CN115595197A - New energy battery shell drawing oil and preparation method thereof - Google Patents
New energy battery shell drawing oil and preparation method thereof Download PDFInfo
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- CN115595197A CN115595197A CN202211159977.9A CN202211159977A CN115595197A CN 115595197 A CN115595197 A CN 115595197A CN 202211159977 A CN202211159977 A CN 202211159977A CN 115595197 A CN115595197 A CN 115595197A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 230000001050 lubricating effect Effects 0.000 claims abstract description 39
- 239000000945 filler Substances 0.000 claims abstract description 36
- 239000000178 monomer Substances 0.000 claims abstract description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052802 copper Inorganic materials 0.000 claims abstract description 22
- 239000010949 copper Substances 0.000 claims abstract description 22
- 239000013384 organic framework Substances 0.000 claims abstract description 19
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims abstract description 14
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 235000014121 butter Nutrition 0.000 claims abstract description 9
- ALRFTTOJSPMYSY-UHFFFAOYSA-N tin disulfide Chemical compound S=[Sn]=S ALRFTTOJSPMYSY-UHFFFAOYSA-N 0.000 claims abstract description 9
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 57
- 238000002156 mixing Methods 0.000 claims description 39
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 22
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 19
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 18
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 16
- 229910017604 nitric acid Inorganic materials 0.000 claims description 16
- 239000000706 filtrate Substances 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- ZBTMRBYMKUEVEU-UHFFFAOYSA-N 1-bromo-4-methylbenzene Chemical compound CC1=CC=C(Br)C=C1 ZBTMRBYMKUEVEU-UHFFFAOYSA-N 0.000 claims description 11
- 235000021355 Stearic acid Nutrition 0.000 claims description 11
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 11
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 11
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 235000019260 propionic acid Nutrition 0.000 claims description 10
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000008096 xylene Substances 0.000 claims description 10
- 238000007792 addition Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 claims description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 229960000583 acetic acid Drugs 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 239000011630 iodine Substances 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 238000003763 carbonization Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 238000010000 carbonizing Methods 0.000 abstract description 2
- 239000011229 interlayer Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 230000008093 supporting effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 25
- 239000003921 oil Substances 0.000 description 24
- 239000011257 shell material Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000005684 electric field Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000005619 boric acid group Chemical group 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 230000007646 directional migration Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/06—Metal compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/06—Metal compounds
- C10M2201/065—Sulfides; Selenides; Tellurides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/24—Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a new energy battery shell drawing oil and a preparation method thereof, wherein the new energy battery shell drawing oil comprises the following raw materials in parts by weight: 40-50 parts of spindle oil, 40-50 parts of butter, 10-15 parts of modified lubricating filler, 3-5 parts of tin disulfide and 1-3 parts of ethanol; the modified lubricating filler is prepared by reacting a modified monomer, 2,3,6,7,10, 11-hexahydroxy triphenyl and copper chloride to form a copper organic framework, roasting, carbonizing and oxidizing the copper organic framework, and is in a multilayer honeycomb pore shape, so that the effect of reducing friction force can be achieved by compressing gaps during stretching, meanwhile, long-chain alkyl of a side chain of the modified monomer can increase gaps among molecules of the modified monomer, further, after carbonization, the interlayer spacing of the modified lubricating filler is increased, and meanwhile, metal copper with a supporting effect is contained in the modified lubricating filler, belongs to soft metal, and can further improve the lubricating property by matching with the structure of the modified lubricating filler.
Description
Technical Field
The invention relates to the technical field of battery preparation, in particular to new energy battery shell stretching oil and a preparation method thereof.
Background
The battery refers to a device which can convert chemical energy into electric energy in part of the space of a cup, a tank or other container or a composite container which is filled with an electrolyte solution and metal electrodes to generate current; the battery is not influenced by external climate and temperature, has stable and reliable performance, and plays a great role in various aspects of modern social life; along with the rapid development of social economy, the demand of human beings on energy is also increasing and the demand is also increasing and the traditional battery can not meet the requirements of people, a large number of mobile power supplies are needed for energy driving of mobile electronic devices, communication devices and hybrid electric vehicles, a new energy battery is accepted and welcomed by the industry due to the advantages of high energy density, large capacity, long service life and the like, a battery shell serving as a necessary protection component of the battery has important influence on the performance of the battery, and the lubricating performance of stretching oil of the battery shell in the stretching process is not enough, so that the material is subjected to spark damage, the strength of the material is influenced, and the effect of protecting the battery cannot be achieved.
Disclosure of Invention
The invention aims to provide new energy battery shell stretching oil and a preparation method thereof, and solves the problem that shell strength is influenced by the fact that the shell material of the existing new energy battery is stretched in the stretching process.
The purpose of the invention can be realized by the following technical scheme:
the new energy battery shell drawing oil comprises the following raw materials in parts by weight: 40-50 parts of spindle oil, 40-50 parts of butter, 10-15 parts of modified lubricating filler, 3-5 parts of tin disulfide and 1-3 parts of ethanol;
the modified lubricating filler is prepared by the following steps:
step A1: uniformly mixing a modified monomer, 2,3,6,7,10, 11-hexahydroxy triphenyl, copper chloride and N, N-dimethylformamide, introducing nitrogen for protection, reacting for 30-40h at the rotation speed of 200-300r/min and the temperature of 60-80 ℃, filtering to remove filtrate, and drying a substrate to obtain a copper organic framework;
step A2: roasting the copper organic framework for 3-5h at the temperature of 800-900 ℃, adding the roasted copper organic framework into a nitric acid solution, stirring for 2-3h at the rotation speed of 600-800r/min and the temperature of 70-80 ℃, filtering to remove filtrate, and drying a substrate to obtain the modified lubricating filler.
Further, the dosage ratio of the modified monomer described in step A1, 2,3,6,7,10, 11-hexahydroxy triphenyl, copper chloride and N, N-dimethylformamide is 2mmol.
Further, the mass fraction of the nitric acid solution in the step A2 is 60-65%.
Further, the modified monomer is prepared by the following steps:
step B1: adding p-bromotoluene into a reaction kettle, stirring and adding mixed acid under the conditions that the rotating speed is 150-200r/min and the temperature is 40-50 ℃, heating to 60-65 ℃ after adding, reacting for 1-1.5h to obtain an intermediate 1, mixing the intermediate 1, acetic anhydride and concentrated sulfuric acid, adding an acetic anhydride solution of chromic anhydride under the conditions that the rotating speed is 200-300r/min and the temperature is 5-10 ℃, reacting for 2-4h, adding ice water until no solid is separated out, filtering to remove filtrate, mixing a filter cake, deionized water, ethanol and concentrated sulfuric acid, and carrying out reflux reaction for 1-1.5h at the temperature of 80-85 ℃ to obtain an intermediate 2;
the reaction process is as follows:
and step B2: uniformly mixing the intermediate 2, propionic acid and dimethylbenzene, stirring and dropwise adding an acetic anhydride solution of pyrrole under the conditions that the rotating speed is 150-200r/min and the temperature is 137-140 ℃, reacting for 10-15min, cooling to room temperature, standing for 10-15h to prepare an intermediate 3, uniformly mixing the intermediate 3, iron powder, deionized water and glacial acetic acid, and performing reflux reaction for 4-6h under the condition that the temperature is 80-85 ℃ to prepare an intermediate 4;
the reaction process is as follows:
and step B3: uniformly mixing the intermediate 4, octadecanoic acid, 1-hydroxybenzotriazole and xylene, reacting for 6-8h at the rotation speed of 200-300r/min and the temperature of 120-130 ℃ to obtain an intermediate 5, dissolving the intermediate 5 in tetrahydrofuran, adding magnesium powder and iodine particles, reacting for 2-3h at the rotation speed of 150-200r/min and the temperature of 20-25 ℃, cooling to the temperature of minus 25-30 ℃, adding a tetrahydrofuran solution of trimethyl borate, raising the temperature to room temperature after the addition is finished, reacting for 2-3h, adding a hydrochloric acid solution, and stirring for 30-40min to obtain the modified monomer.
The reaction process is as follows:
further, in the step B1, the volume ratio of the p-bromotoluene to the mixed acid is 8.9, 17.3, the mixed acid is a mixture of concentrated sulfuric acid with a mass fraction of 98% and concentrated nitric acid with a mass fraction of 68% in a volume ratio of 2.
Furthermore, the dosage ratio of the intermediate 2, propionic acid, xylene and pyrrole in the step B2 is 0.01mol.
Further, the molar ratio of the intermediate 4, the octadecanoic acid and the 1-hydroxybenzotriazole in the step B3 is 1.
A preparation method of new energy battery shell drawing oil specifically comprises the following steps:
after weighing spindle oil, butter, modified lubricating filler, tin disulfide and ethanol, uniformly mixing to prepare the drawing oil.
The invention has the beneficial effects that: the new energy battery shell drawing oil prepared by the invention is prepared by mixing spindle oil, butter, modified lubricating filler, tin disulfide and ethanol, wherein the modified lubricating filler is prepared by reacting modified monomer, 2,3,6,7,10, 11-hexahydroxy triphenyl and copper chloride, and copolymerizing the modified monomer and the 2,3,6,7,10, 11-hexahydroxy triphenyl to ensure that boric acid groups on the modified monomer react with ortho-hydroxyl groups on the 2,3,6,7,10, 11-hexahydroxy triphenyl, and simultaneously coupling the copper chloride with aromatic phenyl rings on the modified monomer to form a copper organic framework, roasting and carbonizing the copper organic framework, oxidizing to prepare the modified lubricating filler, nitrofying the modified monomer by using p-bromotoluene as a raw material by using mixed acid to prepare an intermediate 1, further processing the intermediate 1 to prepare an intermediate 2, reacting the intermediate 2 with pyrrole to prepare an intermediate 3, reducing the intermediate 3 by using iron powder to ensure that nitro groups are converted into amino groups, preparing an intermediate 4, dehydrating and condensing the intermediate 4 and octadecanoic acid to prepare an intermediate 5, reacting the intermediate 5 with trimethyl borate to prepare a modified monomer, wherein the modified lubricating filler is in a multilayer honeycomb pore shape, the friction force can be reduced by compressing gaps during stretching, meanwhile, long-chain alkyl of a side chain of the modified monomer can increase gaps among molecules of the modified monomer, further, after carbonization treatment, the interlayer spacing of the modified lubricating filler is increased, metal copper with a supporting function is contained inside, the metal copper belongs to soft metal and can further improve the lubricity by matching with the self structure, and the modified lubricating filler is oxidized by nitric acid after carbonization, so that the surface of the modified lubricating filler contains a large number of hydroxyl groups which are polar groups, and a large amount of heat can be generated in the stretching process to cause the temperature rise of stretching oil, the kinetic energy of the modified lubricating filler is continuously increased, the non-directional migration speed of the modified lubricating filler in the stretching oil is accelerated, so that more modified lubricating fillers migrate to the surface of the friction pair, the transfer of electrons is caused to form an electric field, the electric field can generate a magnetic field, the magnetic field can adsorb the polar modified lubricating filler to form a lubricating film, and the stretching material is protected from being pulled.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The new energy battery shell drawing oil comprises the following raw materials in parts by weight: 40 parts of spindle oil, 40 parts of butter, 10 parts of modified lubricating filler, 3 parts of tin disulfide and 1 part of ethanol;
the new energy battery shell drawing oil is prepared by uniformly blending the raw materials.
The modified lubricating filler is prepared by the following steps:
step A1: uniformly mixing a modified monomer, 2,3,6,7,10, 11-hexahydroxy triphenyl, copper chloride and N, N-dimethylformamide, introducing nitrogen for protection, reacting for 30 hours at the rotation speed of 200r/min and the temperature of 60 ℃, filtering to remove filtrate, and drying a substrate to obtain a copper organic framework;
step A2: roasting a copper organic framework for 3 hours at the temperature of 800 ℃, adding the roasted copper organic framework into a nitric acid solution, stirring for 2 hours at the rotation speed of 600r/min and at the temperature of 70 ℃, filtering to remove filtrate, and drying a substrate to obtain the modified lubricating filler.
The use ratio of the modified monomer described in step A1, 2,3,6,7,10, 11-hexahydroxy triphenyl, copper chloride and N, N-dimethylformamide is 2mmol.
The mass fraction of the nitric acid solution in the step A2 is 60%.
The modified monomer is prepared by the following steps:
step B1: adding p-bromotoluene into a reaction kettle, stirring and adding mixed acid under the conditions that the rotating speed is 150r/min and the temperature is 40 ℃, heating to the temperature of 60 ℃ after the addition is finished, reacting for 1h to obtain an intermediate 1, mixing the intermediate 1, acetic anhydride and concentrated sulfuric acid, adding an acetic anhydride solution of chromic anhydride under the conditions that the rotating speed is 200r/min and the temperature is 5 ℃, reacting for 2h, adding ice water until no solid is separated out, filtering to remove filtrate, mixing a filter cake, deionized water, ethanol and concentrated sulfuric acid, and performing reflux reaction for 1h at the temperature of 80 ℃ to obtain an intermediate 2;
and step B2: uniformly mixing the intermediate 2, propionic acid and dimethylbenzene, stirring and dropwise adding an acetic anhydride solution of pyrrole under the conditions that the rotating speed is 150r/min and the temperature is 137 ℃, reacting for 10min, cooling to room temperature, standing for 10h to prepare an intermediate 3, uniformly mixing the intermediate 3, iron powder, deionized water and glacial acetic acid, and performing reflux reaction for 4h under the condition that the temperature is 80 ℃ to prepare an intermediate 4;
and step B3: uniformly mixing the intermediate 4, octadecanoic acid, 1-hydroxybenzotriazole and xylene, reacting for 6 hours at the rotation speed of 200r/min and the temperature of 120 ℃ to obtain an intermediate 5, dissolving the intermediate 5 in tetrahydrofuran, adding magnesium powder and iodine particles, reacting for 2 hours at the rotation speed of 150r/min and the temperature of 20 ℃, cooling to the temperature of minus 25 ℃, adding a tetrahydrofuran solution of trimethyl borate, heating to the room temperature after the addition is finished, reacting for 2 hours, adding a hydrochloric acid solution, and stirring for 30 minutes to obtain the modified monomer.
The volume ratio of the p-bromotoluene to the mixed acid in the step B1 is 8.9, the mixed acid is formed by mixing concentrated sulfuric acid with a mass fraction of 98% with concentrated nitric acid with a mass fraction of 68% in a volume ratio of 2.5, the volume ratio of the intermediate 1, acetic anhydride, concentrated sulfuric acid to chromic anhydride is 100ml.
The dosage ratio of the intermediate 2, the propionic acid, the xylene and the pyrrole in the step B2 is 0.01mol.
The molar ratio of the intermediate 4, the octadecanoic acid and the 1-hydroxybenzotriazole in the step B3 is 1.
Example 2
The new energy battery shell drawing oil comprises the following raw materials in parts by weight: 45 parts of spindle oil, 45 parts of butter, 13 parts of modified lubricating filler, 4 parts of tin disulfide and 2 parts of ethanol;
the new energy battery shell drawing oil is prepared by uniformly blending the raw materials.
The modified lubricating filler is prepared by the following steps:
step A1: uniformly mixing a modified monomer, 2,3,6,7,10, 11-hexahydroxy triphenyl, copper chloride and N, N-dimethylformamide, introducing nitrogen for protection, reacting for 35 hours at the rotation speed of 200r/min and the temperature of 70 ℃, filtering to remove filtrate, and drying a substrate to obtain a copper organic framework;
step A2: roasting the copper organic framework for 4 hours at the temperature of 850 ℃, adding the roasted copper organic framework into a nitric acid solution, stirring for 3 hours at the rotation speed of 800r/min and the temperature of 75 ℃, filtering to remove filtrate, and drying a substrate to obtain the modified lubricating filler.
The dosage ratio of the modified monomer in the step A1, 2,3,6,7,10, 11-hexahydroxy triphenyl, copper chloride and N, N-dimethylformamide is 2mmol.
The mass fraction of the nitric acid solution in the step A2 is 63%.
The modified monomer is prepared by the following steps:
step B1: adding p-bromotoluene into a reaction kettle, stirring and adding mixed acid under the conditions of the rotating speed of 180r/min and the temperature of 45 ℃, heating to 63 ℃ after adding, reacting for 1.3h to obtain an intermediate 1, mixing the intermediate 1, acetic anhydride and concentrated sulfuric acid, adding an acetic anhydride solution of chromic anhydride under the conditions of the rotating speed of 200r/min and the temperature of 8 ℃, reacting for 3h, adding ice water until no solid is separated out, filtering to remove filtrate, mixing a filter cake, deionized water, ethanol and concentrated sulfuric acid, and performing reflux reaction for 1.3h at the temperature of 83 ℃ to obtain an intermediate 2;
and step B2: uniformly mixing the intermediate 2, propionic acid and dimethylbenzene, stirring and dropwise adding an acetic anhydride solution of pyrrole under the conditions that the rotating speed is 180r/min and the temperature is 137 ℃, reacting for 13min, cooling to room temperature, standing for 13h to prepare an intermediate 3, uniformly mixing the intermediate 3, iron powder, deionized water and glacial acetic acid, and carrying out reflux reaction for 5h under the condition that the temperature is 83 ℃ to prepare an intermediate 4;
and step B3: uniformly mixing the intermediate 4, octadecanoic acid, 1-hydroxybenzotriazole and xylene, reacting for 7 hours at the rotation speed of 200r/min and the temperature of 125 ℃ to obtain an intermediate 5, dissolving the intermediate 5 in tetrahydrofuran, adding magnesium powder and iodine particles, reacting for 2 hours at the rotation speed of 150r/min and the temperature of 23 ℃, cooling to the temperature of minus 30 ℃, adding a tetrahydrofuran solution of trimethyl borate, raising the temperature to room temperature after the addition is finished, reacting for 2 hours, adding a hydrochloric acid solution, and stirring for 35 minutes to obtain the modified monomer.
The volume ratio of the p-bromotoluene to the mixed acid in the step B1 is 8.9, the mixed acid is formed by mixing concentrated sulfuric acid with a mass fraction of 98% with concentrated nitric acid with a mass fraction of 68% in a volume ratio of 2.5, the volume ratio of the intermediate 1, acetic anhydride, concentrated sulfuric acid to chromic anhydride is 100ml.
The use ratio of the intermediate 2, the propionic acid, the xylene and the pyrrole in the step B2 is 0.01mol.
The molar ratio of the intermediate 4, the octadecanoic acid and the 1-hydroxybenzotriazole in the step B3 is 1.
Example 3
The new energy battery shell drawing oil comprises the following raw materials in parts by weight: 50 parts of spindle oil, 50 parts of butter, 15 parts of modified lubricating filler, 5 parts of tin disulfide and 3 parts of ethanol;
the new energy battery shell drawing oil is prepared by uniformly blending the raw materials.
The modified lubricating filler is prepared by the following steps:
step A1: uniformly mixing a modified monomer, 2,3,6,7,10, 11-hexahydroxy triphenyl, copper chloride and N, N-dimethylformamide, introducing nitrogen for protection, reacting for 40 hours at the rotation speed of 300r/min and the temperature of 80 ℃, filtering to remove filtrate, and drying a substrate to obtain a copper organic framework;
step A2: roasting the copper organic framework for 5 hours at the temperature of 900 ℃, adding the roasted copper organic framework into a nitric acid solution, stirring for 3 hours at the rotation speed of 800r/min and the temperature of 80 ℃, filtering to remove filtrate, and drying a substrate to obtain the modified lubricating filler.
The dosage ratio of the modified monomer in the step A1, 2,3,6,7,10, 11-hexahydroxy triphenyl, copper chloride and N, N-dimethylformamide is 2mmol.
The mass fraction of the nitric acid solution in the step A2 is 65%.
The modified monomer is prepared by the following steps:
step B1: adding p-bromotoluene into a reaction kettle, stirring and adding mixed acid under the conditions that the rotating speed is 200r/min and the temperature is 50 ℃, heating to 65 ℃ after the addition is finished, reacting for 1.5h to obtain an intermediate 1, mixing the intermediate 1, acetic anhydride and concentrated sulfuric acid, adding an acetic anhydride solution of chromic anhydride under the conditions that the rotating speed is 300r/min and the temperature is 10 ℃, reacting for 4h, adding ice water until no solid is separated out, filtering to remove filtrate, mixing a filter cake, deionized water, ethanol and concentrated sulfuric acid, and performing reflux reaction for 1.5h at the temperature of 85 ℃ to obtain an intermediate 2;
and step B2: uniformly mixing the intermediate 2, propionic acid and dimethylbenzene, stirring and dropwise adding an acetic anhydride solution of pyrrole under the conditions of a rotation speed of 200r/min and a temperature of 140 ℃, reacting for 15min, cooling to room temperature, standing for 15h to prepare an intermediate 3, uniformly mixing the intermediate 3, iron powder, deionized water and glacial acetic acid, and carrying out reflux reaction for 6h under the condition of a temperature of 85 ℃ to prepare an intermediate 4;
and step B3: uniformly mixing the intermediate 4, octadecanoic acid, 1-hydroxybenzotriazole and xylene, reacting for 8 hours at the rotation speed of 300r/min and the temperature of 130 ℃ to obtain an intermediate 5, dissolving the intermediate 5 in tetrahydrofuran, adding magnesium powder and iodine particles, reacting for 3 hours at the rotation speed of 200r/min and the temperature of 25 ℃, cooling to the temperature of minus 30 ℃, adding a tetrahydrofuran solution of trimethyl borate, heating to the room temperature after the addition is finished, reacting for 3 hours, adding a hydrochloric acid solution, and stirring for 40 minutes to obtain the modified monomer.
The volume ratio of the p-bromotoluene to the mixed acid in the step B1 is 8.9, the mixed acid is formed by mixing concentrated sulfuric acid with a mass fraction of 98% with concentrated nitric acid with a mass fraction of 68% in a volume ratio of 2.5, the volume ratio of the intermediate 1, acetic anhydride, concentrated sulfuric acid to chromic anhydride is 100ml.
The use ratio of the intermediate 2, the propionic acid, the xylene and the pyrrole in the step B2 is 0.01mol.
The molar ratio of the intermediate 4, the octadecanoic acid and the 1-hydroxybenzotriazole in the step B3 is 1.
Comparative example 1
The comparative example uses graphene instead of the modified lubricating filler with the same remaining steps.
Comparative example 2
The comparative example uses molybdenum disulfide in place of the modified lubricating filler and the remaining steps are the same.
Comparative example 3
The comparative example uses montmorillonite to replace the modified lubricating filler and the other steps are the same.
The tensile oils prepared in examples 1 to 3 and comparative examples 1 to 3 were measured for friction coefficient according to the standard of NB/SH/T0189-2017, and the results are shown in the following table;
| example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Coefficient of friction | 0.019 | 0.021 | 0.023 | 0.058 | 0.062 | 0.105 |
As is apparent from the above table, the tensile oils obtained in examples 1 to 3 had a coefficient of friction of 0.019 to 0.023, and it was revealed that the present invention had a good anti-pulling effect.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (8)
1. The utility model provides a new forms of energy battery shell drawing oil which characterized in that: the feed comprises the following raw materials in parts by weight: 40-50 parts of spindle oil, 40-50 parts of butter, 10-15 parts of modified lubricating filler, 3-5 parts of tin disulfide and 1-3 parts of ethanol;
the modified lubricating filler is prepared by the following steps:
step A1: mixing and reacting modified monomers, 2,3,6,7,10, 11-hexahydroxy triphenyl, copper chloride and N, N-dimethylformamide, filtering to remove filtrate, and drying a substrate to obtain a copper organic framework;
step A2: and (3) roasting the copper organic framework, adding the roasted copper organic framework into a nitric acid solution, stirring, filtering to remove filtrate, and drying a substrate to obtain the modified lubricating filler.
2. The new energy battery shell drawing oil as claimed in claim 1, characterized in that: the use ratio of the modified monomer described in step A1, 2,3,6,7,10, 11-hexahydroxy triphenyl, copper chloride and N, N-dimethylformamide is 2mmol.
3. The new energy battery shell drawing oil as claimed in claim 1, wherein: the mass fraction of the nitric acid solution in the step A2 is 60-65%.
4. The new energy battery shell drawing oil as claimed in claim 1, wherein: the modified monomer is prepared by the following steps:
step B1: adding p-bromotoluene into a reaction kettle, stirring, adding mixed acid, heating for reaction after the addition is finished to obtain an intermediate 1, mixing the intermediate 1, acetic anhydride and concentrated sulfuric acid, adding an acetic anhydride solution of chromic anhydride, adding ice water after the reaction is carried out, filtering to remove filtrate until no solid is separated out, mixing a filter cake, deionized water, ethanol and concentrated sulfuric acid, and carrying out reflux reaction to obtain an intermediate 2;
and step B2: mixing and stirring the intermediate 2, propionic acid and dimethylbenzene, dropwise adding an acetic anhydride solution of pyrrole, reacting, cooling to room temperature, standing to obtain an intermediate 3, mixing and refluxing the intermediate 3, iron powder, deionized water and glacial acetic acid to react, and obtaining an intermediate 4;
and step B3: mixing and reacting the intermediate 4, octadecanoic acid, 1-hydroxybenzotriazole and xylene to obtain an intermediate 5, dissolving the intermediate 5 in tetrahydrofuran, adding magnesium powder and iodine particles, reacting, cooling, adding a tetrahydrofuran solution of trimethyl borate, heating to room temperature after the addition is finished, reacting, adding a hydrochloric acid solution, and stirring to obtain the modified monomer.
5. The new energy battery shell drawing oil as claimed in claim 4, characterized in that: the volume ratio of the p-bromotoluene to the mixed acid in the step B1 is 8.9, the mixed acid is formed by mixing 98% by mass of concentrated sulfuric acid with 68% by mass of concentrated nitric acid in a volume ratio of 2.5, the volume ratio of the intermediate 1, acetic anhydride, concentrated sulfuric acid, and chromic anhydride is 100 ml.
6. The new energy battery shell drawing oil as claimed in claim 4, characterized in that: the use ratio of the intermediate 2, the propionic acid, the xylene and the pyrrole in the step B2 is 0.01mol.
7. The new energy battery shell drawing oil as claimed in claim 4, characterized in that: the molar ratio of the intermediate 4, the octadecanoic acid and the 1-hydroxybenzotriazole in the step B3 is 1.
8. The preparation method of the new energy battery shell drawing oil according to claim 1, characterized by comprising the following steps: the method specifically comprises the following steps:
after spindle oil, butter, modified lubricating filler, tin disulfide and ethanol are weighed and uniformly mixed, the drawing oil is prepared.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106753695A (en) * | 2016-12-14 | 2017-05-31 | 刘兴旺 | A kind of lube oil additive |
| CN110117049A (en) * | 2019-05-07 | 2019-08-13 | 河海大学 | A kind of preparation method of metal-organic framework/polypyrrole hydridization conductive electrode |
| US20210054254A1 (en) * | 2018-04-27 | 2021-02-25 | China University Of Petroleum-Beijing | Drilling fluid lubricant and preparation method and use thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106753695A (en) * | 2016-12-14 | 2017-05-31 | 刘兴旺 | A kind of lube oil additive |
| US20210054254A1 (en) * | 2018-04-27 | 2021-02-25 | China University Of Petroleum-Beijing | Drilling fluid lubricant and preparation method and use thereof |
| CN110117049A (en) * | 2019-05-07 | 2019-08-13 | 河海大学 | A kind of preparation method of metal-organic framework/polypyrrole hydridization conductive electrode |
Non-Patent Citations (2)
| Title |
|---|
| 孙少光,蒋佳,李志强: "拉伸润滑剂助剂机理分析及应用" * |
| 张正修,马新梅,李欠娃: "冲压过程中的摩擦及润滑" * |
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