CN108329216A - A kind of preparation method of high-purity ultracapacitor electrolysis matter quaternary ammonium salt - Google Patents
A kind of preparation method of high-purity ultracapacitor electrolysis matter quaternary ammonium salt Download PDFInfo
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- CN108329216A CN108329216A CN201711295660.7A CN201711295660A CN108329216A CN 108329216 A CN108329216 A CN 108329216A CN 201711295660 A CN201711295660 A CN 201711295660A CN 108329216 A CN108329216 A CN 108329216A
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- quaternary ammonium
- ammonium salt
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- 150000003242 quaternary ammonium salts Chemical class 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 12
- -1 silicic acid class quaternary ammonium salt Chemical class 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- 150000001412 amines Chemical class 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 7
- 239000012265 solid product Substances 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 238000005956 quaternization reaction Methods 0.000 claims abstract description 5
- 230000018044 dehydration Effects 0.000 claims abstract description 3
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical compound SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 6
- 150000004820 halides Chemical class 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 19
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000012043 crude product Substances 0.000 description 8
- 238000002484 cyclic voltammetry Methods 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 0 **1CCCC1 Chemical compound **1CCCC1 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 238000004255 ion exchange chromatography Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- HTLZVHNRZJPSMI-UHFFFAOYSA-N N-ethylpiperidine Chemical compound CCN1CCCCC1 HTLZVHNRZJPSMI-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 125000005910 alkyl carbonate group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- NIUZJTWSUGSWJI-UHFFFAOYSA-M triethyl(methyl)azanium;chloride Chemical compound [Cl-].CC[N+](C)(CC)CC NIUZJTWSUGSWJI-UHFFFAOYSA-M 0.000 description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000254173 Coleoptera Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- AGLSQWBSHDEAHB-UHFFFAOYSA-N azane;boric acid Chemical compound N.OB(O)O AGLSQWBSHDEAHB-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000001035 methylating effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/037—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements with quaternary ring nitrogen atoms
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The present invention provides a kind of preparation method of high-purity ultracapacitor electrolysis matter quaternary ammonium salt, and preparation process includes：(1) quaternization reaction generates silicic acid class quaternary ammonium salt to amine in organic solvent with alkyl silicate；(2) silicic acid class quaternary ammonium salt is reacted with acid generates quaternary ammonium salt, and after reaction solution filters solid, dehydration desolventizing obtains solid product；(3) solid product that step (2) obtains recrystallizes to obtain high-purity quaternary ammonium salt.The method prepares quaternary ammonium salt electrolytes, is participated in without halide, and purity is high.Thus the ultracapacitor that quaternary ammonium salt is made into is electrolysed matter, and content of halide ions is low, and chemical property is preferable.
Description
Technical field
It is specifically a kind of the present invention relates to the preparation method that a kind of high-purity ultracapacitor is electrolysed matter quaternary ammonium salt
After amine is reacted with alkyl silicate, then with sour react prepare the preparation method of quaternary ammonium salt.
Background technology
Ultracapacitor, be called do double layer capacitor (Ectrochemical Double-Layer Capacitors,
EDLCs), there is higher energy density than conventional electrostatic capacitor, be between general than the power density that secondary cell has bigger
Novel energy memory device between energization pond and conventional electrostatic capacitor.Since ultracapacitor has power density high, follow
It the advantages that ring long lifespan, the charge and discharge time is short and use temperature range is wide, has broad application prospects, becomes research
Hot spot.
Electrolyte is the important component of ultracapacitor, is had a great impact to the performance of ultracapacitor.Quaternary ammonium
Salt, especially methyltriethylammonitetrafluoroborate tetrafluoroborate, N, N- dimethyl pyrroles ammonium tetrafluoroborate, 1,3- methylimidazole tetrafluoro boron
Sour ammonium, there is good dissolubility in polar organic solvent, has higher conductivity；Almost without vapour pressure, can eliminate
Because of the pollution generated to environment of volatilizing；Operating temperature range is wide, explosion-proof performance and flame retardant property are preferable, has higher safety
The advantages that performance, is widely used as ultracapacitor electrolysis matter.
Fluoboric acid, the hexafluorophosphoric acid class quaternary ammonium salt of matter are electrolysed as ultracapacitor, such as methyl triethyl group tetrafluoro boric acid
Ammonium, N, N- dimethyl pyrroles ammonium tetrafluoroborate, 1,3- methylimidazole ammonium tetrafluoroborates, synthetic method have following three kinds：
(1) method one, be halogenated quaternary ammonium salt is first converted to quaternary ammonium base, then with corresponding sour neutralization reaction, obtain target product.Specially
Sharp CN 104892433A disclose a kind of preparation method of methyltriethylammonitetrafluoroborate tetrafluoroborate, are first to prepare methyl triethyl group chlorine
Change ammonium, then reacted with sodium hydroxide or potassium hydroxide and be converted to methyl triethyl group hydroxide, then reacted with tetrafluoro boric acid, is obtained
To methyltriethylammonitetrafluoroborate tetrafluoroborate.
The synthetic method has halide participation, halide ion to be not easy removal totally, can influence the electrochemistry of ultracapacitor
Performance.In order to remove halide ion as possible, patent JP 2011192963A are using silver oxide with methyl triethyl ammonium chloride in water
It is reacted in solution, prepares methyl triethyl group hydroxide, then react with tetrafluoro boric acid, obtain methyltriethylammonitetrafluoroborate tetrafluoroborate.
Although the method can almost remove halide ion, cost is too high.(2) method two are alkylation with alkyl sodium sulfate ester
Reagent is reacted with amine prepares sulfuric acid quaternary ammonium salt, then is reacted with corresponding acid, obtains target product.Patent CN 101328128A
It discloses diethylamine or triethylamine and dimethyl suflfate quaternization reaction, generates sulfuric acid quaternary ammonium salt, then anti-with hexafluorophosphoric acid
It should obtain corresponding product.Although this method synthesis technology is simple, high income, and the not introducing of halide ion, sulphur
Acid alkyl ester toxicity is big, and environmental pollution is serious, so limiting its use.(3) method three, using alkyl carbonate as alkyl
Change reagent and react preparation carbonic acid class quaternary ammonium salt with amine, then reacted with corresponding acid, obtains target product.Patent CN
102584602A is disclosed positive tripropyl amine (TPA) or piperazine and dimethyl carbonate quaternization reaction, generation carbonic acid class quaternary ammonium salt, then with
Corresponding product is obtained by the reaction in fluoboric acid or hexafluorophosphoric acid.Although the introducing of the not no halide ion of this method, alkyl carbonate
The activity of ester is low, and reaction needs to carry out in pressure-resistant kettle, and process conditions are complicated, increase production cost.
Invention content
It is an object of the invention to overcome the shortcomings of above-mentioned fluoboric acid, hexafluorophosphoric acid class quaternary ammonium salt synthetic method, one is provided
The preparation method of kind high-purity ultracapacitor electrolysis matter quaternary ammonium salt.
The realization of the object of the invention, includes the following steps：
(1) quaternization reaction generates silicic acid class quaternary ammonium salt to amine in organic solvent with alkyl silicate；
(2) silicic acid class quaternary ammonium salt is reacted with acid generates quaternary ammonium salt, and after reaction solution filters solid, dehydration desolventizing obtains solid
Product；
(3) solid product that step (2) obtains recrystallizes to obtain high-purity quaternary ammonium salt.
In the step (1), amine is with one kind of lower structure：
Wherein：R1Represent hydrogen or C1~C4Alkyl；R2、R3Represent C1~C4Alkyl.
In the step (1), alkyl silicate is one kind in quanmethyl silicate, tetraethyl orthosilicate.
In the step (1), the molar ratio of amine and alkyl silicate is 1.0:1.5~1.0:2.6, reaction temperature 70
DEG C~150 DEG C, the reaction time is 5h~16h.
In the step (1), organic solvent is one kind in the corresponding alcohol of alkyl silicate, DMF, DMSO.
In the step (2), acid is one kind in tetrafluoro boric acid, hexafluorophosphoric acid, thiocyanic acid.
In the step (2), the molar ratio of silicic acid class quaternary ammonium salt and acid is 1.0:1.0~1.0:2.2.
Advantageous effect：The advantage of the invention is that using alkyl silicate as methylating reagent, join without halide
With, therefore there is no halide residual in product, purity is high.Thus the ultracapacitor that quaternary ammonium salt is made into is electrolysed matter, halide ion
Content is low, and chemical property is preferable.
Description of the drawings
Fig. 1 is the cyclic voltammetry curve with acetontrile at electrolyte by methyltriethylammonitetrafluoroborate tetrafluoroborate；
Fig. 2 is by N, and N- dimethyl pyrroles ammonium thiocyanate is with acetontrile at the cyclic voltammetry curve of electrolyte；
Fig. 3 is the cyclic voltammetry curve with acetontrile at electrolyte by 1- methyl -3- ethyl imidazol(e)s ammonium tetrafluoroborate；
Fig. 4 is by N, and N- diethyl phenylpiperidines ammonium hexafluorophosphates are with acetontrile at the cyclic voltammetry curve of electrolyte.
Specific implementation method
The application is illustrated and further understood below in conjunction with specific embodiment, but embodiment only conduct
Example provides, and is not intended as whole technical solutions of the present invention, is not limited overall technical solution.It is all that there is phase
Same or similar technique feature, simple change or replacement, belong to the scope of the present invention.
Embodiment 1
By quanmethyl silicate (22.83g, 0.15mol), triethylamine (10.12g, 0.1mol), 30mL absolute methanols are added
Into autoclave, stirring, 120 DEG C or so reaction 8h.After reaction, desolventizing is rotated, the sticky methyl of 30.81g is obtained
Triethyl group silicic acid class quaternary ammonium salt.
40% tetrafluoroborate solution (32.93g, 0.15mol) is added dropwise in methyl triethyl group silicic acid class quaternary ammonium salt, stirs
Mix reaction 0.5 hour.After reaction, reaction solution muddiness crystallisation by cooling filters solid, and filtrate rotates desolventizing and water,
Crude product 19.98g, yield 98.4% are obtained, crude product is recrystallized with 50mL absolute methanols, obtains the high-purity methyl triethyl groups of 17.23g
Ammonium tetrafluoroborate, yield 84.9%, yield is calculated on the basis of the amount of triethylamine, also has product in filtrate.
Product carries out nucleus magnetic hydrogen spectrum and carbon spectrum test, as a result as follows：
1H-NMR(D2O) δ, ppm：1.21~2.25 (t, 9H, N-CH2-CH3), 2.82~2.91 (s, 3H, N-CH3),
3.19~3.23 (q, 6H, N-CH2)。
13C-NMR(D2O)：
Product is detected through ion chromatography, and with reacted with tetrafluoro boric acid by methyl triethyl ammonium chloride prepare sample pair
Than wherein the former is denoted as sample 1, and contrast sample is denoted as sample 2, as a result as follows.
By the methyltriethylammonitetrafluoroborate tetrafluoroborate of preparation with acetontrile at the electrolyte of 1mol/L, in electrochemical operation
Cyclic voltammetry is carried out on standing referring to attached drawing 1, for curve close to rectangle, chemical property is preferable.
Embodiment 2
By quanmethyl silicate (228.33g, 1.5mol), N- crassitudes (85.14g, 1.0mol), 300mL is without water beetle
Alcohol is added in autoclave, stirring, 115 DEG C or so reaction 8h.After reaction, desolventizing is rotated, 301.56g is obtained
Sticky N, N- dimethyl pyrrole silicic acid class quaternary ammonium salt.
In N, N- dimethyl pyrrole silicic acid class quaternary ammonium salts be added dropwise 50% thiocyanic acid aqueous solution (177.27g,
1.5mol), it is stirred to react 0.5 hour, after reaction, reaction solution muddiness crystallisation by cooling filters solid, filtrate revolving
Desolventizing and water, obtain crude product 156.01g, yield 98.6%, and crude product is recrystallized with 500mL absolute methanols, obtained
131.65g high-purity Ns, N- dimethyl pyrrole ammonium thiocyanates, yield 83.2%, yield are counted on the basis of the amount of N- crassitudes
It calculates, also has product in filtrate.
Product carries out nucleus magnetic hydrogen spectrum and carbon spectrum test, as a result as follows：
1H-NMR(D2O) δ, ppm：2.23~2.29 (t, 4H, CH2), 3.17~3.35 (s, 6H, N-CH3), 3.52~
3.63 (q, 4H, N-CH2)。
13C-NMR(D2O)：
Product is detected through ion chromatography, and with by N, N- dimethyl pyrroles ammonium chloride reacts the sample prepared with thiocyanic acid
Comparison, wherein the former is denoted as sample 3, and contrast sample is denoted as sample 4, as a result as follows.
By the N of preparation, N- dimethyl pyrroles ammonium thiocyanate with acetontrile at the electrolyte of 1mol/L, in electrochemistry work
Upper progress cyclic voltammetry stand referring to attached drawing 2, for curve close to rectangle, chemical property is preferable.
Embodiment 3
By tetraethyl orthosilicate (156.25g, 0.75mol), 1- methylimidazoles (41.05g, 0.5mol), 150mL DMSO add
Enter into autoclave, stirs, 110 DEG C or so reaction 7h.After reaction, desolventizing is rotated, it is sticky to obtain 186.25g
1- methyl -3- ethyl imidazol(e) silicic acid class quaternary ammonium salts.
In 1- methyl -3- ethyl imidazol(e) silicic acid class quaternary ammonium salts be added dropwise 40% tetrafluoroborate solution (164.63g,
0.75mol), it is stirred to react 0.5 hour, after reaction, reaction solution muddiness crystallisation by cooling filters solid, filtrate revolving
Desolventizing and water obtain crude product 97.86g, yield 98.9%, and crude product is recrystallized with 250mL absolute methanols, obtains 81.24g
High-purity 1- methyl -3- ethyl imidazol(e) ammonium tetrafluoroborates, yield 82.1%, yield are calculated on the basis of the amount of 1- methylimidazoles, filter
There is product in liquid.
Product carries out nucleus magnetic hydrogen spectrum and carbon spectrum test, as a result as follows：
1H-NMR(D2O) δ, ppm：0.93~0.96 (s, 3H, CH3), 1.45~1.51 (s, 2H, CH2), 3.81~3.89
(s, 3H, CH3), 7.32~7.41 (s, 2H, CH), 8.72~8.84 (s, 1H, CH).
13C-NMR(D2O)：
Product is detected through ion chromatography, and with reacted with tetrafluoro boric acid by 1- methyl -3- ethyl imidazol(e)s ammonium chlorides prepare
Sample compares, and wherein the former is denoted as sample 5, and contrast sample is denoted as sample 6, as a result as follows.
By the 1- methyl -3- ethyl imidazol(e)s ammonium tetrafluoroborate of preparation with acetontrile at the electrolyte of 1mol/L, in electrification
It learns and carries out cyclic voltammetry on work station referring to attached drawing 3, for curve close to rectangle, chemical property is preferable.
Embodiment 4
By tetraethyl orthosilicate (208.33g, 1.0mol), N-ethylpiperidine (41.05g, 0.5mol), 200mL DMF are added
Into autoclave, stirring, 110 DEG C or so reaction 7h.After reaction, desolventizing is rotated, the sticky N of 239.38g are obtained,
N- diethyl phenylpiperidines silicic acid class quaternary ammonium salts.
In N, N- diethyl phenylpiperidines silicic acid class quaternary ammonium salts be added dropwise 60% hexafluorophosphoric acid aqueous solution (243.31g,
1.0mol), it is stirred to react 0.5 hour, after reaction, reaction solution muddiness crystallisation by cooling filters solid, filtrate revolving
Desolventizing and water, obtain crude product 127.12g, yield 98.1%, and crude product is recrystallized with 300mL absolute methanols, obtained
108.06g high-purity Ns, N- diethyl phenylpiperidines ammonium hexafluorophosphates, yield 83.4%, yield is counted on the basis of the amount of N-ethylpiperidine
It calculates, also has product in filtrate.
Product carries out nucleus magnetic hydrogen spectrum and carbon spectrum test, as a result as follows：
1H-NMR(D2O) δ, ppm：1.29~1.34 (s, 2H, CH2), 1.73~1.79 (s, 4H, CH2), 3.21~3.28
(s, 4H, CH2), 3.37~3.42 (s, 6H, CH3)。
13C-NMR(D2O)：
Product is detected through ion chromatography, and with by N, N- diethyl phenylpiperidines ammonium chlorides react the sample prepared with hexafluorophosphoric acid
Product compare, and wherein the former is denoted as sample 7, and contrast sample is denoted as sample 8, as a result as follows.
By the N of preparation, N- diethyl phenylpiperidines ammonium hexafluorophosphates with acetontrile at the electrolyte of 1mol/L, in electrochemistry
Cyclic voltammetry is carried out on work station referring to attached drawing 4, for curve close to rectangle, chemical property is preferable.
Claims (7)
1. a kind of preparation method of high-purity ultracapacitor electrolysis matter quaternary ammonium salt, it is characterised in that this method includes following step
Suddenly：
(1) quaternization reaction generates silicic acid class quaternary ammonium salt to amine in organic solvent with alkyl silicate；
(2) silicic acid class quaternary ammonium salt is reacted with acid generates quaternary ammonium salt, and after reaction solution filters solid, dehydration desolventizing obtains solid product；
(3) solid product that step (2) obtains recrystallizes to obtain high-purity quaternary ammonium salt.
2. a kind of preparation method of high-purity ultracapacitor electrolysis matter quaternary ammonium salt according to claim 1, feature exist
In amine is with one kind of lower structure in the step (1)：
Wherein：R1Represent hydrogen or C1~C4Alkyl；R2、R3Represent C1~C4Alkyl.
3. a kind of preparation method of high-purity ultracapacitor electrolysis matter quaternary ammonium salt according to claim 1, feature exist
In alkyl silicate is one kind in quanmethyl silicate, tetraethyl orthosilicate in the step (1).
4. a kind of preparation method of high-purity ultracapacitor electrolysis matter quaternary ammonium salt according to claim 1, feature exist
In the molar ratio of amine and alkyl silicate is 1.0 in the step (1):1.5~1.0:2.6, reaction temperature is 70 DEG C~150
DEG C, the reaction time is 5h~16h.
5. a kind of preparation method of high-purity ultracapacitor electrolysis matter quaternary ammonium salt according to claim 1, feature exist
In step (1) organic solvent is one kind in the corresponding alcohol of alkyl silicate, DMF, DMSO.
6. a kind of preparation method of high-purity ultracapacitor electrolysis matter quaternary ammonium salt according to claim 1, feature exist
In acid is one kind in tetrafluoro boric acid, hexafluorophosphoric acid, thiocyanic acid in the step (2).
7. a kind of preparation method of high-purity ultracapacitor electrolysis matter quaternary ammonium salt according to claim 1, feature exist
In the molar ratio of silicic acid class quaternary ammonium salt and acid is 1.0 in the step (2):1.0~1.0:2.2.
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| KR20240022779A (en) | 2022-08-12 | 2024-02-20 | 삼화페인트공업주식회사 | Method for preparing high purity quaternary ammonium salt |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4786429A (en) * | 1986-06-20 | 1988-11-22 | Mitsubishi Petrochemical Co., Ltd. | Electrolyte for aluminum electrolytic capacitor |
| CN102584602A (en) * | 2011-01-05 | 2012-07-18 | 中国科学院长春应用化学研究所 | Quaternary ammonium salt and preparation method thereof |
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2017
- 2017-12-08 CN CN201711295660.7A patent/CN108329216A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4786429A (en) * | 1986-06-20 | 1988-11-22 | Mitsubishi Petrochemical Co., Ltd. | Electrolyte for aluminum electrolytic capacitor |
| CN102584602A (en) * | 2011-01-05 | 2012-07-18 | 中国科学院长春应用化学研究所 | Quaternary ammonium salt and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20240022779A (en) | 2022-08-12 | 2024-02-20 | 삼화페인트공업주식회사 | Method for preparing high purity quaternary ammonium salt |
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