CN102134190B - Polycarboxylic acid for electrolyte as well as preparation method and application thereof - Google Patents
Polycarboxylic acid for electrolyte as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a polycarboxylic acid for electrolyte as well as a preparation method and application thereof. The polycarboxylic acid for the electrolyte has a structural general formula, wherein R1, R2, R3 and R5 are hydrogen radicals and alkyl radicals; n is an integer from 2 to 12; m is an integer from 1 to 3; and R1, R2, R3 and R5 are same or different to each other. The ammonium salt of the polycarboxylic acid for the electrolyte has the advantages of high solubility in a menstruum, high conductivity, excellent high-low temperature resistance, long service life, and the like; and in addition, the invention has the advantages of simple preparation method, high yield, low foreign ion content and suitability for industrial large-scale production.
Description
Technical field
The invention belongs to aluminium electrolutic capacitor electrolytic solution synthesis technical field, refer to particularly a kind of used for electrolyte polycarboxylic acid and its production and use.
Background technology
The acid that the aluminum current electrolyte for electrolytic capacitor is commonly used and ammonium salt thereof have the boric acid ammonium salt, ammonium formiate, ammonium adipate, ammonium succinate, maleic acid ammonium, ammonium phthalate, quaternary ammonium salt, ammonium sebacate, ammonium azelate, ammonium benzoate etc.The acid that above-mentioned Working electrolyte is used and ammonium salt production technology maturation thereof, and accomplished scale production.But they exist, and solubleness in solvent is little, the problem that electrolytic conductivity is low, flash over voltage is not high, resistance to low temperature is poor and work-ing life is short of preparation, can not meet the modern high end Power capacitor industry, as the demand of medium-high voltage aluminum electrolytic capacitor.
In the lot of documents patent, disclose in recent years as: 2-butyl suberic acid (also claims 1; the 6-decane dicarboxylic acid) and ammonium salt; 1; the detailed applications of the materials such as 7-octane dicarboxylic acid and ammonium salt thereof; and this type of material all increases significantly at electrical property and on work-ing life, but be not enough to accomplish scale production about the prior art of its preparation and purification process.
Summary of the invention
The objective of the invention is to provide a kind of used for electrolyte polycarboxylic acid and its production and use; the ammonium salt of this used for electrolyte polycarboxylic acid has the characteristics such as solubleness is large in solvent, specific conductivity is high, high and low temperature resistance is good, long service life; and its preparation method is simple; productive rate is high; impurity ion content is low, is suitable for industrial scale production.
For achieving the above object, the structure of used for electrolyte polycarboxylic acid of the present invention is as shown in general formula (1), and formula (1) is
R wherein
1, R
2, R
3, R
5for hydrogen, alkyl, the integer that n is 2～12, the integer that m is 1～3, R
1, R
2, R
3, R
5mutually identical or different.
Further, R wherein
1, R
2, R
3, R
5for hydrogen, methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, amyl group, isopentyl or a kind of in base.
The preferred technical scheme of the present invention is, described R
1for ethyl, R
2, R
3, R
5for hydrogen, n=2, m=2, polycarboxylic acid is the 4-carboxymethyl-1,2 shown in formula (11), 4,9-undecane tetracarboxylic acid, because, if can descend as oversize its specific conductivity of carbochain number of the polycarboxylic acid of used for electrolyte, if but too short flash over voltage is not high, and its raw materials 2-ethyl cyclopentanone cost is lower.
Formula (11) is:
The preparation method of used for electrolyte polycarboxylic acid of the present invention comprises the following steps successively:
A, under the acid catalysis condition, naphthenone as represented as general formula (2) is reacted in alcoholic solvent with hydrogen peroxide;
B, the methylene-succinic acid diester that a step reaction products therefrom is meaned with general formula (3) react under metal-salt exists, the polycarboxylic acid ester products that the gained reaction product is as represented as general formula (4);
C, the multi-carboxylate that general formula (4) the is meaned reaction that is hydrolyzed in alkali lye, obtain general formula (5) expression polycarboxylic acid metal salt products;
D, the polycarboxylic acid metal-salt that general formula (5) is meaned carry out acidification with mineral acid, obtain with the represented used for electrolyte polycarboxylic acid product of general formula (1), wherein
Formula (2) is:
Formula (3) is:
Formula (4) is:
Formula (5) is
In formula (2), (3), (4) and (5), R
1, R
2, R
3, R
5for hydrogen, methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, amyl group, isopentyl or a kind of in base, the integer that n is 2～12, the integer that m is 1～3, R
1, R
2, R
3, R
5mutually identical or different, R, R
4for methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, amyl group, isopentyl or a kind of in base, M is sodium or potassium.
As preferred version:
Alcoholic solvent described in described a step is a kind of in methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol or the trimethyl carbinol.
Acid catalyst described in described a step is a kind of in sulfuric acid, perchloric acid, phosphoric acid, trifluoroacetic acid.
Naphthenone described in described a step is cyclobutanone, 2-methyl cyclobutanone, 2-ethyl cyclopentanone, 3-n-propyl cyclopentanone, pimelinketone, 3,3, a kind of in 5-trimethylcyclohexanone, 2-normal-butyl suberone or 3-tertiary butyl suberone.
Methylene-succinic acid diester described in described b step is a kind of in dimethyl itaconate, diethyl itaconate, methylene-succinic acid diisopropyl ester or dibutyl itaconate.
A kind of in the low price vitriol that metal-salt described in described b step is iron, copper, cobalt, titanium, tin or lower chloride.
In described c step, hydrolysis reaction alkali lye used can be a kind of in salt of wormwood, sodium carbonate, sodium hydroxide, potassium hydroxide, sodium methylate or sodium ethylate, and the weight concentration of alkali lye is 10～40%, and temperature of reaction is 70～120 ℃, and the reaction times is 4～20h.
The reaction equation of the preparation process of this used for electrolyte polycarboxylic acid is as follows:
R wherein
1, R
2, R
3, R
5for hydrogen, methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, amyl group, isopentyl or a kind of in base, the integer that n is 2～12, the integer that m is 1～3, R
1, R
2, R
3, R
5mutually identical or different; R, R
4can be methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, amyl group, isopentyl or a kind of in base, M be sodium or potassium, and mineral acid is sulfuric acid or hydrochloric acid.
The used for electrolyte polycarboxylic acid that gained general formula (1) is meaned is dissolved in appropriate methyl alcohol or ethanol, carry out passivation by positive resin-column, negative resin exchange column, positive negative resin hybrid switching post successively again, gained solution distillation for removing methanol after purifying, obtain used for electrolyte polycarboxylic acid of the present invention, its detrimental impurity (chlorion, iron ion) content is lower than 1ppm.
While using used for electrolyte polycarboxylic acid of the present invention preparation electrolytic solution, at first the used for electrolyte polycarboxylic acid is dissolved in pure flux, fully reacts to passing into ammonia in solution, can obtain the represented used for electrolyte polybasic carboxylic acid ammonium salt of formula (6),
Formula (6) is:
Its reaction equation is:
R wherein
1, R
2, R
3, R
5for hydrogen, methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, amyl group, isopentyl or base, the integer that n is 2～12, the integer that m is 1～3, R
1, R
2, R
3, R
5mutually identical or different.
Then, by above-mentioned general formula (6), represented used for electrolyte polybasic carboxylic acid ammonium salt is dissolved in ethylene glycol or gamma-butyrolactone, and the concentration of adjusting solution is 10～30%, is mixed with electrolytic solution.
The electrolytic solution that used for electrolyte polybasic carboxylic acid ammonium salt provided by the present invention is mixed with, have advantages of that ion content is low, specific conductivity is high, solubleness is high in the solvents such as ethylene glycol, glycerol, flash over voltage is high.The preparation method of this used for electrolyte polycarboxylic acid is simple simultaneously, productive rate is high, preparation condition is gentle, is suitable for industrial production.In addition, operation is simple to utilize the ammonium salt preparation electrolytic solution of this used for electrolyte polycarboxylic acid.The impurity ion content of the electrolytic solution be mixed with used for electrolyte polybasic carboxylic acid ammonium salt of the present invention is extremely low, and wherein chlorion is less than 1ppm, and sulfate radical is less than 1ppm, and iron ion is less than 1ppm, and heavy metal (in lead) is less than 1ppm.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail.
Embodiment 1
The preparation method of used for electrolyte polycarboxylic acid comprises the following steps:
A, fully dry and have in the 1L four-hole boiling flask of stirring, dropping funnel, thermometer and add anhydrous methanol 500ml, pimelinketone 49g (0.5mol) at a warp, be cooled to-5 ℃.Slowly drip vitriol oil 3.0g from dropping funnel again.After, the H of dropping volumetric concentration 30%
2o
2solution 57.8g, maintain the temperature at 8 ℃ of left and right, after, continue to stir 15min.
B, the dimethyl itaconate 79g (0.5mol) that will dissolve with methanol solvate are added drop-wise in reaction solution, maintain the temperature at-10～5 ℃.After, continue to stir 15min.FeSO by 140g
47H
2o slowly joins in reaction solution, keeps temperature below 5 ℃.After, continue to stir 30min.Add the 100g extracted with diethyl ether, after washing, distillation, except desolventizing, can obtain the carboxylicesters product.
C, above-mentioned carboxylicesters product is joined in the NaOH solution that the 800g weight concentration is 40%, be warming up to 70 ℃, reaction 18h, obtain the carboxylic acid sodium salt product.
D, the dilute sulphuric acid that is 50% by the 150g weight concentration by gained carboxylic acid sodium salt product carry out acidifying, can obtain carboxylic acid product and amount to 150.6g.
This carboxylic acid product is carried out to esterification refining, utilizes the rectified purified structure of determining various carboxylicesterss, then, by gained carboxylicesters product is carried out to nucleus magnetic hydrogen spectrum mensuration, obtain following result:
Wherein 1,2,8-octane tricarboxylic acid esterification resultant, the nucleus magnetic hydrogen spectrum data are as follows:
1h-NMR (CDCl
3, TMS is standard, δ ppm):
3.71(s，9H，OCH
3)，2.9(m，3H)，1.2-1.7(m，10H，CH
2CH
2CH
2)，2.35(t，2H，CH2).
4-(2-methoxyl group-2-oxoethyl)-1,2,4, the esterification resultant of 10-decane tetracarboxylic acid, the nucleus magnetic hydrogen spectrum data are as follows:
1h-NMR (CDCl
3, TMS is standard, δ ppm):
3.73(s，15H，OCH
3)，2.9(m，2H，CH，)，1.2-1.7(m，10H，CH
2CH
2CH
2)，2.35-2.7(t，4H，CH2，).2.0(d，2H，CH
2)
2,4,6-tri-(2-methoxyl group-2-oxoethyl)-dodecane pentacarboxylic acid esterification resultant, the nucleus magnetic hydrogen spectrum data are as follows:
1h-NMR (CDCl
3, TMS is standard, δ ppm):
3.73(s，24H，OCH
3)，2.6-2.7(m，6H，CH2，)，1.2-1.7(m，10H，CH
2CH
2CH
2)，2.35-2.5(t，6H，CH2，).2.0(d，4H，CH
2)。
According to refining data, calculate in known carboxylic acid product, 1,2,8-octane tricarboxylic acid weight percentage is 62%, is converted into 93.4g (0.38mol), and its structural formula is as shown in (7); 4-(2-methoxyl group-2-oxoethyl)-1,2,4,10-decane tetracarboxylic acid weight percentage is 20%, its structural formula is as shown in (8); 2,4,6-tri-(2-methoxyl group-2-oxoethyl)-dodecane pentacarboxylic acid weight percentage is 11%, and its structural formula is as shown in (9), and all the other are impurity.
This embodiment carboxylic acid product is that 8-octane tricarboxylic acid is main with 1,2 shown in formula (7).
According to the account form of mole number of the mole number/initiator of reaction molar yield=product, in the present embodiment 1,2, the tricarboxylic reaction molar yield of 8-octane is 0.38mol/0.5mol=76%.
Formula (7) is:
Formula (8) is:
Formula (9) is:
Embodiment 2
The preparation method of used for electrolyte polycarboxylic acid comprises the following steps:
A, with a step of embodiment 1;
B, the dimethyl itaconate 158g (1mol) that will dissolve with methanol solvate, be added drop-wise in reaction solution, maintains the temperature at-10～5 ℃.After, continue to stir 15min.FeSO by 140g
47H
2o slowly joins in reaction solution, keeps temperature below 5 ℃.After, continue to stir 30min.Add the 100g extracted with diethyl ether, after washing, distillation, except desolventizing, can obtain the carboxylicesters product.
C, above-mentioned carboxylicesters product is joined in the sodium methoxide solution that the 800g weight concentration is 10%, be warming up to 120 ℃, reaction 4h, obtain the carboxylic acid sodium salt product.
D, the dilute sulphuric acid that is 50% by the 150g weight concentration by gained carboxylic acid sodium salt product carry out acidifying, can obtain carboxylic acid product and amount to 243.8g.
This carboxylic acid product is carried out to esterification refining, again by gained carboxylicesters product is carried out to nucleus magnetic hydrogen spectrum mensuration, according to refining data, can be calculated, in the gained carboxylic acid product, structural formula is suc as formula the 4-shown in (8) (2-methoxyl group-2-oxoethyl)-1, the shared weight percent of 2,4,10-decane tetracarboxylic acid is 60%, for 131.6g (0.35mol), the carboxylic acid product of this embodiment is to take the carboxylic acid shown in formula (8) as main.
4-in the present embodiment (2-methoxyl group-2-oxoethyl)-1,2,4, the reaction molar yield of 10-decane tetracarboxylic acid is 0.35mol/0.5mol=70%.
Embodiment 3
The preparation method of used for electrolyte polycarboxylic acid comprises the following steps:
A, with a step of embodiment 1;
B, the dimethyl itaconate 237g (1.5mol) that will dissolve with methanol solvate, be added drop-wise in reaction solution, maintains the temperature at-10～5 ℃.After, continue to stir 15min.FeSO by 140g
47H
2o slowly joins in reaction solution, keeps temperature below 5 ℃.After, continue to stir 30min.Add the 100g extracted with diethyl ether, after washing, distillation, except desolventizing, can obtain the carboxylicesters product.
C, above-mentioned carboxylicesters product is joined to the Na that the 800g weight concentration is 20%
2cO
3in solution, be warming up to 100 ℃, reaction 10h, obtain carboxylic acid sodium salt.
D, the dilute sulphuric acid that is 50% by the 150g weight concentration by the gained sodium salt carry out acidifying, can obtain carboxylic acid product and amount to 286.7g.
This carboxylic acid product is carried out to esterification refining, again by gained carboxylicesters product is carried out to nucleus magnetic hydrogen spectrum mensuration, according to refining data, can be calculated, in the gained carboxylic acid product, structural formula is suc as formula 2 shown in (9), 4,6-tri-(2-methoxyl group-2-oxoethyl)-the shared weight percent of dodecane pentacarboxylic acid is 60%, is 172g (0.34mol), and the carboxylic acid product of this embodiment is to take the carboxylic acid shown in formula (9) as main.。
In the present embodiment 2,4, the reaction molar yield of 6-tri-(2-methoxyl group-2-oxoethyl)-dodecane pentacarboxylic acid is 0.34mol/0.5mol=68%.
Embodiment 4
The preparation method of used for electrolyte polycarboxylic acid comprises the following steps:
A, fully dry and have in the 1L four-hole boiling flask of stirring, dropping funnel, thermometer and add dehydrated alcohol 500ml, 2-ethyl cyclopentanone 56g (0.5mol) at a warp, be cooled to-5 ℃.Slowly drip perchloric acid 6.0g from dropping funnel again.After, the H of dropping volumetric concentration 30%
2o
2solution 57.8g, maintain the temperature at 8 ℃ of left and right, after, continue to stir 15min.
B, the diethyl itaconate 93g (0.5mol) that will dissolve through methanol solvate are added drop-wise in reaction solution, maintain the temperature at-10～5 ℃.After, continue to stir 15min.Cu by 112g
2sO
4slowly join in reaction solution, keep temperature below 5 ℃.After, continue to stir 30min.Add the 100g extracted with diethyl ether, after washing, distillation, except desolventizing, can obtain the carboxylicesters product.
C, above-mentioned carboxylicesters product is joined in the KOH solution that the 1000g weight concentration is 10%, be warming up to 70 ℃, reaction 5h, obtain carboxylic acid sylvite product.
D, the dilute sulphuric acid that is 50% by the 120g weight concentration by gained carboxylic acid sylvite product carry out acidifying, can obtain carboxylic acid product and amount to 156.1g.
This carboxylic acid product is carried out to esterification refining, again by gained carboxylicesters product is carried out to nucleus magnetic hydrogen spectrum mensuration, according to refining data, can be calculated, in the gained carboxylic acid product, structural formula is suc as formula 1 shown in (10), 2, the shared weight percent of 7-nonane tricarboxylic acid is 61.6%, is 96.2g (0.37mol).The carboxylic acid product formula of this embodiment be take the carboxylic acid shown in formula (10) as main.
The present embodiment 1,2, the tricarboxylic reaction molar yield of 7-nonane is 0.37mol/0.5mol=74%.
Formula (10) is:
Embodiment 5
The preparation method of used for electrolyte polycarboxylic acid comprises the following steps:
A, with a step of embodiment 4;
B, the diethyl itaconate 186g (1mol) that will dissolve through methanol solvate are added drop-wise in reaction solution, maintain the temperature at-10～5 ℃.After, continue to stir 15min.Cu by 112g
2sO
4slowly join in reaction solution, keep temperature below 5 ℃.After, continue to stir 30min.Add the 100g extracted with diethyl ether, after washing, distillation, except desolventizing, can obtain the carboxylicesters product.
C, above-mentioned carboxylicesters product is joined in the KOH solution that the 1000g weight concentration is 10%, be warming up to 70 ℃, reaction 5h, obtain carboxylic acid sylvite product.
D, the dilute sulphuric acid that is 50% by the 120g weight concentration by gained carboxylic acid sylvite product carry out acidifying, can obtain carboxylic acid product 217.7g.
This carboxylic acid product is carried out to esterification refining, again by gained carboxylicesters product is carried out to nucleus magnetic hydrogen spectrum mensuration, according to refining data, can be calculated, in the gained carboxylic acid product, structural formula is suc as formula the 4-carboxymethyl-1 shown in (11), 2, the shared weight percent of 4,9-undecane tetracarboxylic acid is 61%, is 132.6g (0.34mol).The carboxylic acid product of this embodiment is to take the carboxylic acid shown in formula (11) as main.
4-carboxymethyl-1,2,4 in the present embodiment, the reaction molar yield of 9-undecane tetracarboxylic acid is 0.34mol/0.5mol=68%.
Formula (11) is:
Embodiment 6
A, with a step of embodiment 4;
B, the diethyl itaconate 279g (1.5mol) that will dissolve through methanol solvate are added drop-wise in reaction solution, maintain the temperature at-10～5 ℃.After, continue to stir 15min.Cu by 112g
2sO
4slowly join in reaction solution, keep temperature below 5 ℃.After, continue to stir 30min.Add the 100g extracted with diethyl ether, after washing, distillation, except desolventizing, can obtain the carboxylicesters product.
C, above-mentioned carboxylicesters product is joined to the K that the 1000g weight concentration is 10%
2cO
3in solution, be warming up to 70 ℃, reaction 15h, obtain carboxylic acid sylvite product.
D, the dilute sulphuric acid that is 50% by the 120g weight concentration by gained carboxylic acid sylvite product carry out acidifying, can obtain carboxylic acid product and amount to 299.3g.
This carboxylic acid product is carried out to esterification refining, again by gained carboxylicesters product is carried out to nucleus magnetic hydrogen spectrum mensuration, according to refining data, can be calculated in the gained carboxylic acid product, structural formula is suc as formula 4 shown in (12), the two carboxymethyls-1,2 of 6-, 4, the shared weight percent of 6,11-tridecane pentacarboxylic acid is 58.2%, is 174.2g (0.335mol).The carboxylic acid product of this embodiment is to take the carboxylic acid shown in formula (12) as main.
In the present embodiment 4, the two carboxymethyls-1,2,4,6 of 6-, the reaction molar yield of 11-tridecane pentacarboxylic acid is 0.335mol/0.5mol=67%.
Formula (12) is:
Embodiment 7
The preparation method of used for electrolyte polycarboxylic acid comprises the following steps:
A, fully dry and have in the 1L four-hole boiling flask of stirring, dropping funnel, thermometer and add anhydrous n-propyl alcohol 500ml, 2-normal-butyl suberone 84g (0.5mol) at a warp, be cooled to-5 ℃.Slowly drip phosphatase 24 .0g from dropping funnel again.After, the H of dropping volumetric concentration 30%
2o
2solution 57.8g, maintain the temperature at 8 ℃ of left and right, after, continue to stir 15min.
B, the methylene-succinic acid diisopropyl ester 107.1g (0.5mol) that will dissolve through methanol solvate are added drop-wise in reaction solution, maintain the temperature at-10～5 ℃.After, continue to stir 15min.CoCl by 65g
2slowly join in reaction solution, keep temperature below 5 ℃.After, continue to stir 30min.Add the 100g extracted with diethyl ether, after washing, distillation, except desolventizing, can obtain the carboxylicesters product.
C, above-mentioned carboxylicesters product is joined in the KOH solution that the 1200g weight concentration is 20%, be warming up to 100 ℃, reaction 10h, obtain carboxylic acid sylvite product.
D, the dilute hydrochloric acid that is 50% by the 160.6g weight concentration by gained carboxylic acid sylvite product carry out acidifying, can obtain carboxylic acid product and amount to 189.7g.
This carboxylic acid product is carried out to esterification refining, again by gained carboxylicesters product is carried out to nucleus magnetic hydrogen spectrum mensuration, according to refining data, can be calculated, in the gained carboxylic acid product structural formula as shown in (13) 1,2, the shared weight percent of 9-tridecane tricarboxylic acid is 61.6%, is 116.9g (0.37mol), and the carboxylic acid product of this embodiment is to take the carboxylic acid shown in formula (13) as main.
In the present embodiment 1,2, the tricarboxylic reaction molar yield of 9-tridecane is 0.37mol/0.5mol=74%.
Formula (13) is:
Embodiment 8
A, with a step of embodiment 7;
B, the methylene-succinic acid diisopropyl ester 214g (1mol) that will dissolve through methanol solvate are added drop-wise in reaction solution, maintain the temperature at-10～5 ℃.After, continue to stir 15min.CoCl by 65g
2slowly join in reaction solution, keep temperature below 5 ℃.After, continue to stir 30min.Add the 100g extracted with diethyl ether, after washing, distillation, except desolventizing, can obtain the carboxylicesters product.
C, above-mentioned carboxylicesters product is joined in the KOH solution that the 1200g weight concentration is 30%, be warming up to 100 ℃, reaction 12h, obtain carboxylic acid sylvite product.
D, the dilute hydrochloric acid that is 50% by the 160.6g weight concentration by gained carboxylic acid sylvite product carry out acidifying, can obtain carboxylic acid product 92.7g
This carboxylic acid product is carried out to esterification refining, again by gained carboxylicesters product is carried out to nucleus magnetic hydrogen spectrum mensuration, according to refining data, can be calculated, in the gained carboxylic acid product, structural formula is suc as formula the 4-carboxymethyl-1 shown in (14), 2, the weight percent that 4,11-pentadecane tetracarboxylic acid accounts for is 60.5%, is 56.1g (0.35mol).The carboxylic acid product of this embodiment is to take the carboxylic acid shown in formula (14) as main.
4-carboxymethyl-1,2,4 in the present embodiment, the reaction molar yield of 11-pentadecane tetracarboxylic acid is 0.35mol/0.5mol=70%.
Formula (14) is:
Embodiment 9
A, with a step of embodiment 7;
B, the methylene-succinic acid diisopropyl ester 321g (1.5mol) that will dissolve through methanol solvate are added drop-wise in reaction solution, maintain the temperature at-10～5 ℃.After, continue to stir 15min.CoCl by 65g
2slowly join in reaction solution, keep temperature below 5 ℃.After, continue to stir 30min.Add the 100g extracted with diethyl ether, after washing, distillation, except desolventizing, can obtain the carboxylicesters product;
C, above-mentioned carboxylicesters product is joined in the KOH solution that the 1200g weight concentration is 30%, be warming up to 70 ℃, reaction 20h, obtain carboxylic acid sylvite product;
D, the dilute hydrochloric acid that is 50% by the 160.6g weight concentration by gained carboxylic acid sylvite product carry out acidifying, can obtain carboxylic acid product 329.6g;
This carboxylic acid product is carried out to esterification refining, again by gained carboxylicesters product is carried out to nucleus magnetic hydrogen spectrum mensuration, according to refining data, can be calculated, in the gained carboxylic acid product, structural formula is suc as formula 4 shown in (15), the two carboxymethyls-1,2 of 6-, 4, the shared weight percent of 6,13-heptadecane pentacarboxylic acid is 59.4%, is 195.8g (0.34mol).The carboxylic acid product of the present embodiment is to take the carboxylic acid shown in formula (15) as main.
In the present embodiment 4, the two carboxymethyls-1,2,4,6 of 6-, the reaction molar yield of 13-heptadecane pentacarboxylic acid is 0.34mol/0.5mol=68%.
Formula (15) is:
Embodiment 10
The preparation method of used for electrolyte polycarboxylic acid comprises the following steps:
A, fully dry and have in the 1L four-hole boiling flask of stirring, dropping funnel, thermometer and add anhydrous normal butyl alcohol 500ml, 3,3 at a warp, 5-trimethylcyclohexanone 70g (0.5mol), be cooled to-5 ℃.Slowly drip trifluoroacetic acid 5.0g from dropping funnel again.After, the H of dropping volumetric concentration 30%
2o
2solution 57.8g, maintain the temperature at 8 ℃ of left and right, after, continue to stir 15min.
B, the dibutyl itaconate 122g (0.5mol) that will dissolve through alcohol solvent are added drop-wise in reaction solution, maintain the temperature at-10～5 ℃.After, continue to stir 15min.SnCl by 95g
2slowly join in reaction solution, keep temperature below 5 ℃.After, continue to stir 30min.Add the 100g extracted with diethyl ether, after washing, distillation, except desolventizing, can obtain the carboxylicesters product.
C, above-mentioned carboxylicesters product is joined in the NaOH solution that the 800g weight concentration is 40%, be warming up to 80 ℃, reaction 5h, obtain the carboxylic acid sodium salt product.
D, the dilute sulphuric acid that is 50% by the 100.6g volumetric concentration by gained carboxylic acid salt adding product carry out acidifying, can obtain carboxylic acid product 166.6g.
This carboxylic acid product is carried out to esterification refining, again by gained carboxylicesters product is carried out to nucleus magnetic hydrogen spectrum mensuration, according to refining data, can be calculated, in the gained carboxylic acid product, structural formula is suc as formula 5,5 shown in (16), 7-trimethylammonium-1,2, the shared weight percent of 8-octane tricarboxylic acid is 62.2%, is 103.6g (0.36mol), and the carboxylic acid product of this embodiment is to take the carboxylic acid shown in formula (16) as main.
In the present embodiment 5,5,7-trimethylammonium-1,2, the tricarboxylic reaction molar yield of 8-octane is 0.36mol/0.5mol=72%.
Formula (16) is:
Embodiment 11
A, with a step of embodiment 10;
B, the dibutyl itaconate 244g (1mol) that will dissolve through alcohol solvent are added drop-wise in reaction solution, maintain the temperature at-10～5 ℃.After, continue to stir 15min.SnCl by 95g
2slowly join in reaction solution, keep temperature below 5 ℃.After, continue to stir 30min.Add the 100g extracted with diethyl ether, after washing, distillation, except desolventizing, can obtain the carboxylicesters product.
C, above-mentioned carboxylicesters product is joined in the NaOH solution that the 800g weight concentration is 40%, be warming up to 100 ℃, reaction 5h, obtain the carboxylic acid sodium salt product.
D, the dilute sulphuric acid that is 50% by the 100.6g volumetric concentration by gained carboxylic acid sodium salt product carry out acidifying, can obtain carboxylic acid product 236.4g.
This carboxylic acid product is carried out to esterification refining, by gained carboxylicesters product is carried out to nucleus magnetic hydrogen spectrum mensuration, according to refining data, can be calculated, in the gained carboxylic acid product, structural formula is suc as formula 4 shown in (17) again, the two carboxymethyls-9 of 6-, 9,11-trimethylammonium-1,2,4, the shared weight percent of 6,12-dodecane pentacarboxylic acid is 60.1%, is 142.1g (0.34mol).The carboxylic acid product of this embodiment is to take the carboxylic acid shown in formula (17) as main.
In the present embodiment 4, the two carboxymethyls-9,9 of 6-, 11-trimethylammonium-1,2,4,6, the reaction molar yield of 12-dodecane pentacarboxylic acid is 0.34mol/0.5mol=68%.
Formula (17) is:
Embodiment 12
A, with a step of embodiment 10;
B, the dibutyl itaconate 366g (1.5mol) that will dissolve through alcohol solvent are added drop-wise in reaction solution, maintain the temperature at-10～5 ℃.After, continue to stir 15min.SnCl by 95g
2slowly join in reaction solution, keep temperature below 5 ℃.After, continue to stir 30min.Add the 100g extracted with diethyl ether, after washing, distillation, except desolventizing, can obtain the carboxylicesters product.
C, above-mentioned carboxylicesters product is joined in the NaOH solution that the 800g weight concentration is 40%, be warming up to 100 ℃, reaction 5h, obtain the carboxylic acid sodium salt product.
D, the dilute sulphuric acid that is 50% by the 100.6g volumetric concentration by the gained sodium salt carry out acidifying, get final product to such an extent that can obtain carboxylic acid product 306.9g.
This carboxylic acid product is carried out to esterification refining, again by gained carboxylicesters product is carried out to nucleus magnetic hydrogen spectrum mensuration, according to refining data, can be calculated, in the gained carboxylic acid product structural formula suc as formula 4 shown in (18), the two carboxymethyls-1 of 6-, 2, the shared weight percent of 4,6,13-heptadecane pentacarboxylic acid is 58.9%, for 180.8g (0.33mol), the carboxylic acid product of this embodiment is to take the carboxylic acid shown in formula (18) as main.
The present embodiment 4, the two carboxymethyls-1,2,4,6 of 6-, the reaction molar yield of 13-heptadecane pentacarboxylic acid is 0.33mol/0.5mol=66%.
Formula (18) is:
During concrete application, the resulting carboxylic acid product of above-mentioned each embodiment is dissolved in 500g methyl alcohol or ethanol, successively by positive resin-column, the negative resin exchange column, sun negative resin hybrid switching post carries out purifying, by gained solution distillation for removing methanol after purifying, obtain detrimental impurity in carboxylic acid product (chlorion, iron ion) content lower than 1ppm.
Then first the carboxylic acid product of each embodiment is dissolved in ethylene glycol, fully react to passing into ammonia in solution, can obtain corresponding ammonium carboxylate salt product, then this ammonium salt product is dissolved in ethylene glycol, the concentration of adjusting solution is 10～30%, the electrolytic solution intermediate that can obtain being mixed with.
Select existing commercially available common electrolytic solution liquid in contrast, compare with solubility property, specific conductivity (30 ℃ of surveys), flash over voltage (room temperature surveys), the dissolution in low temperature performance of the electrolytic solution of above-mentioned 12 embodiment, specifically numerical value is as shown in table 1.
Table 1
From table 1, compare used for electrolyte polybasic carboxylic acid ammonium salt of the present invention with existing commercially available common electrolytic solution and have advantages of that in solvent solubleness is large, specific conductivity is high, high-low temperature resistant, and its impurity ion content is low, long service life.
Claims (6)
1. structure 4-carboxymethyl-1,2,4 as the formula (1), 9-undecane tetracarboxylic acid, its structural formula is:
2. 4-carboxymethyl-1,2,4 claimed in claim 1,9-undecane tetracarboxylic acid is the preparation method comprise the following steps successively:
A, under the acid catalysis condition, the 2-ethyl cyclopentanone that formula (2) is represented reacts in methyl alcohol with hydrogen peroxide;
B, the dimethyl itaconate that a step reaction products therefrom is meaned with formula (3) react under metal-salt exists, the multi-carboxylate that the gained reaction product is represented suc as formula (4);
C, the multi-carboxylate that formula (4) the is meaned reaction that is hydrolyzed in alkali lye, obtain formula (5) expression polycarboxylic acid metal-salt;
D, the polycarboxylic acid metal-salt that formula (5) is meaned carry out acidification with mineral acid, obtain 4-carboxymethyl-1,2,4,9-undecane tetracarboxylic acid, wherein
Formula (2) is:
Formula (3) is:
Formula (4) is:
Formula (5) is:
M is potassium or sodium;
Wherein, in the c step, hydrolysis reaction alkali used is a kind of in salt of wormwood, sodium carbonate, sodium hydroxide, potassium hydroxide, sodium methylate or sodium ethylate.
3. 4-carboxymethyl-1,2,4 according to claim 2, the preparation method of 9-undecane tetracarboxylic acid is characterized in that: the acid catalyst described in a step is a kind of in sulfuric acid, perchloric acid, phosphoric acid, trifluoroacetic acid.
4. 4-carboxymethyl-1,2,4 according to claim 2, the preparation method of 9-undecane tetracarboxylic acid is characterized in that: a kind of in the low price vitriol that the metal-salt described in the b step is iron, copper, cobalt, titanium, tin or lower chloride.
5. 4-carboxymethyl-1 according to claim 2,2,4, the preparation method of 9-undecane tetracarboxylic acid, it is characterized in that: in the c step, hydrolysis reaction alkali used is a kind of in salt of wormwood, sodium carbonate, sodium hydroxide, potassium hydroxide, sodium methylate or sodium ethylate, the weight concentration of alkali lye is 10～40%, and temperature of reaction is 70～120 ℃, and the reaction times is 4～20h.
6. one kind is utilized the described 4-carboxymethyl-1,2,4 of claim 1, and 9-undecane tetracarboxylic acid is mixed with the method for electrolytic solution, comprises the following steps:
At first, by described 4-carboxymethyl-1,2,4,9-undecane tetracarboxylic acid is dissolved in alcoholic solvent, to passing into ammonia in solution, fully reacts, and can obtain the represented used for electrolyte polybasic carboxylic acid ammonium salt of formula (6),
Formula (6) is:
Then, by described formula (6), represented used for electrolyte polybasic carboxylic acid ammonium salt is dissolved in ethylene glycol or gamma-butyrolactone, and the concentration of adjusting solution is 10～30%, the electrolytic solution that can obtain being mixed with.
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Non-Patent Citations (9)
| Title |
|---|
| Bergstrom, Sune * |
| et.al,.Prostaglandins and related factors.《Journal of Biological Chemistry》.1963,第238卷(第11期),P3555-3564. * |
| et.al，.The Addition of olefinic esters to maleic anhydride.《Journal of the American Chemical Society》.1946,第68卷P1373-1376. * |
| et.al,.Total synthesis of DL-prostaglandin E1.《Journal of Organic Chemistry》.1973,第38卷(第26期),P4412-4424. * |
| Finch, Neville * |
| Payne,G.B.,et.al,.Reaction of cyclohexanone and hydrogen peroxide with ferrous sulfate and dimethyl maleate.《Journal of Organic Chemistry》.1958,第23卷P1066-1068. * |
| Ross,John * |
| 于欣伟等.电解电容器使用支链多元羧酸铵盐电解液的研究.《广州大学学报(自然科学版)》.2008,第7卷(第2期),6-9. |
| 电解电容器使用支链多元羧酸铵盐电解液的研究;于欣伟等;《广州大学学报(自然科学版)》;200804;第7卷(第2期);6-9 * |
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