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CN-121990929-A - Antioxidant and preparation method and application thereof

CN121990929ACN 121990929 ACN121990929 ACN 121990929ACN-121990929-A

Abstract

The invention belongs to the field of lubricating oil additives, and particularly relates to an antioxidant and a preparation method and application thereof. The antioxidant at least comprises the following structure: Wherein R 1 、R 2 、R 5 、R 7 is alkyl containing phenyl, is positioned at the para position, the ortho position or both positions of amino, and R 3 、R 4 、R 6 、R 8 is alkyl and is respectively connected to R 1 、R 2 、R 5 、R 7 . The antioxidant has excellent oxidation resistance, better solubility compared with a single amine antioxidant containing benzene ring olefin substituent, and higher thermal stability compared with a single amine antioxidant without phenyl substituent.

Inventors

  • LUO YI
  • XU RUIFENG
  • AN WENJIE
  • XUE WEIGUO
  • ZHENG LAICHANG

Assignees

  • 中国石油天然气股份有限公司

Dates

Publication Date
20260508
Application Date
20241106

Claims (16)

  1. 1. An antioxidant, wherein the antioxidant comprises at least one of the following structures: wherein R 1 、R 2 、R 5 、R 7 is alkyl containing phenyl, is positioned at the para position, the ortho position or both positions of amino, and R 3 、R 4 、R 6 、R 8 is alkyl and is respectively connected to R 1 、R 2 、R 5 、R 7 .
  2. 2. The antioxidant of claim 1, wherein the alkyl group of the phenyl-containing alkyl groups is selected from one or more of C8-C14 olefins.
  3. 3. The antioxidant of claim 1, wherein the alkyl is selected from one or more of C4-C14 olefins.
  4. 4. A process for the preparation of an antioxidant as claimed in any one of claims 1 to 3, comprising the steps of: (1) Mixing an amine source with a catalyst, adding olefin containing benzene rings, reacting, and distilling to obtain a product 1; (2) Adding olefin into the product 1, reacting, cooling, filtering to remove the catalyst, and distilling to obtain the antioxidant.
  5. 5. The method of producing the catalyst according to claim 4, wherein the method of producing the catalyst in step (1) comprises the steps of: S1, adding activated clay, aluminum oxide and silica gel into a mixed solution of trifluoroacetic acid and methanesulfonic acid, reacting, and calcining to obtain a solid substance 1; s2, mixing the solid substance 1 with a mixture of ferric trichloride and cupric chloride, adding the mixture into absolute ethyl alcohol, stirring, drying and calcining to obtain the catalyst.
  6. 6. The preparation method according to claim 5, wherein the mass ratio of the activated clay, the alumina and the silica gel in the step S1 is 6-8:1-3:1, and the volume ratio of the trifluoroacetic acid to the methanesulfonic acid is 1:0.8-1.2.
  7. 7. The preparation method according to claim 5, wherein the mass ratio of the mixed solution of the sum of the masses of activated clay, alumina and silica gel in step S1 is 1:2-10.
  8. 8. The method according to claim 5, wherein the reaction temperature in step S1 is 60 to 120 ℃, the reaction time is 7 to 10 hours, the calcination temperature is 150 to 260 ℃, and the calcination time is 10 to 15 hours.
  9. 9. The preparation method according to claim 5, wherein the mass ratio of the ferric trichloride to the cupric chloride in the step S2 is 1:0.8-1.2, and the mass ratio of the solid substance 1 to the mixture of the ferric trichloride and the cupric chloride is 1:2-4.
  10. 10. The method according to claim 5, wherein the stirring temperature in step S2 is 55-65 ℃, the stirring time is 4-8 hours, the calcining temperature is 280-350 ℃, and the calcining time is 6-12 hours.
  11. 11. The process according to claim 4, wherein the amine source in step (1) is selected from one or both of N-phenylaniline and phenylmenadione.
  12. 12. The method according to claim 4, wherein the catalyst in the step (1) is added in an amount of 10 to 30% by mass of the amine source, and the molar ratio of the amine source to the benzene ring-containing olefin is 1:3 to 10.
  13. 13. The process according to claim 4, wherein the benzene ring-containing olefin in step (1) is added under nitrogen atmosphere, the reaction temperature is 100 to 180 ℃ and the reaction time is 3 to 15 hours.
  14. 14. The process according to claim 4, wherein the molar ratio of the olefin in step (2) to the olefin containing a benzene ring in step (1) is 1 to 2:1.
  15. 15. The process according to claim 4, wherein the temperature of the reaction in the step (2) is 100 to 180 ℃, the reaction time is 5 to 13 hours, and the temperature after the temperature reduction is 50 to 70 ℃.
  16. 16. Use of an antioxidant according to any one of claims 1 to 3 or an antioxidant prepared by a method according to any one of claims 4 to 15 for the preparation of a lubricating oil or grease.

Description

Antioxidant and preparation method and application thereof Technical Field The invention belongs to the field of lubricating oil additives, and particularly relates to an antioxidant and a preparation method and application thereof. Background The antioxidant is an important class in lubricating oil additives, can obviously improve the oxidation stability of the oil, prevent the oil from spoilage and prolong the service life of the oil. The current worldwide antioxidant production is inferior to detergent dispersants and viscosity index improvers and still keeps the potential for strong growth. Especially, the amine antioxidant is the antioxidant with the largest dosage, and can effectively prevent the oxidation of oil products when being used as the free radical scavenging antioxidant. The most common products in amine antioxidants are diphenylamine, and the diphenylamine has strong toxicity, poor oil solubility and limited use of light variability, so that scholars at home and abroad can improve the defect of the diphenylamine by carrying out alkylation reaction on the diphenylamine, and products such as dioctyl diphenylamine, butyl octyl diphenylamine, dinonyl diphenylamine and the like are developed, and the products have the characteristics of good antioxidant performance and ashless and phosphorus-free characteristics, so that the amine antioxidants are widely applied to oil products such as internal combustion engine oil and turbine oil. Chinese patent application CN105646232A discloses a method for preparing 4,4' -di (phenyl isopropyl) diphenylamine, under the action of catalyst activated clay, under the condition of 105-165 deg.C, making diphenylamine and alpha-methyl styrene produce reaction to produce crude product 4,4' -di (phenyl isopropyl) diphenylamine, after filtering, using solvent to make recrystallization, centrifugal drying and pulverizing or granulating so as to obtain the invented high-purity 4,4' -di (phenyl isopropyl) diphenylamine. The solid particle antioxidant is an anti-aging agent commonly used in rubber plastics, and has limited solubility in oil. The Chinese patent application CN101020643A provides a process for preparing nonylated diphenylamine by alkylation reaction, which adopts nonene and diphenylamine as raw materials, carries out alkylation reaction under the condition of taking aluminum trichloride as a catalyst, and obtains a liquid nonylated diphenylamine product through the procedures of acid washing, alkali washing, water washing, decoloring, filtering and vacuum distillation refining after the reaction is finished. Chinese patent application CN105777557A discloses an alkylation reaction of mixed amine, after mixing naphthylamine and aniline, adding mixed olefin to make alkylation reaction so as to obtain a mixed alkylation substituted product of mixed amine, and making substitution at different positions on the raw material. The invention provides a new alkylated amine antioxidant, wherein the first olefin containing benzene ring is alkylated on aniline, and the second olefin is further alkylated on phenyl of olefin containing benzene ring. Compared with a single amine antioxidant containing benzene ring olefin substituent, the structure has better solubility and higher thermal stability compared with a single amine antioxidant without phenyl substituent. There are few reports of such structures. Disclosure of Invention Aiming at the defects of the prior art, the invention provides an antioxidant and a preparation method and application thereof. The antioxidant disclosed by the invention has more excellent solubility and thermal stability, and is not easy to change color. In order to achieve the above purpose of the present invention, the present invention adopts the following specific technical scheme: An antioxidant comprising at least one of the following structures: wherein R 1、R2、R5、R7 is alkyl containing phenyl, is positioned at the para position, the ortho position or both positions of amino, and R 3、R4、R6、R8 is alkyl and is respectively connected to R 1、R2、R5、R7. Preferably, the alkyl group of the phenyl-containing alkyl group is selected from one or more of C8-C14 olefins. Preferably, the alkyl is selected from one or more of C4-C14 olefins. The invention also relates to a preparation method of the antioxidant, which comprises the following steps: (1) Mixing an amine source with a catalyst, adding olefin containing benzene rings, reacting, and distilling to obtain a product 1; (2) Adding olefin into the product 1, reacting, cooling, filtering to remove the catalyst, and distilling to obtain the antioxidant. Preferably, the preparation method of the catalyst in the step (1) comprises the following steps: S1, adding activated clay, aluminum oxide and silica gel into a mixed solution of trifluoroacetic acid and methanesulfonic acid, reacting, and calcining to obtain a solid substance 1; s2, mixing the solid substance 1 with a mixture of ferric trichloride and