CN111100157B - Silole derivative, preparation method and application thereof, and lubricating grease - Google Patents

Silole derivative, preparation method and application thereof, and lubricating grease Download PDF

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CN111100157B
CN111100157B CN201811268014.6A CN201811268014A CN111100157B CN 111100157 B CN111100157 B CN 111100157B CN 201811268014 A CN201811268014 A CN 201811268014A CN 111100157 B CN111100157 B CN 111100157B
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formula
compound
silole derivative
hydrogen
grease
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CN111100157A (en
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刘欣阳
庄敏阳
魏克成
郑会
何懿峰
孙洪伟
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/0805—Compounds with Si-C or Si-Si linkages comprising only Si, C or H atoms
    • C07F7/0807—Compounds with Si-C or Si-Si linkages comprising only Si, C or H atoms comprising Si as a ring atom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • 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
    • C10M139/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00
    • C10M139/04—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00 having a silicon-to-carbon bond, e.g. silanes
    • 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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/06—Mixtures of thickeners and additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1096—Heterocyclic compounds characterised by ligands containing other heteroatoms
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions used as base material
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/128—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof
    • C10M2207/1285—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof used as thickening agents
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type compounds
    • C10M2219/068—Thiocarbamate metal salts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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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)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Lubricants (AREA)

Abstract

The invention provides a silole derivative, a preparation method and application thereof, and lubricating grease containing the silole derivative. The silole derivative has a structure shown in a formula (I):

Description

Silole derivative, preparation method and application thereof, and lubricating grease
Technical Field
The invention relates to a silole derivative, in particular to a silole derivative with a luminescent property.
Background
Traditional organic chromophores generally have strong luminescence at low concentrations, and weak or even no luminescence at high concentrations or in solid states, exhibiting an aggregate fluorescence quenching effect. This is because in the aggregate state, the strong intermolecular interactions lead to an enhancement of the non-radiative decay process of the excited state, with a significant decrease in fluorescence quantum yield. In the practical application process, the practical application of the organic light-emitting material is limited to a great extent by the aggregate fluorescence quenching effect. In recent years, research shows that some compounds show the opposite properties to the traditional organic luminescent compounds, not only do not have aggregation fluorescence quenching effect, but also show Aggregation Induced Emission (AIE) properties, and the appearance of the aggregation induced emission compounds provides a new solution for the application of organic luminescent materials in a solid state or at high concentration. Silole is a typical AIE compound, and in recent decades, researchers have applied it to a variety of research fields, such as light emitting devices, fluorescent probes, and bio-imaging.
The lubricating grease is a solid to semi-fluid product prepared by dispersing a thickening agent in a liquid lubricant, has the functions of lubrication, protection and sealing, and plays a vital role in industrial machinery, agricultural machinery, the transportation industry, the aerospace industry, the electronic information industry and various military equipment. Under some dark working conditions, the monitoring of the lubricating grease has great difficulty. At present, the related report of the luminescent grease is rarely seen.
Disclosure of Invention
The invention provides a silole derivative, a preparation method and application thereof, and lubricating grease containing the silole derivative.
The silole derivative has a structure shown in a formula (I):
Figure BDA0001845343240000011
wherein each R is0Are the same or different from each other and are each independently selected from hydrogen and C1-6Straight or branched chain hydrocarbon radicals (preferably hydrogen, C)1-4A linear or branched alkyl group), each x is independently selected from an integer between 0 and 5; each R is1Each independently selected from hydrogen and C1-6Straight or branched chain hydrocarbon radicals (preferably hydrogen, C)1-4A straight chain or branched alkyl group), each y is independently selected from an integer between 0 and 4, and z is selected from an integer between 0 and 3; r2Selected from hydrogen, C1-6Straight or branched chain hydrocarbon radicals (preferably hydrogen, C)1-4Straight or branched chainA chain alkyl group).
The silole derivative of the present invention may be a silole derivative having the following structure.
Figure BDA0001845343240000021
The method for producing a silole derivative of the present invention comprises the step of reacting a silole derivative represented by formula (II), a compound represented by formula (III), and a compound represented by formula (IV);
Figure BDA0001845343240000022
wherein each R is0Are the same or different from each other and are each independently selected from hydrogen and C1-6Straight or branched chain hydrocarbon radicals (preferably hydrogen, C)1-4A linear or branched alkyl group), each x is independently selected from an integer between 0 and 5; each R is1Each independently selected from hydrogen and C1-6Straight or branched chain hydrocarbon radicals (preferably hydrogen, C)1-4A straight chain or branched alkyl group), each y is independently selected from an integer between 0 and 4, and z is selected from an integer between 0 and 3; r2Selected from hydrogen, C1-6Straight or branched chain hydrocarbon radicals (preferably hydrogen, C)1-4Straight or branched chain alkyl).
According to the preparation method of the present invention, the molar ratio between the silole derivative represented by formula (II), the compound represented by formula (III), and the compound represented by formula (IV) is preferably 1: 0.5-5: 0.5 to 5, most preferably 1: 0.8-1.2: 0.8 to 1.2.
According to the preparation method of the invention, the temperature of the reaction among the silole derivative shown in the formula (II), the compound shown in the formula (III) and the compound shown in the formula (IV) is preferably 0-50 ℃, and preferably 15-35 ℃.
According to the production method of the present invention, it is generally preferable that the reaction time of the silole derivative represented by formula (II), the compound represented by formula (III) and the compound represented by formula (IV) is as long as possible, and it is generally 6 to 96 hours, preferably 12 to 72 hours.
Preparation method according to the inventionIn the method, a solvent may be added or may not be added, preferably a solvent is added in the reaction between the silole derivative represented by the formula (II), the compound represented by the formula (III) and the compound represented by the formula (IV). The solvent is preferably C1～C10For example, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, tetrahydrofuran, dimethylsulfoxide, most preferably C1～C10The mixed solvent of the organic amine and the furan (the volume ratio of the organic amine to the furan is preferably 1: 0.1-10) or dimethyl sulfoxide. The solvent may be removed by a method known in the art after the completion of the reaction, and the removal method is not particularly limited, and includes a method of distillation, evaporation, and column chromatography. Preferably, the silole derivative of the present invention is isolated and purified by column chromatography, and methyl chloride, petroleum ether and C can be used1～C6One or more of alcohols as an eluent. The methyl chloride may be one or more of methyl chloride, methylene chloride, chloroform, and tetrachloromethane.
According to the preparation method of the present invention, a catalyst may or may not be added, preferably a catalyst is added in the reaction of the silole derivative represented by formula (II), the compound represented by formula (III) and the compound represented by formula (IV). The catalyst is preferably one or more of metal phosphine complex, metal halide, hydrocarbyl phosphine compound and azo compound, more preferably a mixture of metal phosphine complex, metal halide and hydrocarbyl phosphine compound, and the molar ratio of the three is preferably 1: 0.1-10: 0.1 to 10, more preferably 1: 0.2-5: 0.2 to 5.
According to the preparation method of the present invention, preferably, the metal phosphine complex has a structure of
Figure BDA0001845343240000031
Wherein M is Pd, Ru or Rh, L is selected from PPh3Ph, F, Cl, Br, I. The metal phosphine complex can be selected from tetrakis (triphenylphosphine) palladium, tris (triphenylphosphine) palladium chloride, bis (triphenylphosphine) palladium dichloride and (triphenylphosphine) palladium trichlorideOne or more of tetrakis (triphenylphosphine) ruthenium, tris (triphenylphosphine) ruthenium chloride, bis (triphenylphosphine) ruthenium dichloride, (triphenylphosphine) ruthenium trichloride, tetrakis (triphenylphosphine) rhodium, tris (triphenylphosphine) rhodium chloride, bis (triphenylphosphine) rhodium dichloride and (triphenylphosphine) rhodium trichloride, preferably one or more of tetrakis (triphenylphosphine) palladium, tris (triphenylphosphine) palladium chloride, bis (triphenylphosphine) palladium dichloride and (triphenylphosphine) palladium trichloride.
According to the preparation method of the present invention, preferably, the metal halide may be one or more of a copper halide, an iron halide and a zinc halide, for example, one or more of cupric chloride, cuprous chloride, cupric bromide, cuprous bromide, cupric iodide, cuprous iodide, ferric chloride, ferrous chloride, ferric bromide, ferrous bromide, ferric iodide, ferrous iodide, zinc chloride, zinc bromide, zinc iodide and zinc iodide may be used, and more preferably one or more of cupric chloride, cuprous chloride, cupric bromide, cuprous bromide, cupric iodide and cuprous iodide.
According to the production method of the present invention, preferably, the hydrocarbyl phosphine compound has a structure of
Figure BDA0001845343240000041
Wherein each R is independently selected from C6～C10Aryl and C1～C6Wherein at least one R is C6～C10Aryl group of (1). Said C is6～C10The aryl group of (a) may be selected from phenyl, naphthyl; said C is1～C6The linear or branched alkyl group of (a) may be selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl or isohexyl. The hydrocarbyl phosphine compound can be selected from triphenylphosphine and diphenylbutylphosphine.
According to the preparation method of the present invention, preferably, the azo compound has a preferred structure of:
Figure BDA0001845343240000042
wherein each R' is the same or different from each other and is independently selectedFrom hydrogen, C1-6Straight or branched alkyl, C3-10Cycloalkyl, C6-10Aryl and C1-6An alkoxy group. The azo compound is preferably selected from one or more of dimethyl azodicarboxylate, diethyl azodicarboxylate, dipropyl azodicarboxylate and dibutyl azodicarboxylate.
According to the preparation method of the invention, the addition amount of the catalyst is preferably 0.1-100% of the silole derivative shown in the formula (II).
According to the preparation method of the present invention, preferably, the silole derivative represented by the formula (II) is reacted with the compound represented by the formula (III), and the product thereof is reacted with the compound represented by the formula (IV). The reaction conditions of the silole derivative shown in the formula (II) and the compound shown in the formula (III) are the same as the reaction conditions among the silole derivative shown in the formula (II), the compound shown in the formula (III) and the compound shown in the formula (IV); the reaction conditions of the reaction product of the silole derivative represented by formula (II) and the compound represented by formula (III) and the compound represented by formula (IV) are the same as those of the above-described silole derivative represented by formula (II), the compound represented by formula (III) and the compound represented by formula (IV).
According to the production method of the present invention, preferably, in the reaction of the reaction product of the silole derivative represented by formula (II) with the compound represented by formula (III) and the compound represented by formula (IV), the molar ratio between the silole derivative represented by formula (II) and the compound represented by formula (IV) is preferably 1: 0.2 to 5, more preferably 1: 0.3 to 3; the reaction temperature is preferably 0-50 ℃, and more preferably 15-35 ℃; generally, the longer the reaction time, the higher the conversion, and the reaction time may be 6 to 96 hours, preferably 12 to 72 hours.
According to the preparation method of the present invention, preferably, a catalyst is added to the reaction of the reaction product of the silole derivative represented by formula (II) with the compound represented by formula (III) and the compound represented by formula (IV). The catalyst is preferably a carbodiimide compound and/or a benzotriazole compound, more preferably a mixture of the carbodiimide compound and the benzotriazole compound, and the molar ratio of the carbodiimide compound to the benzotriazole compound is preferably 1: 0.1 to 10, more preferably 1: 0.2 to 5. The carbodiimide-based compound preferably has a structure of：
Figure BDA0001845343240000051
And salts thereof, wherein each R is independently selected from C6～C10Aryl of (C)1～C6Linear or branched alkyl, mono (C)1～C4Alkyl) amino C1～C10Alkyl, di (C)1～C4Alkyl) amino C1～C10An alkyl group. Said C is6～C10Aryl of (b) is preferably selected from phenyl, naphthyl; said C is1～C6The linear or branched alkyl group of (a) may be selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl or isohexyl; the sheet (C)1～C4Alkyl) amino C1～C10The alkyl group is preferably selected from the group consisting of methylaminoethyl, ethylaminoethyl, propylaminoethyl, methylaminopropyl, ethylaminopropyl, propylaminopropyl; said two (C)1～C4Alkyl) amino C1～C10The alkyl group is preferably selected from dimethylaminoethyl, diethylaminoethyl, dipropylaminoethyl, dimethylaminopropyl, diethylaminopropyl and dipropylaminopropyl. The described
Figure BDA0001845343240000052
The salt is preferably one or more of hydrochloride, sulfate, nitrate and phosphate thereof, and more preferably hydrochloride thereof. The carbodiimide compound can be selected from 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 1- (3-diethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 1- (3-dipropylaminopropyl) -3-ethylcarbodiimide hydrochloride. The carbodiimide-based compound is most preferably selected from
Figure BDA0001845343240000061
A hydrochloride salt wherein each R is independently selected from C6～C10Aryl of, C1～C6Straight or branched alkyl of (2), mono (C)1～C4Alkyl) amino C1～C10Alkyl, di (C)1～C4Alkyl radical)Amino group C1～C10Alkyl, and wherein at least one R is di (C)1～C4Alkyl) amino C1～C10An alkyl group. The preferable structure of the benzotriazole compound is as follows:
Figure BDA0001845343240000062
wherein R' is selected from hydrogen and C1-6Straight or branched alkyl, C3-10Cycloalkyl radical, C6-10Aryl and C1-6An alkoxy group; x is selected from F, Cl, Br, I and OH. The benzotriazole compound can be one or more of 1-hydroxybenzotriazole, 6-methyl-1-hydroxybenzotriazole and 7-methyl-1-hydroxybenzotriazole. The addition amount of the catalyst is preferably 1 to 200 percent of the mass of the silole derivative shown in the formula (II).
According to the preparation method of the present invention, optionally, the compound represented by the formula (IV) is a reaction product of a compound represented by the formula (V) and a compound represented by the formula (VI);
Figure BDA0001845343240000063
wherein each R is1Each independently selected from hydrogen, C1-6Straight or branched chain hydrocarbon radicals (preferably hydrogen, C)1-4A straight chain or branched chain alkyl group), y is selected from an integer between 0 and 4, and z is selected from an integer between 0 and 3; r2Selected from hydrogen, C1-6Straight or branched chain hydrocarbon radicals (preferably hydrogen, C)1-4Straight or branched chain alkyl); x is selected from F, Cl, Br, I and OH.
According to the preparation method of the present invention, in the reaction between the compound represented by the formula (V) and the compound represented by the formula (VI), the molar ratio between the compound represented by the formula (V) and the compound represented by the formula (VI) is preferably 0.5 to 2: 1, most preferably 0.9 to 1.1: 1; the reaction temperature is 80-240 ℃ (preferably 140-180 ℃); the reaction time is preferably 2-24 h (more preferably 4-12 h); a solvent is preferably added in the reaction, and the solvent is preferably one or more of polyphosphoric acid, dimethyl sulfoxide, dimethylformamide and 1, 4-dioxane (more preferably polyphosphoric acid); the reaction is preferably carried out under protection of an inert gas, preferably nitrogen. The reaction product may be purified using these solvents, and the solvents may be removed by a method known in the art after purification, and are not particularly limited.
The silole derivative has excellent photoluminescence performance, can emit light under ultraviolet irradiation, and can be applied to light-emitting parts and devices, fluorescent probes, biological imaging, lubricating oil and lubricating grease.
The invention also provides lubricating grease which comprises the silole derivative, a thickening agent and lubricating base oil. The silole derivative accounts for 0.01-5.0% of the total mass of the lubricating grease, and preferably 0.1-1.0%; the thickening agent accounts for 5-30%, preferably 10-20% of the total mass of the lubricating grease; the lubricating base oil constitutes the main component of the grease.
The thickening agent comprises one or more of a polyurea thickening agent, a lithium-based thickening agent, a composite lithium-based thickening agent, a calcium-based thickening agent and a composite aluminum-based thickening agent, preferably the polyurea thickening agent, the lithium-based thickening agent, the composite lithium-based thickening agent and the composite aluminum-based thickening agent, and most preferably the lithium-based thickening agent.
The base oil may be one or more of mineral oil, vegetable oil and synthetic oil, preferably mineral oil and synthetic oil.
According to the present invention, various additives including antioxidants, extreme pressure anti-wear agents, and rust preventives known in the art may be added to the grease, and are not particularly limited. The antioxidant is preferably an amine antioxidant and/or a phenol antioxidant, and for example, diphenylamine or 2, 6-di-tert-butylphenol can be used. The antirust agent is preferably sulfonate, and for example, barium dinonyl naphthalene sulfonate and barium petroleum sulfonate can be selected. The extreme pressure antiwear agent is preferably one or more of dialkyl dithiocarbamate, aminothioester and phosphate, for example, zinc dialkyl dithiocarbamate can be selected.
The preparation method of the lubricating grease comprises the following steps: mixing lubricating base oil, thickener and silole derivative, refining, and grinding into grease. The refining operation temperature is 160-240 ℃, and preferably 180-220 ℃; the refining operation time is 10-240 min, preferably 20-60 min. All of the lubricating base oil, the silole derivative and the thickening agent can be mixed and refined, or part of the lubricating base oil, part of the silole derivative and the thickening agent can be mixed and refined, and then the lubricating base oil, the silole derivative and the thickening agent are mixed. The preparation method of the lithium-based lubricating grease comprises the following steps: mixing and heating all or part of lubricating base oil and fatty acid in a reaction kettle, heating to 40-90 ℃, adding the aqueous solution of the silole derivative and lithium hydroxide, heating to remove water, continuously heating to 190-220 ℃ for high-temperature refining, cooling to 60-120 ℃ or adding the rest lubricating base oil, cooling to 60-120 ℃, adding an optional additive, and grinding into grease. The fatty acid is C12-C20 fatty acid and/or C12-C20 hydroxy fatty acid, for example, one or more of lauric acid, myristic acid, palmitic acid, stearic acid and 12-hydroxy stearic acid can be selected. The concentration of the aqueous solution of lithium hydroxide is 5 to 30%, preferably 10 to 20%. The molar ratio of the lithium hydroxide in the aqueous solution of the lithium hydroxide to the fatty acid is 0.5-2: 1, preferably 0.8 to 1.2: 1. the time for high-temperature refining is preferably 0.05-1 h, and more preferably 0.1-0.5 h.
According to the method for preparing a grease of the present invention, it is preferable that the silole derivative is dissolved in a solvent in advance. The solvent is preferably an aromatic hydrocarbon solvent, for example, benzene, toluene or xylene, and the weight of the solvent is 0.5 to 100 times (preferably 1 to 20 times) that of the silole derivative.
The lubricating grease has excellent photoluminescence performance and oxidation resistance, and can be used for relevant mechanical equipment in the electrical appliance industry, the metallurgical industry, the food industry, the paper industry, the automobile industry and the airplane industry.
Detailed Description
The main raw material sources are as follows:
chemical reagents such as tolane, trichlorophenylsilane, ethynylmagnesium bromide, p-iodobenzoic acid, cuprous iodide, triphenylphosphine, palladium tetratriphenylphosphine, polyphosphoric acid, o-aminothiophenol, p-aminosalicylic acid, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 1-hydroxybenzotriazole, 12-hydroxystearic acid, lithium hydroxide monohydrate, tetrahydrofuran, triethylamine, dichloromethane, 1, 4-dioxane, methanol, dimethyl sulfoxide and the like are from Bailingwei reagent company, InnoKa reagent company or Sigma reagent company, and the analytical reagents are pure; the PAO10 base oil was from Exxon Mobil, 500SN, 150BS from SK.
The test methods used were as follows:
measuring method GB/T3498 for dropping point in wide temperature range of grease, measuring method GB/T269 for cone penetration of grease and petroleum, measuring method SH/T0325 for oxidation stability of grease, measuring method SH/T0324 for oil separation of grease mesh, measuring method SH/T0202 for extreme pressure performance of grease, measuring method SH/T0204 for antiwear performance of grease, and measuring method GB/T7326 for corrosion of copper sheet of grease.
Example 1
3g (16.8mmol) of tolane and 15mL of dry tetrahydrofuran were charged into a 50mL Schlenk reaction flask, and 100mg (14.3mmol) of freshly prepared lithium chips were added under nitrogen and reacted at room temperature for 12 hours. To a 200mL Schlenk flask were added 0.93mL (5.8mmol) of trichlorophenylsilane and 60mL of dried tetrahydrofuran, and the first-step reaction mixture was added dropwise to the flask and refluxed for 5 hours. After the temperature was decreased to room temperature, 11.6mL of a 0.5M solution of ethynylmagnesium bromide (5.8mmol) in tetrahydrofuran was added dropwise to the reaction flask and reacted at room temperature for 2 hours. After the reaction is finished, the solvent is dried in a spinning mode, chloroform is added to dissolve the solvent, the solvent is washed for three times, and anhydrous sodium sulfate is added to dry the solvent. The product was separated and purified by column chromatography using chloroform/petroleum ether (1/2) as an eluent, and then recrystallized from a toluene/heptane mixed solvent to give 1.1g of a yellowish green solid product in 39% yield. Melting point: 175-177 ℃; 1H NMR (400MHz, CDCl3), delta (TMS, ppm):7.78(d,2H, ArH),7.37(M,3H, ArH), 7.03-6.85 (M,20H, ArH),2.70(s,1H, -C.ident.CH) MS (MALDI-TOF): M/z calcd:486.2[ M/z calcd ≡ 486.2 ]]+,found:486.2。
The reaction formula of example 1 is as follows:
Figure BDA0001845343240000081
example 2
486mg (1mmol) of 1-alkynyl-1, 2,3,4, 5-pentaphenylsilole, 372mg (1.5mmol) of p-iodobenzoic acid, 19mg (0.1mmol) of cuprous iodide, and 26mg (0.1mmol) of triphenylphosphine were charged into a 100mL Schlenk reaction flask. 23mg (0.02mmol) of tetratriphenylphosphine palladium, 30mL of tetrahydrofuran/triethylamine (2/1, v/v) were added under nitrogen, and the reaction was carried out at room temperature for 48 hours. After the reaction was completed, the product was separated and purified by column chromatography using a dichloromethane/methanol (40/3, v/v) mixed solvent as an eluent by filtration and spin-drying of the filtrate, to obtain 460mg of a yellow solid product in a yield of 76%.1H NMR(400MHz,CDCl3),δ(TMS,ppm):8.07(d,2H,ArH),7.83(d,2H,ArH),7.66(d,2H,ArH),7.41(m,3H,ArH),7.11–6.95(m,16H,ArH),6.94–6.85(m,4H,ArH).MS(MALDI-TOF):m/z calcd:606.2[M]+,found:606.4。
The reaction formula for example 2 is shown below:
Figure BDA0001845343240000091
example 3
200mL of polyphosphoric acid (PPA), 0.2mol of o-aminosulfol and 0.2mol of p-aminosalicylic acid are added to a 500mL three-necked flask, and the mixture is stirred and reacted for 6 hours at 160 ℃ under the protection of nitrogen. After the reactant is cooled, a large amount of ice water is used for diluting, 10% sodium hydroxide solution and saturated sodium carbonate solution are used for adjusting the reactant to be neutral, a large amount of solids are separated out, and a crude product is obtained by filtration. Dissolving the crude product with 1, 4-dioxane, filtering to remove insoluble impurities, adding appropriate amount of water into the filtrate, collecting the precipitated solid, and oven drying at 60 deg.C in a vacuum oven to obtain 2- (2 '-hydroxy-4' -aminophenyl) benzothiazole with a yield of 59%. The melting point is 212-214 ℃.1H NMR(400MHz,DMSO-d6)δ(ppm):11.71(s,1H,ArOH),8.02(d,1H,ArH),7.88(d,1H,ArH),7.62(d,1H,ArH),7.45(m,1H,ArH),7.33(m,1H,ArH),6.24(d,1H,ArH),6.15(d,1H,ArH),5.95(s,2H,ArNH2).MS(ESI-TOF):243.0582([M+H]+)。
The reaction formula for example 3 is shown below:
Figure BDA0001845343240000092
example 4
4mmol of 1- (4 ' -carboxyphenylacetynyl) -1,2,3,4, 5-pentaphenylsilole, 5.6mmol of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 4mmol of 1-hydroxyphenylbenzotriazole and 50mL of dimethyl sulfoxide (DMSO) were added to a 250mL three-necked flask, and 10mL of a DMSO solution containing 4mmol of 2- (2 ' -hydroxy-4 ' -aminophenyl) benzothiazole was slowly added dropwise with stirring to react at room temperature for 24 hours. After the reaction is finished, the reaction solution is filled into a dialysis bag, is placed into water and methanol for dialysis for multiple times, and the solvent is dried by spinning to obtain a crude product. The crude product was isolated and purified by column chromatography using chloroform/petroleum ether (1/2) as eluent to give the product as a yellow solid in 88% yield.1H NMR(400MHz,DMSO-d6),δ(TMS,ppm):11.71(s,1H,ArOH),8.10(d,2H,ArH),8.02(d,1H,ArH),7.88(d,1H,ArH),7.84(d,2H,ArH),7.67(d,2H,ArH),7.62(d,1H,ArH),7.45(m,4H,ArH),7.33(m,1H,ArH),7.13–6.83(m,20H,ArH),6.24(d,1H,ArH),6.15(d,1H,ArH).MS(MALDI-TOF):m/z calcd:830.2[M]+,found:830.3。
The reaction formula of example 4 is as follows:
Figure BDA0001845343240000101
example 5
Mixing 60 g of 500SN base oil and 7.84 g of 12-hydroxystearic acid in a reaction kettle, heating to 85 ℃, dissolving 0.5g of Silole-HBT in 5g of toluene, adding the toluene to the reaction kettle, mixing 1.21 g of lithium hydroxide monohydrate and 8 g of distilled water, heating to 95 ℃, adding the mixture to the reaction kettle after all the lithium hydroxide is dissolved, performing saponification for 20min, stirring, heating to 110 ℃ and 150 ℃, performing dehydration and debenzolization, continuing heating to 210 ℃, performing high-temperature refining for 10min, adding 32 g of 500SN base oil, cooling to 110 ℃, adding 0.5g of barium petroleum sulfonate and 1g of dialkyl dithiocarbamate, cooling to room temperature, and grinding for three times. The product properties are shown in Table 1.
Example 6
Mixing 60 g of 150BS base oil and 7.84 g of 12-hydroxystearic acid in a reaction kettle, heating to 85 ℃, dissolving 0.5g of Silole-HBT in 5g of toluene, adding the toluene to the reaction kettle, mixing 1.21 g of lithium hydroxide monohydrate and 8 g of distilled water, heating to 95 ℃, adding the mixture to the reaction kettle after the lithium hydroxide is completely dissolved, performing saponification for 20min, stirring, heating to 110 ℃ and 150 ℃, performing dehydration and debenzolization, continuing heating to 210 ℃, performing high-temperature refining for 10min, adding 32 g of 150BS base oil, cooling to 110 ℃, adding 0.5g of barium petroleum sulfonate and 1g of dialkyl dithiocarbamate, cooling to room temperature, and grinding for three times. The product properties are shown in Table 1.
Example 7
60 g of PAO10 base oil and 7.84 g of 12-hydroxystearic acid are mixed and heated to 85 ℃ in a reaction kettle, 0.2 g of Silole-HBT is dissolved in 5g of toluene and then added into the reaction kettle, 1.21 g of lithium hydroxide monohydrate and 8 g of distilled water are mixed and heated to 95 ℃, the mixture is added into the reaction kettle after the lithium hydroxide is completely dissolved for saponification reaction for 20min, the mixture is stirred and heated to 110 ℃ for dehydration and debenzolization, then the mixture is continuously heated to 210 ℃ for high-temperature refining for 10min, 32 g of PAO10 base oil is added, barium dinonylnaphthalene sulfonate 0.5g and dialkyl dithiocarbamate 1g are added after the mixture is cooled to 110 ℃, and the mixture is ground for three times after being cooled to room temperature. The product properties are shown in Table 1.
Comparative example 1
Mixing 60 g of 500SN base oil and 7.84 g of 12-hydroxystearic acid in a reaction kettle, heating to 85 ℃, mixing 1.21 g of lithium hydroxide monohydrate and 8 g of distilled water, heating to 95 ℃, adding the mixture into the reaction kettle after the lithium hydroxide is completely dissolved, carrying out saponification reaction for 20min, stirring, heating to 110-150 ℃, dehydrating, continuously heating to 210 ℃, carrying out high-temperature refining for 10min, adding 32 g of 500SN base oil, cooling to 110 ℃, adding 0.5g of diphenylamine, 0.5g of barium petroleum sulfonate and 1g of dialkyl dithiocarbamate, cooling to room temperature, and grinding for three times. The product properties are shown in Table 1.
Comparative example 2
Mixing 60 g of 150BS base oil and 7.84 g of 12-hydroxystearic acid in a reaction kettle, heating to 85 ℃, mixing 1.21 g of lithium hydroxide monohydrate and 8 g of distilled water, heating to 95 ℃, adding the mixture into the reaction kettle after the lithium hydroxide is completely dissolved, carrying out saponification reaction for 20min, stirring, heating to 110 ℃ and 150 ℃ for dehydration, then continuously heating to 210 ℃ for high-temperature refining for 10min, adding 32 g of 150BS base oil, cooling to 110 ℃, adding 0.5g of diphenylamine, 0.5g of barium petroleum sulfonate and 1g of dialkyl dithiocarbamate, cooling to room temperature, and grinding for three times. The product properties are shown in Table 1.
Comparative example 3
Mixing 60 g of PAO10 base oil and 7.84 g of 12-hydroxystearic acid in a reaction kettle, heating to 85 ℃, mixing 1.21 g of lithium hydroxide monohydrate and 8 g of distilled water, heating to 95 ℃, adding the mixture into the reaction kettle after the lithium hydroxide is completely dissolved, carrying out saponification reaction for 20min, stirring, heating to 110 ℃ and 150 ℃ for dehydration, then continuously heating to 210 ℃ for high-temperature refining for 10min, adding 32 g of base oil, cooling to 110 ℃, adding 0.5g of diphenylamine, 0.5g of barium dinonylnaphthalene sulfonate and 1g of dialkyl dithiocarbamate, cooling to room temperature, and grinding for three times.
The greases of example 5, example 6, example 7, comparative example 1, comparative example 2 and comparative example 3 were evaluated for performance by GB/T3498, GB/T269, SH/T0325, SH/T0324, SH/T0202, SH/T0204 and GB/T7326, and the evaluation results are shown in Table 1.
TABLE 1 grease Properties
Figure BDA0001845343240000121

Claims (26)

1. A silole derivative has a structure shown in a formula (I):
Figure 388516DEST_PATH_IMAGE002
（I）
wherein each R is0Are identical or different from each otherAnd each is independently selected from hydrogen and C1-6A straight chain or branched chain alkyl group, each x is independently selected from an integer between 0 and 5; each R is1Each independently selected from hydrogen and C1-6A straight or branched chain hydrocarbyl group, each y is independently selected from an integer between 0 and 4, and z is selected from an integer between 0 and 3; r is2Selected from hydrogen, C1-6A straight or branched chain hydrocarbon group.
2. Silole derivatives according to claim 1, characterized in that each R is0Each independently of the others, is selected from hydrogen, C1-4A linear or branched alkyl group; each R is1Each independently selected from hydrogen and C1-4A linear or branched alkyl group; r2Selected from hydrogen, C1-4Straight or branched chain alkyl.
3. The silole derivative according to claim 1, having the structure:
Figure DEST_PATH_IMAGE003
。
4. the method for producing a silole derivative according to claim 1 or 2, which comprises the step of reacting a silole derivative represented by formula (II), a compound represented by formula (III), and a compound represented by formula (IV);
Figure DEST_PATH_IMAGE005
（II），
Figure DEST_PATH_IMAGE006
（III），
Figure DEST_PATH_IMAGE008
（IV）
wherein each R is0Are the same or different from each other and are each independently selected from hydrogen,C1-6A straight chain or branched chain alkyl group, each x is independently selected from an integer between 0 and 5; each R is1Each independently selected from hydrogen and C1-6A straight or branched chain hydrocarbyl group, each y is independently selected from an integer between 0 and 4, and z is selected from an integer between 0 and 3; r2Selected from hydrogen, C1-6A straight or branched chain hydrocarbon group.
5. The method of claim 4, wherein each R is0Each independently of the others, is selected from hydrogen, C1-4A linear or branched alkyl group; each R is1Each independently selected from hydrogen and C1-4A linear or branched alkyl group; r2Selected from hydrogen, C1-4Straight or branched chain alkyl.
6. The method according to claim 4, wherein the molar ratio between the silole derivative of formula (II), the compound of formula (III) and the compound of formula (IV) is 1: 0.5-5: 0.5 to 5.
7. The method according to claim 4, wherein the molar ratio between the silole derivative of formula (II), the compound of formula (III) and the compound of formula (IV) is 1: 0.8-1.2: 0.8 to 1.2.
8. The method according to claim 4, wherein the silole derivative of formula (II), the compound of formula (III) and the compound of formula (IV) are reacted at a temperature of 0 to 50 ℃.
9. The method according to claim 4, wherein the temperature at which the silole derivative of formula (II), the compound of formula (III) and the compound of formula (IV) are reacted is 15 to 35 ℃.
10. The method according to claim 4, wherein a catalyst is added to the reaction of the silole derivative represented by the formula (II), the compound represented by the formula (III) and the compound represented by the formula (IV), and the catalyst is one or more selected from a metal phosphine complex, a metal halide, a hydrocarbyl phosphine compound and an azo compound.
11. The process according to claim 4, wherein a catalyst comprising a mixture of a metal phosphine complex, a metal halide and a hydrocarbyl phosphine compound is added to the reaction of the silole derivative of formula (II), the compound of formula (III) and the compound of formula (IV) in a molar ratio of 1: 0.1-10: 0.1 to 10.
12. A process according to claim 4, wherein the silole derivative of formula (II) is reacted with the compound of formula (III) and the product is reacted with the compound of formula (IV).
13. The process according to claim 12, wherein in the reaction of the reaction product of the silole derivative of formula (II) with the compound of formula (III) and the compound of formula (IV), the molar ratio between the silole derivative of formula (II) and the compound of formula (IV) is 1: 0.2 to 5; the reaction temperature is 0-50 ℃.
14. The process according to claim 12, wherein in the reaction of the reaction product of the silole derivative of formula (II) with the compound of formula (III) and the compound of formula (IV), the molar ratio between the silole derivative of formula (II) and the compound of formula (IV) is 1: 0.3 to 3; the reaction temperature is 15-35 ℃.
15. The method according to claim 12, wherein a catalyst is added to the reaction of the reaction product of the silole derivative represented by the formula (II) with the compound represented by the formula (III) and the compound represented by the formula (IV), and the catalyst is a carbodiimide-based compound and/or a benzotriazole-based compound.
16. The process according to claim 12, wherein a catalyst is added to the reaction of the reaction product of the silole derivative of formula (II) with the compound of formula (III) and the compound of formula (IV), said catalyst being a mixture of a carbodiimide-based compound and a benzotriazole-based compound in a molar ratio of 1: 0.1 to 10.
17. The method according to claim 4, wherein the compound of formula (IV) is a reaction product of a compound of formula (V) with a compound of formula (VI);
Figure DEST_PATH_IMAGE010
（V），
Figure DEST_PATH_IMAGE012
（VI），
wherein each R1Each independently selected from hydrogen and C1-6A straight chain or branched chain alkyl group, y is an integer from 0 to 4, and z is an integer from 0 to 3; r is2Selected from hydrogen, C1-6A straight or branched chain hydrocarbon group; x is selected from F, Cl, Br, I and OH.
18. The method of claim 17, wherein each R is1Each independently selected from hydrogen and C1-4A linear or branched alkyl group; r2Selected from hydrogen, C1-4Straight or branched chain alkyl.
19. Use of the silole derivative according to any of claims 1 to 3 or prepared according to any of claims 4 to 18 in light-emitting components and devices, fluorescent probes, bio-imaging, lubricating oils and greases.
20. A grease comprising the silole derivative according to any one of claims 1 to 3 or the silole derivative obtained by the process according to any one of claims 4 to 18, a thickener and a lubricating base oil.
21. The grease of claim 20 wherein the silole derivative comprises from 0.01% to 5.0% of the total mass of the grease; the thickening agent accounts for 5-30% of the total mass of the lubricating grease; the lubricating base oil constitutes the main component of the grease.
22. The grease of claim 20 wherein the silole derivative comprises from 0.1% to 1.0% of the total mass of the grease; the thickening agent accounts for 10-20% of the total mass of the lubricating grease; the lubricating base oil constitutes the main component of the grease.
23. The grease of claim 20 wherein the thickener comprises one or more of a polyurea thickener, a lithium-based thickener, a complex lithium-based thickener, a calcium-based thickener, and a complex aluminum-based thickener; the lubricating base oil is one or more of mineral oil, vegetable oil and synthetic oil.
24. A method of preparing a grease of any of claims 20-23 comprising: mixing lubricating base oil, thickener and silole derivative, refining, and grinding into grease.
25. The method of claim 24, wherein the grease is a lithium-based grease prepared by a method comprising: mixing and heating all or part of lubricating base oil and fatty acid in a reaction kettle, heating to 40-90 ℃, adding a silole derivative and a lithium hydroxide aqueous solution, heating to remove water, continuously heating to 190-220 ℃ for high-temperature refining, cooling to 60-120 ℃ or adding the rest lubricating base oil, cooling to 60-120 ℃, adding an optional additive, and grinding into grease.
26. The method according to claim 24 or 25, wherein the silole derivative is dissolved in a solvent in advance, and the solvent is an aromatic hydrocarbon solvent.
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