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CN-117800883-B - Dicyclopentanyl mercapto hydrogenated bisphenol antioxidant, and preparation method and application thereof

CN117800883BCN 117800883 BCN117800883 BCN 117800883BCN-117800883-B

Abstract

The invention discloses a dicyclopentadienyl mercapto-hydrogenated bisphenol antioxidant, a preparation method and application thereof, wherein the structural formula of the dicyclopentadienyl mercapto-hydrogenated bisphenol antioxidant is shown as formula I: Wherein R 1 、R 2 is independently selected from one of hydrogen, alkyl, amino, hydroxyl and ester. The modifier and replaceability of the side group of the dicyclopentadienyl mercapto hydrogenated bisphenol antioxidant greatly enriches the variety of the phenol antioxidant, and provides a new idea for the design and preparation of high-efficiency phenol antioxidants. In addition, the dicyclopentadienyl mercapto hydrogenated bisphenol antioxidant has long-acting antioxidation capability and aging resistance.

Inventors

  • LIU MIN
  • ZHAO ZHIQUAN
  • Wei Dingjun
  • YU XI
  • SHI ZHIWEN
  • WANG DONGXIN
  • WANG BAOLONG

Assignees

  • 本源精化环保科技有限公司

Dates

Publication Date
20260512
Application Date
20231226

Claims (10)

  1. 1. The dicyclopentadienyl mercapto-hydrogenated bisphenol antioxidant is characterized in that the structural formula of the dicyclopentadienyl mercapto-hydrogenated bisphenol antioxidant is shown as formula I: Wherein R 1 、R 2 is independently selected from one of hydrogen, alkyl, amino, hydroxyl and ester.
  2. 2. A process for the preparation of the dicyclopentane mercapto-hydrogenated bisphenol antioxidant of claim 1, comprising the steps of: carrying out nucleophilic addition reaction on hydrogenated bisphenol A shown in a formula II and 3- (2-bromoethyl) -2, 5-disubstituted cyclopentane-1-thiol shown in a formula III, and purifying to obtain a dicyclopentanyl mercapto hydrogenated bisphenol antioxidant shown in a formula I, wherein R 1 、R 2 in the formula III is independently selected from one of hydrogen, alkyl, amino, hydroxyl and ester; The reaction scheme is as follows:
  3. 3. The method for preparing the dicyclopentadienyl mercapto-hydrogenated bisphenol antioxidant according to claim 2, wherein the step of subjecting hydrogenated bisphenol a shown in formula II and 3- (2-bromoethyl) -2, 5-disubstituted cyclopentane-1-thiol shown in formula III to nucleophilic addition reaction and purifying to obtain the dicyclopentadienyl mercapto-hydrogenated bisphenol antioxidant shown in formula I specifically comprises the following steps: Mixing hydrogenated bisphenol A shown in a formula II, 3- (2-bromoethyl) -2, 5-disubstituted cyclopentane-1-thiol shown in a formula III, a first solvent and a catalyst, and reacting for 2-12 h at 60-120 ℃; And after the reaction is finished, adding a second solvent for crystallization, filtering, washing the obtained filter cake with the second solvent, and finally, vacuum drying the washed filter cake at the temperature of 60-100 ℃ to obtain the dicyclopentadienyl mercapto hydrogenated bisphenol antioxidant shown in the formula I.
  4. 4. The method for producing a dicyclopentane mercapto-hydrogenated bisphenol antioxidant according to claim 2, wherein the equivalent ratio of hydrogenated bisphenol a to 3- (2-bromoethyl) -2, 5-disubstituted cyclopentane-1-thiol is 1 (2 to 4).
  5. 5. The method for producing a dicyclopentane mercapto-hydrogenated bisphenol antioxidant according to claim 3, wherein the ratio of the volume of the first solvent to the sum of the mass of the hydrogenated bisphenol A and 3- (2-bromoethyl) -2, 5-disubstituted cyclopentane-1-thiol is (2 to 10) mL/1 g.
  6. 6. The method for producing a dicyclopentane mercapto-hydrogenated bisphenol antioxidant according to claim 3, wherein the molar ratio of the catalyst to hydrogenated bisphenol A is 1.3 to 5:1.
  7. 7. The method for producing a dicyclopentane mercapto-hydrogenated bisphenol antioxidant according to claim 3, wherein the amount of the second solvent is 20% to 150% by volume of the amount of the first solvent.
  8. 8. The method for producing a dicyclopentane mercapto-hydrogenated bisphenol antioxidant according to claim 3, wherein the first solvent is one or more selected from toluene, xylene, solvent oil, chlorobenzene, dimethylsulfoxide, N-dimethylformamide, acetonitrile, tetrahydrofuran and 1, 2-dichloroethane, and the second solvent is one or more selected from isopropanol, t-butanol, isobutanol, acetonitrile, dioxane, ethylene glycol dimethyl ether and methyl t-butyl ether.
  9. 9. The method for producing a dicyclopentane mercapto-hydrogenated bisphenol antioxidant according to claim 3, wherein the catalyst is one or more selected from the group consisting of potassium carbonate, cesium carbonate, sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate and sodium hydrogencarbonate.
  10. 10. Use of the dicyclopentadienyl mercapto-hydrogenated bisphenol antioxidant according to claim 1 or the dicyclopentanyl mercapto-hydrogenated bisphenol antioxidant prepared by the preparation method according to any one of claims 2 to 9 in a polymer material.

Description

Dicyclopentanyl mercapto hydrogenated bisphenol antioxidant, and preparation method and application thereof Technical Field The invention relates to the technical field of organic synthesis and high polymer materials, in particular to a dicyclopentadienyl mercapto hydrogenated bisphenol antioxidant, and a preparation method and application thereof. Background The polymer material has the characteristics of high performance, easy modification, light weight and the like, and becomes an indispensable material in the production and life of people. However, the polymer material can be oxidized and aged in the processing, storage and use processes, and the method for delaying the oxidization of the polymer material is more, so that the method for adding the antioxidant is simple and effective. Amine antioxidants are the earliest antioxidants used and developed most rapidly in high molecular material antioxidants, but the application of the amine antioxidants is limited due to the problems of pollution to the color of products and high toxicity of partial varieties, so that the amine antioxidants are gradually replaced by light-colored low-toxicity phenol antioxidants. However, phenolic antioxidants have inferior oxidation resistance compared to aminic antioxidants, and thus further improvement of their oxidation resistance is required. Disclosure of Invention In view of the defects in the prior art, the invention provides a dicyclopentanyl mercapto hydrogenated bisphenol antioxidant, and a preparation method and application thereof, so as to solve the problem that the oxidation resistance of the existing phenol antioxidant can not meet the requirements. The technical scheme adopted by the invention for solving the technical problems is as follows: In a first aspect of the present invention, there is provided a dicyclopentadienyl mercapto-hydrogenated bisphenol antioxidant having the structural formula shown in formula I: Wherein R 1、R2 is independently selected from one of hydrogen, alkyl, amino, hydroxyl and ester. In a second aspect of the present invention, there is provided a method for preparing the above-mentioned dicyclopentadienyl mercapto-hydrogenated bisphenol antioxidant, the method comprising the steps of: carrying out nucleophilic addition reaction on hydrogenated bisphenol A shown in a formula II and 3- (2-bromoethyl) -2, 5-disubstituted cyclopentane-1-thiol shown in a formula III, and purifying to obtain a dicyclopentanyl mercapto hydrogenated bisphenol antioxidant shown in a formula I, wherein R 1、R2 in the formula III is independently selected from one of hydrogen, alkyl, amino, hydroxyl and ester; The reaction scheme is as follows: Preferably, the step of subjecting hydrogenated bisphenol A shown in formula II and 3- (2-bromoethyl) -2, 5-disubstituted cyclopentane-1-thiol shown in formula III to nucleophilic addition reaction and purifying to obtain dicyclopentanyl mercapto hydrogenated bisphenol antioxidant shown in formula I specifically comprises the following steps: Mixing hydrogenated bisphenol A shown in a formula II, 3- (2-bromoethyl) -2, 5-disubstituted cyclopentane-1-thiol shown in a formula III, a first solvent and a catalyst, and reacting for 2-12 h at 60-120 ℃; And after the reaction is finished, adding a second solvent for crystallization, filtering, washing the obtained filter cake with the second solvent, and finally, vacuum drying the washed filter cake at the temperature of 60-100 ℃ to obtain the dicyclopentadienyl mercapto hydrogenated bisphenol antioxidant shown in the formula I. Preferably, the equivalent ratio of the hydrogenated bisphenol A to the 3- (2-bromoethyl) -2, 5-disubstituted cyclopentane-1-thiol is 1 (2-4). Preferably, the ratio of the volume of the first solvent to the mass sum of the hydrogenated bisphenol A and the 3- (2-bromoethyl) -2, 5-disubstituted cyclopentane-1-thiol is (2-10) mL to 1g. Preferably, the molar ratio of the catalyst to the hydrogenated bisphenol A is (1.3-5): 1. Preferably, the second solvent is used in an amount of 20% -150% by volume of the first solvent. Preferably, the first solvent is selected from one or more of toluene, xylene, solvent oil, chlorobenzene, dimethylsulfoxide, N-dimethylformamide, acetonitrile, tetrahydrofuran or 1, 2-dichloroethane, and the second solvent is selected from one or more of isopropanol, tert-butanol, isobutanol, acetonitrile, dioxane, ethylene glycol dimethyl ether or methyl tert-butyl ether. Preferably, the catalyst is selected from one or more of potassium carbonate, cesium carbonate, sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate and sodium bicarbonate. Preferably, the dicyclopentadienyl mercapto hydrogenated bisphenol antioxidant or the dicyclopentadienyl mercapto hydrogenated bisphenol antioxidant prepared by the preparation method is applied to high polymer materials. The beneficial effects are that: The invention discloses a dicyclopentanyl mercapto hydrogenated bisphenol ant