CN116162045A - Preparation method of tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt - Google Patents
Preparation method of tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt Download PDFInfo
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- CN116162045A CN116162045A CN202310209991.3A CN202310209991A CN116162045A CN 116162045 A CN116162045 A CN 116162045A CN 202310209991 A CN202310209991 A CN 202310209991A CN 116162045 A CN116162045 A CN 116162045A
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- trifluoromethanesulfonyl
- methyl ammonium
- imide salt
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- XALVHDZWUBSWES-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;tributyl(methyl)azanium Chemical class CCCC[N+](C)(CCCC)CCCC.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F XALVHDZWUBSWES-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 28
- IPILPUZVTYHGIL-UHFFFAOYSA-M tributyl(methyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](C)(CCCC)CCCC IPILPUZVTYHGIL-UHFFFAOYSA-M 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims description 71
- 229920005989 resin Polymers 0.000 claims description 71
- 239000002798 polar solvent Substances 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 36
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 31
- 239000002250 absorbent Substances 0.000 claims description 29
- 238000005406 washing Methods 0.000 claims description 28
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- 238000001291 vacuum drying Methods 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- 238000002425 crystallisation Methods 0.000 claims description 18
- 230000008025 crystallization Effects 0.000 claims description 18
- 239000012071 phase Substances 0.000 claims description 18
- -1 1-allyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt Chemical class 0.000 claims description 15
- 230000002745 absorbent Effects 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 11
- DWLAVVBOGOXHNH-UHFFFAOYSA-L magnesium;prop-2-enoate Chemical compound [Mg+2].[O-]C(=O)C=C.[O-]C(=O)C=C DWLAVVBOGOXHNH-UHFFFAOYSA-L 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- 239000008346 aqueous phase Substances 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 9
- 239000013065 commercial product Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 239000012074 organic phase Substances 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- AEXDMFVPDVVSQJ-UHFFFAOYSA-N trifluoro(trifluoromethylsulfonyl)methane Chemical group FC(F)(F)S(=O)(=O)C(F)(F)F AEXDMFVPDVVSQJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 8
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 8
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052753 mercury Inorganic materials 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 150000003949 imides Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 239000002608 ionic liquid Substances 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 231100000252 nontoxic Toxicity 0.000 abstract description 4
- 230000003000 nontoxic effect Effects 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 3
- 238000004821 distillation Methods 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 description 7
- 125000005463 sulfonylimide group Chemical group 0.000 description 7
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 3
- 101150058243 Lipf gene Proteins 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 150000002466 imines Chemical group 0.000 description 3
- 229910013872 LiPF Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 150000005677 organic carbonates Chemical class 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 206010057040 Temperature intolerance Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 230000008543 heat sensitivity Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical group [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 125000005496 phosphonium group Chemical group 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000004023 quaternary phosphonium compounds Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
- C07C303/40—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reactions not involving the formation of sulfonamide groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
- C07C303/38—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reaction of ammonia or amines with sulfonic acids, or with esters, anhydrides, or halides thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/42—Separation; Purification; Stabilisation; Use of additives
- C07C303/44—Separation; Purification
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to the field of fine chemical industry, in particular to a preparation method of tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt; the invention adopts methyl tributyl ammonium chloride and bis (trifluoromethyl sulfonyl) imide to prepare tributyl methyl ammonium bis (trifluoromethyl sulfonyl) imide salt; the method can obtain the high-purity tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt by removing the solvent through normal pressure distillation, vacuumizing and other methods, does not need further purification, and has simple process; the invention adopts nontoxic and harmless raw materials, has mild reaction conditions, has low requirements on production equipment and is simple to operate; the tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide ionic liquid prepared by the invention has better thermal stability and long battery cycle life.
Description
Technical Field
The invention relates to the field of fine chemical industry, in particular to a preparation method of tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt.
Background
The energy is the basic industry of national economy, and is an important guarantee for ensuring the stable development of the economy of each country and the continuous improvement of the life quality of people. In the twenty-first century, along with rapid development of socioeconomic performance, technological innovation is becoming more and more advanced, and global population and economic scale are increasing, energy sources are being used as the most basic power sources and are being widely applied and demanded. However, the increasingly depleted non-renewable energy resources cause the contradiction between energy supply and demand to be raised, and the problems of environmental pollution, ecological damage and the like caused in the development and utilization of fossil energy and the discharge process are raised, so that the energy and the environment become two serious problems which must be faced in the twenty-first century, and the development and research of clean renewable new energy are the hot spot fields and policy guidance of the vigorous development of the world. The mode of chemical power supply as energy storage and conversion has been widely used in daily life and production work of people, and secondary batteries have mainly undergone several stages such as lead-acid batteries, nickel-cadmium batteries, nickel-hydrogen batteries, and lithium ion batteries. Compared with other secondary batteries, the lithium ion battery has the advantages of high working voltage and energy density, long service life, small self-discharge, no memory effect, environmental friendliness and the like. The device is not only suitable for small-sized electronic devices and portable measuring instruments, but also is a preferred high-energy power source of large-sized energy storage equipment, pure electric vehicles, hybrid electric vehicles and plug-in hybrid electric vehicles.
Such as chinese patent CN201710201730.1: a rechargeable ionic liquid dual-ion battery and its preparing process are disclosed. The double-ion battery comprises an anode, a cathode, electrolyte and a diaphragm, wherein the anode and cathode materials are graphite structure carbon materials, and the electrolyte is double-trifluoro methanesulfonimide ionic liquid. During preparation, the carbon material with the positive and negative electrode graphite structure and the diaphragm are firstly processed into sheets, then the button cell is assembled in a nitrogen glove box, and a three-layer glass fiber diaphragm is arranged between the positive and negative electrodes. When in charge, positive ions in the battery are embedded into negative graphite from electrolyte, and bis (trifluoromethanesulfonyl) anions are embedded into positive graphite; during discharge, the two ions are respectively desorbed from the graphite and enter the electrolyte. The battery has a discharge voltage platform of 4.4V, a specific capacity of 82mAh/g and an energy density of 258Wh/kg under the discharge current of 30 mA/g; has a very wide charge-discharge voltage interval of 1.0-5.0V.
Another example is chinese patent CN201310532457.2: the preparation method of the ionic liquid comprises the following steps: a. reacting a tertiary amine compound, a tertiary imine compound or a tertiary phosphorus compound with a carbonate to obtain an intermediate containing a quaternary ammonium cation or a quaternary phosphonium cation; b. reacting the intermediate formed in step a with an imine compound; or the intermediate generated in the step a is hydrolyzed and then reacts with an imine compound or an imine salt. The imine quaternary ammonium or quaternary phosphonium ionic liquid prepared by the method is particularly suitable for electrochemical systems sensitive to halogen ions, such as lithium ion secondary batteries, electrochemical supercapacitors and the like. According to the method, the raw materials are nontoxic and harmless, the reaction condition is mild, the requirement on production equipment is low, all conventional reaction vessels suitable for liquid phase reaction can be used in principle, and the operations of feeding, mixing, distilling, filtering and the like are simple.
Another example is chinese patent CN201510575017.4: relates to a preparation method of ionic liquid, in particular to a method for synthesizing quaternary ammonium or quaternary phosphonium compound by a one-step method. The method adds nitrogen compound or phosphorus compound, proton compound and carbonic ester into a reactor to react together to synthesize the corresponding quaternary ammonium salt or quaternary phosphonium salt ionic liquid in one step, namely a one-pot reaction, which is a one-step reaction involving three reactants. The invention also provides a lithium ion secondary battery containing the ionic liquid prepared by the preparation method. The ionic liquid preparation method can widen the selection range of ionic liquid preparation raw materials, further widens the variety of synthesized ionic liquid, and the raw materials in the preparation method are nontoxic and harmless, have mild reaction conditions, have low requirements on production equipment and low production cost, and are suitable for the requirements of green industry and large-scale industrial production.
The nonaqueous electrolyte is one of the key materials of lithium (ion) batteries, and is closely related to the cycle life, high temperature resistance, safety and other key performances of the batteries. The electrolyte of the secondary lithium (ion) battery which is commercialized is mainly composed of organic carbonates such as dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate and ethylene carbonate, liPF 6 Conductive salts, various functional additives, and the like. The organic carbonate electrolyte has the defects of easy volatilization and inflammability of solvents, and the like, and when the battery is improperly used, such as overcharge, short circuit, and the like, the battery is easy to cause thermal runaway, and safety accidents such as combustion, explosion, and the like occur. LiPF (LiPF) 6 The chemical activity is high, the thermal decomposition is generated by water and heat sensitivity, and the sum is an important factor influencing the cycle life of the battery. Thus conventional carbonates and LiPF 6 The electrolyte system becomes a technical bottleneck for the enlargement and the high power of the secondary energy storage battery.
Disclosure of Invention
The invention aims to solve the problems in the prior art, and provides a preparation method of tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt, which is simple to operate and mild in process conditions.
The specific technical scheme is as follows: a preparation method of tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt comprises the following operation steps:
s1: slowly dripping 22-30 parts of methyltributylammonium chloride into 28-36 parts of bistrifluoromethylsulfonyl imide at normal temperature, and controlling the reaction temperature;
s2: separating oil phase from water phase after reaction is completed: extracting the aqueous phase with 100-150 parts of weak polar solvent, and mixing the organic phases;
s3: repeatedly washing with water until chloride ions are not detected and the pH is 6-7;
s4: and distilling at normal pressure to remove the weak polar solvent, vacuumizing, and further removing the weak polar solvent to obtain tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt.
Preferably, the dripping time of the methyltributylammonium chloride is 1-1.5h.
Preferably, the reaction temperature is 70-90 ℃ and the reaction time is 1-3h.
Preferably, the weak polar solvent comprises one or more of dichloromethane, cyclohexane, toluene, chloroform or n-hexane.
As a preferable scheme, the preparation method of the bis (trifluoromethyl) sulfonyl imide comprises the following steps:
adding 35-50 parts of triethylamine by weight into a reactor, cooling to-50 to-65 ℃, dissolving 25-35 parts of ammonia into the reactor, and dropwise adding 22-30 parts of CF (CF) while stirring 3 SO 2 After Cl, the mixture is heated to room temperature, stirred for 3 to 5 hours, heated to boiling, reacted for 1 to 3 hours, extracted by methylene dichloride, washed by water for 3 times, dried by modified water-absorbent resin for an organic liquid layer, filtered, decompressed, distilled to remove a weak polar solvent, crystallized, filtered and dried in vacuum to obtain the bistrifluoromethylsulfonylimide.
Preferably, the stirring speed is 100-300rpm.
Preferably, the crystallization temperature is-25 to-10 ℃ and the crystallization time is 2-5h.
As a preferable scheme, the vacuum drying temperature is 50-70 ℃, the pressure is-0.09 to-0.1 MPa, and the time is 3-8h.
As a preferred scheme, the preparation method of the modified water absorbent resin comprises the following steps:
s1: washing 100-130 parts of sulfhydryl resin with ethanol for 2-5 times, vacuum drying, and vacuum degree is-0.06 Mpa to-0.10 Mpa to obtain anhydrous sulfhydryl resin;
s2: adding 1000-1500 parts of ethylene dichloride into a closed reaction kettle, heating to 60-70 ℃ under the protection of nitrogen, stirring and reacting for 90-150min, adding 0.1-0.6 part of 1-allyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt, CAS (CAS) 655249-87-9,4-7 parts of organic amine, stirring and reacting for 20-60min, adding 10-20 parts of magnesium acrylate, 0.5-2 parts of benzoyl peroxide, reacting for 50-120min at 70-90 ℃, filtering after the completion, washing with ethanol for 2-5 times, and vacuum drying to obtain the modified water-absorbent resin.
Preferably, the sulfhydryl resin is a commercial product, such as D190 big Kongji resin or LSC-400 mercury removal special resin.
Reaction mechanism:
the sulfhydryl resin firstly carries out addition reaction with 1-allyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt, then carries out addition reaction with magnesium acrylate, and then carries out crosslinking and drying to obtain the modified water-absorbent resin, so that the compatibility of the modified water-absorbent resin and the bistrifluoromethylsulfonyl imide can be improved, and the magnesium acrylate can increase the water absorption and improve the water absorption effect.
The technical effects are as follows:
compared with the prior art, the preparation method of tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt has the following remarkable effects:
1. the invention adopts nontoxic and harmless raw materials, has mild reaction conditions, has low requirements on production equipment and is simple to operate;
2. the method can obtain the high-purity tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt by removing the solvent through normal pressure distillation, vacuumizing and other methods, does not need further purification, and has simple process;
3. the tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide ionic liquid prepared by the invention has better thermal stability and long battery cycle life.
Drawings
FIG. 1 is an infrared spectrum of the product of example 2.
Detailed Description
In order that the above-recited objects, features and advantages of embodiments of the present invention may be more clearly understood, a detailed description of the invention will be rendered by reference to specific embodiments thereof. In addition, features in the embodiments of the present application may be combined with each other without conflict.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of embodiments of the invention, and the described embodiments are merely some, rather than all, of the embodiments of the invention. All other embodiments, based on the embodiments of the invention, which are obtained by a person of ordinary skill in the art without making any inventive effort, are within the scope of the embodiments of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which embodiments of the invention belong. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Example 1
A preparation method of tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt comprises the following operation steps:
s1: slowly dripping 22g of methyltributylammonium chloride into 28g of bistrifluoromethyl sulfonyl imide at normal temperature, and controlling the reaction temperature;
s2: separating oil phase from water phase after reaction is completed: extracting the aqueous phase with 100g of a weak polar solvent, and combining the organic phases;
s3: repeatedly washing with water until chloride ions are not detected and the pH value is 6;
s4: and distilling at normal pressure to remove the weak polar solvent, vacuumizing, and further removing the weak polar solvent to obtain tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt.
The dripping time of the methyl tributyl ammonium chloride is 1h.
The reaction temperature is 70 ℃ and the reaction time is 1h.
The weak polar solvent is dichloromethane.
The preparation method of the bis (trifluoromethyl) sulfonyl imide comprises the following steps:
into a reactor, 35g of triethylamine was charged, cooled to-50℃and 25g of ammonia was dissolved therein, and 22g of CF was added dropwise with stirring 3 SO 2 After Cl, the mixture is heated to room temperature, stirred for 3 hours, heated to boiling, reacted for 1 hour, extracted by methylene dichloride, washed by water for 3 times, dried by modified water-absorbent resin for an organic liquid layer, filtered, decompressed, distilled to remove a weak polar solvent, crystallized, filtered and dried in vacuum to obtain the bistrifluoromethyl sulfonimide.
The stirring speed is 100rpm.
The crystallization temperature is-25 ℃, and the crystallization time is 2h.
The vacuum drying temperature is 50 ℃, the pressure is-0.09 MPa, and the time is 3 hours.
The preparation method of the modified water absorbent resin comprises the following steps:
s1: washing 100g of mercapto resin with ethanol for 2 times, and vacuum drying to vacuum degree of-0.06 Mpa to obtain anhydrous mercapto resin;
s2: adding anhydrous sulfhydryl resin and 1000g dichloroethane into a closed reaction kettle, heating to 60 ℃ under the protection of nitrogen, stirring and reacting for 90min, then adding 0.1g of 1-allyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt (CAS: 655249-87-9,4g of organic amine), stirring and reacting for 20min, adding 10g of magnesium acrylate, 0.5g of benzoyl peroxide, reacting for 50min at 70 ℃, filtering after the completion, washing with ethanol for 2 times, and vacuum drying to obtain the modified water-absorbent resin.
The sulfhydryl resin is a commercial product D190 big Kongji resin.
Example 2
A preparation method of tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt comprises the following operation steps:
s1: slowly dripping 24g of methyltributylammonium chloride into 30g of bistrifluoromethyl sulfonyl imide at normal temperature, and controlling the reaction temperature;
s2: separating oil phase from water phase after reaction is completed: extracting the aqueous phase with 110g of a weak polar solvent, and combining the organic phases;
s3: repeatedly washing with water until chloride ions are not detected and the pH value is 6;
s4: and distilling at normal pressure to remove the weak polar solvent, vacuumizing, and further removing the weak polar solvent to obtain tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt.
The dripping time of the methyl tributyl ammonium chloride is 1h.
The reaction temperature is 75 ℃, and the reaction time is 2 hours.
The weak polar solvent is cyclohexane.
The preparation method of the bis (trifluoromethyl) sulfonyl imide comprises the following steps:
40g of triethylamine was introduced into the reactor, cooled to-55℃and 28g of ammonia was dissolved therein, and 24g of CF was added dropwise with stirring 3 SO 2 After Cl, the mixture is heated to room temperature, stirred for 4 hours, heated to boiling, reacted for 2 hours, extracted by methylene dichloride, washed by water for 3 times, dried by modified water-absorbent resin for an organic liquid layer, filtered, decompressed, distilled to remove a weak polar solvent, crystallized, filtered and dried in vacuum to obtain the bistrifluoromethyl sulfonimide.
The stirring speed was 200rpm.
The crystallization temperature is-20 ℃ and the crystallization time is 3 hours.
The vacuum drying temperature is 55 ℃, the pressure is-0.09 MPa, and the time is 4 hours.
The preparation method of the modified water absorbent resin comprises the following steps:
s1: washing 110g of mercapto resin with ethanol for 3 times, and vacuum drying to vacuum degree of-0.07 Mpa to obtain anhydrous mercapto resin;
s2: adding 1100g of ethylene dichloride into a closed reaction kettle, heating to 65 ℃ under the protection of nitrogen, stirring and reacting for 120min, adding 0.2g of 1-allyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt (CAS: 655249-87-9,5g of organic amine), stirring and reacting for 30min, adding 14g of magnesium acrylate, 1g of benzoyl peroxide, reacting for 80min at 75 ℃, filtering after the completion, washing with ethanol for 3 times, and vacuum drying to obtain the modified water absorbent resin.
The sulfhydryl resin is a commercial product D190 big Kongji resin.
Example 3
A preparation method of tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt comprises the following operation steps:
s1: slowly dripping 28g of methyltributylammonium chloride into 34g of bistrifluoromethyl sulfonyl imide at normal temperature, and controlling the reaction temperature;
s2: separating oil phase from water phase after reaction is completed: extracting the aqueous phase with 140g of a weak polar solvent, and combining the organic phases;
s3: repeatedly washing with water until chloride ions are not detected and the pH value is 7;
s4: and distilling at normal pressure to remove the weak polar solvent, vacuumizing, and further removing the weak polar solvent to obtain tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt.
The dripping time of the methyl tributyl ammonium chloride is 1.5h.
The reaction temperature is 85 ℃ and the reaction time is 2 hours.
The weak polar solvent is toluene.
The preparation method of the bis (trifluoromethyl) sulfonyl imide comprises the following steps:
45g of triethylamine was added to the reactor, cooled to-60℃and 32g of ammonia were dissolved therein, 28g of CF were added dropwise with stirring 3 SO 2 After Cl, the mixture is heated to room temperature, stirred for 4 hours, heated to boiling, reacted for 2 hours, extracted by methylene dichloride, washed by water for 3 times, dried by modified water-absorbent resin for an organic liquid layer, filtered, decompressed, distilled to remove a weak polar solvent, crystallized, filtered and dried in vacuum to obtain the bistrifluoromethyl sulfonimide.
The stirring speed was 200rpm.
The crystallization temperature is-15 ℃, and the crystallization time is 4 hours.
The vacuum drying temperature is 65 ℃, the pressure is-0.1 MPa, and the time is 7 hours.
The preparation method of the modified water absorbent resin comprises the following steps:
s1: washing 120g of mercapto resin with ethanol for 4 times, and vacuum drying to vacuum degree of-0.08 Mpa to obtain anhydrous mercapto resin;
s2: adding 1400g of ethylene dichloride into a closed reaction kettle, heating to 65 ℃ under the protection of nitrogen, stirring and reacting for 140min, adding 0.5g of 1-allyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt (CAS: 655249-87-9) and 6g of organic amine, stirring and reacting for 50min, adding 18g of magnesium acrylate, 1.5g of benzoyl peroxide, reacting for 100min at 85 ℃, filtering after the completion, washing with ethanol for 4 times, and vacuum drying to obtain the modified water-absorbent resin.
The sulfhydryl resin is a commercial product LSC-400 mercury removal special resin.
Example 4
A preparation method of tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt comprises the following operation steps:
s1: slowly dripping 30g of methyltributylammonium chloride into 36g of bistrifluoromethyl sulfonyl imide at normal temperature, and controlling the reaction temperature;
s2: separating oil phase from water phase after reaction is completed: extracting the aqueous phase with 150g of a weak polar solvent, and combining the organic phases;
s3: repeatedly washing with water until chloride ions are not detected and the pH value is 7;
s4: and distilling at normal pressure to remove the weak polar solvent, vacuumizing, and further removing the weak polar solvent to obtain tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt.
The dripping time of the methyl tributyl ammonium chloride is 1.5h.
The reaction temperature is 90 ℃ and the reaction time is 3 hours.
The weak polar solvent comprises one or more of dichloromethane, cyclohexane, toluene, chloroform or n-hexane.
The preparation method of the bis (trifluoromethyl) sulfonyl imide comprises the following steps:
50g of triethylamine was added to the reactor, cooled to-65℃and 35g of ammonia was dissolved therein, and 30g of CF was added dropwise with stirring 3 SO 2 After Cl, the mixture was warmed to room temperature, stirred for 5 hours, heated to boiling, reacted for 3 hours, and extracted with dichloromethaneAnd (3) washing the mixture for 3 times, drying the organic liquid layer by using the modified water absorbent resin, filtering the dried mixture, taking filtrate, distilling the filtrate under reduced pressure to remove the weak polar solvent, and crystallizing, filtering and drying the filtrate in vacuum to obtain the bistrifluoromethylsulfonylimide.
The stirring speed was 300rpm.
The crystallization temperature is-10 ℃ and the crystallization time is 5 hours.
The vacuum drying temperature is 70 ℃, the pressure is-0.1 MPa, and the time is 8 hours.
The preparation method of the modified water absorbent resin comprises the following steps:
s1: washing 130g of mercapto resin with ethanol for 5 times, and vacuum drying to vacuum degree of-0.10 Mpa to obtain anhydrous mercapto resin;
s2: adding 1500g of ethylene dichloride into a closed reaction kettle, heating to 70 ℃ under the protection of nitrogen, stirring and reacting for 150min, adding 0.6g of 1-allyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt (CAS: 655249-87-9,7g of organic amine), stirring and reacting for 60min, adding 20g of magnesium acrylate, 2g of benzoyl peroxide, reacting for 120min at 90 ℃, filtering after the completion, washing with ethanol for 5 times, and vacuum drying to obtain the modified water absorbent resin.
The sulfhydryl resin is a commercial product LSC-400 mercury removal special resin.
Comparative example 1
A preparation method of tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt comprises the following operation steps:
s1: slowly dripping 22g of methyltributylammonium chloride into 28g of bistrifluoromethyl sulfonyl imide at normal temperature, and controlling the reaction temperature;
s2: separating oil phase from water phase after reaction is completed: extracting the aqueous phase with 100g of a weak polar solvent, and combining the organic phases;
s3: repeatedly washing with water until chloride ions are not detected and the pH value is 6;
s4: and distilling at normal pressure to remove the weak polar solvent, vacuumizing, and further removing the weak polar solvent to obtain tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt.
The dripping time of the methyl tributyl ammonium chloride is 1h.
The reaction temperature is 70 ℃ and the reaction time is 1h.
The weak polar solvent is dichloromethane.
The preparation method of the bis (trifluoromethyl) sulfonyl imide comprises the following steps:
into a reactor, 35g of triethylamine was charged, cooled to-50℃and 25g of ammonia was dissolved therein, and 22g of CF was added dropwise with stirring 3 SO 2 After Cl, the mixture is heated to room temperature, stirred for 3 hours, heated to boiling, reacted for 1 hour, extracted by methylene dichloride, washed by water for 3 times, dried by modified water-absorbent resin for an organic liquid layer, filtered, decompressed, distilled to remove a weak polar solvent, crystallized, filtered and dried in vacuum to obtain the bistrifluoromethyl sulfonimide.
The stirring speed is 100rpm.
The crystallization temperature is-25 ℃, and the crystallization time is 2h.
The vacuum drying temperature is 50 ℃, the pressure is-0.09 MPa, and the time is 3 hours.
The preparation method of the modified water absorbent resin comprises the following steps:
s1: washing 100g of mercapto resin with ethanol for 2 times, and vacuum drying to vacuum degree of-0.06 Mpa to obtain anhydrous mercapto resin;
s2: adding 1000g of ethylene dichloride into a closed reaction kettle, heating to 60 ℃ under the protection of nitrogen, stirring and reacting for 90min, adding 4g of organic amine, stirring and reacting for 20min, adding 10g of magnesium acrylate, 0.5g of benzoyl peroxide, reacting for 50min at 70 ℃, filtering after completion, washing with ethanol for 2 times, and vacuum drying to obtain the modified water absorbent resin.
The sulfhydryl resin is a commercial product D190 big Kongji resin.
Comparative example 2
A preparation method of tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt comprises the following operation steps:
s1: slowly dripping 22g of methyltributylammonium chloride into 28g of bistrifluoromethyl sulfonyl imide at normal temperature, and controlling the reaction temperature;
s2: separating oil phase from water phase after reaction is completed: extracting the aqueous phase with 100g of a weak polar solvent, and combining the organic phases;
s3: repeatedly washing with water until chloride ions are not detected and the pH value is 6;
s4: and distilling at normal pressure to remove the weak polar solvent, vacuumizing, and further removing the weak polar solvent to obtain tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt.
The dripping time of the methyl tributyl ammonium chloride is 1h.
The reaction temperature is 70 ℃ and the reaction time is 1h.
The weak polar solvent is dichloromethane.
The preparation method of the bis (trifluoromethyl) sulfonyl imide comprises the following steps:
into a reactor, 35g of triethylamine was charged, cooled to-50℃and 25g of ammonia was dissolved therein, and 22g of CF was added dropwise with stirring 3 SO 2 After Cl, the mixture is heated to room temperature, stirred for 3 hours, heated to boiling, reacted for 1 hour, extracted by methylene dichloride, washed by water for 3 times, dried by modified water-absorbent resin for an organic liquid layer, filtered, decompressed, distilled to remove a weak polar solvent, crystallized, filtered and dried in vacuum to obtain the bistrifluoromethyl sulfonimide.
The stirring speed is 100rpm.
The crystallization temperature is-25 ℃, and the crystallization time is 2h.
The vacuum drying temperature is 50 ℃, the pressure is-0.09 MPa, and the time is 3 hours.
The preparation method of the modified water absorbent resin comprises the following steps:
s1: washing 100g of mercapto resin with ethanol for 2 times, and vacuum drying to vacuum degree of-0.06 Mpa to obtain anhydrous mercapto resin;
s2: adding anhydrous sulfhydryl resin and 1000g dichloroethane into a closed reaction kettle, heating to 60 ℃ under the protection of nitrogen, stirring and reacting for 90min, adding 0.1g 1-allyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt (CAS: 655249-87-9,4g organic amine), stirring and reacting for 20min, adding 0.5g benzoyl peroxide, reacting for 50min at 70 ℃, filtering after completion, washing with ethanol for 2 times, and vacuum drying to obtain the modified water-absorbent resin.
The sulfhydryl resin is a commercial product D190 big Kongji resin.
Comparative example 3
A preparation method of tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt comprises the following operation steps:
s1: slowly dripping 22g of methyltributylammonium chloride into 28g of bistrifluoromethyl sulfonyl imide at normal temperature, and controlling the reaction temperature;
s2: separating oil phase from water phase after reaction is completed: extracting the aqueous phase with 100g of a weak polar solvent, and combining the organic phases;
s3: repeatedly washing with water until chloride ions are not detected and the pH value is 6;
s4: and distilling at normal pressure to remove the weak polar solvent, vacuumizing, and further removing the weak polar solvent to obtain tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt.
The dripping time of the methyl tributyl ammonium chloride is 1h.
The reaction temperature is 70 ℃ and the reaction time is 1h.
The weak polar solvent is dichloromethane.
The preparation method of the bis (trifluoromethyl) sulfonyl imide comprises the following steps:
into a reactor, 35g of triethylamine was charged, cooled to-50℃and 25g of ammonia was dissolved therein, and 22g of CF was added dropwise with stirring 3 SO 2 After Cl, the mixture is heated to room temperature, stirred for 3 hours, heated to boiling, reacted for 1 hour, extracted by methylene dichloride, washed by water for 3 times, dried by modified water-absorbent resin for an organic liquid layer, filtered, decompressed, distilled to remove a weak polar solvent, crystallized, filtered and dried in vacuum to obtain the bistrifluoromethyl sulfonimide.
The stirring speed is 100rpm.
The crystallization temperature is-25 ℃, and the crystallization time is 2h.
The vacuum drying temperature is 50 ℃, the pressure is-0.09 MPa, and the time is 3 hours.
The preparation method of the modified water absorbent resin comprises the following steps:
s1: washing 100g of mercapto resin with ethanol for 2 times, and vacuum drying to vacuum degree of-0.06 Mpa to obtain anhydrous mercapto resin;
s2: adding anhydrous sulfhydryl resin and 1000g dichloroethane into a closed reaction kettle, heating to 60 ℃ under the protection of nitrogen, stirring and reacting for 90min, adding 0.1g 1-allyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt (CAS: 655249-87-9,4g organic amine), stirring and reacting for 20min, adding 10g magnesium acrylate, reacting for 50min at 70 ℃, filtering after completion, washing with ethanol for 2 times, and vacuum drying to obtain the modified water-absorbent resin.
The sulfhydryl resin is a commercial product D190 big Kongji resin.
The product purity and reaction yield test schemes in the specific embodiments are as follows, and the results are shown in the following table:
1. purity: purity of tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt = mass of tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt in mixture ≡mass of mixture x 100%;
2. yield: yield of tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt = actual yield of tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt/theoretical yield of tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt x 100%.
| Purity/% | Yield/% | Water absorption/g | |
| Example 1 | 98.06 | 93.23 | 1691 |
| Example 2 | 98.57 | 93.96 | 1732 |
| Example 3 | 99.37 | 95.17 | 1789 |
| Example 4 | 98.95 | 94.61 | 1764 |
| Comparative example 1 | 83.79 | 78.55 | 1006 |
| Comparative example 2 | 88.62 | 82.70 | 1357 |
| Comparative example 3 | 90.15 | 84.13 | 1433 |
The foregoing embodiments are merely for illustrating the technical solution of the embodiment of the present invention, but not for limiting the same, although the embodiment of the present invention has been described in detail with reference to the foregoing preferred embodiments, it will be understood by those skilled in the art that modifications and equivalent substitutions may be made to the technical solution of the embodiment of the present invention without departing from the spirit and scope of the technical solution of the embodiment of the present invention.
Claims (10)
1. A preparation method of tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt comprises the following operation steps:
s1: slowly dripping 22-30 parts of methyltributylammonium chloride into 28-36 parts of bistrifluoromethylsulfonyl imide at normal temperature, and controlling the reaction temperature;
s2: separating oil phase from water phase after reaction is completed: extracting the aqueous phase with 100-150 parts of weak polar solvent, and mixing the organic phases;
s3: repeatedly washing with water until chloride ions are not detected and the pH is 6-7;
s4: and distilling at normal pressure to remove the weak polar solvent, vacuumizing, and further removing the weak polar solvent to obtain tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt.
2. The method for preparing tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt according to claim 1, which is characterized in that: the dripping time of the methyl tributyl ammonium chloride is 1-1.5h.
3. The method for preparing tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt according to claim 1, which is characterized in that: the reaction temperature is 70-90 ℃ and the reaction time is 1-3h.
4. The method for preparing tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt according to claim 1, which is characterized in that: the weak polar solvent comprises one or more of dichloromethane, cyclohexane, toluene, chloroform or n-hexane.
5. The method for preparing tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt according to claim 1, which is characterized in that: the preparation method of the bis (trifluoromethyl) sulfonyl imide comprises the following steps:
adding 35-50 parts of triethylamine by weight into a reactor, cooling to-50 to-65 ℃, dissolving 25-35 parts of ammonia into the reactor, and dropwise adding 22-30 parts of CF (CF) while stirring 3 SO 2 After Cl, the mixture is heated to room temperature, stirred for 3 to 5 hours, heated to boiling, reacted for 1 to 3 hours, extracted by methylene dichloride, washed by water for 3 times, dried by modified water-absorbent resin for an organic liquid layer, filtered, decompressed, distilled to remove a weak polar solvent, crystallized, filtered and dried in vacuum to obtain the bistrifluoromethylsulfonylimide.
6. The method for preparing tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt according to claim 5, wherein the method comprises the following steps: the stirring speed is 100-300rpm.
7. The method for preparing tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt according to claim 5, wherein the method comprises the following steps: the crystallization temperature is-25 to-10 ℃, and the crystallization time is 2-5h.
8. The method for preparing tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt according to claim 5, wherein the method comprises the following steps: the vacuum drying temperature is 50-70 ℃, the pressure is-0.09 to-0.1 MPa, and the time is 3-8h.
9. The method for preparing tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt according to claim 5, wherein the method comprises the following steps: the preparation method of the modified water absorbent resin comprises the following steps:
s1: washing 100-130 parts of sulfhydryl resin with ethanol for 2-5 times, vacuum drying, and vacuum degree is-0.06 Mpa to-0.10 Mpa to obtain anhydrous sulfhydryl resin;
s2: adding 1000-1500 parts of ethylene dichloride into a closed reaction kettle, heating to 60-70 ℃ under the protection of nitrogen, stirring and reacting for 90-150min, adding 0.1-0.6 part of 1-allyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt, CAS (CAS) 655249-87-9,4-7 parts of organic amine, stirring and reacting for 20-60min, adding 10-20 parts of magnesium acrylate, 0.5-2 parts of benzoyl peroxide, reacting for 50-120min at 70-90 ℃, filtering after the completion, washing with ethanol for 2-5 times, and vacuum drying to obtain the modified water-absorbent resin.
10. The method for preparing tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide salt according to claim 5, wherein the method comprises the following steps: the sulfhydryl resin is a commercial product, such as D190 big Kongji resin or LSC-400 mercury removal special resin.
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