WO2020206754A1 - Procédé de préparation sans solvant d'un antioxydant par couplage oxydatif à haute température - Google Patents

Procédé de préparation sans solvant d'un antioxydant par couplage oxydatif à haute température Download PDF

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Publication number
WO2020206754A1
WO2020206754A1 PCT/CN2019/084407 CN2019084407W WO2020206754A1 WO 2020206754 A1 WO2020206754 A1 WO 2020206754A1 CN 2019084407 W CN2019084407 W CN 2019084407W WO 2020206754 A1 WO2020206754 A1 WO 2020206754A1
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Prior art keywords
reaction
solvent
oxidation
catalyst
temperature
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PCT/CN2019/084407
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English (en)
Chinese (zh)
Inventor
张健雄
王忠冬
熊畅
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Jiangsu Feiya Chemical Industry Co Ltd
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Jiangsu Feiya Chemical Industry Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
    • C07C211/55—Diphenylamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • 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
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M133/12—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to a carbon atom of a six-membered aromatic ring

Definitions

  • the invention belongs to the technical field of organic polymer compounds, and relates to a preparation method of an oxidation coupling high temperature antioxidant.
  • amine antioxidants are the earliest and most widely used antioxidants in the field of lubricants. Among them, there are mainly para-phenylenediamine antioxidants, diphenylamine antioxidants, aniline antioxidants, naphthalene Amine antioxidants, etc. Except for a few polymeric phenolic antioxidants, amine antioxidants have stronger stability in oils and can be used at higher temperatures, especially alkylated diphenylamine antioxidants, which can be applied to minerals Among the base oils, it is used as a general-purpose internal combustion engine oil, and can also be used in lipid synthetic oils as aero engine lubricants. In recent years, as people's research on the antioxidant mechanism of oil products has become more and more in-depth, various new antioxidants have been continuously developed, which has greatly improved the efficiency of oil products.
  • U.S. Patent No. 3573206 discloses a low-crossing polymer formed by the polymerization of diphenylamine (DPA) and N-phenyl ⁇ -methylnaphthylamine (PNA).
  • DPA diphenylamine
  • PNA N-phenyl ⁇ -methylnaphthylamine
  • the yield of the polymer is low and contains a large amount of Unreacted DPA and PNA.
  • DPA diphenylamine
  • PNA N-phenyl ⁇ -methylnaphthylamine
  • RHY533 developed by the Lanzhou Lubricant Research Center of PetroChina and Vanlube9317 produced by R.T.Vanderbilt Company of the United States are all the oxidation coupling products of this kind of amine antioxidant, and the yield is low.
  • US Pat. No. 6,204,412 discloses a method for preparing alkylated diphenylamine polymers.
  • the method includes the alkylation reaction of unsubstituted diphenylamine with a variety of olefins to produce alkylated diphenylamine and other amines.
  • Antioxidants polymerize to form an alkylated diphenylamine composition, and the oxidative coupling agent used is formamide peroxide.
  • U.S. Pat. No. 2008045425 provides antioxidants for industrial, automotive and aviation lubricants and their preparation methods. It is formed as an alkylated diphenylamine and alkylated naphthylamine under the action of a metal catalyst.
  • the metal catalyst is a combination of cations and organic anions, such as metal acetylacetonate. This reaction occurs in the presence of oxygen, thereby forming an antioxidant comprising the alkylated diphenylamine and the oligomer of the alkylated naphthylamine and the metal component of the catalyst.
  • Chinese patent CN.101348720A provides a composite amine antioxidant, which contains at least the following two substances: (1) alkylated diphenylamine; (2) alkylated N-phenyl- ⁇ -naphthylamine.
  • the composite amine antioxidant is prepared by adding diisobutylene to the mixture of diphenylamine and N-phenyl- ⁇ -naphthylamine in the presence of an acid catalyst to carry out alkylation reaction.
  • the amine antioxidant provided by the invention has good oil-soluble properties and antioxidant properties, and can be widely used in various lubricating oils.
  • the antioxidant in this patent is prepared by the addition reaction of two amine compounds using the same catalyst and the same olefin. The two amine compounds have different structures and different reaction temperatures from olefins. The product composition obtained by this reaction is more complex, and Product stability is poor.
  • Chinese patent CN.105733740A provides an amine oligomer antioxidant.
  • This patented antioxidant is synthesized from alkylated diphenylamine compounds and N-phenyl- ⁇ -naphthylamine compounds in organic solvents using a variety of oxidation coupling catalysts.
  • This patent uses organic plus inorganic composite catalysts to react with good reaction effects. The reaction is mild and the product coupling is high. However, this method uses a low flash point organic solvent. To avoid risks, the reaction temperature is low, the reaction time is long, and the solvent needs to be distilled off for post-processing.
  • the catalyst used in this method is an organic-inorganic hybrid catalyst. The catalyst has strong acidity and complex components, and a large amount of water is required to remove the residual acidic catalyst, and the three wastes generated during the production process are relatively large.
  • the purpose of the present invention is to provide a more reasonable and efficient preparation method for amine oxidation coupled high-temperature antioxidants, which overcomes the existing complex reaction conditions, long reaction time, low product yield, low polymerization degree and stable product Poor performance, difficulty in post-processing and other defects.
  • the solvent-free preparation method of an oxidation-coupled high-temperature antioxidant of the present invention has the following specific preparation steps:
  • reaction temperature is 80 ⁇ 160°C, the oxidation coupling catalyst is added, and the reaction is 3 ⁇ 10h;
  • the oxidation coupling catalyst is at least one of dialkyl peroxides, peroxy lipids, and diacyl peroxides.
  • the oxidation coupling catalyst is di-tert-butyl peroxide.
  • the oxidation coupling catalyst used in the reaction process is one kind, and the molar ratio of the oxidation coupling catalyst to the alkyl diphenylamine compound is 1:0.2-1.
  • the reaction vacuum degree is 200-300 mmHG column.
  • the reaction temperature is 120-140°C.
  • the temperature of the removal catalyst is 170-180°C.
  • the preparation method of the present invention adopts the direct melting reaction of raw materials, the oxidation coupling catalyst itself plays a dual role of reaction solvent and catalysis, no additional organic solvent is needed, the materials are uniformly mixed, the reaction conditions are mild, and the reaction effect is good.
  • the catalyst component used in the method of the present invention is single, and a single-component alcohol is produced after the reaction is consumed, which is quickly separated from the reactant under negative pressure and can be sold separately as a product.
  • the post-treatment of the product is simpler and has less three wastes.
  • the catalyst is stable, the reaction temperature is relatively high, and the reaction time is short, which can effectively improve production efficiency.
  • Figure 1 is a mass spectrum of Example 2 of the present invention.
  • a solvent-free preparation method of an oxidation-coupled high-temperature antioxidant of the present invention the preparation steps of the method are as follows:
  • reaction temperature is 80 ⁇ 160°C, the oxidation coupling catalyst is added, and the reaction is 3 ⁇ 10h;
  • the initial thermal decomposition temperature of the products of Examples 1 to 6 is higher than that of alkyl diphenylamine, N-phenyl- ⁇ -methylnaphthylamine, and alkylated N-phenyl ⁇ -methylnaphthylamine
  • the initial thermal decomposition temperature is 20-50°C higher, and the products of Examples 2 and 5 have the best effect.
  • the base oil uses pentaerythritol esters
  • the product of the invention has a higher degree of oxidation coupling, a higher thermal decomposition temperature, and a more stable product, which is suitable for various special high-temperature lubricating oil products.
  • the preparation method of this patent is cleaner and simpler. There is no need to add a large amount of organic solvents during cleaning.
  • the reaction by-products are single and recyclable.
  • the reaction temperature is high.
  • the reaction time is short.
  • the catalyst does not contain inorganic acid.
  • the liquid does not need a large amount of water to wash, it has little damage to the equipment, and has less three wastes.
  • the oxidation-coupled high-temperature antioxidant prepared by the method of the present invention is a polymer mixture of amine antioxidants, and its product is different from the prior art oligomeric coupling AB, and is mostly dimer.
  • the oxidation-coupled high-temperature antioxidant prepared by the method of the present invention has more excellent results reflected in thermal stability, has a higher thermal decomposition temperature, and is higher than the thermal decomposition temperature of the existing oligomeric coupling antioxidant by more than 10°C.
  • the method of the present invention uses N-phenyl- ⁇ -naphthylamine compounds (PNA) and alkylated diphenylamine compounds (ODPA) to couple into an amine polymer under the action of an oxidation coupling catalyst, and the polymer side reaction
  • PNA N-phenyl- ⁇ -naphthylamine compounds
  • ODPA alkylated diphenylamine compounds
  • the product has low content and high effective ingredients. It is suitable for various base oils and has excellent high temperature oxidation resistance, especially suitable for aviation lubricants and high temperature special industrial oils.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Lubricants (AREA)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de préparation sans solvant d'un antioxydant par couplage oxydatif à haute température, les étapes de préparation spécifiques étant les suivantes consistant à : ajouter du N-phényl-α-méthylnaphtylamine ou du N-phényl-α-méthylnaphtylamine alkylée et d'un composé de diphénylamine alkylée à un récipient de réaction, le rapport molaire correspondant étant de 1 : 0,2 à 4,0 ; établir un vide, chauffer à 80-160 °C pour faire fondre les matériaux, et démarrer l'agitation ; à une température de réaction de 80-160 °C, ajouter un catalyseur de couplage oxydatif, et faire réagir pendant 3 à 10 h ; après achèvement de la réaction, établir lentement un vide jusqu'à 2 mmHg, chauffer à 160-200 °C, et retirer le catalyseur de façon à obtenir un produit solide jaune-brun. Le procédé de préparation selon l'invention utilise une réaction de fusion directe de matières premières, et un catalyseur de couplage oxydatif joue les deux rôles d'un solvant de réaction et d'un catalyseur, aucun solvant organique supplémentaire n'étant nécessaire ; les matériaux sont mélangés uniformément, les conditions de réaction sont modérées, et l'effet de réaction est bon.
PCT/CN2019/084407 2019-04-12 2019-04-25 Procédé de préparation sans solvant d'un antioxydant par couplage oxydatif à haute température Ceased WO2020206754A1 (fr)

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CN201910291587.9A CN109942435B (zh) 2019-04-12 2019-04-12 一种氧化耦合高温抗氧剂无溶剂制备方法
CN201910291587.9 2019-04-12

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3114816B1 (fr) * 2020-10-06 2022-10-21 Nyco Procédé continu de polymérisation ou d’oligomérisation de diphénylamines
CN114426901A (zh) * 2022-01-21 2022-05-03 中国石油化工股份有限公司 一种高温抗氧剂溶液及其制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5489711A (en) * 1994-12-20 1996-02-06 The B. F. Goodrich Company Synthetic lubricant antioxidant from monosubstituted diphenylamines
CN105733740A (zh) * 2014-12-08 2016-07-06 中国石油天然气股份有限公司 一种胺类低聚物抗氧剂及其制备方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5489711A (en) * 1994-12-20 1996-02-06 The B. F. Goodrich Company Synthetic lubricant antioxidant from monosubstituted diphenylamines
CN105733740A (zh) * 2014-12-08 2016-07-06 中国石油天然气股份有限公司 一种胺类低聚物抗氧剂及其制备方法

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CN109942435A (zh) 2019-06-28

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