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CN-121974848-A - Quinoline anti-aging agent and preparation method thereof

CN121974848ACN 121974848 ACN121974848 ACN 121974848ACN-121974848-A

Abstract

The invention provides a quinoline antioxidant and a preparation method thereof, belonging to the technical field of fine chemical engineering. The preparation method of the quinoline anti-aging agent comprises the following steps of reacting 2, 4-dimethyl-3-pentene-2-amine with 4-bromophenylaniline or bis (4-bromophenyl) amine with amino protected to obtain a quaternary amine anti-aging agent, carrying out methylation on the quaternary amine anti-aging agent, and removing an amino protecting group to obtain the quinoline anti-aging agent. The quinoline antioxidant prepared by the invention is used in the rubber field, has better ozone protection effect, and can improve the phenomenon that the antioxidant is easy to migrate and change color in rubber products.

Inventors

  • ZHANG HAO
  • YANG ZHENLIN
  • ZHAO ZHENWEI
  • WANG WENBO
  • MA DELONG
  • XUE BOYONG
  • MENG YUTING
  • MENG QINGYONG

Assignees

  • 山东阳谷华泰化工股份有限公司

Dates

Publication Date
20260505
Application Date
20260127

Claims (10)

  1. 1. A quinoline anti-aging agent is characterized in that the structural formula of the quinoline anti-aging agent is as follows Or (b) 。
  2. 2. The preparation method of the quinoline anti-aging agent according to claim 1, which is characterized by comprising the steps of reacting 2, 4-dimethyl-3-pentene-2-amine with 4-bromophenylaniline or bis (4-bromophenyl) amine with amino groups protected to obtain a quaternary amine anti-aging agent, carrying out methylation on the quaternary amine anti-aging agent, and removing amino protecting groups to obtain the quinoline anti-aging agent.
  3. 3. The preparation method of the quinoline anti-aging agent according to claim 2, wherein the specific preparation method comprises the following steps: (1) Mixing 4-bromophenyl aniline or bis (4-bromophenyl) amine with a solvent, heating to 40-50 ℃, then dropwise adding (BOC) 2 O for reaction, and obtaining a solution A after the reaction is completed; (2) Adding solid alkali and polymerization inhibitor into the solution A, heating to 70-100 ℃, then dropwise adding 2, 4-dimethyl-3-pentene-2-amine, and obtaining solution B containing quaternary amine anti-aging agent after the reaction is completed; (3) And continuously introducing methyl bromide into the solution B to carry out methylation of the quaternary amine anti-aging agent, adding acid to neutralize and remove amino protecting groups after the reaction is finished, and then adding water to precipitate, filtering and washing to obtain the quinoline anti-aging agent.
  4. 4. The method according to claim 3, wherein in the step (1), the solvent is one of N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, and 1, 4-dioxane; In the step (1), the mass ratio of the 4-bromophenyl aniline or the bis (4-bromophenyl) amine to the solvent is 1:2-10.
  5. 5. The method according to claim 3, wherein in the step (1), the molar ratio of 4-bromophenyl aniline or bis (4-bromophenyl) amine to (BOC) 2 O is 1:0.5 to 0.6; The dropping time of (BOC) 2 O is 30-90 min.
  6. 6. The preparation method of claim 3, wherein in the step (2), the solid base is one of caustic soda flakes, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate, and the molar ratio of the solid base to the 4-bromophenylaniline or the bis (4-bromophenyl) amine is 2-5:1; The polymerization inhibitor is one of p-benzoquinone, hydroquinone, p-hydroxyanisole and 2-tertiary butyl hydroquinone, and the added mass of the polymerization inhibitor is 0.5% -2% of the mass of 4-bromophenylaniline or bis (4-bromophenyl) amine.
  7. 7. The preparation method according to claim 3, wherein in the step (2), the molar ratio of 2, 4-dimethyl-3-pentene-2-amine to 4-bromophenylaniline is 1-1.2:1, the dropping acceleration of 2, 4-dimethyl-3-pentene-2-amine is controlled to be 1-10 g/min, and in the step (3), the molar ratio of the introduced bromomethane to 4-bromophenylaniline is 1.1-1.5:1; Or in the step (2), the mol ratio of the 2, 4-dimethyl-3-pentene-2-amine to the bis (4-bromophenyl) amine is 2-2.2:1, and in the step (3), the mol ratio of the introduced bromomethane to the bis (4-bromophenyl) amine is 2.1-2.5:1.
  8. 8. The preparation method according to claim 3 or 7, wherein the introduction rate of methyl bromide is 3-10 ml/min.
  9. 9. The method according to claim 3, wherein in the step (3), a dilute acid is added to neutralize and remove the amino protecting group, the dilute acid being one of hydrochloric acid with a mass fraction of 10%, sulfuric acid with a mass fraction of 30%, formic acid and acetic acid.
  10. 10. The process according to claim 3, wherein in the step (3), a dilute acid is added for neutralization and deamination of the protecting group, and the dilute acid is added until the pH is maintained at 1 or less and the pH is maintained for not less than 30 minutes without change.

Description

Quinoline anti-aging agent and preparation method thereof Technical Field The invention relates to the technical field of fine chemical engineering, in particular to a quinoline anti-aging agent and a preparation method thereof. Background Many materials, such as plastics, elastomers, elastomeric articles (tires, belts, hoses, bushings, supports, shock absorbers, etc.), lubricants and petroleum products (such as hydraulic oils, fuels, and oil/fuel additives for automotive and aerospace applications) are susceptible to aging under prolonged exposure to light, heat, oxygen, ozone, repeated mechanical action, etc., while the use of antioxidants can prevent or retard the aging of such products. The addition of the anti-aging agent cannot have adverse effects on the performances of rubber products and the like, such as reduction of the mechanical properties of the products, and the service life of the products can be influenced if the mechanical properties are reduced, and the existing anti-aging agent is easy to have the problems of poor ozone protection effect and easy migration and discoloration in the use process. In addition, when the existing antioxidant RD is applied to rubber products, the scorch time is too long, the processing efficiency is affected, and the problem of further shortening is to be solved. Patent document CN104017122B discloses a high-performance quinoline anti-aging agent and a preparation method thereof, the anti-aging agent keeps the excellent thermal-oxidative aging resistance of the high-dimer-content anti-aging agent RD under dynamic and static conditions, simultaneously, the migration loss problem of dimers is relieved, and the service life of rubber products is prolonged. However, compared with the anti-aging agent RD, the tensile strength of the sizing material prepared by the quinoline anti-aging agent is slightly reduced. Disclosure of Invention In view of the above, the invention provides a quinoline anti-aging agent, a preparation method and application thereof, which not only have better ozone protection effect in the rubber field, but also improve the phenomenon that the anti-aging agent is easy to migrate and change color in rubber products. In order to achieve the above object, the present invention provides a quinoline anti-aging agent having the structural formula Or (b)。 A preparation method of a quinoline anti-aging agent comprises the following steps of reacting 2, 4-dimethyl-3-pentene-2-amine with 4-bromophenylaniline or bis (4-bromophenyl) amine with amino protected to obtain a quaternary amine anti-aging agent, carrying out methylation on the quaternary amine anti-aging agent, and removing an amino protecting group to obtain the quinoline anti-aging agent. Further, the specific preparation method of the quinoline anti-aging agent comprises the following steps: (1) Mixing 4-bromophenyl aniline or bis (4-bromophenyl) amine with a solvent, heating to 40-50 ℃, then dropwise adding di-tert-butyl dicarbonate ((BOC) 2 O) for reaction, and obtaining a solution A after the reaction is completed; (2) Adding solid alkali and polymerization inhibitor into the solution A, heating to 70-100 ℃, then dropwise adding 2, 4-dimethyl-3-pentene-2-amine (CAS: 64760-62-9), and obtaining solution B containing quaternary amine anti-aging agent after the reaction is completed; (3) And continuously introducing methyl bromide into the solution B to carry out methylation of the quaternary amine anti-aging agent, adding acid to neutralize and remove amino protecting groups after the reaction is finished, and then adding water to precipitate, filtering and washing to obtain the quinoline anti-aging agent. Further, in the step (1), the solvent is one of N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide (DMSO) and 1, 4-dioxane, and preferably, the solvent is dimethyl sulfoxide (DMSO). Further, in the step (1), the mass ratio of the 4-bromophenylaniline or the bis (4-bromophenyl) amine to the solvent is 1:2-10, for example, 1:2,1:3,1:4,1:5,1:6,1:7,1:8,1:9,1:10, and preferably, the mass ratio of the 4-bromophenylaniline or the bis (4-bromophenyl) amine to the solvent is 1:3-4. Further, in the step (1), the molar ratio of 4-bromophenylaniline or bis (4-bromophenyl) amine to (BOC) 2 O is 1:0.5-0.6, for example, 1:0.5,1:0.52,1:0.54,1:0.56,1:0.58,1:0.6, preferably, the molar ratio of 4-bromophenylaniline or bis (4-bromophenyl) amine to (BOC) 2 O is 1:0.5. Further, in the step (1), the dropping time of (BOC) 2 O is 30-90 min, for example 30min,35min,40min,45min,50min,55min,60min,65min,70min,75min,80min,85min,90min. Preferably, (BOC) 2 O is added dropwise for 50-60 min. Further, in step (1), heating is performed to 40-50 ℃, e.g. 40 ℃,45 ℃,50 ℃, preferably to 45 ℃. Further, in the step (2), the solid base is one of caustic soda flakes, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate, and preferably, the solid base is caustic soda flakes. Further, in th