CN114075125A - Long-chain alkyl fluorine-containing sulfonate ionic membrane compound for blocking water permeation of lithium-air battery - Google Patents
Long-chain alkyl fluorine-containing sulfonate ionic membrane compound for blocking water permeation of lithium-air battery Download PDFInfo
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Abstract
The invention relates to an ionic membrane compound of long-chain alkyl diene fluorine-containing sulfonate and a synthesis method thereof, the ionic membrane compound can obtain a solid electrolyte of a compact cross-linked sulfonic acid ionic membrane through free radical polymerization, has high Li + ion conductivity, can efficiently prevent water, O2 and organic solvent from permeating, and the polymerized saturated fluorine-containing alkyl main chain is very oxidation-resistant and highly stable to strong acid and strong alkali; the flexible saturated fluorine-containing alkyl main chain can resist severe mechanical force impact of temperature and pressure change without damage; is the best technical solution for the core problem of the solid electrolyte diaphragm of the lithium air battery at present. In the leading industrialization of water/organic combined electrolyte lithium-air batteries, the solid electrolyte of the compact cross-linked sulfonic acid ion membrane is a key core new material.
Description
Technical Field
The invention relates to a long-chain alkyl diene fluorine-containing sulfonate ionic membrane new compound capable of being densely crosslinked, belonging to the field of new energy of lithium air batteries.
Background
The theoretical energy density of the rechargeable lithium-air battery reaches up to 11400 Wh/kg, is close to the energy density of 13000Wh/kg of gasoline of a fuel vehicle, has the advantages of environmental protection and the like, and is an electrochemical energy storage system which is concerned at present. Since the construction of the first rechargeable lithium-air battery by k.m. Abraham in 1996, scientists around the world have conducted a great deal of research.
Wangyonggang in J. Power Sources 2010,195: p.358-361, discloses a Lithium-air battery using water/organic combined electrolyte design, wherein organic electrolyte is used on the side of the anode of a metal Lithium sheet, water-based electrolyte is used on the side of the air anode, and a solid electrolyte inorganic membrane of a super Lithium ion conductive glass membrane (LISICON) is adopted to separate electrolytes of two poles and transmit Li between the two poles+At 0.5mA/cm2The low current density is continuously discharged for 500h, the specific discharge capacity reaches 50000mAh/g (carbon + catalyst + binder), and the discharge voltage reaches 2.8V. Water/organic combined electrolyte lithium air batteries are still in the initial research phase at present. The combined electrolyte has the advantages that: the air anode discharge product is lithium hydroxide which is easily dissolved in water-based electrolyte, and an oxygen delivery channel is not easy to block; while the metallic lithium electrode is protected in an organic electrolyte. But due to LISICON inorganic membrane Li+The movement internal resistance is too large, the ionic conductivity is less than or equal to 0.1mS/cm, and the large-current charging and discharging cannot be realized; the LISICON inorganic membrane is brittle and hard and is easy to break under the impact of temperature and pressure change; .
Wangwongginjust in Angewandte Chemie International Edition 2017, doi: 10,1002/anie,201701142, introduces and synthesizes a modified LISICON membrane containing 0.05 mol/L LiI doped hydrophobic gel electrolyte, which can ensure that a lithium-air battery stably circulates for 400 times in air with air humidity of 15%, but the higher air humidity is difficult to use, because the lithium-air battery is an inorganic membrane, is brittle, hard and inelastic, needs very thick membrane thickness to resist impact, and the membrane below 100 microns is easy to be crushed by impact caused by temperature and pressure change; furthermore, the ionic conductivity is improved by adding an electrolyte and LiI, and it is difficult to achieve a separation of 0.001S/cm or moreSub-conductivity, Li+The internal resistance in motion is still high; because the inorganic raw materials for synthesizing the diaphragm are too many, and LiOH generated by discharge is strong alkali, the service life of the LISICON diaphragm with poor alkali resistance is short, and the performance of the diaphragm is not uniform and stable.
The key problem of the water/organic combined electrolyte lithium-air battery is that a high-ionic conductivity solid electrolyte diaphragm with stable and excellent comprehensive performance is needed, the water/organic electrolyte can be separated, and Li can be efficiently conducted+And stopping water and O2The lithium ion battery anode material enters a metal lithium sheet cathode, has good corrosion resistance to organic electrolyte and water phase, and has good mechanical strength for resisting temperature and pressure changes.
The water/organic combined electrolyte lithium-air battery requires a flexible/temperature pressure and mechanical force impact resistant high-ionic conductivity solid electrolyte membrane, needs to completely block the permeation of water and oxygen, and has very strict performance requirements; because Li + has strong oxygen coordination capacity and weak acidity, the Li + is coordinated and complexed with the electron-rich oxygen group+The post dissociation is difficult, the migration movement internal resistance is very high, the battery internal resistance is very high, and the large current charging and discharging can not be realized; the existing inorganic LISICON diaphragm has no super-strong acid anion group, the Li +/oxygen complex motion resistance is very large, the impedance is very high, and the diaphragm cannot be used for large-current charge and discharge; at present, no lithium air battery solid electrolyte diaphragm with excellent comprehensive performance exists at home and abroad.
Disclosure of Invention
Aiming at the harsh technical problem of the water/organic combined electrolyte lithium-air battery on the solid electrolyte diaphragm, the invention provides a method for completely blocking organic solvent/water/O (oxygen/oxygen) of the lithium-air battery2The penetrated long-chain alkyl diene fluorine-containing sulfonate ion membrane new compound can completely block organic solvent/water/O through free radical polymerization of diene in molecules without doping2Penetration and high Li+A dense cross-linked sulfonic acid ionic membrane solid electrolyte of ionic conductivity; the flexible saturated fluorine-containing alkyl main chain of the ionic membrane after polymerization can resist severe mechanical force impact caused by temperature/pressure change. This ability to block water/O2Permeated long chain alkyl diene fluorosulfonate ionA membrane compound which is tetracosene diene difluoromethyl sulfonate with a chemical structure shown as formula A, wherein the chemical formula is 2,5,5,6,6,9,9,10,10, -nonamethyl-13-trifluoromethyl-2, 12-diene-1, 1-difluoro tetradecyl sulfonate;
wherein: m = Li+、K+Or Na+。
The ionic membrane compound of the formula A has the unique advantages that the harsh performance requirements of a water/organic combined electrolyte lithium air battery on a solid electrolyte diaphragm are intensively designed into a novel ionic membrane compound of the long-chain alkyl diene fluorine-containing sulfonate through the screening combination of molecular groups, and the solid electrolyte of the compact cross-linked sulfonic acid ionic membrane polymerized by diene in molecules is high in uniformity and stability in quality and excellent in repeatability due to the fact that the ionic membrane is a single-molecule polymerized compact cross-linked sulfonic acid ionic membrane solid electrolyte, the cross-linking degree, the size and the distribution of ionic channels of the ionic membrane are very uniform, the preparation is easy, the ionic membrane compound is the solid electrolyte of the compact cross-linked sulfonic acid ionic membrane which is most beneficial to stably industrialization of high performance, and the quality performance difference can not occur among synthesis batches. These advantages are far superior to the existing inorganic LISICON separator and ionic membrane solid electrolytes polymerized by various ethylenic monomers.
The diene interval of the compound of the formula A ion membrane is very short and is 1.3nm, and the difluoromethylsulfonic acid ion membrane solid electrolyte after the compound of the formula A is subjected to free radical polymerization has very uniform dense crosslinking and can completely block organic solvents/water/O of various organic electrolytes for a long time2The electrolyte permeates through the electrolyte and cannot be swelled and damaged by the electrolyte solvent.
The HLB value of the compound of the formula A is 5.81, the compound is a completely hydrophobic sulfonic acid ionic membrane polymerization monomer, and the polymerized compact cross-linked sulfonic acid ionic membrane solid electrolyte has excellent hydrophobicity; crosslinked Li formed by polymerization of difluoromethylsulfonate of tail olefinic bond+The moving channel is less than or equal to 0.5nm, and water and O are completely blocked2The penetration of (2).
Since difluoromethylsulfonic acid has super strong acidity and thus has very weak ion coordination resistance, it is providedHigh Li+The movement speed reduces the movement heat and impedance; and Li+The metal ions have strong oxygen coordination capacity, and the stronger the acidity of the solid electrolyte group of the ionic membrane, the weaker the coordination and complexation resistance to Li +; the acid strength pKa of p-toluenesulfonic acid is = -7.6, the super-strong acid pKa of the compound of the formula A is = -11.30, and the acid strength is close to 10 compared with that of toluenesulfonic acid4Double, super strong acidic difluoro methyl sulfonic acid anion pair Li+The oxygen complex has very weak movement resistance which is far lower than that of Li of p-toluenesulfonic acid+The oxygen complexation movement resistance is far lower than the Li + complexation movement resistance of the LISICON inorganic conducting glass diaphragm, so that the harsh requirements of large-current charge-discharge on high ion conductivity are met.
The compact cross-linked fluorine-containing saturated main chain after the compound of the formula A is polymerized is flexible and oxidation-resistant for a long time, can completely resist the impact of the temperature and pressure change of the lithium-air battery on a polymerization film, cannot be cracked and damaged, and can stably protect a metal lithium sheet from contacting water and O for a long time2And the lithium air battery is very stable to strongly alkaline LiOH generated by discharge, so that the high cycle number and high operation safety of the lithium air battery are guaranteed.
The ionic capacity of the compound in the formula A is more than or equal to 1.8mmol/g, the ionic capacity is high, the difluoromethyl sulfonic acid super-strong acid is adopted, the ionic conductivity of the polymer membrane can be more than 0.05S/cm, the polymer membrane has ultralow internal impedance, and the harsh requirements of heavy current charge and discharge on high ionic conductivity are met.
The synthesis method of the long-chain fluorine-containing alkyl diene difluoromethyl sulfonate ionic membrane compound with the chemical structure of the formula A needs to adopt 2, 5-dimethyl-2, 5-hexanediol of the chemical structure of the formula H as a starting material;
the synthesis method of the long-chain fluorine-containing alkyl diene difluoromethyl sulfonate ionic membrane compound with the chemical structure of the formula A needs six-step synthesis reaction of coupling reaction, diene chlorination reaction, ozonization reaction, trifluoromethyl addition, difluoromethyl addition and dehydrated diene:
(1) coupling reaction: reacting excessive 2, 5-dimethyl-2, 5-hexanediol with concentrated hydrochloric acid at 30-50 ℃ to obtain an oil layer mixture of 2, 5-dimethyl-2, 5-dichlorohexane and excessive 2, 5-dimethyl-5-chloro-2-hexanol; washing the oil layer mixture to be neutral by using sodium bicarbonate, reacting with hydrazine hydrate at room temperature, removing carbon-chlorine bonds, adding NaOH and an oxidation catalyst, introducing oxygen, carrying out catalytic oxidation at 50-60 ℃ to obtain azo groups, finally heating to 160-200 ℃, carrying out coupling by cracking the azo groups to obtain free radicals, and separating to obtain 2,5,5,6,6,9,9,10,10, 13-decamethyl-2, 13-tetradecanediol with a chemical structure shown as a formula B:
(2) and (3) diene chlorination reaction: mixing the compound of the formula B with a hydrogen chloride methanol solution, completely chlorinating the tertiary hydroxyl of the compound of the formula B at 30-50 ℃, then adding NaOH, heating, refluxing, dechlorinating, refining and separating to obtain a C24 alkyldiene compound with a chemical structure of a formula C, wherein the chemical name is 2,5,5,6,6,9,9,10,10, 13-decamethyl-1, 14-tetradecadiene;
(3) ozonization reaction: dissolving the diene compound shown in the formula C in n-butyl alcohol, introducing ozone at room temperature to break olefinic bonds completely, adding sodium bisulfite aqueous solution to decompose ozonized products, and separating to obtain a C22 alkyl diketone compound shown in the formula D, wherein the chemical name is 5,5,6,6,9,9,10, 10-octamethyl-2, 13-tetradecanedione;
(4) and (3) trifluoromethyl addition reaction: dissolving excessive compound in formula D and fluoride salt catalyst in solvent, catalyzing trifluoromethyl trimethylsilane by fluoride salt catalyst at room temperature, adding trifluoromethyl into ketone group of compound in formula D, refining and separating with sodium thiosulfate to obtain compound in chemical structure in formula E, wherein chemical name is 5,5,6,6,9,9,10, 10-octamethyl-2-trifluoromethyl-13-ketone-2-tetradecanol;
(5) difluoromethyl addition reaction: dissolving the compound shown in the formula E in an alcohol solvent, uniformly mixing the compound shown in the formula F with the compound shown in the formula E, adding strong base for catalysis at room temperature, adding difluoromethyl carbanion to ketone group of the compound shown in the formula E, oxidizing the obtained crude product with chlorine or hypochlorite under strong base, adding water for hydrolysis and separation to obtain the long-chain fluorine-containing alkyl dihydroxy difluoromethyl sulfonate compound shown in the formula G:
wherein: r = methyl or tert-butyl;
wherein: x = Li+、K+Or Na+；
(6) And (3) dehydrating diene reaction: adding trichloroacetic acid and cyclohexane into the long-chain fluorine-containing alkyl dihydroxy difluoromethyl sulfonate compound with the chemical structure shown in the formula G, heating and refluxing, cracking tertiary alcohol into olefinic bond, and separating to obtain the compound shown in the formula A. The chemical formula is 2,5,5,6,6,9,9,10,10, -nonamethyl-13-trifluoromethyl-2, 12-diene-1, 1-difluorotetradecyl sulfonate.
In the coupling reaction, the molar ratio of 2, 5-dimethyl-2, 5-dichlorohexane to the excessive 2, 5-dimethyl-5-chloro-2-hexanol is controlled to be 1: 3-5;
in the coupling reaction, the catalyst for oxidizing hydrazino is 4-hydroxy-2, 2,6, 6-tetramethyl piperidine nitroxide radical (4-hydroxy TEMPO).
In the trifluoromethyl addition reaction of the compound shown in the formula D, tetrabutylammonium fluoride is adopted as a villiaumite catalyst;
in the difluoromethyl addition reaction of the compound of formula E, sodium hydroxide, potassium hydroxide or lithium hydroxide is used as the strong base.
Description of the drawings:
FIG. 1: c24 long-chain alkyl fluorine-containing diene difluoro methyl lithium sulfonate.
The specific implementation mode is as follows:
for better understanding of the method for synthesizing the lithium compound of the ionic membrane of the fluorine-containing long-chain alkyl diene difluoromethylsulfonic acid of the invention, the invention provides the following examples, but the invention is not limited to the examples.
Example 1:
(1) coupling reaction: adding 1172, 5-dimethyl-2, 5-hexanediol (1172 g (8 mol)) and 36% concentrated hydrochloric acid (1120 g (11.2 mol)) into a 3000ml three-neck flask, heating in a water bath, keeping the temperature at 30-50 ℃ for chlorination reaction, continuously separating out an oil layer, collecting the oil layer after 5 hours of reaction, washing the oil layer to be neutral by using a sodium bicarbonate water solution to obtain 1351g, and directly reacting with hydrazine hydrate;
adding 1351g of neutral oil layer mixture and 2000g of anhydrous methanol into a 5000ml three-neck bottle, adding 320g of 85% hydrazine hydrate at room temperature, reacting at 30-40 ℃ for 10h, then eliminating carbon-chlorine bonds, adding solid NaOH, stirring to obtain a homogeneous phase, then adding 30g of 4-hydroxy TEMPO, introducing oxygen, keeping the temperature at 50-60 ℃ and oxidizing to obtain an azo-based mixture, and oxidizing unreacted hydrazine hydrate to obtain N2；
Distilling the azo mixture to remove methanol, adding water to dissolve inorganic salt, separating a water layer, collecting water-insoluble azo compound solid at room temperature, adding the water-insoluble azo compound solid into a 5000ml three-necked bottle with a reflux condenser tube, heating to maintain the temperature at 160-200 ℃, and continuously cracking N2Discharging, in the tail gas bubble N2Stopping discharging, cooling to 60-70 ℃, adding 3 times of cyclohexane, quickly stirring for recrystallization, cooling to 15-20 ℃, performing suction filtration to remove crystals to obtain a cyclohexane solution, and distilling to remove cyclohexane to obtain a compound white solid of the formula B632g (1.7 mol), purity 95.3%;
(2) and (3) diene chlorination reaction:
adding 465g (1.2 mol) of a compound shown as a formula B of C24 alkyl diol and 1500g of anhydrous methanol into a 3000ml three-necked flask, dissolving the compound at room temperature to be transparent, introducing 102g of anhydrous hydrogen chloride, heating and keeping the mixture at 30-40 ℃ for chlorination reaction, monitoring the disappearance of spots of the compound shown as the formula B by TLC, adding 150g of solid NaOH, heating and refluxing the mixture for dechlorination for 5-6 hours, and separating out a large amount of white sodium chloride crystals; cooling to room temperature, performing suction filtration to remove NaCl, distilling the obtained filtrate to recover most of methanol, pouring into water, collecting 380.2g of white solid of C24 alkyldiene compound C, and performing GC analysis to obtain 98.6% purity;
(3) ozonization:
335g (1.0 mol) of the compound of the formula C and 600g of n-butanol are dissolved homogeneously. Continuously introducing ozone under normal pressure for oxidation, detecting that the spots of the compound shown in the formula C disappear by TLC (thin-layer chromatography), only having one spot with enhanced polarity, adding 260g of saturated aqueous solution of sodium bisulfite at room temperature after ozone introduction is stopped to decompose peroxy groups for 4-5 hours, azeotropically removing n-butyl alcohol aqueous solution, adding water into the rest material, stirring, removing a water layer, and obtaining 326g of water-insoluble white solid of the compound shown in the formula D of C22 alkyl diketone with the purity of 98.2%;
(4) and (3) addition of trifluoromethyl:
adding 295g (0.8 mol) of a compound shown in a formula D and 10g of anhydrous tetrabutylammonium fluoride into 600g of dioxane dehydrated by sodium in a 3000ml three-necked bottle, stirring, dissolving and transparent, slowly dropwise adding 56g of trifluoromethyl trimethylsilane (0.4 mol) at 20-30 ℃, reacting mildly and releasing heat, continuing to react for 5-6 h after dropwise adding is finished, and finishing the reaction after the trifluoromethyl trimethylsilane disappears by GC analysis;
distilling under reduced pressure to recover dioxane, adding 300g of isoamyl alcohol and 250g of 30% wt aqueous solution of sodium thiosulfate, completely condensing with ketone group at room temperature, collecting oil layer, adding 8% sodium hypochlorite aqueous solution into the oil layer, and completely oxidizing at room temperature to recover ketone group; collecting the oil layer again in layers, and removing isoamylol under reduced pressure to obtain 148.4g of a white solid of the compound shown in the formula E, wherein the purity is 82.6%;
(5) addition of difluoromethyl:
adding 148.4G of the compound shown in the formula E, 55G of the compound shown in the formula F (R = methyl) and 240G of anhydrous methanol into a 1000ml three-neck flask, mixing, dropwise adding 210G of a 20% sodium methoxide solution to catalyze ketone group addition, adding 460G of 8% sodium hypochlorite at room temperature to oxidize for 8 hours after the ketone group disappears, removing the salt at room temperature, heating to boil to remove the methanol, adding concentrated hydrochloric acid at 40-50 ℃ to adjust the pH to be strong acid with the pH = 1-2, cooling to be less than or equal to 10 ℃ to precipitate a water-containing crystal of the compound shown in the formula G, and drying to remove water to obtain 170.6G of a white crystal of the compound shown in the formula G, wherein the purity is 97.5%;
(6) and (3) dehydrating diene:
170.6G of the compound of the formula G (0.3 mol), 2G of p-methoxyphenol as a polymerization inhibitor, 120G of trichloroacetic acid and 300G of cyclohexane are added into a 2000ml three-neck flask, and heated, refluxed and azeotropically dehydrated until no water is discharged;
cooling to room temperature, adding water for layering, collecting an oil layer, removing cyclohexane from the oil layer under reduced pressure to obtain a white solid, and recrystallizing with ethyl acetate to obtain 137.8g of fluorine-containing long-chain alkyl diene difluoromethyl sodium sulfonate white crystal with the chemical structure of formula A, wherein the purity is 98.2%;
example 2:
(1) coupling reaction: adding 1318g (9 mol) of 2, 5-dimethyl-2, 5-hexanediol and 1120g (11.2 mol) of 36% concentrated hydrochloric acid into a 3000ml three-necked bottle, heating in a water bath, keeping at 30-50 ℃ for chlorination reaction, continuously separating out an oil layer, collecting the oil layer after 5 hours of reaction, washing with a sodium bicarbonate water solution to be neutral to obtain 1503g, and directly reacting with hydrazine hydrate;
adding 1503g of neutral oil layer mixture and 2000g of anhydrous methanol into a 5000ml three-neck flask, adding 330g of 85% hydrazine hydrate at room temperature, reacting at 30-40 ℃ for 10h, removing carbon-chlorine bonds, adding solid NaOH, stirring to obtain a homogeneous phase, adjusting the pH of the material to be 11-12, adding 30g of 4-hydroxy TEMPO, introducing oxygen, keeping the temperature at 50-60 ℃ to oxidize the material completely into an azo-based mixture, and oxidizing unreacted hydrazine hydrate into N2；
Distilling the azo mixture to remove methanol, adding water to dissolve inorganic salt, separating a water layer, collecting water-insoluble azo compound solid at room temperature, adding the water-insoluble azo compound solid into a 5000ml three-necked bottle with a reflux spherical condenser tube, heating and keeping the temperature at 160-200 ℃, and continuously cracking N2Discharging, in the tail gas bubble N2Stopping discharging, cooling to 60-70 ℃, adding 3 times of cyclohexane, quickly stirring and recrystallizing, cooling to 15-20 ℃, then performing suction filtration to remove crystals to obtain a cyclohexane solution, and distilling to remove cyclohexane to obtain 705g (1.9 mol) of a compound white solid of the formula B, wherein the purity of the compound white solid is 96.7%;
(2) and (3) diene chlorination reaction:
adding 705g (1.9 mol) of a compound shown in a formula B and containing C24 alkyl diol and 1500g of anhydrous methanol into a 3000ml three-necked flask, dissolving the mixture at room temperature to be transparent, introducing 150g of anhydrous hydrogen chloride, heating and keeping the mixture at 30-40 ℃ for chlorination reaction, monitoring the disappearance of spots of the compound shown in the formula B by TLC, adding 180g of solid NaOH, heating and refluxing the mixture for dechlorination for 5-6 hours, and separating out a large amount of white sodium chloride crystals; cooling to room temperature, filtering to remove NaCl, distilling the obtained filtrate to recover most of methanol, pouring into water, collecting 618.6g of white solid of C24 alkyldiene compound C, and analyzing by GC to obtain 97.8% purity product;
(3) ozonization:
618.6g (1.85 mol) of compound C of the formula and 800g of n-butanol are dissolved homogeneously. Continuously introducing ozone under normal pressure for oxidation, detecting that spots of the compound shown in the formula C disappear by TLC (thin-layer chromatography), only having one spot with enhanced polarity, adding 400g of saturated aqueous solution of sodium bisulfite at room temperature after ozone introduction is stopped to decompose peroxy groups for 4-5 hours, azeotropically removing n-butyl alcohol aqueous solution, adding water into the rest material, stirring, removing a water layer, and obtaining 558g of water-insoluble white solid of the compound shown in the formula D of C22 alkyl diketone, wherein the purity is 98.4%;
(4) and (3) addition of trifluoromethyl:
adding 558g (1.65 mol) of the compound shown in the formula D and 20g of anhydrous tetrabutylammonium fluoride into 600g of dioxane dehydrated by sodium in a 5000ml three-necked bottle, stirring to dissolve and transparent, slowly dropwise adding 113.6g of trifluoromethyl trimethylsilane (0.8 mol) at 20-30 ℃, reacting mildly and releasing heat, continuing to react for 5-6 h after dropwise adding is finished, and finishing the reaction after analyzing that the trifluoromethyl trimethylsilane disappears by GC;
distilling under reduced pressure to recover dioxane, adding 600g of isoamyl alcohol and 550g of 30% wt aqueous solution of sodium thiosulfate, completely condensing with ketone group at room temperature, collecting oil layer, adding 8% sodium hypochlorite aqueous solution into the oil layer, and completely oxidizing at room temperature to recover ketone group; collecting oil layers again in a layered manner, and removing isoamylol under reduced pressure to obtain 308.5g of a white solid of the compound shown in the formula E, wherein the purity is 87.6%;
(5) addition of difluoromethyl:
adding 308.5G of the compound shown in the formula E, 115G of the compound shown in the formula F (R = methyl/1 mol) and 400G of anhydrous methanol into a 3000ml three-neck flask, mixing, dropwise adding 280G of 20% sodium methoxide solution to catalyze ketone group addition, adding 1260G of 8% sodium hypochlorite at room temperature to oxidize for 8 hours after the ketone group disappears, heating to boil to remove the methanol after desalting at room temperature, adding concentrated hydrochloric acid at 40-50 ℃ to adjust the pH value to be strong acid with pH = 1-2, cooling to be less than or equal to 10 ℃ to precipitate an aqueous crystal of the compound shown in the formula G, and drying to remove water to obtain 387.6G of white crystals of the compound shown in the formula G, wherein the purity is 98.4%;
(6) and (3) dehydrating diene:
adding 387.6G of a compound (0.68 mol) of the formula G, 5G of p-methoxyphenol serving as a polymerization inhibitor, 180G of trichloroacetic acid and 300G of cyclohexane into a 2000ml three-neck flask, and heating, refluxing and azeotropically dehydrating until no water is discharged;
and cooling to room temperature, adding water for layering, collecting an oil layer, removing cyclohexane from the oil layer under reduced pressure to obtain a white solid, and recrystallizing with ethyl acetate to obtain 341.6g of a fluorine-containing long-chain alkyl diene difluoromethyl sodium sulfonate white crystal with the chemical structure of the formula A, wherein the purity of the crystal is 98.5%.
Example 3:
(1) coupling reaction: adding 1460g (10 mol) of 2, 5-dimethyl-2, 5-hexanediol and 1220g (12.2 mol) of 36% concentrated hydrochloric acid into a 3000ml three-necked bottle, heating in a water bath, keeping the temperature at 30-50 ℃ for chlorination reaction, continuously separating out an oil layer, collecting the oil layer after reacting for 5 hours, washing the oil layer to be neutral by using a sodium bicarbonate aqueous solution to obtain 1659g, and directly reacting with 360g of 85% hydrazine hydrate;
other operations/charges, the same as in example 2, gave 718g (1.9 mol) of the compound of formula B as a white solid with a purity of 98.3%;
(2) and (3) diene chlorination reaction: in a 3000ml three-necked flask, 718g (1.94 mol) of the compound of formula B of C24 alkyl diol and 1500g of anhydrous methanol were added, and the mixture was dissolved at room temperature to be transparent, and other operations/charge amounts were changed in the same manner as in example 2, and 623.5g of a white solid of the compound of formula C of C24 alkyl diene was collected, and the purity by GC analysis was 98.8%;
(3) ozonization: 623.5g (1.86 mol) of compound C and 800g of n-butanol are dissolved homogeneously. Under normal pressure, continuously introducing ozone for oxidation, and obtaining 576g of water-insoluble C22 alkyl diketone compound of formula D white solid with purity of 98.2% by the same operation/feeding amount as the example 2;
(4) and (3) addition of trifluoromethyl: 576g (1.7 mol) of the compound of formula D and 20g of anhydrous tetrabutylammonium fluoride were added to 600g of sodium-dehydrated dioxane in a 5000ml three-necked flask, the other operations/charge amounts were the same as in example 2; 319g of a white solid of the compound of the formula E is obtained, the purity is 83.8%;
(5) addition of difluoromethyl: adding 319G and 162G of the compound shown in the formula E (R = tert-butyl/1 mol) and 300G of anhydrous methanol into a 3000ml three-necked bottle, mixing and dissolving, dropwise adding a strong alkaline methanol solution dissolved by 700G of methanol and 116G of solid potassium hydroxide (2 mol), catalyzing ketone group addition, introducing 180G of chlorine gas at room temperature for oxidation for 8 hours after the ketone group disappears, heating and boiling to remove the methanol after desalting at room temperature, adding concentrated hydrochloric acid at 40-50 ℃ to adjust the pH value to be strong acid of 1-2, cooling to be less than or equal to 10 ℃, precipitating a water-containing crystal of the compound shown in the formula G, drying and removing water to obtain 422.5G of a white crystal of the compound shown in the formula G, wherein the purity is 98.4%;
(6) and (3) dehydrating diene:
in a 2000ml three-necked flask, 422.5G of the compound of formula G (0.73 mol), 5G of p-methoxyphenol serving as a polymerization inhibitor, 180G of trichloroacetic acid and 300G of cyclohexane are added, and heating reflux azeotropic dehydration is carried out until no water is discharged;
and cooling to room temperature, adding water for layering, collecting an oil layer, removing cyclohexane from the oil layer under reduced pressure to obtain a white solid, and recrystallizing with ethyl acetate to obtain 364g of fluorine-containing long-chain alkyl diene difluoromethyl potassium sulfonate white crystal with the chemical structure of the formula A, wherein the purity is 97.8%.
Example 4:
(1) coupling reaction: adding 1460g (10 mol) of 2, 5-dimethyl-2, 5-hexanediol and 1220g (12.2 mol) of 36% concentrated hydrochloric acid into a 3000ml three-necked bottle, heating in a water bath, keeping the temperature at 30-50 ℃ for chlorination reaction, continuously separating out an oil layer, collecting the oil layer after 5 hours of reaction, washing the oil layer to be neutral by using a sodium bicarbonate aqueous solution to obtain 1648g, and directly reacting with 360g of 85% hydrazine hydrate;
other operations/charges, the same as in example 2, gave 712g (1.9 mol) of the compound of formula B as a white solid with a purity of 98.6%;
(2) and (3) diene chlorination reaction: 712g (1.9 mol) of the compound of formula B of C24 alkyldiol and 1500g of anhydrous methanol were added to a 3000ml three-necked flask, and the mixture was dissolved at room temperature to be transparent, and other operations/amounts were carried out in the same manner as in example 2, and 628.1g of a white solid of the compound of formula C of C24 alkyldiene was collected and analyzed by GC to have a purity of 97.9%;
(3) ozonization: 628.1g (1.86 mol) of the compound of the formula C and 800g of n-butanol are dissolved homogeneously. Under normal pressure, continuously introducing ozone for oxidation, and obtaining 585g of white solid of the compound shown in the formula D of the C22 alkyl diketone insoluble in water with purity of 97.5% in the same way as in example 2 except for the operation/feeding amount;
(4) and (3) addition of trifluoromethyl: in a 5000ml three-necked flask, 585g (1.7 mol) of the compound of formula D and 25g of anhydrous tetrabutylammonium fluoride were added to 600g of dioxane dehydrated with sodium, the other operations/charge amounts being the same as in example 2; 326g of a compound of formula E is obtained as a white solid with a purity of 81.7%;
(5) addition of difluoromethyl: adding 319G and 162G of the compound shown in the formula E (R = tert-butyl/1 mol) and 300G of anhydrous methanol into a 3000ml three-necked bottle, mixing and dissolving, dropwise adding a strong alkaline methanol solution dissolved by 800G of methanol and 50G of solid lithium hydroxide (2 mol), catalyzing ketone group addition, introducing 180G of chlorine gas at room temperature for oxidation for 8 hours after the ketone group disappears, heating and boiling to remove the methanol after desalting at room temperature, adding concentrated hydrochloric acid at 40-50 ℃ to adjust the pH value to be strong acid of 1-2, cooling to be less than or equal to 10 ℃, precipitating a water-containing crystal of the compound shown in the formula G, drying and removing water to obtain 396G of a white crystal of the compound shown in the formula G, wherein the purity is 98.1%;
(6) and (3) dehydrating diene:
396G of the compound of the formula G (0.7 mol), 5G of p-methoxyphenol serving as a polymerization inhibitor, 180G of trichloroacetic acid and 300G of cyclohexane are added into a 2000ml three-neck flask, and heated, refluxed and azeotropically dehydrated until no water is discharged;
and cooling to room temperature, adding water for layering, collecting an oil layer, removing cyclohexane from the oil layer under reduced pressure to obtain a white solid, and recrystallizing with ethyl acetate to obtain 335g of fluorine-containing long-chain alkyl diene difluoromethyl lithium sulfonate white crystal with the chemical structure of the formula A, wherein the purity is 98.3%.
Example 5:
(1) coupling reaction: adding 1460g (10 mol) of 2, 5-dimethyl-2, 5-hexanediol and 1220g (12.2 mol) of 36% concentrated hydrochloric acid into a 3000ml three-necked bottle, heating in a water bath, keeping the temperature at 30-50 ℃ for chlorination reaction, continuously separating out an oil layer, collecting the oil layer after 5 hours of reaction, washing the oil layer to be neutral by using a sodium bicarbonate water solution to obtain 1632g, and directly reacting with 360g of 85% hydrazine hydrate;
other operations/charges, in the same manner as in example 2, gave 695g (1.85 mol) of the compound of formula B as a white solid, 97.6% pure;
(2) and (3) diene chlorination reaction: in a 3000ml three-necked flask, 695g (1.85 mol) of the compound of formula B of C24 alkyldiol and 1500g of anhydrous methanol were added, and the solution was transparent at room temperature, and other operations/amounts were carried out in the same manner as in example 2, to collect 601g of a white solid of the compound of formula C of C24 alkyldiene, having a purity of 97.5% by GC analysis;
(3) ozonization: 601g (1.8 mol) of the compound of the formula C and 800g of n-butanol are dissolved homogeneously. Under normal pressure, continuously introducing ozone for oxidation, and obtaining 551g of water-insoluble C22 alkyl diketone compound white solid with the formula D and the purity of 97.8 percent in the same way as the example 2 except for the operation/feeding amount;
(4) and (3) addition of trifluoromethyl: in a 5000ml three-necked flask, 551g (1.6 mol) of the compound of formula D and 25g of anhydrous tetrabutylammonium fluoride were added to 600g of dioxane dehydrated with sodium, and the other operations/charge amounts were the same as in example 2; 312g of the compound of the formula E is obtained as a white solid with the purity of 83.5 percent;
(5) addition of difluoromethyl: adding 312G of the compound shown in the formula E, 162G of the compound shown in the formula F (R = tert-butyl/1 mol) and 300G of anhydrous methanol into a 3000ml three-necked bottle, mixing and dissolving, dropwise adding a strong alkaline methanol solution dissolved by 800G of methanol and 50G of solid lithium hydroxide (2 mol), catalyzing ketone group addition, introducing 180G of chlorine gas at room temperature for oxidation for 8 hours after ketone groups disappear, heating and boiling to remove methanol after desalting at room temperature, adding concentrated hydrochloric acid at 40-50 ℃ to adjust the pH value to be strong acid of 1-2, cooling to be less than or equal to 10 ℃, precipitating a water-containing crystal of the compound shown in the formula G, and drying to remove water to obtain 378G of a white crystal of the compound shown in the formula G, wherein the purity is 98.6%;
(6) and (3) dehydrating diene:
378G of a compound of the formula G (0.7 mol), 5G of p-methoxyphenol serving as a polymerization inhibitor, 180G of trichloroacetic acid and 300G of cyclohexane are added into a 2000ml three-neck flask, and heated, refluxed and azeotropically dehydrated until no water is discharged; and cooling to room temperature, adding water for layering, collecting an oil layer, removing cyclohexane from the oil layer under reduced pressure to obtain a white solid, and recrystallizing with ethyl acetate to obtain 326g of fluorine-containing long-chain alkyl diene difluoromethyl lithium sulfonate white crystal with the chemical structure of the formula A, wherein the purity of the crystal is 98.8%.
Claims (7)
1. Lithium air battery blocks water and O2The permeable long-chain alkyl diene fluorine-containing sulfonate ionic membrane compound is tetracosene alkyl diene fluorine-containing sulfonate with a chemical structure of a formula A, wherein the chemical name is 2,5,5,6,6,9,9,10,10, -nonamethyl-13-trifluoromethyl-2, 12-diene-1, 1-difluoro tetradecyl sulfonate;
wherein: m = Li+、K+Or Na+。
2. The method for synthesizing the long-chain alkyl diene fluorine-containing sulfonate ionic membrane compound with the chemical structure of the formula A as claimed in claim 1 is mainly characterized in that 2, 5-dimethyl-2, 5-hexanediol with the chemical structure of the formula H is used as a starting material;
3. the method for synthesizing the long-chain alkyl diene fluorine-containing sulfonate ionic membrane compound with the chemical structure of the formula A as claimed in claim 1 is mainly characterized in that the ionic membrane compound is synthesized by six steps of coupling reaction, diene chloride reaction, ozonization reaction, trifluoromethyl addition, difluoromethyl addition and dehydrated diene:
(1) coupling reaction: reacting 2, 5-dimethyl-2, 5-hexanediol with concentrated hydrochloric acid at 30-50 ℃ to obtain an oil layer mixture of 2, 5-dimethyl-2, 5-dichlorohexane and excessive 2, 5-dimethyl-5-chloro-2-hexanol, washing the oil layer mixture with sodium bicarbonate to be neutral, reacting with hydrazine hydrate at room temperature to eliminate carbon-chlorine bonds, adding NaOH and an oxidation catalyst, introducing oxygen to catalyze and oxidize to azo groups at 50-60 ℃, finally heating to 160-200 ℃, cracking the azo groups to form free radicals for coupling, and separating to obtain 2,5,5,6,6,9,9,10,10, 13-decamethyl-2, 13-tetradecanediol with a chemical structure shown as a formula B:
(2) and (3) diene chlorination reaction: mixing the compound of the formula B with a hydrogen chloride methanol solution, completely chlorinating the tertiary hydroxyl of the compound of the formula B at 30-50 ℃, then adding NaOH, heating, refluxing, dechlorinating, refining and separating to obtain a diene compound with a chemical structure of a formula C, wherein the chemical name is 2,5,5,6,6,9,9,10,10, 13-decamethyl-1, 14-diene tetradecane;
(3) ozonization reaction: dissolving the diene compound shown in the formula C in n-butyl alcohol, introducing ozone at room temperature to break olefinic bonds completely, adding sodium bisulfite aqueous solution to decompose ozonized products, and separating to obtain a C22 alkyl diketone compound shown in the formula D, wherein the chemical name is 5,5,6,6,9,9,10, 10-octamethyl-2, 13-tetradecanedione;
(4) and (3) trifluoromethyl addition reaction: dissolving excessive compound in formula D and fluoride salt catalyst in solvent, catalyzing trifluoromethyl trimethylsilane by fluoride salt catalyst at room temperature, adding trifluoromethyl into ketone group of compound in formula D, refining and separating the addition product with sodium thiosulfate to obtain compound in chemical structure in formula E, wherein the chemical name is 5,5,6,6,9,9,10, 10-octamethyl-2-trifluoromethyl-13-ketone-2-tetradecanol;
(5) difluoromethyl addition reaction: dissolving the compound shown in the formula E in an alcohol solvent, uniformly mixing the compound with the compound shown in the formula F, adding strong base for catalysis at room temperature, adding difluoromethyl carbanion to ketone group of the compound shown in the formula E, completely oxidizing the obtained crude product with chlorine or hypochlorite under strong base, adding water for hydrolysis and separation to obtain a C24 alkyl bishydroxy difluoromethyl sulfonate compound with a chemical structure shown in the formula G:
wherein: r = methyl or tert-butyl;
wherein: x = Li+、K+Or Na+；
(6) And (3) dehydrating diene reaction: adding trichloroacetic acid and cyclohexane into a long-chain fluorine-containing alkyl dihydroxy difluoromethyl sulfonate compound with a chemical structure shown in a formula G, heating and refluxing, cracking tertiary alcohol into olefinic bond, and separating to obtain a compound shown in a formula A, wherein the chemical name is 2,5,5,6,6,9,9,10,10, -nonamethyl-13-trifluoromethyl-2, 12-diene-1, 1-difluoro tetradecyl sulfonate;
wherein: m = Li+、K+Or Na+。
4. The coupling reaction of claim 3, wherein the molar ratio of 2, 5-dimethyl-2, 5-dichlorohexane to excess 2, 5-dimethyl-5-chloro-2-hexanol is controlled to be 1: 3-5.
5. The coupling reaction of claim 3 wherein the oxidation catalyst is 4-hydroxy-2, 2,6, 6-tetramethylpiperidinyloxy (4-HO-TEMPO).
6. The trifluoromethyl reaction of claim 3 wherein the fluoride salt catalyst is tetrabutylammonium fluoride.
7. The difluoromethyl addition reaction of claim 3, wherein said strong base is selected from the group consisting of sodium hydroxide, potassium hydroxide, and lithium hydroxide.
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| CN102746078A (en) * | 2011-04-18 | 2012-10-24 | 东丽纤维研究所（中国）有限公司 | Preparation method for organic sulfonic acid compound |
| CN103456981A (en) * | 2013-09-13 | 2013-12-18 | 宋大余 | Manufacturing method of organic lithium-containing polymer solid electrolyte film |
| US20140087298A1 (en) * | 2012-09-26 | 2014-03-27 | Xerox Corporation | Imaging member with fluorosulfonamide-containing overcoat layer |
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| CN102746078A (en) * | 2011-04-18 | 2012-10-24 | 东丽纤维研究所（中国）有限公司 | Preparation method for organic sulfonic acid compound |
| US20140087298A1 (en) * | 2012-09-26 | 2014-03-27 | Xerox Corporation | Imaging member with fluorosulfonamide-containing overcoat layer |
| CN103456981A (en) * | 2013-09-13 | 2013-12-18 | 宋大余 | Manufacturing method of organic lithium-containing polymer solid electrolyte film |
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