, is concentrated into semi-solid.Concentrated solution adds ethanol in proper amount after being cooled to 60 DEG C, namely produces a large amount of white crystal, filters and obtains trifluoromethanesulfonic acid 1,1 '-bis-pyrroles's quaternary ammonium salt crude product, and then use recrystallized from acetonitrile dry, yield is 88%.
Ion chromatography product purity is 99.5%
Detect through ICP: Na:1.9ppm, K:1.1ppm, Fe:0.88ppm, Ca:1.2ppm.
Through potentiometric titration: halogen does not detect.
Embodiment 7: the preparation of two (trimethyl fluoride sulfonyl) imines spiral shell 1,1 '-bis-pyrroles's quaternary ammonium salt
In 2L tetrafluoro autoclave, under whipped state, add inert solvent acetone (464g, 8mol) successively, Pyrrolidine (71g, 1mol), 1,4 butyleneglycols (75g, 0.83mol), composite catalyst (0.046g deoxidation type palladium catalyst; 1.375g polystyrene storng-acid cation exchange resin), then slowly add two (trimethyl fluoride sulfonyl) imidic acid (257g), be warming up to 150 DEG C of reactions 8 hours.Above-mentioned reaction solution is down to room temperature, filtration under diminished pressure, under vacuum 120 DEG C of conditions, is concentrated into semi-solid.Concentrated solution adds ethanol in proper amount after being cooled to 60 DEG C, namely produces a large amount of white crystal, filters and obtains trifluoromethanesulfonic acid 1,1 '-bis-pyrroles's quaternary ammonium salt crude product, and then use recrystallized from acetonitrile dry, yield is 91%.
Ion chromatography product purity is 99.4%
Detect through ICP: Na:1.4ppm, K:1.7ppm, Fe:0.75ppm, Ca:1.4ppm.
Through potentiometric titration: halogen does not detect.
Embodiment 8 ~ 17 sees the following form 1, and the embodiment in table 1 employs different cyclic amine, strong acid and diol system, and concrete preparation method is identical with embodiment 1.
Table 1
Above-described embodiment is only for illustrating technical conceive of the present invention and feature; its object is to person skilled in the art can be understood content of the present invention and implement according to this; can not limit the scope of the invention with this, all equivalences done according to spirit of the present invention change or modification all should be encompassed within protection scope of the present invention.
Claims (10)
1. the preparation method of a spiro quaternary ammonium salt electrolyte, it is characterized in that: in polar organic solvent, by cyclic amine, glycol and strong acid under the effect of catalyzer, at 120 DEG C ~ 180 DEG C, carry out condensation reaction 8 ~ 16h, then purifying obtains described spiro quaternary ammonium salt electrolyte;
Wherein, described cyclic amine is any one in Pyrrolidine, hexahydropyridine, morpholine;
Described glycol is Isosorbide-5-Nitrae butyleneglycol or 1,5 pentanediols;
Described strong acid is any one in Tetrafluoroboric acid, trifluoromethanesulfonic acid, two (trimethyl fluoride sulfonyl) imidic acid;
The molar ratio of described cyclic amine, described glycol, described strong acid is 1:0.7 ~ 0.9:0.8 ~ 1.
2. the preparation method of spiro quaternary ammonium salt electrolyte according to claim 1, is characterized in that: the aqueous solution form that described Tetrafluoroboric acid is 30 ~ 50% with massfraction feeds intake.
3. the preparation method of spiro quaternary ammonium salt electrolyte according to claim 1, is characterized in that: the molar ratio of described cyclic amine, described glycol, described strong acid is 1:0.8 ~ 0.85:0.9 ~ 0.95.
4. the preparation method of spiro quaternary ammonium salt electrolyte according to claim 1, is characterized in that: described catalyzer is polystyrene storng-acid cation exchange resin and deoxidation type palladium catalyst is the composite catalyst that 20 ~ 50:1 is mixed to get in mass ratio.
5. the preparation method of spiro quaternary ammonium salt electrolyte according to claim 4, is characterized in that: the mass ratio of described polystyrene storng-acid cation exchange resin and described deoxidation type palladium catalyst is 28 ~ 35:1.
6. the preparation method of spiro quaternary ammonium salt electrolyte according to claim 1, is characterized in that: the charging capacity of described catalyzer is 1% ~ 5% of described cyclic amine quality.
7. the preparation method of spiro quaternary ammonium salt electrolyte according to claim 6, is characterized in that: the charging capacity of described catalyzer is 1.5% ~ 2.5% of described cyclic amine quality.
8. the preparation method of spiro quaternary ammonium salt electrolyte according to claim 1, is characterized in that: described polar organic solvent is nitrile organic solvent or organic solvent of ketone.
9. the preparation method of spiro quaternary ammonium salt electrolyte according to claim 1, it is characterized in that: the concrete steps of described purification are: after reacting liquid filtering condensation reaction obtained, vacuum concentration at 115 DEG C ~ 125 DEG C, then carry out crystallization in ethanol and obtain spiro quaternary ammonium salt crude product, then described spiro quaternary ammonium salt crude product is with an organic solvent carried out recrystallization and obtain described spiro quaternary ammonium salt electrolyte.
10. the preparation method of spiro quaternary ammonium salt electrolyte according to claim 9, is characterized in that: the organic solvent that described recrystallization uses is nitrile organic solvent, alcohol organic solvent or organic solvent of ketone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410596816.5A CN104387397B (en) | 2014-10-29 | 2014-10-29 | A kind of preparation method of spiro quaternary ammonium salt electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410596816.5A CN104387397B (en) | 2014-10-29 | 2014-10-29 | A kind of preparation method of spiro quaternary ammonium salt electrolyte |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104387397A true CN104387397A (en) | 2015-03-04 |
| CN104387397B CN104387397B (en) | 2016-08-17 |
Family
ID=52605371
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410596816.5A Active CN104387397B (en) | 2014-10-29 | 2014-10-29 | A kind of preparation method of spiro quaternary ammonium salt electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104387397B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105448538A (en) * | 2015-12-07 | 2016-03-30 | 江苏国泰超威新材料有限公司 | Cyclic quaternary ammonium salt electrolyte, preparation method and application therefor |
| CN106117218A (en) * | 2016-06-23 | 2016-11-16 | 东莞东阳光科研发有限公司 | A kind of preparation method of Tetrafluoroboric acid spiro quaternary ammonium salt |
| CN108264513A (en) * | 2017-01-04 | 2018-07-10 | 三和涂料株式会社 | It is used to prepare the method for spiro quaternary ammonium salt |
| CN109020973A (en) * | 2018-09-06 | 2018-12-18 | 天津工业大学 | A kind of fluorine-containing sulfimide spiro quaternary ammonium salt electrolyte, preparation method and the usage |
| CN110357895A (en) * | 2019-07-15 | 2019-10-22 | 湖北锂诺新能源科技有限公司 | The preparation method of tetrafluoro boric acid spiro quaternary ammonium salt |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101300260A (en) * | 2005-08-30 | 2008-11-05 | 霍尼韦尔国际公司 | Method for synthesizing spiro quaternary ammonium systems |
| CN102093367A (en) * | 2010-12-18 | 2011-06-15 | 渤海大学 | Preparation method of spiro quaternary ammonium salt for organic electrolyte of super capacitor |
| CN102942581A (en) * | 2012-11-21 | 2013-02-27 | 渤海大学 | Spirocyclo-quaternary ammonium salt for supercapacitor and preparation method of spirocyclo-quaternary ammonium salt |
-
2014
- 2014-10-29 CN CN201410596816.5A patent/CN104387397B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101300260A (en) * | 2005-08-30 | 2008-11-05 | 霍尼韦尔国际公司 | Method for synthesizing spiro quaternary ammonium systems |
| US20130264510A1 (en) * | 2005-08-30 | 2013-10-10 | Honeywell International Inc. | Method for synthesizing quaternary ammonium systems |
| CN102093367A (en) * | 2010-12-18 | 2011-06-15 | 渤海大学 | Preparation method of spiro quaternary ammonium salt for organic electrolyte of super capacitor |
| CN102942581A (en) * | 2012-11-21 | 2013-02-27 | 渤海大学 | Spirocyclo-quaternary ammonium salt for supercapacitor and preparation method of spirocyclo-quaternary ammonium salt |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105448538A (en) * | 2015-12-07 | 2016-03-30 | 江苏国泰超威新材料有限公司 | Cyclic quaternary ammonium salt electrolyte, preparation method and application therefor |
| CN105448538B (en) * | 2015-12-07 | 2018-04-03 | 江苏国泰超威新材料有限公司 | A kind of cyclic quaternary salt electrolyte, its preparation method and application |
| CN106117218A (en) * | 2016-06-23 | 2016-11-16 | 东莞东阳光科研发有限公司 | A kind of preparation method of Tetrafluoroboric acid spiro quaternary ammonium salt |
| 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 |
| CN108264513A (en) * | 2017-01-04 | 2018-07-10 | 三和涂料株式会社 | It is used to prepare the method for spiro quaternary ammonium salt |
| EP3345908A1 (en) | 2017-01-04 | 2018-07-11 | Samhwa Paints Industries Co., Ltd. | Method for preparing spiro quaternary ammonium salt |
| JP2018108976A (en) * | 2017-01-04 | 2018-07-12 | 三和ペイント工業株式会社Ｓａｍｈｗａ Ｐａｉｎｔｓ Ｉｎｄ．Ｃｏ．，Ｌｔｄ． | Method for producing spiro quaternary ammonium salt |
| US10093677B2 (en) | 2017-01-04 | 2018-10-09 | Samhwa Paints Industries Co., Ltd. | Method for preparing spiro quaternary ammonium salt |
| CN108264513B (en) * | 2017-01-04 | 2020-12-22 | 三和涂料株式会社 | Process for preparing spiro quaternary ammonium salts |
| CN109020973A (en) * | 2018-09-06 | 2018-12-18 | 天津工业大学 | A kind of fluorine-containing sulfimide spiro quaternary ammonium salt electrolyte, preparation method and the usage |
| CN109020973B (en) * | 2018-09-06 | 2019-10-29 | 天津工业大学 | A kind of fluorine-containing sulfimide spiro quaternary ammonium salt electrolyte, preparation method and the usage |
| CN110357895A (en) * | 2019-07-15 | 2019-10-22 | 湖北锂诺新能源科技有限公司 | The preparation method of tetrafluoro boric acid spiro quaternary ammonium salt |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104387397B (en) | 2016-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104387397B (en) | A kind of preparation method of spiro quaternary ammonium salt electrolyte | |
| CN102942581B (en) | Ultracapacitor spiro quaternary ammonium salt and preparation method thereof | |
| CN102093367B (en) | Preparation method of spiro quaternary ammonium salt for organic electrolyte of super capacitor | |
| KR101016268B1 (en) | Electric double-layer capacitor | |
| EP3355400A1 (en) | Additive for electrolyte solutions | |
| WO2006077894A1 (en) | Quaternary ammonium salt, electrolyte, electrolyte solution and electrochemical device | |
| JP6671079B2 (en) | Ionic liquid, its production method and its use | |
| EP2973631A2 (en) | Methods of enhancing electrochemical double layer capacitor (edlc) performance and edlc devices formed therefrom | |
| US9257723B2 (en) | Aryl diazonium salt and use in an electrolytic solution of an electrochemical generator | |
| KR102118480B1 (en) | Electrolyte salt and electrolyte for electricity storage device, and electricity storage device | |
| EP1715496A1 (en) | Electric double layer capacitor | |
| CN102070651B (en) | Method for preparing organic electrolyte oxaspiro quatemary ammonium salt of super capacitor | |
| JP5947300B2 (en) | Electrochemical power generation device and method for producing such a power generation device | |
| CN104387386B (en) | A kind of preparation method of symmetrical spiro quaternary ammonium salt electrolyte | |
| JP2013519672A (en) | Low viscosity ionic liquid | |
| JP2016192435A (en) | Ion liquid, manufacturing method thereof and application thereof | |
| CN114105907A (en) | Pyrrolidine ionic liquid and preparation method and application thereof | |
| WO2013029237A1 (en) | Double-center bipyridyl cationic ion liquid, preparation method therefor and use thereof | |
| KR101462883B1 (en) | Manufacturing method of electrolyte | |
| CN106117217B (en) | A kind of preparation method of fluozirconate | |
| CN110498815B (en) | Bismuth porphyrin compound, preparation method and super capacitor applying same | |
| KR101763562B1 (en) | Manufacturing method of quaternary ammonium salt using methyl iodide | |
| CN108003033A (en) | A kind of preparation method of quaternary ammonium salt for super capacitor | |
| KR101781801B1 (en) | Electric double layer capacitor using the ethyldimethylpropylammonium tetrafluoroborate | |
| CN115124454A (en) | Synthesis method of spiro quaternary ammonium salt with complex structure, product and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |