CN116554942B - Composite antioxidant and preparation method thereof - Google Patents
Composite antioxidant and preparation method thereof Download PDFInfo
- Publication number
- CN116554942B CN116554942B CN202310442201.6A CN202310442201A CN116554942B CN 116554942 B CN116554942 B CN 116554942B CN 202310442201 A CN202310442201 A CN 202310442201A CN 116554942 B CN116554942 B CN 116554942B
- Authority
- CN
- China
- Prior art keywords
- zirconium dioxide
- ethanol solution
- parts
- modifier
- ferrous oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 106
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 101
- 239000002131 composite material Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 228
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 151
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 145
- ZTHYODDOHIVTJV-UHFFFAOYSA-N Propyl gallate Chemical compound CCCOC(=O)C1=CC(O)=C(O)C(O)=C1 ZTHYODDOHIVTJV-UHFFFAOYSA-N 0.000 claims abstract description 124
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 104
- 239000003607 modifier Substances 0.000 claims abstract description 81
- 239000000473 propyl gallate Substances 0.000 claims abstract description 62
- 229940075579 propyl gallate Drugs 0.000 claims abstract description 62
- 235000010388 propyl gallate Nutrition 0.000 claims abstract description 62
- 238000003756 stirring Methods 0.000 claims abstract description 55
- 239000002244 precipitate Substances 0.000 claims abstract description 49
- 239000000725 suspension Substances 0.000 claims abstract description 44
- 238000001035 drying Methods 0.000 claims abstract description 22
- 238000000227 grinding Methods 0.000 claims abstract description 22
- 230000032683 aging Effects 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims description 48
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 39
- 239000004327 boric acid Substances 0.000 claims description 39
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 22
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 20
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical group [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 19
- 238000005303 weighing Methods 0.000 claims description 18
- KPTRDYONBVUWPD-UHFFFAOYSA-N naphthalen-2-ylboronic acid Chemical compound C1=CC=CC2=CC(B(O)O)=CC=C21 KPTRDYONBVUWPD-UHFFFAOYSA-N 0.000 claims description 9
- 239000007822 coupling agent Substances 0.000 claims description 5
- DQVXWCCLFKMJTQ-UHFFFAOYSA-N (4-methylphenoxy)boronic acid Chemical compound CC1=CC=C(OB(O)O)C=C1 DQVXWCCLFKMJTQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- BIWQNIMLAISTBV-UHFFFAOYSA-N (4-methylphenyl)boronic acid Chemical compound CC1=CC=C(B(O)O)C=C1 BIWQNIMLAISTBV-UHFFFAOYSA-N 0.000 claims description 2
- 230000002431 foraging effect Effects 0.000 claims 1
- DCMWJXWYTURQIM-UHFFFAOYSA-N naphthalen-2-yloxyboronic acid Chemical compound C1=CC=CC2=CC(OB(O)O)=CC=C21 DCMWJXWYTURQIM-UHFFFAOYSA-N 0.000 claims 1
- 239000010687 lubricating oil Substances 0.000 abstract description 40
- 230000006866 deterioration Effects 0.000 abstract description 6
- 230000008021 deposition Effects 0.000 abstract description 5
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 16
- 238000001291 vacuum drying Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 238000007254 oxidation reaction Methods 0.000 description 15
- 238000004090 dissolution Methods 0.000 description 14
- 230000003647 oxidation Effects 0.000 description 13
- 150000003254 radicals Chemical class 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 230000003064 anti-oxidating effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 230000003993 interaction Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 230000007760 free radical scavenging Effects 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000006078 metal deactivator Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 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
- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/12—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic compound containing atoms of elements not provided for in groups C10M141/02 - C10M141/10
-
- 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
- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/10—Metal oxides, hydroxides, carbonates or bicarbonates
-
- 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
- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Lubricants (AREA)
- Anti-Oxidant Or Stabilizer Compositions (AREA)
Abstract
The application relates to the technical field of lubricating oil additives, and particularly discloses a composite antioxidant and a preparation method thereof, wherein the composite antioxidant comprises 30-50 parts of zirconium dioxide, 5-6 parts of ferrous oxide, 15-25 parts of propyl gallate, 4-8 parts of a modifier and 80-100 parts of an ethanol solution; the preparation method comprises the steps of equally dividing an ethanol solution into 5 equal parts; firstly, adding modifier into 4 equal parts of ethanol solution, stirring, sequentially adding zirconium dioxide and propyl gallate, and carrying out ultrasonic treatment to obtain modified zirconium dioxide suspension; pre-dispersing ferrous oxide and the rest 1 equal part of ethanol solution, adding modified zirconium dioxide suspension, stirring and mixing, standing and aging, centrifugally collecting precipitate, drying and grinding to obtain the composite material; the compound antioxidant is simple in formula, simple in preparation method, mild in preparation condition and suitable for industrial production, and the obtained compound antioxidant is used for protecting lubricating oil, has remarkable antioxidant effect, can effectively prevent the lubricating oil from oxidative deterioration and can improve the problem of lubricating oil deposition.
Description
Technical Field
The application relates to the technical field of lubricating oil additives, in particular to a composite antioxidant and a preparation method thereof.
Background
Lubricating oils are used in various types of automobiles and machinery to reduce friction, protect machinery and work pieces, and are liquid or semisolid lubricants that primarily serve as lubrication, auxiliary cooling, rust protection, cleaning, sealing, buffering, and the like. Lubricating oil is known as "mechanical operation blood", and directly affects the normal operation and service life of equipment. During the production and use of the lubricating oil, impurities or conditions such as heating, metal, oxygen and the like are encountered, so that the components of the lubricating oil are inevitably oxidized to generate oxidized monomers, and oil sludge, insoluble polar colloid, paint film, sediment and the like are generated through free radical reaction, thereby bringing a series of hazards to the performance of the lubricating oil and the use of machinery.
In the related art, in order to alleviate the conditions and effects of oxidation of lubricating oils, antioxidants are added to prevent and retard the oxidative deterioration of lubricating oils. Antioxidants for lubricating oils can be classified into the following three types according to their mechanism of action: radical terminators, peroxide decomposers and metal deactivators. In general, the antioxidants are used in combination, wherein the radical terminator is often used as a primary antioxidant, and the peroxide decomposer and the metal deactivator are used as secondary antioxidants. The addition of the compound antioxidant plays a positive role in improving the quality of lubricating oil, improving the oxidation resistance, prolonging the service life and the like.
Radical terminators are of the two general types, phenolic and amine. The phenolic antioxidant has low toxicity, excellent non-discoloration and non-pollution properties, but low use temperature and low antioxidation efficiency; while amine antioxidants are relatively high in service temperature, they are toxic, contaminating, susceptible to discoloration and themselves are susceptible to oxidation. With the continuous update and development of mechanical equipment, the standards for lubricating oil products for the mechanical equipment are also continuously improved. The existing commonly used phenol-type and amine-type free radical terminators are used as main antioxidants of lubricating oil, so that the problems of limited use environment, effective antioxidation effect, incapability of effectively improving oxidative deterioration, deposition and the like of the lubricating oil exist. Based on the above statement, the application provides a compound antioxidant and a preparation method thereof.
Disclosure of Invention
The application provides a compound antioxidant and a preparation method thereof, aiming at solving the problems that the prior antioxidant is limited in use environment, effective in antioxidation effect and incapable of effectively improving oxidative deterioration, deposition and the like of lubricating oil.
In a first aspect, the application provides a composite antioxidant, which adopts the following technical scheme:
A composite antioxidant comprises the following raw materials in parts by weight: 30-50 parts of zirconium dioxide, 5-6 parts of ferrous oxide, 15-25 parts of propyl gallate, 4-8 parts of modifier and 80-100 parts of ethanol solution.
Preferably, the composite antioxidant comprises the following raw materials in parts by weight: 38.5 parts of zirconium dioxide, 5.5 parts of ferrous oxide, 20 parts of propyl gallate, 6 parts of modifier and 90 parts of ethanol solution.
By adopting the technical scheme, the zirconium dioxide has outstanding high-temperature stability and corrosion resistance, and is commonly used for friction pair lubrication under severe working conditions such as high temperature, high pressure, high friction and the like; propyl gallate has remarkable free radical scavenging ability, and can inhibit oxidation reaction by capturing free radicals; the application adopts zirconium dioxide as a main material, and the composite antioxidant is prepared by interaction with ferrous oxide, propyl gallate, a modifier and an ethanol solution, and the obtained composite antioxidant is used for adding lubricating oil, can effectively adsorb and neutralize free radicals in the lubricating oil, prevent the lubricating oil from being oxidized and thermally decomposed under high temperature and high pressure, and remarkably improve the oxidation resistance of the lubricating oil. The application has scientific formula, strict proportion and addition of the modifier, can obviously improve the dispersibility and stability of zirconium dioxide, promote the interaction of zirconium dioxide and other raw materials and ensure the antioxidation effect of the prepared composite antioxidant.
Preferably, the mass ratio of the zirconium dioxide to the ferrous oxide is 6-8:1.
By adopting the technical scheme, the ferrous oxide has outstanding high temperature resistance, corrosion resistance, wear resistance and durability, the ferrous oxide and the zirconium dioxide are compounded for use, the mass ratio of the ferrous oxide to the zirconium dioxide is controlled to be 6-8:1, and the antioxidation effect of the composite antioxidant can be remarkably improved.
Preferably, the raw materials further comprise: 2-5 parts of organic boric acid.
Preferably, the organic boric acid is p-tolueneboric acid and/or 2-naphthalene boric acid.
Preferably, the mass ratio of the p-tolueneboronic acid to the 2-naphthalene boronic acid is 1:4-5.
By adopting the technical scheme, the organic boric acid is added into the formula, so that on one hand, a stable complex can be formed with iron ions in ferrous oxide, the generation of oxygen free radicals is reduced, and on the other hand, the organic boric acid can react with zirconium dioxide containing surface hydroxyl functional groups, the synergistic effect of the ferrous oxide and the zirconium dioxide is promoted, the free radical scavenging capability of the composite antioxidant is improved, and the occurrence of oxidation reaction is reduced. The organic boric acid is selected from a compound of the p-tolueneboric acid and the 2-naphthalene boric acid, and the mass ratio of the p-tolueneboric acid to the 2-naphthalene boric acid is controlled to be 1:4-5, so that the antioxidation capability of the compound antioxidant can be further improved.
Preferably, the modifier comprises a silane coupling agent and maleic anhydride in a mass ratio of 1:20-24.
Preferably, the silane coupling agent is an aminosilane coupling agent.
By adopting the technical scheme, the modifier is a compound of the aminosilane coupling agent and the maleic anhydride, the mass ratio of the aminosilane coupling agent to the maleic anhydride is controlled to be 1:20-24, molecules containing active functional groups are firstly introduced into the surface of the maleic anhydride, then zirconium dioxide is modified, the dispersibility and the stability of the zirconium dioxide are improved, the interaction of the zirconium dioxide and other raw materials is promoted, and the antioxidation effect of the prepared composite antioxidant is further ensured.
In a second aspect, the application provides a preparation method of a composite antioxidant, which adopts the following technical scheme:
The preparation method of the composite antioxidant comprises the following preparation steps:
s1, weighing raw materials of zirconium dioxide, ferrous oxide, propyl gallate, a modifier and an ethanol solution according to parts by weight, and equally dividing the ethanol solution into 5 equal parts for standby;
s2, firstly taking 4 equal parts of ethanol solution, adding a modifier, stirring and dissolving, then adding zirconium dioxide for ultrasonic pretreatment, and finally adding propyl gallate for continuous ultrasonic treatment to obtain modified zirconium dioxide suspension;
s3, pre-dispersing ferrous oxide and the rest 1 equal part of ethanol solution, adding the pre-dispersed ferrous oxide and the rest 1 equal part of ethanol solution into the modified zirconium dioxide suspension, stirring and uniformly mixing, standing for ageing, centrifugally collecting precipitate, drying and grinding to obtain the required composite antioxidant.
Preferably, the raw materials in the step S1 further include organic boric acid, and the step S3 specifically includes the following steps:
And (3) pre-dispersing ferrous oxide, organic boric acid and the rest 1 equal part of ethanol solution, adding the pre-dispersed solution into the modified zirconium dioxide suspension, stirring and uniformly mixing, standing for ageing, centrifugally collecting precipitate, drying and grinding to obtain the required composite antioxidant.
Preferably, the specific operation in step S2 is as follows:
Firstly, adding a modifier into 4 equal parts of ethanol solution, stirring at normal temperature for dissolution, then adding zirconium dioxide, controlling the ultrasonic frequency to be 40-60kHz, carrying out ultrasonic pretreatment for 20-30min, and finally adding propyl gallate, and continuing ultrasonic treatment for 1-2h to obtain modified zirconium dioxide suspension.
Preferably, the specific operation in the step S3 is as follows:
And (3) stirring and pre-dispersing ferrous oxide and the rest 1 equal part of ethanol solution for 10-20min at a rotating speed of 400-500r/min, adding the mixture into the modified zirconium dioxide suspension, continuously stirring and mixing for 10-20min, standing and ageing for 3-5h, centrifuging for 5-8min at a rotating speed of 1000-1200r/min, collecting a precipitate, placing the precipitate in a vacuum drying oven at 100-120 ℃ for drying for 2-3h, and grinding the dried substance until the particle size of D 50 is less than or equal to 50nm, thus obtaining the required composite antioxidant.
By adopting the technical scheme, the modified zirconium dioxide suspension is prepared by dissolving the modifier in ethanol solution, modifying zirconium dioxide and then interacting with propyl gallate; preparing ferrous oxide dispersion liquid and modified zirconium dioxide suspension, stirring and mixing, and wrapping ferrous oxide inside zirconium dioxide to prepare the required composite antioxidant; the raw materials are simple to select, the preparation method is simple, the preparation conditions are mild, the method is suitable for industrial production, the obtained composite antioxidant is used for protecting lubricating oil, the antioxidant effect is obvious, and the oxidation and deterioration of the lubricating oil can be effectively prevented and the problem of lubricating oil deposition can be solved by only adding 0.1-0.3% of the total mass of the lubricating oil.
In summary, the application has the following beneficial effects:
The application has simple raw materials and scientific formula, adopts zirconium dioxide as a main material, and prepares the composite antioxidant through interaction with ferrous oxide, propyl gallate, a modifier and an ethanol solution, and the obtained composite antioxidant is used for adding lubricating oil, can effectively adsorb and neutralize free radicals in the lubricating oil, prevent the lubricating oil from being oxidized and thermally decomposed under high temperature and high pressure, and obviously improve the oxidation resistance of the lubricating oil.
The composite antioxidant has outstanding high-temperature stability, can be applied to the protection of lubricating oil under severe working conditions such as high temperature, high pressure, high friction and the like, has remarkable oxidation resistance effect, and can effectively prevent the oxidation and deterioration of the lubricating oil and improve the problem of lubricating oil deposition by only adding 0.1-0.3% of the total mass of the lubricating oil.
The composite antioxidant disclosed by the application is nontoxic and odorless, has good thermal oxidation stability and corrosion resistance, can be stably dispersed in lubricating oil, adsorbs insoluble substances, inhibits sediment generation, effectively improves the quality of the lubricating oil, prolongs the service life of the lubricating oil, effectively ensures the normal operation of mechanical equipment, improves the performance of the mechanical equipment, and further prolongs the service life of the mechanical equipment.
Detailed Description
The present application will be described in further detail with reference to examples.
Examples 1-10 provide a compound antioxidant and a preparation method thereof.
Example 1
A composite antioxidant comprises the following raw materials: 30Kg of zirconium dioxide, 5Kg of ferrous oxide, 15Kg of propyl gallate, 4Kg of modifier and 80Kg of ethanol solution;
Wherein, the zirconium dioxide is spherical zirconium dioxide with the grain diameter of 50nm;
The modifier comprises HD-M8372 amino silane coupling agent and maleic anhydride in a mass ratio of 1:20;
The mass fraction of the ethanol solution is 55%.
The preparation method of the composite antioxidant comprises the following preparation steps:
s1, weighing raw materials of zirconium dioxide, ferrous oxide, propyl gallate, a modifier and an ethanol solution, and equally dividing the ethanol solution into 5 equal parts for standby;
S2, firstly taking 4 equal parts of ethanol solution, adding a modifier, stirring at normal temperature for dissolution, then adding zirconium dioxide, controlling the ultrasonic frequency to be 40kHz, carrying out ultrasonic pretreatment for 30min, and finally adding propyl gallate, and continuing ultrasonic treatment for 2h to obtain modified zirconium dioxide suspension;
S3, stirring and pre-dispersing ferrous oxide and the rest 1 equal part of ethanol solution for 20min at the rotating speed of 400r/min, adding the mixture into the modified zirconium dioxide suspension, continuously stirring and mixing for 20min, standing and ageing for 3h, centrifuging for 8min at the rotating speed of 1000r/min, collecting the precipitate, placing the precipitate in a vacuum drying oven at 100 ℃ for drying for 3h, and grinding the dried precipitate until the particle size of D 50 is 50nm, thus obtaining the required composite antioxidant.
Example 2
A composite antioxidant comprises the following raw materials: 38.5Kg of zirconium dioxide, 5.5Kg of ferrous oxide, 20Kg of propyl gallate, 6Kg of modifier and 90Kg of ethanol solution;
Wherein, the zirconium dioxide is spherical zirconium dioxide with the grain diameter of 50nm;
the modifier comprises HD-M8372 amino silane coupling agent and maleic anhydride in a mass ratio of 1:22;
The mass fraction of the ethanol solution is 55%.
The preparation method of the composite antioxidant comprises the following preparation steps:
s1, weighing raw materials of zirconium dioxide, ferrous oxide, propyl gallate, a modifier and an ethanol solution, and equally dividing the ethanol solution into 5 equal parts for standby;
s2, firstly taking 4 equal parts of ethanol solution, adding a modifier, stirring at normal temperature for dissolution, then adding zirconium dioxide, controlling the ultrasonic frequency to be 50kHz, carrying out ultrasonic pretreatment for 25min, and finally adding propyl gallate, and continuing ultrasonic treatment for 1.5h to obtain modified zirconium dioxide suspension;
S3, stirring and pre-dispersing ferrous oxide and the rest 1 equal part of ethanol solution at the rotating speed of 450r/min for 15min, adding the mixture into the modified zirconium dioxide suspension, continuously stirring and mixing for 15min, standing and ageing for 4h, centrifuging at the rotating speed of 1100r/min for 6min, collecting a precipitate, placing the precipitate in a vacuum drying oven at 110 ℃ for drying for 2.5h, and grinding the dried precipitate until the particle size of D 50 is 30nm, thus obtaining the required composite antioxidant.
Example 3
A composite antioxidant comprises the following raw materials: 50Kg of zirconium dioxide, 6Kg of ferrous oxide, 25Kg of propyl gallate, 8Kg of modifier and 100Kg of ethanol solution;
Wherein, the zirconium dioxide is spherical zirconium dioxide with the grain diameter of 50nm;
the modifier comprises HD-M8372 amino silane coupling agent and maleic anhydride in a mass ratio of 1:24;
The mass fraction of the ethanol solution is 55%.
The preparation method of the composite antioxidant comprises the following preparation steps:
s1, weighing raw materials of zirconium dioxide, ferrous oxide, propyl gallate, a modifier and an ethanol solution, and equally dividing the ethanol solution into 5 equal parts for standby;
S2, firstly taking 4 equal parts of ethanol solution, adding a modifier, stirring at normal temperature for dissolution, then adding zirconium dioxide, controlling the ultrasonic frequency to be 60kHz, carrying out ultrasonic pretreatment for 20min, and finally adding propyl gallate, and continuing ultrasonic treatment for 1h to obtain modified zirconium dioxide suspension;
S3, stirring and pre-dispersing ferrous oxide and the rest 1 equal part of ethanol solution for 10min at the rotating speed of 500r/min, adding the mixture into the modified zirconium dioxide suspension, continuously stirring and mixing for 10min, standing and ageing for 5h, centrifuging for 5min at the rotating speed of 1200r/min, collecting the precipitate, placing the precipitate in a vacuum drying oven at 120 ℃ for drying for 2h, and grinding the dried precipitate until the particle size of D 50 is 10nm, thus obtaining the required composite antioxidant.
Example 4
A composite antioxidant comprises the following raw materials: 37.7Kg of zirconium dioxide, 6.3Kg of ferrous oxide, 20Kg of propyl gallate, 6Kg of modifier and 90Kg of ethanol solution;
Wherein, the zirconium dioxide is spherical zirconium dioxide with the grain diameter of 50nm;
the modifier comprises HD-M8372 amino silane coupling agent and maleic anhydride in a mass ratio of 1:22;
The mass fraction of the ethanol solution is 55%.
The preparation method of the composite antioxidant comprises the following preparation steps:
s1, weighing raw materials of zirconium dioxide, ferrous oxide, propyl gallate, a modifier and an ethanol solution, and equally dividing the ethanol solution into 5 equal parts for standby;
s2, firstly taking 4 equal parts of ethanol solution, adding a modifier, stirring at normal temperature for dissolution, then adding zirconium dioxide, controlling the ultrasonic frequency to be 50kHz, carrying out ultrasonic pretreatment for 25min, and finally adding propyl gallate, and continuing ultrasonic treatment for 1.5h to obtain modified zirconium dioxide suspension;
S3, stirring and pre-dispersing ferrous oxide and the rest 1 equal part of ethanol solution at the rotating speed of 450r/min for 15min, adding the mixture into the modified zirconium dioxide suspension, continuously stirring and mixing for 15min, standing and ageing for 4h, centrifuging at the rotating speed of 1100r/min for 6min, collecting a precipitate, placing the precipitate in a vacuum drying oven at 110 ℃ for drying for 2.5h, and grinding the dried precipitate until the particle size of D 50 is 30nm, thus obtaining the required composite antioxidant.
Example 5
A composite antioxidant comprises the following raw materials: 39.1Kg of zirconium dioxide, 4.9Kg of ferrous oxide, 20Kg of propyl gallate, 6Kg of modifier and 90Kg of ethanol solution;
Wherein, the zirconium dioxide is spherical zirconium dioxide with the grain diameter of 50nm;
the modifier comprises HD-M8372 amino silane coupling agent and maleic anhydride in a mass ratio of 1:22;
The mass fraction of the ethanol solution is 55%.
The preparation method of the composite antioxidant comprises the following preparation steps:
s1, weighing raw materials of zirconium dioxide, ferrous oxide, propyl gallate, a modifier and an ethanol solution, and equally dividing the ethanol solution into 5 equal parts for standby;
s2, firstly taking 4 equal parts of ethanol solution, adding a modifier, stirring at normal temperature for dissolution, then adding zirconium dioxide, controlling the ultrasonic frequency to be 50kHz, carrying out ultrasonic pretreatment for 25min, and finally adding propyl gallate, and continuing ultrasonic treatment for 1.5h to obtain modified zirconium dioxide suspension;
S3, stirring and pre-dispersing ferrous oxide and the rest 1 equal part of ethanol solution at the rotating speed of 450r/min for 15min, adding the mixture into the modified zirconium dioxide suspension, continuously stirring and mixing for 15min, standing and ageing for 4h, centrifuging at the rotating speed of 1100r/min for 6min, collecting a precipitate, placing the precipitate in a vacuum drying oven at 110 ℃ for drying for 2.5h, and grinding the dried precipitate until the particle size of D 50 is 30nm, thus obtaining the required composite antioxidant.
Example 6
A composite antioxidant comprises the following raw materials: 38.5Kg of zirconium dioxide, 5.5Kg of ferrous oxide, 20Kg of propyl gallate, 6Kg of modifier, 90Kg of ethanol solution and 3.5Kg of organic boric acid;
Wherein, the zirconium dioxide is spherical zirconium dioxide with the grain diameter of 50nm;
the modifier comprises HD-M8372 amino silane coupling agent and maleic anhydride in a mass ratio of 1:22;
the mass fraction of the ethanol solution is 55%;
The organic boric acid is p-methyl phenylboric acid.
The preparation method of the composite antioxidant comprises the following preparation steps:
s1, weighing raw materials of zirconium dioxide, ferrous oxide, propyl gallate, a modifier, an ethanol solution and organic boric acid, and equally dividing the ethanol solution into 5 equal parts for standby;
s2, firstly taking 4 equal parts of ethanol solution, adding a modifier, stirring at normal temperature for dissolution, then adding zirconium dioxide, controlling the ultrasonic frequency to be 50kHz, carrying out ultrasonic pretreatment for 25min, and finally adding propyl gallate, and continuing ultrasonic treatment for 1.5h to obtain modified zirconium dioxide suspension;
S3, stirring and pre-dispersing ferrous oxide, organic boric acid and the rest 1 equal part of ethanol solution at the rotating speed of 450r/min for 15min, adding the mixture into the modified zirconium dioxide suspension, continuously stirring and mixing for 15min, standing and aging for 4h, centrifuging at the rotating speed of 1100r/min for 6min, collecting the precipitate, placing the precipitate in a vacuum drying oven at 110 ℃ for drying for 2.5h, and grinding the dried product until the particle size of D 50 is 30nm, thus obtaining the required composite antioxidant.
Example 7
A composite antioxidant comprises the following raw materials: 38.5Kg of zirconium dioxide, 5.5Kg of ferrous oxide, 20Kg of propyl gallate, 6Kg of modifier, 90Kg of ethanol solution and 3.5Kg of organic boric acid;
Wherein, the zirconium dioxide is spherical zirconium dioxide with the grain diameter of 50nm;
the modifier comprises HD-M8372 amino silane coupling agent and maleic anhydride in a mass ratio of 1:22;
the mass fraction of the ethanol solution is 55%;
The organic boric acid is 2-naphthalene boric acid.
The preparation method of the composite antioxidant comprises the following preparation steps:
s1, weighing raw materials of zirconium dioxide, ferrous oxide, propyl gallate, a modifier, an ethanol solution and organic boric acid, and equally dividing the ethanol solution into 5 equal parts for standby;
s2, firstly taking 4 equal parts of ethanol solution, adding a modifier, stirring at normal temperature for dissolution, then adding zirconium dioxide, controlling the ultrasonic frequency to be 50kHz, carrying out ultrasonic pretreatment for 25min, and finally adding propyl gallate, and continuing ultrasonic treatment for 1.5h to obtain modified zirconium dioxide suspension;
S3, stirring and pre-dispersing ferrous oxide, organic boric acid and the rest 1 equal part of ethanol solution at the rotating speed of 450r/min for 15min, adding the mixture into the modified zirconium dioxide suspension, continuously stirring and mixing for 15min, standing and aging for 4h, centrifuging at the rotating speed of 1100r/min for 6min, collecting the precipitate, placing the precipitate in a vacuum drying oven at 110 ℃ for drying for 2.5h, and grinding the dried product until the particle size of D 50 is 30nm, thus obtaining the required composite antioxidant.
Example 8
A composite antioxidant comprises the following raw materials: 38.5Kg of zirconium dioxide, 5.5Kg of ferrous oxide, 20Kg of propyl gallate, 6Kg of modifier, 90Kg of ethanol solution and 3.5Kg of organic boric acid;
Wherein, the zirconium dioxide is spherical zirconium dioxide with the grain diameter of 50nm;
the modifier comprises HD-M8372 amino silane coupling agent and maleic anhydride in a mass ratio of 1:22;
the mass fraction of the ethanol solution is 55%;
the organic boric acid comprises p-tolueneboric acid and 2-naphthalene boric acid in a mass ratio of 1:4.
The preparation method of the composite antioxidant comprises the following preparation steps:
s1, weighing raw materials of zirconium dioxide, ferrous oxide, propyl gallate, a modifier, an ethanol solution and organic boric acid, and equally dividing the ethanol solution into 5 equal parts for standby;
s2, firstly taking 4 equal parts of ethanol solution, adding a modifier, stirring at normal temperature for dissolution, then adding zirconium dioxide, controlling the ultrasonic frequency to be 50kHz, carrying out ultrasonic pretreatment for 25min, and finally adding propyl gallate, and continuing ultrasonic treatment for 1.5h to obtain modified zirconium dioxide suspension;
S3, stirring and pre-dispersing ferrous oxide, organic boric acid and the rest 1 equal part of ethanol solution at the rotating speed of 450r/min for 15min, adding the mixture into the modified zirconium dioxide suspension, continuously stirring and mixing for 15min, standing and aging for 4h, centrifuging at the rotating speed of 1100r/min for 6min, collecting the precipitate, placing the precipitate in a vacuum drying oven at 110 ℃ for drying for 2.5h, and grinding the dried product until the particle size of D 50 is 30nm, thus obtaining the required composite antioxidant.
Example 9
A composite antioxidant comprises the following raw materials: 38.5Kg of zirconium dioxide, 5.5Kg of ferrous oxide, 20Kg of propyl gallate, 6Kg of modifier, 90Kg of ethanol solution and 3.5Kg of organic boric acid;
Wherein, the zirconium dioxide is spherical zirconium dioxide with the grain diameter of 50nm;
the modifier comprises HD-M8372 amino silane coupling agent and maleic anhydride in a mass ratio of 1:22;
the mass fraction of the ethanol solution is 55%;
the organic boric acid comprises p-tolueneboric acid and 2-naphthalene boric acid in a mass ratio of 1:4.5.
The preparation method of the composite antioxidant comprises the following preparation steps:
s1, weighing raw materials of zirconium dioxide, ferrous oxide, propyl gallate, a modifier, an ethanol solution and organic boric acid, and equally dividing the ethanol solution into 5 equal parts for standby;
s2, firstly taking 4 equal parts of ethanol solution, adding a modifier, stirring at normal temperature for dissolution, then adding zirconium dioxide, controlling the ultrasonic frequency to be 50kHz, carrying out ultrasonic pretreatment for 25min, and finally adding propyl gallate, and continuing ultrasonic treatment for 1.5h to obtain modified zirconium dioxide suspension;
S3, stirring and pre-dispersing ferrous oxide, organic boric acid and the rest 1 equal part of ethanol solution at the rotating speed of 450r/min for 15min, adding the mixture into the modified zirconium dioxide suspension, continuously stirring and mixing for 15min, standing and aging for 4h, centrifuging at the rotating speed of 1100r/min for 6min, collecting the precipitate, placing the precipitate in a vacuum drying oven at 110 ℃ for drying for 2.5h, and grinding the dried product until the particle size of D 50 is 30nm, thus obtaining the required composite antioxidant.
Example 10
A composite antioxidant comprises the following raw materials: 38.5Kg of zirconium dioxide, 5.5Kg of ferrous oxide, 20Kg of propyl gallate, 6Kg of modifier, 90Kg of ethanol solution and 3.5Kg of organic boric acid;
Wherein, the zirconium dioxide is spherical zirconium dioxide with the grain diameter of 50nm;
the modifier comprises HD-M8372 amino silane coupling agent and maleic anhydride in a mass ratio of 1:22;
the mass fraction of the ethanol solution is 55%;
The organic boric acid comprises p-tolueneboric acid and 2-naphthalene boric acid in a mass ratio of 1:5.
The preparation method of the composite antioxidant comprises the following preparation steps:
s1, weighing raw materials of zirconium dioxide, ferrous oxide, propyl gallate, a modifier, an ethanol solution and organic boric acid, and equally dividing the ethanol solution into 5 equal parts for standby;
s2, firstly taking 4 equal parts of ethanol solution, adding a modifier, stirring at normal temperature for dissolution, then adding zirconium dioxide, controlling the ultrasonic frequency to be 50kHz, carrying out ultrasonic pretreatment for 25min, and finally adding propyl gallate, and continuing ultrasonic treatment for 1.5h to obtain modified zirconium dioxide suspension;
S3, stirring and pre-dispersing ferrous oxide, organic boric acid and the rest 1 equal part of ethanol solution at the rotating speed of 450r/min for 15min, adding the mixture into the modified zirconium dioxide suspension, continuously stirring and mixing for 15min, standing and aging for 4h, centrifuging at the rotating speed of 1100r/min for 6min, collecting the precipitate, placing the precipitate in a vacuum drying oven at 110 ℃ for drying for 2.5h, and grinding the dried product until the particle size of D 50 is 30nm, thus obtaining the required composite antioxidant.
In order to verify the antioxidant properties of the composite antioxidants prepared in examples 1 to 10 of the present application, the applicant set comparative examples 1 to 5, which are specifically as follows:
comparative example 1
A composite antioxidant comprises the following raw materials: 40Kg of zirconium dioxide, 4Kg of ferrous oxide, 20Kg of propyl gallate, 6Kg of modifier and 90Kg of ethanol solution;
Wherein, the zirconium dioxide is spherical zirconium dioxide with the grain diameter of 50nm;
the modifier comprises HD-M8372 amino silane coupling agent and maleic anhydride in a mass ratio of 1:22;
The mass fraction of the ethanol solution is 55%.
The preparation method of the composite antioxidant comprises the following preparation steps:
s1, weighing raw materials of zirconium dioxide, ferrous oxide, propyl gallate, a modifier and an ethanol solution, and equally dividing the ethanol solution into 5 equal parts for standby;
s2, firstly taking 4 equal parts of ethanol solution, adding a modifier, stirring at normal temperature for dissolution, then adding zirconium dioxide, controlling the ultrasonic frequency to be 50kHz, carrying out ultrasonic pretreatment for 25min, and finally adding propyl gallate, and continuing ultrasonic treatment for 1.5h to obtain modified zirconium dioxide suspension;
S3, stirring and pre-dispersing ferrous oxide and the rest 1 equal part of ethanol solution at the rotating speed of 450r/min for 15min, adding the mixture into the modified zirconium dioxide suspension, continuously stirring and mixing for 15min, standing and ageing for 4h, centrifuging at the rotating speed of 1100r/min for 6min, collecting a precipitate, placing the precipitate in a vacuum drying oven at 110 ℃ for drying for 2.5h, and grinding the dried precipitate until the particle size of D 50 is 30nm, thus obtaining the required composite antioxidant.
Comparative example 2
A composite antioxidant comprises the following raw materials: 44Kg of zirconium dioxide, 20Kg of propyl gallate, 6Kg of modifier and 90Kg of ethanol solution;
Wherein, the zirconium dioxide is spherical zirconium dioxide with the grain diameter of 50nm;
the modifier comprises HD-M8372 amino silane coupling agent and maleic anhydride in a mass ratio of 1:22;
The mass fraction of the ethanol solution is 55%.
The preparation method of the composite antioxidant comprises the following preparation steps:
s1, weighing raw materials of zirconium dioxide, propyl gallate, a modifier and an ethanol solution for standby;
S2, firstly taking an ethanol solution, adding a modifier, stirring and dissolving at normal temperature, then adding zirconium dioxide, controlling the ultrasonic frequency to be 50kHz, carrying out ultrasonic pretreatment for 25min, and finally adding propyl gallate, and continuing ultrasonic treatment for 1.5h to obtain a modified zirconium dioxide suspension;
S3, standing and aging the modified zirconium dioxide suspension for 4 hours, centrifuging for 6 minutes at the rotating speed of 1100r/min, collecting a precipitate, drying the precipitate in a vacuum drying oven at 110 ℃ for 2.5 hours, and grinding the dried precipitate until the particle size of D 50 is 30nm, thus obtaining the required composite antioxidant.
Comparative example 3
A composite antioxidant comprises the following raw materials: 38.5Kg of zirconium dioxide, 5.5Kg of ferrous oxide, 20Kg of propyl gallate, 6Kg of modifier and 90Kg of ethanol solution;
Wherein, the zirconium dioxide is spherical zirconium dioxide with the grain diameter of 50nm;
the modifier comprises silane coupling agent A-171 and maleic anhydride in a mass ratio of 1:22;
The mass fraction of the ethanol solution is 55%.
The preparation method of the composite antioxidant comprises the following preparation steps:
s1, weighing raw materials of zirconium dioxide, ferrous oxide, propyl gallate, a modifier and an ethanol solution, and equally dividing the ethanol solution into 5 equal parts for standby;
s2, firstly taking 4 equal parts of ethanol solution, adding a modifier, stirring at normal temperature for dissolution, then adding zirconium dioxide, controlling the ultrasonic frequency to be 50kHz, carrying out ultrasonic pretreatment for 25min, and finally adding propyl gallate, and continuing ultrasonic treatment for 1.5h to obtain modified zirconium dioxide suspension;
S3, stirring and pre-dispersing ferrous oxide and the rest 1 equal part of ethanol solution at the rotating speed of 450r/min for 15min, adding the mixture into the modified zirconium dioxide suspension, continuously stirring and mixing for 15min, standing and ageing for 4h, centrifuging at the rotating speed of 1100r/min for 6min, collecting a precipitate, placing the precipitate in a vacuum drying oven at 110 ℃ for drying for 2.5h, and grinding the dried precipitate until the particle size of D 50 is 30nm, thus obtaining the required composite antioxidant.
Comparative example 4
A composite antioxidant comprises the following raw materials: 38.5Kg of zirconium dioxide, 5.5Kg of ferrous oxide, 20Kg of propyl gallate, 6Kg of modifier, 90Kg of ethanol solution and 3.5Kg of organic boric acid;
Wherein, the zirconium dioxide is spherical zirconium dioxide with the grain diameter of 50nm;
the modifier comprises HD-M8372 amino silane coupling agent and maleic anhydride in a mass ratio of 1:22;
the mass fraction of the ethanol solution is 55%;
The organic boric acid is p-methyl phenylboric acid.
The preparation method of the composite antioxidant comprises the following preparation steps:
s1, weighing raw materials of zirconium dioxide, ferrous oxide, propyl gallate, a modifier, an ethanol solution and organic boric acid, and equally dividing the ethanol solution into 5 equal parts for standby;
S2, firstly taking 4 equal parts of ethanol solution, adding a modifier, stirring at normal temperature for dissolution, then adding zirconium dioxide, controlling the ultrasonic frequency to be 50kHz, carrying out ultrasonic pretreatment for 25min, and finally adding propyl gallate and organic boric acid, and continuing ultrasonic treatment for 1.5h to obtain modified zirconium dioxide suspension;
S3, stirring and pre-dispersing ferrous oxide and the rest 1 equal part of ethanol solution at the rotating speed of 450r/min for 15min, adding the mixture into the modified zirconium dioxide suspension, continuously stirring and mixing for 15min, standing and ageing for 4h, centrifuging at the rotating speed of 1100r/min for 6min, collecting a precipitate, placing the precipitate in a vacuum drying oven at 110 ℃ for drying for 2.5h, and grinding the dried precipitate until the particle size of D 50 is 30nm, thus obtaining the required composite antioxidant.
Comparative example 5
A composite antioxidant comprises the following raw materials: 38.5Kg of zirconium dioxide, 5.5Kg of ferrous oxide, 20Kg of propyl gallate, 6Kg of modifier, 90Kg of ethanol solution and 3.5Kg of organic boric acid;
Wherein, the zirconium dioxide is spherical zirconium dioxide with the grain diameter of 50nm;
the modifier comprises HD-M8372 amino silane coupling agent and maleic anhydride in a mass ratio of 1:22;
the mass fraction of the ethanol solution is 55%;
The organic boric acid is p-methyl phenylboric acid.
The preparation method of the composite antioxidant comprises the following preparation steps:
S1, weighing raw materials of zirconium dioxide, ferrous oxide, propyl gallate, a modifier, an ethanol solution and organic boric acid for standby;
S2, firstly taking an ethanol solution, adding a modifier, stirring and dissolving at normal temperature, then adding zirconium dioxide and ferrous oxide, controlling the ultrasonic frequency to be 50kHz, carrying out ultrasonic pretreatment for 25min, and finally adding propyl gallate and organic boric acid, and continuing ultrasonic treatment for 1.5h to obtain a modified zirconium dioxide suspension;
S3, standing and aging the modified zirconium dioxide suspension for 4 hours, centrifuging for 6 minutes at the rotating speed of 1100r/min, collecting a precipitate, drying the precipitate in a vacuum drying oven at 110 ℃ for 2.5 hours, and grinding the dried precipitate until the particle size of D 50 is 30nm, thus obtaining the required composite antioxidant.
Performance testing
The compound antioxidants prepared in examples 1 to 10 and comparative examples 1 to 5 of the present application were added to lubricating oils (brand: shell Helix Ultra; model: SN 0W-20 total synthetic engine oil), respectively, and the addition amount of the compound antioxidant was controlled to be 0.2% of the total mass of the lubricating oils, and the mixture was mechanically stirred for 30min under the protection of nitrogen atmosphere and uniformly mixed.
The oxidation stability of the lubricating oil at 150 ℃ is measured by adopting a rotary oxygen bomb method (RPVOT) by referring to a standard SH/T0193-2008; the precipitate content after oxidation and the acid value were tested with reference to standard SH/T0811-2010, and the results are shown in Table 1.
Table 1:
As can be seen from the data shown in table 1: the composite antioxidant prepared in the embodiments 1-10 of the application has obviously improved comprehensive performance compared with the composite antioxidant prepared in the comparative examples 1-5, which shows that under the preferable raw material proportion and technological parameters of the application, the raw materials in the formula can interact and synergistically increase, thereby improving the comprehensive performance of the finally prepared composite antioxidant.
Comparative example 2 and comparative examples 1-2 show that: the oxidation induction time is obviously prolonged, the acid value is reduced, and the sediment is obviously reduced compared with the comparative example 1-2 in the embodiment 2 of the application.
Comparative example 2 and comparative example 3 show that: the modifier is a compound of an aminosilane coupling agent and maleic anhydride, and can further improve the antioxidation effect of the composite antioxidant compared with a compound of a vinyl silane coupling agent and maleic anhydride.
Comparative example 6 and comparative examples 4 to 5 are shown as follows: preparing a modified zirconium dioxide dispersion liquid and a modified ferrous oxide dispersion liquid respectively; preparing a modified zirconium dioxide dispersion liquid and a ferrous oxide dispersion liquid respectively, wherein the ferrous oxide dispersion liquid is not modified; or all the raw materials are directly mixed to prepare modified zirconium dioxide dispersion liquid; the oxidation resistance of the composite antioxidant prepared in the embodiment 6 of the application is obviously improved.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (9)
1. The composite antioxidant is characterized by comprising the following raw materials in parts by weight: 30-50 parts of zirconium dioxide, 5-6 parts of ferrous oxide, 15-25 parts of propyl gallate, 4-8 parts of modifier and 80-100 parts of ethanol solution;
The modifier comprises a silane coupling agent and maleic anhydride in a mass ratio of 1:20-24;
the preparation method of the composite antioxidant comprises the following preparation steps:
S1, weighing raw materials of zirconium dioxide, ferrous oxide, propyl gallate, a modifier and an ethanol solution according to parts by weight;
S2, adding a modifier into part of the ethanol solution, stirring and dissolving, then adding zirconium dioxide for pretreatment, and finally adding propyl gallate to obtain a modified zirconium dioxide suspension;
S3, adding the pre-dispersed ferrous oxide and the residual ethanol solution into the modified zirconium dioxide suspension, stirring and mixing uniformly, standing for aging, centrifugally collecting precipitate, drying and grinding to obtain the required composite antioxidant.
2. The compound antioxidant as claimed in claim 1, comprising the following raw materials in parts by weight: 38.5 parts of zirconium dioxide, 5.5 parts of ferrous oxide, 20 parts of propyl gallate, 6 parts of modifier and 90 parts of ethanol solution.
3. The composite antioxidant according to claim 1, wherein the mass ratio of zirconium dioxide to ferrous oxide is 6-8:1.
4. The composite antioxidant of claim 1, wherein the raw materials further comprise: 2-5 parts of organic boric acid.
5. The compound antioxidant according to claim 4, wherein the organic boric acid is p-methylphenylboric acid and/or 2-naphthylboric acid.
6. The compound antioxidant according to claim 5, wherein the mass ratio of the p-tolueneboronic acid to the 2-naphthalene boronic acid is 1:4-5.
7. The composite antioxidant according to claim 1, wherein the silane coupling agent is an aminosilane coupling agent.
8. A method for preparing the compound antioxidant as claimed in any one of claims 1 to 7, comprising the following steps:
s1, weighing raw materials of zirconium dioxide, ferrous oxide, propyl gallate, a modifier and an ethanol solution according to parts by weight, and equally dividing the ethanol solution into 5 equal parts for standby;
s2, firstly taking 4 equal parts of ethanol solution, adding a modifier, stirring and dissolving, then adding zirconium dioxide for ultrasonic pretreatment, and finally adding propyl gallate for continuous ultrasonic treatment to obtain modified zirconium dioxide suspension;
s3, pre-dispersing ferrous oxide and the rest 1 equal part of ethanol solution, adding the pre-dispersed ferrous oxide and the rest 1 equal part of ethanol solution into the modified zirconium dioxide suspension, stirring and uniformly mixing, standing for ageing, centrifugally collecting precipitate, drying and grinding to obtain the required composite antioxidant.
9. The method for preparing the compound antioxidant according to claim 8, wherein the raw materials in the step S1 further comprise organic boric acid, and the step S3 specifically comprises the following steps:
And (3) pre-dispersing ferrous oxide, organic boric acid and the rest 1 equal part of ethanol solution, adding the pre-dispersed solution into the modified zirconium dioxide suspension, stirring and uniformly mixing, standing for ageing, centrifugally collecting precipitate, drying and grinding to obtain the required composite antioxidant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310442201.6A CN116554942B (en) | 2023-04-23 | 2023-04-23 | Composite antioxidant and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310442201.6A CN116554942B (en) | 2023-04-23 | 2023-04-23 | Composite antioxidant and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116554942A CN116554942A (en) | 2023-08-08 |
| CN116554942B true CN116554942B (en) | 2024-05-28 |
Family
ID=87489037
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310442201.6A Active CN116554942B (en) | 2023-04-23 | 2023-04-23 | Composite antioxidant and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116554942B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11140476A (en) * | 1997-08-05 | 1999-05-25 | Nippon Shokubai Co Ltd | Lubricant |
| CN102356129A (en) * | 2009-01-15 | 2012-02-15 | 康奈尔大学 | Nanoparticle organic hybrid materials (nohms) |
| CN102682869A (en) * | 2012-04-11 | 2012-09-19 | 中国电力科学研究院 | Vegetable insulating oil, and preparation method of vegetable insulating oil |
| CN103113658A (en) * | 2011-11-16 | 2013-05-22 | 深圳金大全科技有限公司 | Plastic powder or particle toughener and processing method thereof |
| CN103666640A (en) * | 2013-11-26 | 2014-03-26 | 成都新柯力化工科技有限公司 | Inorganic lubricant powder and preparation method thereof |
| CN106433887A (en) * | 2016-09-19 | 2017-02-22 | 铜陵日科电子有限责任公司 | Low temperature resistant wearproof transformer vegetable insulating oil and preparing method thereof |
| CN107254342A (en) * | 2017-04-21 | 2017-10-17 | 天长市润达金属防锈助剂有限公司 | A kind of anti-rust metal cutting fluid with excellent permeance property |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114149844B (en) * | 2021-12-07 | 2022-06-17 | 上海海事大学 | Preparation method of multifunctional modified molybdenum disulfide nano additive |
-
2023
- 2023-04-23 CN CN202310442201.6A patent/CN116554942B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11140476A (en) * | 1997-08-05 | 1999-05-25 | Nippon Shokubai Co Ltd | Lubricant |
| CN102356129A (en) * | 2009-01-15 | 2012-02-15 | 康奈尔大学 | Nanoparticle organic hybrid materials (nohms) |
| CN103113658A (en) * | 2011-11-16 | 2013-05-22 | 深圳金大全科技有限公司 | Plastic powder or particle toughener and processing method thereof |
| CN102682869A (en) * | 2012-04-11 | 2012-09-19 | 中国电力科学研究院 | Vegetable insulating oil, and preparation method of vegetable insulating oil |
| CN103666640A (en) * | 2013-11-26 | 2014-03-26 | 成都新柯力化工科技有限公司 | Inorganic lubricant powder and preparation method thereof |
| CN106433887A (en) * | 2016-09-19 | 2017-02-22 | 铜陵日科电子有限责任公司 | Low temperature resistant wearproof transformer vegetable insulating oil and preparing method thereof |
| CN107254342A (en) * | 2017-04-21 | 2017-10-17 | 天长市润达金属防锈助剂有限公司 | A kind of anti-rust metal cutting fluid with excellent permeance property |
Non-Patent Citations (3)
| Title |
|---|
| "Reinforced composite membranes based on expanded polytetrafluoroethylene ";Liu等;《Energy and fuels》;20210805;12482-12494 * |
| 二氢杨梅素-铜配合物抗氧化活性的研究;袁娟;郭清泉;徐勇;;广东工业大学学报(第02期);全文 * |
| 袁娟 ; 郭清泉 ; 徐勇 ; .二氢杨梅素-铜配合物抗氧化活性的研究.广东工业大学学报.(第02期),全文. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116554942A (en) | 2023-08-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5358992A (en) | Die-attach composition comprising polycyanate ester monomer | |
| CN116554942B (en) | Composite antioxidant and preparation method thereof | |
| CN114751805A (en) | Green environment-friendly styrene polymerization inhibitor and preparation method thereof | |
| CN111676081A (en) | Antioxidant for reducing environmental pollution of lubricating oil and preparation method thereof | |
| CN110776314A (en) | Wide-high-frequency anti-EMI manganese-zinc ferrite material and preparation method thereof | |
| CN110444359B (en) | Method for reducing oxygen content of sintered neodymium-iron-boron material and additive | |
| CN107573986A (en) | A kind of electric power electrical apparatus conserves protective agent and its production and use online | |
| CN110257139A (en) | A kind of preparation method of thermally conductive high temperature resistant long-term lubricant | |
| CN110054218B (en) | Compound organic matter for removing multiple impurities of crude titanium tetrachloride in synergistic depth and preparation method thereof | |
| Duan et al. | Preparation of rare-earth terephthalic acid stabilizer and its effect on thermal stability of polyvinyl chloride | |
| CN112521999A (en) | Lubricating oil metal deactivator mixture and preparation method thereof | |
| CN110591801A (en) | Compressor lubricating oil composition and preparation method thereof | |
| CN110194751B (en) | Preparation method of thiadiazole derivative | |
| CN113896945A (en) | PVC composite heat stabilizer, application thereof and polyvinyl chloride product | |
| CN112592755A (en) | Efficient ashless hydraulic oil complexing agent composition and preparation method thereof | |
| CN113248878B (en) | Halogen-free flame-retardant PET/ABS plastic alloy and preparation method thereof | |
| CN112608465B (en) | Antioxidant and preparation method thereof | |
| JPS61233088A (en) | Synthetic oil composition | |
| CN111117727B (en) | Efficient lubricating oil composite antioxidant and preparation method thereof | |
| CN111234203A (en) | Polyether amine triazole derivative and preparation method and application thereof | |
| CN111054449A (en) | Environment-friendly multi-metal passivator and preparation method thereof | |
| CN113755007B (en) | Nylon 6 composite material with electromagnetic shielding effect | |
| CN114479990B (en) | Lubricating oil additive and preparation method and application thereof | |
| CN104629318A (en) | Flame retardant PC/ABS alloy having excellent wear resistance | |
| CN112480683B (en) | Halogen-free flame-retardant heat-resistant silicone rubber composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240623 Address after: 334500 Industrial Park, Qianshan County, Shangrao City, Jiangxi Province Patentee after: JIANGXI LIANGHUA TECHNOLOGY Co.,Ltd. Country or region after: China Patentee after: SHANGHAI QIKE FLUORINE AND SILICONE MATERIAL Co.,Ltd. Address before: No. 1035 Youyi, Longquan Village, Tinglin Town, Jinshan District, Shanghai, 200540 Patentee before: SHANGHAI QIKE FLUORINE AND SILICONE MATERIAL Co.,Ltd. Country or region before: China |
|
| TR01 | Transfer of patent right |