CN113444527A - Preparation method of antioxidant stabilizer for lithium ion diaphragm pore-forming oil - Google Patents
Preparation method of antioxidant stabilizer for lithium ion diaphragm pore-forming oil Download PDFInfo
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- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 125
- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 124
- 239000003381 stabilizer Substances 0.000 title claims abstract description 123
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims description 90
- 239000003921 oil Substances 0.000 claims description 57
- 238000003756 stirring Methods 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 45
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 42
- 238000010438 heat treatment Methods 0.000 claims description 35
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 29
- 238000004519 manufacturing process Methods 0.000 claims description 29
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 28
- 238000010992 reflux Methods 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 21
- 239000007822 coupling agent Substances 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- -1 acyloxy titanate Chemical compound 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 14
- 239000002270 dispersing agent Substances 0.000 claims description 13
- 239000003995 emulsifying agent Substances 0.000 claims description 13
- 229920000768 polyamine Polymers 0.000 claims description 13
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 8
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 7
- 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 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 7
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 7
- QAPVYZRWKDXNDK-UHFFFAOYSA-N P,P-Dioctyldiphenylamine Chemical compound C1=CC(CCCCCCCC)=CC=C1NC1=CC=C(CCCCCCCC)C=C1 QAPVYZRWKDXNDK-UHFFFAOYSA-N 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 239000007983 Tris buffer Substances 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 7
- 230000003064 anti-oxidating effect Effects 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 7
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 7
- 230000001276 controlling effect Effects 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- ONIHPYYWNBVMID-UHFFFAOYSA-N diethyl benzene-1,4-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(C(=O)OCC)C=C1 ONIHPYYWNBVMID-UHFFFAOYSA-N 0.000 claims description 7
- WUUBVRZLVWWXDM-UHFFFAOYSA-N dioctoxy phosphono phosphate Chemical compound C(CCCCCCC)OOP(=O)(OOCCCCCCCC)OP(=O)(O)O WUUBVRZLVWWXDM-UHFFFAOYSA-N 0.000 claims description 7
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 7
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 7
- 239000003822 epoxy resin Substances 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 7
- 230000008020 evaporation Effects 0.000 claims description 7
- 239000012065 filter cake Substances 0.000 claims description 7
- 229910021389 graphene Inorganic materials 0.000 claims description 7
- 238000004811 liquid chromatography Methods 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- 229920000647 polyepoxide Polymers 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 7
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 7
- 238000010898 silica gel chromatography Methods 0.000 claims description 7
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 230000002194 synthesizing effect Effects 0.000 claims description 7
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 7
- 229960001124 trientine Drugs 0.000 claims description 7
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 7
- 235000005074 zinc chloride Nutrition 0.000 claims description 7
- 239000011592 zinc chloride Substances 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 abstract description 14
- 238000007254 oxidation reaction Methods 0.000 abstract description 14
- 239000000126 substance Substances 0.000 abstract description 7
- 238000000034 method Methods 0.000 description 14
- 239000013522 chelant Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000007707 calorimetry Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000010325 electrochemical charging Methods 0.000 description 1
- 238000010326 electrochemical discharging Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
- C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
- C09K15/32—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing two or more of boron, silicon, phosphorus, selenium, tellurium or a metal
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
-
- 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 an antioxidant stabilizer for lithium ion diaphragm pore-forming oil, which is used for preparing a main antioxidant stabilizer, an auxiliary antioxidant stabilizer and an intermediate, wherein the auxiliary antioxidant stabilizer is modified after the main antioxidant stabilizer is prepared, so that the dispersibility is improved, the intermediate is used for combining the main antioxidant stabilizer and the auxiliary antioxidant stabilizer, and finally the antioxidant stabilizer is synthesized, so that the problems that the conventional white oil for producing the lithium ion diaphragm pore-forming oil is insufficient in antioxidant stability, the chemical stability is to be improved, the oxidation stability is insufficient after the white oil is further produced, and the oil performance is changed after the white oil is placed for a long time are solved.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a production and preparation method of an antioxidant stabilizer for lithium ion diaphragm pore-forming oil.
Background
In recent years, lithium ion batteries have been rapidly developed for their excellent electrical properties such as high energy density, long cycle life, and high voltage. The lithium ion battery consists of a positive electrode, a negative electrode, an electrolyte and a diaphragm, wherein one important function of the diaphragm is to isolate the positive electrode from the negative electrode and prevent the positive electrode from penetrating through the battery, and simultaneously, ions can be allowed to pass through the diaphragm, so that the lithium ions are rapidly transmitted between the positive electrode and the negative electrode in the electrochemical charging and discharging process. The quality of the performance of the separator directly affects the discharge capacity and cycle life of the battery.
The diaphragm is used as a high molecular functional material with nano-scale micropores, and has two production methods, namely a wet method and a dry method. In the existing production process, besides general polyolefin materials, white oil, methylene chloride and the like are also included. Wherein, the white oil is also called liquid paraffin, is colorless transparent oily liquid, is tasteless, has a flash point of 164-223 ℃, is a mixture of liquid hydrocarbons, has a molecular weight of usually 250-450, has certain oxidation stability and chemical stability, and is one of essential raw materials for the prior process production of the diaphragm.
In the process of oil production, as the result of oil oxidation is deepening the color of the oil, increasing the viscosity and increasing the acid substances, the oxidation stability is the content of continuous research on oil production. The white oil for producing the existing lithium ion diaphragm pore-forming oil has insufficient oxidation stability, the chemical stability needs to be improved, the oxidation stability is insufficient after the white oil is further produced, and the condition of oil product performance change can occur after the white oil is placed for a long time.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The invention is provided in view of the problems of the antioxidant stabilizer for the conventional lithium ion diaphragm pore-forming oil.
Therefore, the technical problem solved by the invention is as follows: the problems that the white oil for producing the existing lithium ion diaphragm pore-forming oil is insufficient in oxidation stability, the chemical stability needs to be improved, the oxidation stability is insufficient after the white oil is further produced, and the performance of the oil product can be changed after the white oil is placed for a long time are solved.
In order to solve the technical problems, the invention provides the following technical scheme: a production and preparation method of an antioxidant stabilizer for lithium ion diaphragm pore-forming oil is characterized by comprising the following preparation steps:
preparing a main anti-oxidation stabilizing agent:
1-5 parts of diethyl terephthalate, 7-10 parts of ethylene glycol, 10-15 parts of polyethylene glycol and N are sequentially added into a reaction kettle2Heating to 60 ℃ at a speed of 5 ℃/min under protection, stirring for 30min at a speed of 200-300 r/min to form a homogeneous mixed solution, adding 30-45 parts of carbon-based-4, 4-diiso-methylene-fatty alcohol-phosphate chelate, stirring for 3h, adding 5-10 parts of polyamine compound and 70-90 parts of ethyl acetate, gradually heating to 100-120 ℃ at a speed of 5 ℃/min, when a reflux phenomenon occurs, keeping the temperature for reflux reaction for more than 3h to reach a set requirement, stopping stirring, gradually recovering to room temperature, and collecting a distillate for later use;
preparing an antioxidant stabilizer:
mixing 5-10 parts of graphene, 10-25 parts of 4,4' -dioctyl diphenylamine, 5-7 parts of hexadecyl trimethyl ammonium bromide and 10-12 parts of molybdenum dioxide, introducing into a ball mill, and mixing and ball-milling for more than 1.5 hours;
oscillating under ultrasonic to disperse, adding 3-5 parts of coupling agent and 1-2 parts of distillate, heating to 35 ℃, and slowly stirring at the speed of 1r/s for 30 min;
preparing an intermediate:
1-5 parts of dispersing agent, 40-45 parts of solvent, 3-7 parts of emulsifier, 20-30 parts of epoxy resin and N are sequentially added into a reaction kettle2Heating to 90 ℃ at the speed of 5 ℃/min under protection, and stirring to obtain a homogeneous mixed solution;
adding 1-3 parts of initiator and 1 part of Tris buffer solution, and stirring for 2-3 hours at the rotating speed of 200-300 r/min;
dropwise adding 3 parts of dodecylamine, controlling the dropwise adding speed to be 1 s/drop, heating to 120 ℃ after the dropwise adding is finished, carrying out reflux reaction for 72 hours, carrying out vacuum concentration on the reacted mixed solution at 120 ℃ to 1/5 of the original volume, carrying out silica gel column chromatography with the volume ratio of petroleum ether to ethyl acetate being 10:1, and carrying out evaporation and spin drying to obtain the intermediate;
fourth, synthesizing an antioxidant stabilizer:
adding 40-55 parts of the main antioxidant stabilizer, 15-20 parts of the auxiliary antioxidant stabilizer and 2-5 parts of the intermediate into a reaction kettle, and adding 70-90 parts of a solvent, N2Stirring for 2-3 h at constant temperature of 120 ℃ under protection at a speed of 100-200 r/min, cooling to 80-85 ℃ when a brownish red solid is separated out, adding 10-20 parts of deionized water, washing until the pH value is 6, then maintaining the temperature, aging for 1h, carrying out suction filtration while the solution is hot, washing a filter cake for 2 times by 5 parts of deionized water, and drying in an oven at 100 ℃ for more than 8h to obtain the antioxidant stabilizer.
As a preferred scheme of the production and preparation method of the antioxidant stabilizer for the lithium ion diaphragm pore-forming oil, the method comprises the following steps: in the preparation process of the main antioxidant stabilizer, the added polyamine compound is any one of N-aminoethyl piperazine, diethylenetriamine, triethylene tetramine and tetraethylenepentamine.
As a preferred scheme of the production and preparation method of the antioxidant stabilizer for the lithium ion diaphragm pore-forming oil, the method comprises the following steps: in the preparation process of the main antioxidant stabilizer, the content of the distillate is monitored by liquid chromatography in real time, and when the carbon element content of the distillate which is just distilled is increased to 15%, the heat-preservation reflux reaction is regulated to meet the set requirement.
As a preferred scheme of the production and preparation method of the antioxidant stabilizer for the lithium ion diaphragm pore-forming oil, the method comprises the following steps: in the preparation process of the antioxidant stabilizer, the ultrasonic power is 1000-1200W, the ultrasonic frequency is 10 MKz-20 MHz, and the ultrasonic time is 20 min.
As a preferred scheme of the production and preparation method of the antioxidant stabilizer for the lithium ion diaphragm pore-forming oil, the method comprises the following steps: in the preparation process of the antioxidant stabilizer, the coupling agent is a titanate coupling agent, and specifically is one or more of isopropyl trioleate acyloxy titanate, isopropyl triisostearate titanate, bis (dioctyloxy pyrophosphate) ethylene titanate, isopropyl trihydroxy acyl titanate and isopropyl tristearate titanate.
As a preferred scheme of the production and preparation method of the antioxidant stabilizer for the lithium ion diaphragm pore-forming oil, the method comprises the following steps: in the preparation process of the intermediate, the dispersing agent is one or a mixture of polyvinyl alcohol, polyoxyethylene ether and polyvinyl pyrrolidone.
As a preferred scheme of the production and preparation method of the antioxidant stabilizer for the lithium ion diaphragm pore-forming oil, the method comprises the following steps: in the preparation process of the intermediate, the solvent is one or a mixture of ethanol, methanol and acetone.
As a preferred scheme of the production and preparation method of the antioxidant stabilizer for the lithium ion diaphragm pore-forming oil, the method comprises the following steps: in the preparation process of the intermediate, the emulsifier is one or a mixture of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, and polycondensate of alkylphenol and ethylene oxide.
As a preferred scheme of the production and preparation method of the antioxidant stabilizer for the lithium ion diaphragm pore-forming oil, the method comprises the following steps: in the preparation process of the intermediate, the initiator is compounded by zinc chloride and dibenzoyl peroxide in a ratio of 2: 1.
The invention has the beneficial effects that: the invention provides an antioxidant stabilizer for lithium ion diaphragm pore-forming oil, which is used for preparing a main antioxidant stabilizer, an auxiliary antioxidant stabilizer and an intermediate, wherein the auxiliary antioxidant stabilizer is modified after the main antioxidant stabilizer is prepared, so that the dispersibility is improved, the intermediate is used for combining the main antioxidant stabilizer and the auxiliary antioxidant stabilizer, and finally the antioxidant stabilizer is synthesized, so that the problems that the conventional white oil for producing the lithium ion diaphragm pore-forming oil is insufficient in antioxidant stability, the chemical stability is to be improved, the oxidation stability is insufficient after the white oil is further produced, and the oil performance is changed after the white oil is placed for a long time are solved.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanying specific embodiments of the present invention are described in detail below, and it is apparent that the described embodiments are a part of the embodiments of the present invention, but not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making creative efforts based on the embodiments of the present invention, shall fall within the protection scope of the present invention.
It should be noted that oil oxidation proceeds via a radical chain reaction mechanism, usually through the processes of chain initiation, chain propagation and chain termination, and the reaction is expressed as:
chain initiation
R－H→R.+H.
R.+O2→.R－O－O.
R－O－O.+R－H→R－O－O－H+R.
R－O－O－H→R－O.－HO.
R－H－R－O.→R－O－H－R.
R－H－H－O.→R－O－H－R.
R－H－H－O.→H2O－R.
Chain termination
R. -r. → stable final product;
r. + R-O-o. → stable final product;
R-O. + R-O. → stable final product.
The antioxidant functions to interrupt the oxidation chain reaction.
Example (b):
example 1
A production and preparation method of an antioxidant stabilizer for lithium ion diaphragm pore-forming oil comprises the following preparation steps:
preparing a main anti-oxidation stabilizing agent:
adding 1 part of diethyl terephthalate, 7 parts of ethylene glycol, 10 parts of polyethylene glycol and N into a reaction kettle in sequence2Heating to 60 ℃ at a speed of 5 ℃/min under protection, stirring for 30min at a speed of 200r/min to form a homogeneous mixed solution, adding 30 parts of carbon-based-4, 4-dimethylidene-fatty alcohol-phosphate chelate, stirring for 3h, adding 5 parts of N-aminoethyl piperazine and 70 parts of ethyl acetate, gradually heating to 100 ℃ at a speed of 5 ℃/min, when a reflux phenomenon occurs, keeping the temperature for reflux reaction for more than 3h to meet a set requirement, stopping stirring, gradually recovering to room temperature, and collecting a distillate for later use;
preparing an antioxidant stabilizer:
mixing 5 parts of graphene, 10 parts of 4,4' -dioctyl diphenylamine, 5 parts of hexadecyl trimethyl ammonium bromide and 10 parts of molybdenum dioxide, introducing the mixture into a ball mill, and mixing and ball-milling for more than 1.5 hours;
oscillating under ultrasonic to disperse, adding 3 parts of isopropyl trioleate acyloxy titanate and 1 part of distillate, heating to 35 ℃, and slowly stirring at the speed of 1r/s for 30 min;
preparing an intermediate:
adding 1 part of polyvinyl alcohol, 40 parts of ethanol, 3 parts of sodium dodecyl sulfate, 20 parts of epoxy resin and N into a reaction kettle in sequence2Heating to 90 ℃ at the speed of 5 ℃/min under protection, and stirring to obtain a homogeneous mixed solution;
adding 1 part of initiator and 1 part of Tris buffer solution, and stirring for 2 hours at the rotating speed of 200 r/min;
dropwise adding 3 parts of dodecylamine, controlling the dropwise adding speed to be 1 s/drop, heating to 120 ℃ after the dropwise adding is finished, carrying out reflux reaction for 72 hours, carrying out vacuum concentration on the reacted mixed solution at 120 ℃ to 1/5 of the original volume, carrying out silica gel column chromatography with the volume ratio of petroleum ether to ethyl acetate being 10:1, and carrying out evaporation and spin drying to obtain the intermediate;
fourth, synthesizing an antioxidant stabilizer:
adding 40 parts of main antioxidant stabilizer, 15 parts of auxiliary antioxidant stabilizer and 2 parts of intermediate into a reaction kettle, and adding 70 parts of solvent, N2Stirring for 2h at constant temperature of 120 ℃ under protection at a speed of 100r/min, cooling to 80 ℃ when a brownish red solid is separated out, adding 10 parts of deionized water, washing until the pH value is 6, maintaining the temperature, aging for 1h, carrying out suction filtration while the solution is hot, washing a filter cake for 2 times by using 5 parts of deionized water, and drying in an oven at 100 ℃ for more than 8h to obtain the antioxidant stabilizer.
Furthermore, during the preparation process of the main antioxidant stabilizer, the content of distillate is monitored by liquid chromatography in real time, and when the carbon element content of the distillate which is just distilled is increased to 15%, the heat-preservation reflux reaction is regulated to meet the set requirement.
Furthermore, in the preparation process of the antioxidant stabilizer, the ultrasonic power is 1000-1200W, the ultrasonic frequency is 10 MKz-20 MHz, and the ultrasonic time is 20 min.
Wherein, in the preparation process of the main antioxidant stabilizer, the added polyamine compound is any one of N-aminoethyl piperazine, diethylenetriamine, triethylene tetramine and tetraethylenepentamine.
In the preparation process of the antioxidant stabilizer, the coupling agent is a titanate coupling agent, and specifically is one or more of isopropyl trioleate acyloxy titanate, isopropyl triisostearate titanate, bis (dioctyloxy pyrophosphate) ethylene titanate, isopropyl trihydroxy acyl titanate and isopropyl tristearate titanate.
Wherein, in the preparation process of the intermediate, the dispersant is one or a mixture of polyvinyl alcohol, polyoxyethylene ether and polyvinylpyrrolidone.
Wherein, in the preparation process of the intermediate, the solvent is one or a mixture of ethanol, methanol and acetone.
Wherein, in the preparation process of the intermediate, the emulsifier is one or a mixture of more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and polycondensate of alkylphenol and ethylene oxide.
Wherein, in the preparation process of the intermediate, the initiator is zinc chloride and dibenzoyl peroxide which are compounded in a ratio of 2: 1.
Example 2
A production and preparation method of an antioxidant stabilizer for lithium ion diaphragm pore-forming oil comprises the following preparation steps:
preparing a main anti-oxidation stabilizing agent:
adding 5 parts of diethyl terephthalate, 10 parts of ethylene glycol and 15 parts of polyethylene glycol into a reaction kettle in sequence, heating to 60 ℃ at a speed of 5 ℃/min under the protection of N2, stirring at 300r/min for 30min to obtain a homogeneous mixed solution, adding 45 parts of carbon-based-4, 4-diiso-methylene-fatty alcohol-phosphate chelate, stirring for 3h, adding 10 parts of polyamine compound and 90 parts of ethyl acetate, gradually heating to 120 ℃ at a speed of 5 ℃/min, when a reflux phenomenon occurs, keeping the temperature for reflux reaction for more than 3h, stopping stirring and gradually recovering to room temperature, and collecting a distillate for later use;
preparing an antioxidant stabilizer:
mixing 10 parts of graphene, 25 parts of 4,4' -dioctyl diphenylamine, 7 parts of hexadecyl trimethyl ammonium bromide and 12 parts of molybdenum dioxide, introducing into a ball mill, and mixing and ball-milling for more than 1.5 hours;
oscillating under ultrasonic to disperse, adding 5 parts of coupling agent and 2 parts of distillate, heating to 35 ℃, and slowly stirring at the speed of 1r/s for 30 min;
preparing an intermediate:
adding 5 parts of dispersant, 45 parts of solvent, 7 parts of emulsifier and 30 parts of epoxy resin into a reaction kettle in sequence, heating to 90 ℃ at a speed of 5 ℃/min under the protection of N2, and stirring to obtain homogeneous mixed solution;
adding 3 parts of initiator and 1 part of Tris buffer solution, and stirring for 3 hours at the rotating speed of 300 r/min;
dropwise adding 3 parts of dodecylamine, controlling the dropwise adding speed to be 1 s/drop, heating to 120 ℃ after the dropwise adding is finished, carrying out reflux reaction for 72 hours, carrying out vacuum concentration on the reacted mixed solution at 120 ℃ to 1/5 of the original volume, carrying out silica gel column chromatography with the volume ratio of petroleum ether to ethyl acetate being 10:1, and carrying out evaporation and spin drying to obtain the intermediate;
fourth, synthesizing an antioxidant stabilizer:
adding 55 parts of main antioxidant stabilizer, 20 parts of assistant antioxidant stabilizer and 5 parts of intermediate into a reaction kettle, adding 90 parts of solvent, stirring at constant temperature of 120 ℃ for 3 hours at 200r/min under the protection of N2, cooling to 85 ℃ when a brownish red solid is separated out, adding 20 parts of deionized water, washing until the pH value is 6, maintaining the temperature, aging for 1 hour, carrying out hot suction filtration, washing a filter cake for 2 times by using 5 parts of deionized water, and drying in an oven at 100 ℃ for more than 8 hours to obtain the antioxidant stabilizer.
Wherein, in the preparation process of the main antioxidant stabilizer, the added polyamine compound is any one of N-aminoethyl piperazine, diethylenetriamine, triethylene tetramine and tetraethylenepentamine.
During the preparation process of the main antioxidant stabilizer, the content of the distillate is monitored by liquid chromatography in real time, and when the carbon element content of the distillate which is just distilled is increased to 15%, the heat-preservation reflux reaction is regulated to meet the set requirement.
Wherein, in the preparation process of the antioxidant stabilizer, the ultrasonic power is 1000-1200W, the ultrasonic frequency is 10 MKz-20 MHz, and the ultrasonic time is 20 min.
In the preparation process of the antioxidant stabilizer, the coupling agent is a titanate coupling agent, and specifically is one or more of isopropyl trioleate acyloxy titanate, isopropyl triisostearate titanate, bis (dioctyloxy pyrophosphate) ethylene titanate, isopropyl trihydroxy acyl titanate and isopropyl tristearate titanate.
Wherein, in the preparation process of the intermediate, the dispersant is one or a mixture of polyvinyl alcohol, polyoxyethylene ether and polyvinylpyrrolidone.
Wherein, in the preparation process of the intermediate, the solvent is one or a mixture of ethanol, methanol and acetone.
Wherein, in the preparation process of the intermediate, the emulsifier is one or a mixture of more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and polycondensate of alkylphenol and ethylene oxide.
Wherein, in the preparation process of the intermediate, the initiator is zinc chloride and dibenzoyl peroxide which are compounded in a ratio of 2: 1.
Example 3
A production and preparation method of an antioxidant stabilizer for lithium ion diaphragm pore-forming oil comprises the following preparation steps:
preparing a main anti-oxidation stabilizing agent:
3 parts of diethyl terephthalate, 8 parts of ethylene glycol, 13 parts of polyethylene glycol and N are sequentially added into a reaction kettle2Heating to 60 ℃ at a speed of 5 ℃/min under protection, stirring for 30min at a speed of 250r/min to form a homogeneous mixed solution, adding 40 parts of carbon-based-4, 4-diiso-methylene-fatty alcohol-phosphate chelate, stirring for 3h, adding 5-10 parts of polyamine compound and 80 parts of ethyl acetate, gradually heating to 110 ℃ at a speed of 5 ℃/min, when a reflux phenomenon occurs, keeping the temperature for reflux reaction for more than 3h to meet a set requirement, stopping stirring, gradually recovering to room temperature, and collecting a distillate for later use;
preparing an antioxidant stabilizer:
mixing 8 parts of graphene, 20 parts of 4,4' -dioctyl diphenylamine, 6 parts of hexadecyl trimethyl ammonium bromide and 11 parts of molybdenum dioxide, introducing into a ball mill, and mixing and ball-milling for more than 1.5 hours;
oscillating under ultrasonic to disperse, adding 4 parts of coupling agent and 1.5 parts of distillate, heating to 35 ℃, and slowly stirring at the speed of 1r/s for 30 min;
preparing an intermediate:
3 parts of dispersant, 43 parts of solvent, 5 parts of emulsifier, 25 parts of epoxy resin and N are sequentially added into a reaction kettle2Heating to 90 ℃ at the speed of 5 ℃/min under protection, and stirring to obtain a homogeneous mixed solution;
adding 2 parts of initiator and 1 part of Tris buffer solution, and stirring for 2-3 h at the rotating speed of 250 r/min;
dropwise adding 3 parts of dodecylamine, controlling the dropwise adding speed to be 1 s/drop, heating to 120 ℃ after the dropwise adding is finished, carrying out reflux reaction for 72 hours, carrying out vacuum concentration on the reacted mixed solution at 120 ℃ to 1/5 of the original volume, carrying out silica gel column chromatography with the volume ratio of petroleum ether to ethyl acetate being 10:1, and carrying out evaporation and spin drying to obtain an intermediate;
fourth, synthesizing an antioxidant stabilizer:
adding 50 parts of main antioxidant stabilizer, 18 parts of auxiliary antioxidant stabilizer and 3 parts of intermediate into a reaction kettle, and adding 80 parts of solvent, N2Stirring for 2.5h at the constant temperature of 120 ℃ under protection at the speed of 150r/min, cooling to 83 ℃ when a brownish red solid is separated out, adding 15 parts of deionized water, washing until the pH value is 6, maintaining the temperature, aging for 1h, carrying out hot suction filtration, washing a filter cake for 2 times by using 5 parts of deionized water, and drying in an oven at the temperature of 100 ℃ for more than 8h to obtain the antioxidant stabilizer.
Wherein, in the preparation process of the main antioxidant stabilizer, the added polyamine compound is any one of N-aminoethyl piperazine, diethylenetriamine, triethylene tetramine and tetraethylenepentamine.
During the preparation process of the main antioxidant stabilizer, the content of distillate is monitored by liquid chromatography in real time, and when the carbon element content of the distillate which is just distilled is increased to 15%, the heat-preservation reflux reaction is regulated to meet the set requirement.
Wherein, in the preparation process of the antioxidant stabilizer, the ultrasonic power is 1000-1200W, the ultrasonic frequency is 10 MKz-20 MHz, and the ultrasonic time is 20 min.
In the preparation process of the antioxidant stabilizer, the coupling agent is a titanate coupling agent, and specifically is one or more of isopropyl trioleate acyloxy titanate, isopropyl triisostearate titanate, bis (dioctyloxy pyrophosphate) ethylene titanate, isopropyl trihydroxy acyl titanate and isopropyl tristearate titanate.
Wherein, in the preparation process of the intermediate, the dispersant is one or a mixture of polyvinyl alcohol, polyoxyethylene ether and polyvinylpyrrolidone.
Wherein, in the preparation process of the intermediate, the solvent is one or a mixture of ethanol, methanol and acetone.
Wherein, in the preparation process of the intermediate, the emulsifier is one or a mixture of more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and polycondensate of alkylphenol and ethylene oxide.
Wherein, in the preparation process of the intermediate, the initiator is zinc chloride and dibenzoyl peroxide which are compounded in a ratio of 2: 1.
Example 4
A production and preparation method of an antioxidant stabilizer for lithium ion diaphragm pore-forming oil comprises the following preparation steps:
preparing a main anti-oxidation stabilizing agent:
4 parts of diethyl terephthalate, 8 parts of ethylene glycol, 14 parts of polyethylene glycol and N are sequentially added into a reaction kettle2Heating to 60 ℃ at a speed of 5 ℃/min under protection, stirring for 30min at a speed of 300r/min to form a homogeneous mixed solution, adding 38 parts of carbon-based-4, 4-diiso-methylene-fatty alcohol-phosphate chelate, stirring for 3h, adding 9 parts of polyamine compound and 88 parts of ethyl acetate, gradually heating to 120 ℃ at a speed of 5 ℃/min, when a reflux phenomenon occurs, keeping the temperature for reflux reaction for more than 3h to meet a set requirement, stopping stirring, gradually recovering to room temperature, and collecting a distillate for later use;
preparing an antioxidant stabilizer:
mixing 9 parts of graphene, 22 parts of 4,4' -dioctyl diphenylamine, 5.5 parts of hexadecyl trimethyl ammonium bromide and 10.5 parts of molybdenum dioxide, introducing into a ball mill, and mixing and ball-milling for more than 1.5 hours;
oscillating under ultrasonic to disperse, adding 3.5 parts of coupling agent and 1.5 parts of distillate, heating to 35 ℃, and slowly stirring at the speed of 1r/s for 30 min;
preparing an intermediate:
2 parts of dispersant, 41 parts of solvent, 4 parts of emulsifier, 24 parts of epoxy resin and N are sequentially added into a reaction kettle2Heating to 90 ℃ at the speed of 5 ℃/min under protection, and stirring to obtain a homogeneous mixed solution;
adding 3 parts of initiator and 1 part of Tris buffer solution, and stirring for 3 hours at the rotating speed of 300 r/min;
dropwise adding 3 parts of dodecylamine, controlling the dropwise adding speed to be 1 s/drop, heating to 120 ℃ after the dropwise adding is finished, carrying out reflux reaction for 72 hours, carrying out vacuum concentration on the reacted mixed solution at 120 ℃ to 1/5 of the original volume, carrying out silica gel column chromatography with the volume ratio of petroleum ether to ethyl acetate being 10:1, and carrying out evaporation and spin drying to obtain an intermediate;
fourth, synthesizing an antioxidant stabilizer:
adding 45 parts of main antioxidant stabilizer, 19 parts of auxiliary antioxidant stabilizer and 4 parts of intermediate into a reaction kettle, and adding 80 parts of solvent, N2Stirring for 3h at constant temperature of 120 ℃ under protection at 200r/min, cooling to 84 ℃ when a brownish red solid is separated out, adding 16 parts of deionized water, washing until the pH value is 6, maintaining the temperature, aging for 1h, carrying out suction filtration while the solution is hot, washing a filter cake for 2 times by 5 parts of deionized water, and drying in an oven at 100 ℃ for more than 8h to obtain the antioxidant stabilizer.
Wherein, in the preparation process of the main antioxidant stabilizer, the added polyamine compound is any one of N-aminoethyl piperazine, diethylenetriamine, triethylene tetramine and tetraethylenepentamine.
During the preparation process of the main antioxidant stabilizer, the content of distillate is monitored by liquid chromatography in real time, and when the carbon element content of the distillate which is just distilled is increased to 15%, the heat-preservation reflux reaction is regulated to meet the set requirement.
Wherein, in the preparation process of the antioxidant stabilizer, the ultrasonic power is 1000-1200W, the ultrasonic frequency is 10 MKz-20 MHz, and the ultrasonic time is 20 min.
In the preparation process of the antioxidant stabilizer, the coupling agent is a titanate coupling agent, and specifically is one or more of isopropyl trioleate acyloxy titanate, isopropyl triisostearate titanate, bis (dioctyloxy pyrophosphate) ethylene titanate, isopropyl trihydroxy acyl titanate and isopropyl tristearate titanate.
Wherein, in the preparation process of the intermediate, the dispersant is one or a mixture of polyvinyl alcohol, polyoxyethylene ether and polyvinylpyrrolidone.
Wherein, in the preparation process of the intermediate, the solvent is one or a mixture of ethanol, methanol and acetone.
Wherein, in the preparation process of the intermediate, the emulsifier is one or a mixture of more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and polycondensate of alkylphenol and ethylene oxide.
Wherein, in the preparation process of the intermediate, the initiator is zinc chloride and dibenzoyl peroxide which are compounded in a ratio of 2: 1.
Example 5
A production and preparation method of an antioxidant stabilizer for lithium ion diaphragm pore-forming oil comprises the following preparation steps:
preparing a main anti-oxidation stabilizing agent:
2 parts of diethyl terephthalate, 8 parts of ethylene glycol, 15 parts of polyethylene glycol and N are sequentially added into a reaction kettle2Heating to 60 ℃ at a speed of 5 ℃/min under protection, stirring for 30min at a speed of 200r/min to form a homogeneous mixed solution, adding 43 parts of carbon-based-4, 4-diiso-methylene-fatty alcohol-phosphate chelate, stirring for 3h, adding 6 parts of polyamine compound and 88 parts of ethyl acetate, gradually heating to 100 ℃ at a speed of 5 ℃/min, when a reflux phenomenon occurs, keeping the temperature for reflux reaction for more than 3h, stopping stirring and gradually recovering to room temperature, and collecting a distillate for later use;
preparing an antioxidant stabilizer:
mixing 8 parts of graphene, 23 parts of 4,4' -dioctyl diphenylamine, 7 parts of hexadecyl trimethyl ammonium bromide and 10 parts of molybdenum dioxide, introducing into a ball mill, and mixing and ball-milling for more than 1.5 hours;
oscillating under ultrasonic to disperse, adding 5 parts of coupling agent and 2 parts of distillate, heating to 35 ℃, and slowly stirring at the speed of 1r/s for 30 min;
preparing an intermediate:
2 parts of dispersant, 41 parts of solvent, 5 parts of emulsifier, 29 parts of epoxy resin and N are sequentially added into a reaction kettle2Heating to 90 ℃ at the speed of 5 ℃/min under protection, and stirring to obtain a homogeneous mixed solution;
adding 3 parts of initiator and 1 part of Tris buffer solution, and stirring for 2 hours at the rotating speed of 200 r/min;
dropwise adding 3 parts of dodecylamine, controlling the dropwise adding speed to be 1 s/drop, heating to 120 ℃ after the dropwise adding is finished, carrying out reflux reaction for 72 hours, carrying out vacuum concentration on the reacted mixed solution at 120 ℃ to 1/5 of the original volume, carrying out silica gel column chromatography with the volume ratio of petroleum ether to ethyl acetate being 10:1, and carrying out evaporation and spin drying to obtain an intermediate;
fourth, synthesizing an antioxidant stabilizer:
adding 53 parts of main antioxidant stabilizer, 18 parts of auxiliary antioxidant stabilizer and 4 parts of intermediate into a reaction kettle, and adding 88 parts of solvent, N2Stirring for 2h at constant temperature of 120 ℃ under protection at a speed of 100r/min, cooling to 80 ℃ when a brownish red solid is separated out, adding 17 parts of deionized water, washing until the pH value is 6, maintaining the temperature, aging for 1h, carrying out suction filtration while the solution is hot, washing a filter cake for 2 times by using 5 parts of deionized water, and drying in an oven at 100 ℃ for more than 8h to obtain the antioxidant stabilizer.
Wherein, in the preparation process of the main antioxidant stabilizer, the added polyamine compound is any one of N-aminoethyl piperazine, diethylenetriamine, triethylene tetramine and tetraethylenepentamine.
During the preparation process of the main antioxidant stabilizer, the content of the distillate is monitored by liquid chromatography in real time, and when the carbon element content of the distillate which is just distilled is increased to 15%, the heat-preservation reflux reaction is regulated to meet the set requirement.
Wherein, in the preparation process of the antioxidant stabilizer, the ultrasonic power is 1000-1200W, the ultrasonic frequency is 10 MKz-20 MHz, and the ultrasonic time is 20 min.
In the preparation process of the antioxidant stabilizer, the coupling agent is a titanate coupling agent, and specifically is one or more of isopropyl trioleate acyloxy titanate, isopropyl triisostearate titanate, bis (dioctyloxy pyrophosphate) ethylene titanate, isopropyl trihydroxy acyl titanate and isopropyl tristearate titanate.
Wherein, in the preparation process of the intermediate, the dispersant is one or a mixture of polyvinyl alcohol, polyoxyethylene ether and polyvinylpyrrolidone.
Wherein, in the preparation process of the intermediate, the solvent is one or a mixture of ethanol, methanol and acetone.
Wherein, in the preparation process of the intermediate, the emulsifier is one or a mixture of more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and polycondensate of alkylphenol and ethylene oxide.
Wherein, in the preparation process of the intermediate, the initiator is zinc chloride and dibenzoyl peroxide which are compounded in a ratio of 2: 1.
The invention provides an antioxidant stabilizer for lithium ion diaphragm pore-forming oil and a preparation method thereof, and the quality and technical requirements of the antioxidant stabilizer are shown in Table 1.
Table 1: product quality technical requirement table
| Item | Quality index | Test method |
| Appearance of the product | Brownish red solid | Visual inspection of |
| Kinematic viscosity (40 ℃ C.) (mm)2) | 23～31 | According to GB/T265 |
| Flash point (opening), too | 134～156 | According to the GB/T267 regulation |
| Mechanical impurities,% m/m is less than or equal to | 0.413 | According to GB/T511 |
| Water content (m/m) is less than or equal to | 0.102 | According to GB/T260 |
Comparative example:
selecting the prior common antioxidant: zinc dialkyldithiophosphate (ZDDP), dialkyldithiocarbamate (ADTC), dialkyldithiophosphate (ADDP) were used as comparative antioxidants.
1. Pressurized differential calorimetry (PDSC) test; the determination was carried out according to ASTM D6186-1998 using a standard test method for testing the oxidation induction time of oils by pressure differential scanning calorimetry (PSDC).
2. Rotary pressurized vessel oxidation test: according to the determination of the national standard ASTM D2272-2009, the antioxidant property of the compound and the existing antioxidant is considered, and the longer the time is, the better the antioxidant effect is.
3. The detergency test: the results were classified into seven grades 0-6 according to SH/T0269-1992. No. 0 is cleanest, the color is lightest, No. 6 is dirtiest, and the smaller the number, the better the detergency.
The comparative results are shown in Table 2:
table 2: conventional performance comparison table
As can be seen from table 2 above, the antioxidant stability of the compound of the present invention is superior to that of the conventional oxidizing agent.
The invention provides an antioxidant stabilizer for lithium ion diaphragm pore-forming oil, which is used for preparing a main antioxidant stabilizer, an auxiliary antioxidant stabilizer and an intermediate, wherein the auxiliary antioxidant stabilizer is modified after the main antioxidant stabilizer is prepared, so that the dispersibility is improved, the intermediate is used for combining the main antioxidant stabilizer and the auxiliary antioxidant stabilizer, and finally the antioxidant stabilizer is synthesized, so that the problems that the conventional white oil for producing the lithium ion diaphragm pore-forming oil is insufficient in antioxidant stability, the chemical stability is to be improved, the oxidation stability is insufficient after the white oil is further produced, and the oil performance is changed after the white oil is placed for a long time are solved.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (9)
1. A production and preparation method of an antioxidant stabilizer for lithium ion diaphragm pore-forming oil is characterized by comprising the following preparation steps:
preparing a main anti-oxidation stabilizing agent:
1-5 parts of diethyl terephthalate, 7-10 parts of ethylene glycol, 10-15 parts of polyethylene glycol and N are sequentially added into a reaction kettle2Heating to 60 ℃ at a speed of 5 ℃/min under protection, stirring for 30min at a speed of 200-300 r/min to obtain a homogeneous mixed solution, and adding 30-45 parts of carbon-based-4, 4-diiso-methylene-fatty alcohol-phosphate chelateStirring for 3h, adding 5-10 parts of polyamine compound and 70-90 parts of ethyl acetate, gradually heating to 100-120 ℃ at a speed of 5 ℃/min, when a reflux phenomenon occurs, keeping the temperature for reflux reaction for more than 3h to reach a set requirement, stopping stirring, gradually recovering to room temperature, and collecting distillate for later use;
preparing an antioxidant stabilizer:
mixing 5-10 parts of graphene, 10-25 parts of 4,4' -dioctyl diphenylamine, 5-7 parts of hexadecyl trimethyl ammonium bromide and 10-12 parts of molybdenum dioxide, introducing into a ball mill, and mixing and ball-milling for more than 1.5 hours;
oscillating under ultrasonic to disperse, adding 3-5 parts of coupling agent and 1-2 parts of distillate, heating to 35 ℃, and slowly stirring at the speed of 1r/s for 30 min;
preparing an intermediate:
1-5 parts of dispersing agent, 40-45 parts of solvent, 3-7 parts of emulsifier, 20-30 parts of epoxy resin and N are sequentially added into a reaction kettle2Heating to 90 ℃ at the speed of 5 ℃/min under protection, and stirring to obtain a homogeneous mixed solution;
adding 1-3 parts of initiator and 1 part of Tris buffer solution, and stirring for 2-3 hours at the rotating speed of 200-300 r/min;
dropwise adding 3 parts of dodecylamine, controlling the dropwise adding speed to be 1 s/drop, heating to 120 ℃ after the dropwise adding is finished, carrying out reflux reaction for 72 hours, carrying out vacuum concentration on the reacted mixed solution at 120 ℃ to 1/5 of the original volume, carrying out silica gel column chromatography with the volume ratio of petroleum ether to ethyl acetate being 10:1, and carrying out evaporation and spin drying to obtain the intermediate;
fourth, synthesizing an antioxidant stabilizer:
adding 40-55 parts of the main antioxidant stabilizer, 15-20 parts of the auxiliary antioxidant stabilizer and 2-5 parts of the intermediate into a reaction kettle, and adding 70-90 parts of a solvent, N2Stirring for 2-3 h at constant temperature of 120 ℃ under protection at a speed of 100-200 r/min, cooling to 80-85 ℃ when a brownish red solid is separated out, adding 10-20 parts of deionized water, washing until the pH value is 6, then maintaining the temperature, aging for 1h, carrying out suction filtration while the solution is hot, washing a filter cake for 2 times by 5 parts of deionized water, and drying in an oven at 100 ℃ for more than 8h to obtain the antioxidant stabilizer.
2. The production and preparation method of the antioxidant stabilizer for the lithium ion diaphragm pore-forming oil according to claim 1 is characterized in that: in the preparation process of the main antioxidant stabilizer, the added polyamine compound is any one of N-aminoethyl piperazine, diethylenetriamine, triethylene tetramine and tetraethylenepentamine.
3. The production and preparation method of the antioxidant stabilizer for the lithium ion diaphragm pore-forming oil according to claim 1 or 2 is characterized in that: in the preparation process of the main antioxidant stabilizer, the content of the distillate is monitored by liquid chromatography in real time, and when the carbon element content of the distillate which is just distilled is increased to 15%, the heat-preservation reflux reaction is regulated to meet the set requirement.
4. The production and preparation method of the antioxidant stabilizer for the lithium ion diaphragm pore-forming oil according to claim 3 is characterized in that: in the preparation process of the antioxidant stabilizer, the ultrasonic power is 1000-1200W, the ultrasonic frequency is 10 MKz-20 MHz, and the ultrasonic time is 20 min.
5. The production and preparation method of the antioxidant stabilizer for the lithium ion diaphragm pore-forming oil according to claim 4 is characterized in that: in the preparation process of the antioxidant stabilizer, the coupling agent is a titanate coupling agent, and specifically is one or more of isopropyl trioleate acyloxy titanate, isopropyl triisostearate titanate, bis (dioctyloxy pyrophosphate) ethylene titanate, isopropyl trihydroxy acyl titanate and isopropyl tristearate titanate.
6. The production and preparation method of the antioxidant stabilizer for the lithium ion diaphragm pore-forming oil according to claim 5 is characterized in that: in the preparation process of the intermediate, the dispersing agent is one or a mixture of polyvinyl alcohol, polyoxyethylene ether and polyvinyl pyrrolidone.
7. The production and preparation method of the antioxidant stabilizer for the lithium ion diaphragm pore-forming oil according to claim 6 is characterized in that: in the preparation process of the intermediate, the solvent is one or a mixture of ethanol, methanol and acetone.
8. The production and preparation method of the antioxidant stabilizer for the lithium ion diaphragm pore-forming oil according to claim 7 is characterized in that: in the preparation process of the intermediate, the emulsifier is one or a mixture of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, and polycondensate of alkylphenol and ethylene oxide.
9. The production and preparation method of the antioxidant stabilizer for the lithium ion diaphragm pore-forming oil according to claim 8 is characterized in that: in the preparation process of the intermediate, the initiator is compounded by zinc chloride and dibenzoyl peroxide in a ratio of 2: 1.
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