WO2024146158A1 - Procédé de préparation d'antioxydant 3052 - Google Patents

Procédé de préparation d'antioxydant 3052 Download PDF

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Publication number
WO2024146158A1
WO2024146158A1 PCT/CN2023/117360 CN2023117360W WO2024146158A1 WO 2024146158 A1 WO2024146158 A1 WO 2024146158A1 CN 2023117360 W CN2023117360 W CN 2023117360W WO 2024146158 A1 WO2024146158 A1 WO 2024146158A1
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WO
WIPO (PCT)
Prior art keywords
antioxidant
reaction
tert
methylphenol
butyl
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PCT/CN2023/117360
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English (en)
Chinese (zh)
Inventor
石慧敏
唐赟
张秀秀
吴春业
王轲
Original Assignee
安徽新秀化学股份有限公司
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Publication of WO2024146158A1 publication Critical patent/WO2024146158A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/29—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of oxygen-containing functional groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds

Definitions

  • step S2 After the reaction of step S1 is completed, methylal and a catalyst are added to the reactor of step S1 under nitrogen protection, and 2-tert-butyl-4-methylphenol is slowly added dropwise to the reactor under stirring conditions for reflux reaction. After the reaction is completed, the antioxidant 3052 product is obtained through post-treatment.
  • step S2 the molar ratio of 2-tert-butyl-4-methylphenol to methylal in step S2 is 1:(2-3);
  • the entire preparation process does not require high temperature and high pressure conditions, the reaction process conditions are mild, the post-treatment is simple, and the operation cost is low.
  • the preparation method of the present invention can obtain a high-yield antioxidant 3052 product.
  • the solvent is any one of toluene and high-boiling-point petroleum ether or a mixture of the two.
  • the high-boiling-point petroleum ether is petroleum ether with a boiling point of 90°C-120°C.
  • step S1 the molar ratio of 2-tert-butyl-4-methylphenol to acrylic anhydride is: (1-1.1): 1;
  • the molar ratio of 2-tert-butyl-4-methylphenol in step S2 to 2-tert-butyl-4-methylphenol in step S1 is 1:1;
  • step S2 Under nitrogen protection, add methylal (1.1 mol 83.6 g), concentrated sulfuric acid (2.5 g) and titanium dioxide SO 4 2- /TiO 2 solid acid catalyst (2.5 g) into the reactor of step S1. Under stirring, slowly add 2-tert-butyl-4-methylphenol (0.55 mol 90.2 g) dropwise into the reactor. During the reaction, the liquid phase tracks the progress of the reaction. The reaction is kept warm for 3 hours. After the reaction is completed, the solid acid catalyst is separated by filtration. The solvent is then removed by distillation under reduced pressure to obtain a molten material. The molten material is recrystallized with ethanol and dried to obtain an antioxidant 3052 product. The purity of the antioxidant 3052 product is 99.3% and the yield is 86.5% as determined by liquid phase.
  • step S2 Under nitrogen protection, add methylal (1.05mol 79.8g), concentrated sulfuric acid (4.3g) and titanium dioxide SO42- / TiO2 solid acid catalyst (4.3g) into the reactor of step S1. Under stirring, slowly add 2-tert-butyl-4-methylphenol (0.525mol 86.1g) dropwise into the reactor. During the reaction, the liquid phase tracks the progress of the reaction. The reaction is kept warm for 2.5h. After the reaction is completed, the solid acid catalyst is separated by filtration. The solvent is then removed by distillation under reduced pressure to obtain a molten material. The molten material is recrystallized with methanol and dried to obtain an antioxidant 3052 product. The purity of the antioxidant 3052 product is 78.6% and the yield is 35.2% as determined by liquid phase.
  • the antioxidant 3052 product was prepared by the same method as in Example 1, except that concentrated sulfuric acid was not added in step S2.
  • the final antioxidant 3052 product has a purity of 83.2% and a yield of 50.2%.
  • step S2 From the comparison of the experimental data of Comparative Example 3 and Example 1, it can be seen that no more concentrated sulfuric acid is added in step S2, which will lead to a decrease in product yield, because in step S2, concentrated sulfuric acid can provide an acidic environment, which is more conducive to the catalytic reaction.
  • the antioxidant 3052 product was prepared by the same method as in Example 1, except that the amount of methylal added in step S2 was 39.9 g (0.525 mol).
  • the final antioxidant 3052 product had a purity of 96.1% and a yield of 58.9%.
  • step S2 reducing the amount of methylal added in step S2 will cause the purity and yield of the product to decrease.
  • Methylal plays the role of a bridging agent in the reaction, and the presence of methylal is conducive to the smooth progress of the reaction. If the amount of methylal is reduced, the reaction yield will be significantly reduced. However, if methylal is excessive, resulting in a reaction residue, methylal will be removed from the system in the vacuum distillation of the post-treatment, which will not affect the purity of the final product.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention relève du domaine technique de la synthèse organique, et concerne en particulier un procédé de préparation d'un antioxydant 3052. Le procédé de préparation comprend les étapes suivantes : S1, qui consiste à ajouter, sous une protection d'azote, du 2-tert-butyl-4-méthylphénol, un solvant et un catalyseur acide à un réacteur, faire chauffer et agiter le mélange, puis ajouter lentement un anhydride acrylique goutte à goutte au réacteur, et après achèvement de l'addition, soumettre le mélange à une réaction de conservation de chaleur; et S2, qui consiste à ajouter, après la fin de la réaction de l'étape S1, du méthylal et un catalyseur au réacteur de l'étape S1, ajouter lentement du 2-tert-butyl-4-méthylphénol goutte à goutte au réacteur dans une condition d'agitation, soumettre le mélange à une réaction de reflux, et après achèvement de la réaction, soumettre le produit de réaction à un post-traitement pour obtenir un produit antioxydant 3052. L'utilisation de matières premières irritantes et dangereuses telles que le chlorure d'acyle peut être évitée dans le procédé de préparation ; en outre, aucun sel organique n'est généré pendant le procédé de préparation, ce qui permet d'éviter la génération de déchets solides, de telle sorte que le procédé de préparation est plus respectueux de l'environnement et mieux approprié pour une utilisation industrielle.
PCT/CN2023/117360 2023-01-05 2023-09-07 Procédé de préparation d'antioxydant 3052 WO2024146158A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202310013379.9 2023-01-05
CN202310013379.9A CN116217390B (zh) 2023-01-05 2023-01-05 一种抗氧剂3052的制备方法

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WO2024146158A1 true WO2024146158A1 (fr) 2024-07-11

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WO (1) WO2024146158A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116217390B (zh) * 2023-01-05 2024-04-19 安徽新秀化学股份有限公司 一种抗氧剂3052的制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5214193A (en) * 1991-02-18 1993-05-25 Sumitomo Chemical Company, Limited Production of bisphenol monoester
CN101693662A (zh) * 2009-10-14 2010-04-14 山西万化科技有限公司 一种双酚单丙烯酸酯类耐热稳定剂的制备方法
CN105523899A (zh) * 2015-07-06 2016-04-27 中国科学院宁波材料技术与工程研究所 一种双酚类化合物抗氧剂的清洁生产方法及应用
CN116217390A (zh) * 2023-01-05 2023-06-06 安徽新秀化学股份有限公司 一种抗氧剂3052的制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5214193A (en) * 1991-02-18 1993-05-25 Sumitomo Chemical Company, Limited Production of bisphenol monoester
CN101693662A (zh) * 2009-10-14 2010-04-14 山西万化科技有限公司 一种双酚单丙烯酸酯类耐热稳定剂的制备方法
CN105523899A (zh) * 2015-07-06 2016-04-27 中国科学院宁波材料技术与工程研究所 一种双酚类化合物抗氧剂的清洁生产方法及应用
CN116217390A (zh) * 2023-01-05 2023-06-06 安徽新秀化学股份有限公司 一种抗氧剂3052的制备方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JUN-LIN GUO, TONG XI-WAN, ;XIN MING, YU LI-YING, NING BO: "Synthesis of Antioxidant 3052 by Multi-component One-pot Reaction", SULIAO KEJI - PLASTICS SCIENCE AND TECHNOLOGY, DALIAN SULIAO YANJIUSUO, DALIAN, CN, vol. 48, no. 4, 27 March 2020 (2020-03-27), CN , pages 99 - 102, XP093189466, ISSN: 1005-3360, DOI: 10.15925/j.cnki.issn1005-3360.2020.04.025 *
TIAN-YONG ZHANG, CHI LI-FENG, XIA WEN-JUAN, CHAI YI, ZHANG YOU-LAN: "Synthesis of Antioxidant 2246", CHEMICAL INDUSTRY AND ENGINEERING, vol. 26, no. 1, 15 January 2009 (2009-01-15), pages 19 - 22, XP093189464 *

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CN116217390A (zh) 2023-06-06
CN116217390B (zh) 2024-04-19

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