Search

CN-121990952-A - Preparation method of sulfurized alkylphenol salt

CN121990952ACN 121990952 ACN121990952 ACN 121990952ACN-121990952-A

Abstract

The invention relates to a preparation method of sulfurized alkylphenol salt. The oxidation resistance of the obtained vulcanized alkylphenol salt is obviously improved, and the content of free phenol is reduced to below 2%.

Inventors

  • WANG QINGJING
  • KONG SHENG
  • GUO PENGFEI
  • GUO CHAO
  • ZHENG FEI

Assignees

  • 锦州康泰润滑油添加剂有限公司
  • 天津利安隆新材料股份有限公司

Dates

Publication Date
20260508
Application Date
20260130

Claims (10)

  1. 1. A method for preparing sulfurized alkylphenol salt, comprising the steps of: S1, adding C 8-16 alkylphenol, a diluting solvent, a first alkaline earth metal source, an accelerator, a phase transfer catalyst and a vulcanizing agent into a reactor, and performing a first reaction to obtain a first reaction product liquid; Wherein the phase transfer catalyst is a quaternary ammonium salt compound containing or consisting of quaternary ammonium cations and anions of the structure of the formula I, (R 1 )(R 2 ) 3 N + I is a kind of Wherein R 1 or R 2 are the same or different and are each independently selected from C 1-18 alkyl, said C 1-18 alkyl being optionally substituted by C 6-10 aryl.
  2. 2. The method according to claim 1, wherein, R 1 and R 2 are independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, wherein the methyl, ethyl, propyl, and butyl groups may be substituted with phenyl groups; preferably, R 1 is selected from methyl, ethyl, butyl, octyl, dodecyl or tetradecyl, wherein methyl and ethyl may be substituted by phenyl, R 2 is selected from methyl, ethyl, butyl; More preferably, R 1 is selected from methyl, ethyl, butyl, octyl, dodecyl, tetradecyl or benzyl, and/or The anions are selected from chloride, bromide, bisulfate, sulfate, phosphate, dihydrogen phosphate, acetate, formate, preferably from chloride, bromide, bisulfate.
  3. 3. The process according to claim 1, wherein the C 8-16 alkylphenol is selected from one or more of octylphenol, nonylphenol, decylphenol, dodecylphenol, tetradecylphenol and hexadecylphenol, preferably the C 8-16 alkylphenol is one or more of para-octylphenol, para-nonylphenol, para-decylphenol, para-dodecylphenol, para-tetradecylphenol or para-hexadecylphenol, and/or The diluent solvent is selected from one or more of mineral base oil, aliphatic hydrocarbon solvent, naphthene hydrocarbon solvent and aromatic hydrocarbon solvent, preferably 150N base oil, 6# base oil, 150SN base oil, one or more of N-hexane, N-heptane, cyclohexane, methylcyclohexane, isopar E, isopar G, toluene or xylene, more preferably 150N base oil, 6# base oil, 150SN base oil, and/or The first alkaline earth metal source is selected from one or more of calcium hydroxide, calcium oxide, magnesium hydroxide and magnesium oxide, and/or The promoter is one or more of water, C 1-6 fatty alcohol, C 2-6 fatty carboxylic acid, preferably one or more of water, methanol, ethanol, isopropanol, n-butanol, propylene glycol, glycerol, ethylene glycol, 1, 4-butanediol, acetic acid, propionic acid or 2-ethylhexanoic acid, more preferably propylene glycol, glycerol, ethylene glycol or 1, 4-butanediol, and/or The vulcanizing agent is a compound capable of providing active sulfur, preferably sulfur, and/or The phase transfer catalyst is selected from one or more of tetrabutylammonium bisulfate, tetrabutylammonium bromide, tetrabutylammonium chloride, benzyl triethyl ammonium chloride, trioctyl methyl ammonium chloride, dodecyl trimethyl ammonium chloride and tetradecyl trimethyl ammonium chloride.
  4. 4. The method according to claim 1, wherein, Based on 200 parts by mass of C 8-16 alkylphenol, The mass part of the diluting solvent is 150-250 parts, preferably 200 parts; The mass part of the first alkaline earth metal source is 40-60 parts, preferably 45-52 parts; 6-18 parts by weight of an accelerator, preferably 8-15 parts by weight; 3-18 parts by mass of a phase transfer catalyst, preferably 5-10 parts by mass; the vulcanizing agent is 20-60 parts by mass, preferably 30-40 parts by mass.
  5. 5. The method according to claim 1, wherein in step S1, the first reaction is performed by adding C 8-16 alkylphenol, a diluting solvent, a first alkaline earth metal source, an accelerator, a phase transfer catalyst, and a vulcanizing agent to the reactor and then heating the mixture; preferably, in step S1, the temperature is raised to 130-170 ℃, preferably to 140-160 ℃, more preferably to 140-150 ℃, and/or In the step S1, the reaction temperature is 130-170 ℃, preferably 140-160 ℃, more preferably 140-150 ℃, and the reaction time is 1-4 hours, preferably 1-3 hours, more preferably 2 hours.
  6. 6. The method of manufacturing according to claim 1, characterized in that the method of manufacturing further comprises: S2, adding a second alkaline earth metal source, a carbonating reagent and optional C 8-10 fatty alcohol into the first reaction product liquid, and performing a second reaction to obtain a second reaction product liquid; preferably, the base number of the sulfurized alkylphenol salt in step S2 is 50 to 350mgKOH/g, preferably 100 to 300mgKOH/g, more preferably 200 to 280mgKOH/g.
  7. 7. The method according to claim 6, wherein, The second alkali metal source is selected from one or more of calcium hydroxide, calcium oxide, magnesium hydroxide and magnesium oxide, and/or The first alkaline earth metal source and the second alkaline earth metal source being the same or different, and/or The C 8-10 fatty alcohol is selected from n-octanol, isooctanol, n-nonanol or n-decanol, preferably isooctanol, and/or The carbonation reagent is carbon dioxide.
  8. 8. The method according to claim 6, wherein, Based on 200 parts by mass of C 8-16 alkylphenol, 8-40 Parts by weight of C 8-10 fatty alcohol, preferably 10-20 parts by weight; The mass part of the second alkaline earth metal source is 40-80 parts, preferably 50-70 parts, and more preferably 56-64 parts; The mass portion of the carbonating agent is 10-40 portions, preferably 15-25 portions.
  9. 9. The method according to claim 6, wherein in step S2, the reaction time is 1 to 4 hours, preferably 1 to 3 hours, more preferably 2 hours, and the reaction temperature is 130 to 170 ℃, preferably 140 to 160 ℃, more preferably 140 to 150 ℃.
  10. 10. The process according to claim 6, wherein the reaction temperature in step S2 is the same as the reaction temperature in step S1, and/or In the step S2, after the reaction is finished, the solvent is removed, and the residue is removed by filtration, so that the vulcanized alkylphenol salt is obtained.

Description

Preparation method of sulfurized alkylphenol salt Technical Field The invention belongs to the field of lubricating oil additives, and particularly relates to a preparation method of sulfurized alkylphenol salt. Background Alkylphenol salts are one of the larger variety used in lubricating oil detergents and are used on a scale inferior to sulfonates. Sulfurized alkylphenoates have become the current mainstream detergent type due to their more comprehensive properties compared to conventional alkylphenoates. In particular, in supercharged diesel engine oil, the sulfurized alkylphenol salt shows excellent high-temperature detergency and has remarkable effect of inhibiting carbon deposition in the area of a piston top ring groove, so that the sulfurized alkylphenol salt is regarded as an indispensable key additive for the oil. The sulfurized alkylphenol salt is generally prepared by using alkylphenol such as dodecylphenol as a raw material, and reacting the sulfurized alkylphenol salt with an alkaline earth metal compound. The phenolic hydroxyl functional groups remain in the molecular structure, so that the product has certain internal oxidation resistance. This characteristic constitutes an important distinction between phenate detergents and sulfonates, which, although having good peptization dispersibility and alkali storage capacity, are relatively weak in oxidation resistance. Therefore, in the practical formula, the phenolate and the sulfonate are often compounded for use so as to synergistically improve the comprehensive performance of the oil product, and especially make up for the defect of the sulfonate in terms of antioxidation. Notably, dodecylphenol has been identified as having reproductive toxicity according to the global chemical universal classification and labeling system (GHS). During the synthesis of sulfurized alkylphenol salts, dodecylphenol is often difficult to convert completely, resulting in the presence of free phenol residues in the final product, subject to reaction equilibrium and process conditions. Industrial practice shows that the content of free phenol in the vulcanized alkylphenol salt prepared by the conventional process is generally higher than 4 weight percent, which not only brings potential health and environmental risks, but also can influence the storage stability and the service performance of the product. Therefore, how to effectively reduce the free phenol residue in the vulcanized alkylphenol salt product and further improve the oxidation resistance thereof has become an important direction of technical development in the field. Disclosure of Invention The invention aims to provide a preparation method of vulcanized alkylphenol salt, which can improve the oxidation resistance of the vulcanized alkylphenol salt and reduce the free phenol content in the vulcanized alkylphenol salt. The invention provides a preparation method of sulfurized alkylphenol salt, which comprises the following steps: S1, adding C 8-16 alkylphenol, a diluting solvent, a first alkaline earth metal source, an accelerator, a phase transfer catalyst and a vulcanizing agent into a reactor, and performing a first reaction to obtain a first reaction product liquid; Wherein the phase transfer catalyst is a quaternary ammonium salt compound containing or consisting of quaternary ammonium cations and anions of the structure of the formula I, (R1)(R2)3N+ I is a kind of Wherein R 1 or R 2 are the same or different and are each independently selected from C 1-18 alkyl, said C 1-18 alkyl being optionally substituted by C 6-10 aryl. In some embodiments, R 1 and R 2 are independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, wherein the methyl, ethyl, propyl, and butyl groups may be substituted with phenyl; preferably, R 1 is selected from methyl, ethyl, butyl, octyl, dodecyl or tetradecyl, wherein methyl and ethyl may be substituted by phenyl, R 2 is selected from methyl, ethyl, butyl; More preferably, R 1 is selected from methyl, ethyl, butyl, octyl, dodecyl, tetradecyl or benzyl, and/or The anions are selected from chloride, bromide, bisulfate, sulfate, phosphate, dihydrogen phosphate, acetate, formate, preferably from chloride, bromide, bisulfate. In some embodiments, the C 8-16 alkylphenol is selected from one or more of octylphenol, nonylphenol, decylphenol, dodecylphenol, tetradecylphenol, and hexadecylphenol, preferably the C 8-16 alkylphenol is one or more of para-octylphenol, para-nonylphenol, para-decylphenol, para-dodecylphenol, para-tetradecylphenol, or para-hexadecylphenol, and/or The diluent solvent is selected from one or more of mineral base oil, aliphatic hydrocarbon solvent, naphthene hydrocarbon solvent and aromatic hydrocarbon solvent, preferably 150N base oil, 6# base oil, 150SN base oil, one or more of N-hexane, N-heptane, cycloh