CN114380684A - Carboxylic acid electrolyte with branched chain and preparation method thereof - Google Patents
Carboxylic acid electrolyte with branched chain and preparation method thereof Download PDFInfo
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- CN114380684A CN114380684A CN202210157753.8A CN202210157753A CN114380684A CN 114380684 A CN114380684 A CN 114380684A CN 202210157753 A CN202210157753 A CN 202210157753A CN 114380684 A CN114380684 A CN 114380684A
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 title claims abstract description 68
- 239000003792 electrolyte Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- 230000032050 esterification Effects 0.000 claims abstract description 9
- 238000005886 esterification reaction Methods 0.000 claims abstract description 9
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 6
- 150000001733 carboxylic acid esters Chemical class 0.000 claims abstract description 6
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 75
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 15
- DCZFGQYXRKMVFG-UHFFFAOYSA-N cyclohexane-1,4-dione Chemical compound O=C1CCC(=O)CC1 DCZFGQYXRKMVFG-UHFFFAOYSA-N 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 238000001704 evaporation Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000000706 filtrate Substances 0.000 claims description 10
- -1 alkyl acrylic acid Chemical compound 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 5
- 150000007522 mineralic acids Chemical class 0.000 claims description 5
- 238000007127 saponification reaction Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000012028 Fenton's reagent Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 238000007086 side reaction Methods 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- MGZTXXNFBIUONY-UHFFFAOYSA-N hydrogen peroxide;iron(2+);sulfuric acid Chemical group [Fe+2].OO.OS(O)(=O)=O MGZTXXNFBIUONY-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims 2
- 239000003990 capacitor Substances 0.000 abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- FLDCSPABIQBYKP-UHFFFAOYSA-N 5-chloro-1,2-dimethylbenzimidazole Chemical compound ClC1=CC=C2N(C)C(C)=NC2=C1 FLDCSPABIQBYKP-UHFFFAOYSA-N 0.000 description 1
- 239000001741 Ammonium adipate Substances 0.000 description 1
- ZBRFXUYITSEQPN-FLGDTWEASA-N C(CCCCCCC\C=C/CCCCCCCC)(=O)[O-].C(CCCCCCC\C=C/CCCCCCCC)(=O)[O-].C(CCCCCCC\C=C/CCCCCCCC)(=O)[O-].C(CCCCCCC\C=C/CCCCCCCC)(=O)[O-].C(CCCCCCC\C=C/CCCCCCCC)(=O)[O-].C(CCCCCCC\C=C/CCCCCCCC)(=O)[O-].C(CCCCCCC\C=C/CCCCCCCC)(=O)[O-].C(CCCCCCC\C=C/CCCCCCCC)(=O)[O-].C(CCCCCCC\C=C/CCCCCCCC)(=O)[O-].C(CCCCCCC\C=C/CCCCCCCC)(=O)[O-].C(CCCCCCC\C=C/CCCCCCCC)(=O)[O-].C(CCCCCCC\C=C/CCCCCCCC)(=O)[O-].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+] Chemical compound C(CCCCCCC\C=C/CCCCCCCC)(=O)[O-].C(CCCCCCC\C=C/CCCCCCCC)(=O)[O-].C(CCCCCCC\C=C/CCCCCCCC)(=O)[O-].C(CCCCCCC\C=C/CCCCCCCC)(=O)[O-].C(CCCCCCC\C=C/CCCCCCCC)(=O)[O-].C(CCCCCCC\C=C/CCCCCCCC)(=O)[O-].C(CCCCCCC\C=C/CCCCCCCC)(=O)[O-].C(CCCCCCC\C=C/CCCCCCCC)(=O)[O-].C(CCCCCCC\C=C/CCCCCCCC)(=O)[O-].C(CCCCCCC\C=C/CCCCCCCC)(=O)[O-].C(CCCCCCC\C=C/CCCCCCCC)(=O)[O-].C(CCCCCCC\C=C/CCCCCCCC)(=O)[O-].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+] ZBRFXUYITSEQPN-FLGDTWEASA-N 0.000 description 1
- 235000019293 ammonium adipate Nutrition 0.000 description 1
- SATJMZAWJRWBRX-UHFFFAOYSA-N azane;decanedioic acid Chemical compound [NH4+].[NH4+].[O-]C(=O)CCCCCCCCC([O-])=O SATJMZAWJRWBRX-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/235—Saturated compounds containing more than one carboxyl group
- C07C59/347—Saturated compounds containing more than one carboxyl group containing keto groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/02—Preparation of carboxylic acid esters by interreacting ester groups, i.e. transesterification
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
- H01G9/035—Liquid electrolytes, e.g. impregnating materials
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A carboxylic acid electrolyte with a branched chain and a preparation method thereof relate to the technical field of aluminum electrolytic capacitors, in particular to a preparation method of a carboxylic acid electrolyte with a branched chain. The invention aims to solve the problems that the prior straight-chain electrolytic liquid system has serious esterification of electrolyte, sharply reduced conductivity and electric conductivity along with the passage of temperature and time in the using processAnd a problem of a low service life. The structural general formula of the carboxylic acid electrolyte with the branched chain is as follows:
or
The method comprises the following steps: firstly, ring opening to prepare straight chain carboxylic acid; secondly, esterifying straight chain carboxylic acid; thirdly, saponifying branched chain carboxylic ester; and fourthly, acidifying the branched chain carboxylate to obtain the carboxylic acid electrolyte with the branched chain. The carboxylic acid electrolyte with the branched chain prepared by the invention has good charge conductivity and fluidity, can effectively increase open-circuit voltage, and prolongs the service life of the electrolyte. The present invention can obtain a carboxylic acid electrolyte having a branched chain.
Description
Technical Field
The invention relates to the technical field of aluminum electrolytic capacitors, in particular to a preparation method of a carboxylic acid electrolyte with a branched chain.
Background
At present, the solute mainly used at home and abroad adopts straight-chain and branched-chain electrolytes, medium and high voltage products such as straight-chain electrolytes, ammonium adipate, ammonium sebacate, ammonium dodecaoleate and the like, and branched-chain electrolytes such as 1-6DDA, 1-4DDA and the like. Because the solubility and the thermal stability of some branched chain dicarboxylic acid salts in glycol solution are superior to those of straight chain carboxylic acid salts, and the branched chain dicarboxylic acid salts have chemical self-repairing capability, the glycol system containing the branched chain dicarboxylic acid salts can be used for manufacturing capacitor products with high voltage resistance, low effective resistance, high ripple current bearing capability, high heat resistance and long service life. Therefore, the development of the branched carboxylic acid electrolyte system with high conductivity and wide working temperature range has important significance and application prospect.
And because the carboxyl groups at two ends of the straight-chain electrolyte system do not have protective groups, the problems that the esterification of the electrolyte is serious, the conductivity is rapidly reduced and the like are solved along with the passage of temperature and time in the using process, so that the ESR value of the capacitor is increased, the heating of the capacitor is serious, the electrolyte volatilizes to cause the opening of the capacitor, the capacitor fails in advance and the like are caused.
Disclosure of Invention
The invention aims to solve the problems that the esterification of an electrolyte is serious, the conductivity is reduced sharply and the conductivity and the service life are low along with the passage of temperature and time in the using process of the conventional straight-chain electrolytic liquid system, and provides a carboxylic acid electrolyte with a branched chain and a preparation method thereof.
In order to enable the electrolyte to have better thermal stability and solubility, and enable the electrolyte to have better conductivity and longer service life, the invention develops the carboxylic acid electrolyte with the branched chain with good performance; the general structural formula of the electrolyte is as follows:
wherein, R is1Is hydrogen, methyl, ethyl or propyl; said R2Is methyl, ethyl or propyl.
A preparation method of a carboxylic acid electrolyte with a branched chain is specifically completed according to the following steps:
firstly, ring-opening preparation of straight-chain carboxylic acid:
reacting 1, 4-cyclohexanedione with anhydrous methanol under the conditions of a catalyst and low temperature, filtering, and collecting filtrate to obtain a solution I;
secondly, esterification of straight chain carboxylic acid:
reacting the solution I with alkyl acrylic acid or alkyl acrylate according to a proportion at a low temperature, and adding distilled water to evaporate low-boiling-point impurities to obtain a solution II;
thirdly, saponification of branched chain carboxylic ester:
adding absolute methanol into the solution II, adding sodium hydroxide, reacting at 10-50 ℃, filtering, and collecting filtrate to obtain a solution III;
fourthly, acidifying branched carboxylate:
adding inorganic acid into the solution III to ensure that the pH value of the solution III is acidic, and evaporating the solvent in the solution III to obtain a branched chain organic carboxylic acid mixture;
washing the branched chain organic carboxylic acid mixture with anhydrous methanol, filtering, evaporating the solvent from the solid matter, and drying to obtain the branched chain carboxylic acid electrolyte.
Due to the adoption of the technical scheme, the invention has the beneficial effects that:
the branched chain alkoxy side chain is introduced to serve as an electron-donating solubilizer, so that the conductive charge and the fluidity of an electrolyte are increased, and the open-circuit voltage (Voc) is effectively increased; meanwhile, the side chain of the branched alkoxy group can also increase the steric hindrance near the carboxylic acid group, thus delaying the esterification speed of the carboxylic acid and prolonging the service life of the electrolyte;
secondly, the carboxylic acid electrolyte with the branched chain prepared by the invention has better thermal stability and solubility;
thirdly, the carboxylic acid electrolyte with the branched chain prepared by the invention is configured into glycol electrolyte, when the concentration of the glycol electrolyte is 10g/L, the conductivity is 1.21 ms/cm-1.24 ms/cm, and the impedance is measured to be 857.4 omega-cm-878.6 omega-cm.
The present invention can obtain a carboxylic acid electrolyte having a branched chain.
Drawings
FIG. 1 is an infrared spectrum of a carboxylic acid electrolyte having a branched chain prepared in example 2;
fig. 2 is a mass spectrum of the carboxylic acid electrolyte having a linear chain prepared in example 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention. The following conductivities are measured by a thunder magnetic DDBJ-351L type portable conductivity meter, and the measured conductivity values meet the industry standard range.
The first embodiment is as follows: the structural general formula of the carboxylic acid electrolyte having a branched chain of the present embodiment is:
The second embodiment is as follows: the present embodiment differs from the present embodiment in that: the preparation method of the carboxylic acid electrolyte with the branched chain is specifically completed according to the following steps:
firstly, ring-opening preparation of straight-chain carboxylic acid:
reacting 1, 4-cyclohexanedione with anhydrous methanol under the conditions of a catalyst and low temperature, filtering, and collecting filtrate to obtain a solution I;
secondly, esterification of straight chain carboxylic acid:
reacting the solution I with alkyl acrylic acid or alkyl acrylate according to a proportion at a low temperature, and adding distilled water to evaporate low-boiling-point impurities to obtain a solution II;
thirdly, saponification of branched chain carboxylic ester:
adding absolute methanol into the solution II, adding sodium hydroxide, reacting at 10-50 ℃, filtering, and collecting filtrate to obtain a solution III;
fourthly, acidifying branched carboxylate:
adding inorganic acid into the solution III to ensure that the pH value of the solution III is acidic, and evaporating the solvent in the solution III to obtain a branched chain organic carboxylic acid mixture;
washing the branched chain organic carboxylic acid mixture with anhydrous methanol, filtering, evaporating the solvent from the solid matter, and drying to obtain the branched chain carboxylic acid electrolyte. Other steps are the same as in the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the molar ratio of the 1, 4-cyclohexanedione to the anhydrous methanol in the step one is 1: 30; the catalyst in the step one is Fe2+And H2O2Composition of Fenton's reagent, in which Fe2+And H2O2The molar ratio of (0.25-4) to (1). The other steps are the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is as follows: the reaction time in the step one is 2-10 h; the low temperature in the first step is-20 ℃ to 20 ℃. The other steps are the same as those in the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: the molar ratio of the alkyl acrylic acid or the alkyl acrylate in the second step to the 1, 4-cyclohexanedione in the first step is (0.5-2): 1; the alkyl acrylic acid in the second step is methacrylic acid or acrylic acid; the alkyl acrylate is methyl acrylate, ethyl acrylate or methyl methacrylate. The other steps are the same as those in the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is as follows: the low temperature in the second step is-20 ℃ to 20 ℃; the reaction time in the second step is 2-10 h. The other steps are the same as those in the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: the low-boiling-point impurities in the step two are residual alkyl acrylic acid or methyl acrylate and other low-boiling-point side reaction products which are reacted in a solvent at the temperature of 0-95 ℃ under normal pressure; and the volume ratio of the distilled water to the solution I in the step two is 1: 1. The other steps are the same as those in the first to sixth embodiments.
The specific implementation mode is eight: the difference between this embodiment and one of the first to seventh embodiments is: the molar ratio of the sodium hydroxide in the third step to the 1, 4-cyclohexanedione in the first step is 1 (2-10); the reaction time in the third step is 2-10 h; the volume ratio of the anhydrous methanol to the solution II in the third step is 1: 1. The other steps are the same as those in the first to seventh embodiments.
The specific implementation method nine: the difference between this embodiment and the first to eighth embodiments is: the inorganic acid in the step IV is sulfuric acid, hydrochloric acid, phosphoric acid or nitric acid; and the pH value in the step IV is 3-4. The other steps are the same as those in the first to eighth embodiments.
The detailed implementation mode is ten: the difference between this embodiment and one of the first to ninth embodiments is as follows: in the fourth step, the drying temperature is 80-90 ℃, and the drying time is 6-12 h. The other steps are the same as those in the first to ninth embodiments.
The following examples were used to demonstrate the beneficial effects of the present invention:
example 1: the preparation method of the carboxylic acid electrolyte with the branched chain is specifically completed according to the following steps:
firstly, ring-opening preparation of straight-chain carboxylic acid:
reacting 11g of 1, 4-cyclohexanedione with anhydrous methanol in the presence of a catalyst in an ice salt bath at the temperature of-5 ℃ for 9 hours, filtering, and collecting filtrate to obtain a solution I;
the molar ratio of the 1, 4-cyclohexanedione to the anhydrous methanol in the step one is 1: 30;
the catalyst in the step one is a Fenton reagent consisting of 6g of ferrous sulfate heptahydrate and 10mL of hydrogen peroxide reagent;
secondly, esterification of straight chain carboxylic acid:
reacting the solution I with 9mL of methyl acrylate according to a proportion at 10 ℃ for 2h, adding distilled water, and gradually evaporating the rest methyl acrylate, methanol and other side reaction products under a temperature gradient to obtain a solution II;
the volume ratio of the distilled water to the solution I in the step II is 1: 1;
thirdly, saponification of branched chain carboxylic ester:
adding absolute methanol into the solution II, adding 9g of sodium hydroxide, reacting for 2 hours at 50 ℃, filtering, and collecting filtrate to obtain a solution III;
the volume ratio of the anhydrous methanol to the solution II in the third step is 1: 1;
fourthly, acidifying branched carboxylate:
adding 65 mass percent nitric acid into the solution III to ensure that the pH value of the solution III is 3, and evaporating the solvent in the solution III to obtain a branched chain organic carboxylic acid mixture;
② washing the branched organic carboxylic acid mixture by using absolute methanol, filtering, evaporating the solvent in the solid matter, and drying at 80 ℃ for 6h to obtain the carboxylic acid electrolyte with branched chains, wherein the yield is 42.37%.
The carboxylic acid electrolyte having a branched chain prepared in example 1 was prepared as an ethylene glycol-based electrolyte having a mass fraction of 10%, an electric conductivity of 1.24ms/cm, and a measured impedance of 857.4 Ω · cm.
The structural formula of the carboxylic acid electrolyte having a branched chain prepared in example 1 is:
structural formula 1
And structural formula 2
Example 2: the preparation method of the carboxylic acid electrolyte with the branched chain is specifically completed according to the following steps:
firstly, ring-opening preparation of straight-chain carboxylic acid:
reacting 5.6g of 1, 4-cyclohexanedione with anhydrous methanol in the presence of a catalyst in a 0 ℃ ice salt bath for 6 hours, filtering, and collecting filtrate to obtain a solution I;
the molar ratio of the 1, 4-cyclohexanedione to the anhydrous methanol in the step one is 1: 30;
the catalyst in the step one is a Fenton reagent consisting of 27g of ferrous sulfate heptahydrate and 11mL of hydrogen peroxide reagent;
secondly, esterification of straight chain carboxylic acid:
reacting the solution I with 5mL of methyl acrylate according to a proportion at 10 ℃ for 4h, adding distilled water, and gradually evaporating the rest methyl acrylate, methanol and other side reaction products under a temperature gradient to obtain a solution II;
the volume ratio of the distilled water to the solution I in the step II is 1: 1;
thirdly, saponification of branched chain carboxylic ester:
adding anhydrous methanol into the solution II, adding 5g of sodium hydroxide, reacting for 4 hours at 50 ℃, filtering, and collecting filtrate to obtain a solution III;
the volume ratio of the anhydrous methanol to the solution II in the third step is 1: 1;
fourthly, acidifying branched carboxylate:
adding sulfuric acid with the mass fraction of 98% into the solution III to enable the pH value of the solution III to be 3, and then evaporating the solvent in the solution III to obtain a branched chain organic carboxylic acid mixture;
② washing the branched organic carboxylic acid mixture by using absolute methanol, filtering, evaporating the solvent in the solid matter, and drying at 80 ℃ for 6h to obtain the carboxylic acid electrolyte with branched chains, wherein the yield is 54.76%.
The carboxylic acid electrolyte having a branched chain prepared in example 2 was prepared as an ethylene glycol-based electrolyte having a mass fraction of 10%, an electric conductivity of 1.21ms/cm, and a measured impedance of 878.6 Ω · cm.
Fig. 1 is an infrared spectrum of a carboxylic acid electrolyte having a branched chain prepared in example 2.
From FIG. 1, it can be seen that 1714cm in infrared spectrum-1Strong C ═ O stretching vibration band, 1290cm-1，950cm-1The strong spike is an out-of-plane angular oscillation of the carboxylic acid associated hydrogen bonds, indicating the presence of carboxylic acid in the sample.
Fig. 2 is a mass spectrum of the carboxylic acid electrolyte having a linear chain prepared in example 2.
As can be seen from FIG. 2, m/z73 and 129 in the mass spectrum are (CH)2COOH-And (CH)6COOH-Ion peak of D, m/z187, 201 in the mass spectrum are ion peaks of formula 1 and formula 2, respectively, for the preparation of the carboxylic acid electrolyte with branched chains of example 2.
The structural formula of the carboxylic acid electrolyte having a branched chain prepared in example 2:
structural formula 1
And structural formula 2
Claims (10)
1. A carboxylic acid electrolyte with a branched chain is characterized in that the structural general formula of the carboxylic acid electrolyte with the branched chain is as follows:
wherein, R is1Is hydrogen, methyl, ethyl or propyl; said R2Is methyl, ethyl or propyl.
2. The method for preparing the carboxylic acid electrolyte having a branched chain according to claim 1, wherein the method for preparing the carboxylic acid electrolyte having a branched chain is specifically performed by the following steps:
firstly, ring-opening preparation of straight-chain carboxylic acid:
reacting 1, 4-cyclohexanedione with anhydrous methanol under the conditions of a catalyst and low temperature, filtering, and collecting filtrate to obtain a solution I;
secondly, esterification of straight chain carboxylic acid:
reacting the solution I with alkyl acrylic acid or alkyl acrylate according to a proportion at a low temperature, and adding distilled water to evaporate low-boiling-point impurities to obtain a solution II;
thirdly, saponification of branched chain carboxylic ester:
adding absolute methanol into the solution II, adding sodium hydroxide, reacting at 10-50 ℃, filtering, and collecting filtrate to obtain a solution III;
fourthly, acidifying branched carboxylate:
adding inorganic acid into the solution III to ensure that the pH value of the solution III is acidic, and evaporating the solvent in the solution III to obtain a branched chain organic carboxylic acid mixture;
washing the branched chain organic carboxylic acid mixture with anhydrous methanol, filtering, evaporating the solvent from the solid matter, and drying to obtain the branched chain carboxylic acid electrolyte.
3. The method of claim 2, wherein the molar ratio of 1, 4-cyclohexanedione to anhydrous methanol in step one is 1: 30; the catalyst in the step one is Fe2+And H2O2Composition of Fenton's reagent, in which Fe2+And H2O2The molar ratio of (0.25-4) to (1).
4. The method for preparing a carboxylic acid electrolyte having a branched chain according to claim 2 or 3, wherein the reaction time in the first step is 2 to 10 hours; the low temperature in the first step is-20 ℃ to 20 ℃.
5. The method according to claim 2 or 3, wherein the molar ratio of the alkyl acrylic acid or the alkyl acrylate in the second step to the 1, 4-cyclohexanedione in the first step is (0.5-2): 1; the alkyl acrylic acid in the second step is methacrylic acid or acrylic acid; the alkyl acrylate is methyl acrylate, ethyl acrylate or methyl methacrylate.
6. The method for preparing a carboxylic acid electrolyte having a branched chain according to claim 2 or 3, wherein the low temperature in the second step is-20 ℃ to 20 ℃; the reaction time in the second step is 2-10 h.
7. The method for preparing the carboxylic acid electrolyte with the branch chain according to claim 2 or 3, wherein the low-boiling impurities in the second step are alkyl acrylic acid or methyl acrylate and other low-boiling side reaction products remained in the solvent at 0-95 ℃ under normal pressure; and the volume ratio of the distilled water to the solution I in the step two is 1: 1.
8. The method according to claim 2 or 3, wherein the molar ratio of the sodium hydroxide in the third step to the 1, 4-cyclohexanedione in the first step is 1 (2 to 10); the reaction time in the third step is 2-10 h; the volume ratio of the anhydrous methanol to the solution II in the third step is 1: 1.
9. The method for preparing a carboxylic acid electrolyte having a branched chain according to claim 2 or 3, wherein the inorganic acid in the fourth (r) step is sulfuric acid, hydrochloric acid, phosphoric acid or nitric acid; and the pH value in the step IV is 3-4.
10. The method for preparing a carboxylic acid electrolyte having a branched chain according to claim 2 or 3, wherein the drying temperature in the fourth step is 80 to 90 ℃ and the drying time is 6 to 12 hours.
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