CN112552330B - Silole derivative, preparation method and application thereof, and photoluminescent lubricating grease - Google Patents

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

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CN112552330B
CN112552330B CN201910910402.8A CN201910910402A CN112552330B CN 112552330 B CN112552330 B CN 112552330B CN 201910910402 A CN201910910402 A CN 201910910402A CN 112552330 B CN112552330 B CN 112552330B
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grease
base oil
formula
silole
silole derivative
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CN112552330A (en
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刘欣阳
何懿峰
郑会
庄敏阳
刘伟
李朝宇
刘中其
姜靓
陈靖
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 Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
    • C07F7/0816—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring comprising Si as a ring atom
    • 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 Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
    • C07F7/083—Syntheses without formation of a Si-C bond
    • 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
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • 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
    • 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
    • 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
    • C10M2207/126—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 monocarboxylic
    • C10M2207/1265—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 monocarboxylic used as thickening agent
    • 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
    • C10M2207/127—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 polycarboxylic
    • 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
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions

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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)
  • Lubricants (AREA)

Abstract

The invention provides a silole derivative, a preparation method and application thereof, and photoluminescent 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 photoluminescent lubricating grease
Technical Field
The invention relates to a silole derivative, in particular to a silole derivative with a light-emitting 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 aggregation state, strong interactions between molecules 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.
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 reports of the luminescent grease are rarely seen.
Disclosure of Invention
The invention provides a silole derivative, a preparation method and application thereof, and photoluminescent grease containing the silole derivative, which are described in the specification.
In a first aspect, the present invention provides a silole derivative.
The silole derivative has a structure shown in a formula (I):
Figure BDA0002214528300000011
wherein each R is 0 Are the same or different from each other and are each independently selected from hydrogen and C 1-6 Straight or branched chain hydrocarbon radicals (preferably hydrogen, C) 1-4 Straight or branched chain alkyl), each x is independently selected from an integer between 0 and 5 (preferably 0, 1,2, 3); the L' group is selected from
Figure BDA0002214528300000021
C 1-6 Straight or branched chain hydrocarbon radicals (preferred is device for selecting or keeping>
Figure BDA0002214528300000022
C 1-4 Straight or branched alkyl), wherein R 0 Selected from hydrogen, C 1-6 Straight or branched chain hydrocarbon radicals (preferably hydrogen, C) 1-4 Linear or branched alkyl), x is selected from integers between 0 and 5 (preferably 0, 1,2, 3);
n is an integer of 1 to 10 (preferably an integer of 1 to 5);
n A groups, which are the same or different from each other, are each independently selected from the group represented by formula (II), C 1-6 A linear or branched alkyl group and H, and at least one A group is selected from the group represented by formula (II),
Figure BDA0002214528300000023
in formula (II), each R' is independently selected from H and C 1-6 Straight or branched alkyl (preferably selected from H and C) 1-4 Straight or branched alkyl, more preferably t-butyl); each R is independently selected from H and C 1-6 Straight or branched alkyl (preferably selected from H and C) 1-4 Straight or branched alkyl, more preferably selected from H);
the group L is a single bond or (n + 1) -valent C 1-30 A hydrocarbon group (preferably a single bond or (n + 1) -valent C 1-10 A straight or branched alkyl group, more preferably a single bond or (n + 1) -valent C 1-4 Straight or branched chain alkyl).
According to the present invention, the silole derivative may have the following structure:
Figure BDA0002214528300000024
in a second aspect, the present invention provides a method for preparing a silole derivative.
A method for producing a silole derivative of the present invention comprises a step of reacting a silole compound represented by the formula (III) with a compound represented by the formula (IV),
Figure BDA0002214528300000031
in the formula (III), each R 0 Are the same or different from each other and are each independently selected from hydrogen, C 1-6 Straight or branched chain hydrocarbon radicals (preferably hydrogen, C) 1-4 Straight or branched chain alkyl), each x is independently selected from an integer between 0 and 5 (preferably 0, 1,2, 3); the L' group is selected from
Figure BDA0002214528300000032
C 1-6 Straight or branched chain hydrocarbon radicals (preferred is device for selecting or keeping>
Figure BDA0002214528300000033
C 1-4 Straight or branched alkyl), wherein R is 0 Selected from hydrogen, C 1-6 Straight or branched chain hydrocarbon radicals (preferably hydrogen, C) 1-4 Linear or branched alkyl), x is selected from integers between 0 and 5 (preferably 0, 1,2, 3); in formula (IV), the X group is F, cl, br, I or OH (preferably Cl, br); n is an integer of 1 to 10 (preferably an integer of 1 to 5); n A groups, which are the same or different from each other, are each independently selected from the group represented by the formula (V), C 1-6 A linear or branched alkyl group and H, and at least one A group is selected from the group represented by formula (V),
Figure BDA0002214528300000034
in formula (V), each R' is independently selected from H and C 1-6 Straight or branched chain alkyl (preferably selected from H and C) 1-4 Straight or branched chain alkyl, more preferably t-butyl); each R is independently selected from H and C 1-6 Straight or branched chain alkyl (preferably selected from H and C) 1-4 Straight or branched alkyl, more preferably selected from H);
the group L is a single bond or (n + 1) -valent C 1-30 A hydrocarbon group (preferably a single bond or (n + 1) -valent C 1-10 A straight or branched alkyl group, more preferably a single bond or (n + 1) -valent C 1-4 Straight or branched chain alkyl).
According to the preparation method of the present invention, the silole compound represented by formula (III) may be one or more selected from the following compounds:
Figure BDA0002214528300000041
according to the preparation method of the present invention, the compound represented by the formula (IV) may be selected from one or more of the following compounds:
Figure BDA0002214528300000042
according to the production method of the present invention, in the reaction, the molar ratio between the silole compound represented by the formula (III) and the compound represented by the formula (IV) is preferably 1:0.5 to 5, most preferably 1:0.8 to 1.2.
According to the preparation method of the present invention, preferably, the temperature of the reaction is 0 to 50 ℃, preferably 15 to 35 ℃.
According to the preparation method of the invention, the reaction time is preferably 6 to 96 hours, preferably 12 to 72 hours.
According to the invention, a catalyst is preferably added to the reaction. The catalyst is preferably one or more of a metal phosphine complex, a metal halide and a hydrocarbyl phosphine compound, more preferably a mixture of a metal phosphine complex, a metal halide and a hydrocarbyl phosphine compound, the molar ratio of the three preferably being 1:0.1 to 10:0.1 to 10, more preferably 1:0.2 to 5:0.2 to 5.
According to the present invention, preferably, the metal phosphine complex has the structure
Figure BDA0002214528300000043
Wherein M is Pd, ru or Rh, L is selected from PPh 3 Ph, F, cl, br, I. The metal phosphine complex can be one or more of tetrakis (triphenylphosphine) palladium, tris (triphenylphosphine) palladium chloride, bis (triphenylphosphine) palladium dichloride, (triphenylphosphine) palladium trichloride, 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 present invention, preferably, the metal halide may be one or more of copper halide, iron halide and zinc halide, for example, one or more of copper chloride, cuprous chloride, copper bromide, cuprous bromide, copper iodide, cuprous iodide, ferric chloride, ferrous chloride, ferric bromide, ferrous bromide, ferric iodide, ferrous iodide, zinc chloride, zinc chlorite, zinc bromide, zinc iodide and zinc iodide may be used, and more preferably one or more of copper chloride, cuprous chloride, copper bromide, cuprous bromide, copper iodide and cuprous iodide.
According to the present invention, preferably, the hydrocarbyl phosphine compound has the structure
Figure BDA0002214528300000051
Wherein each R is independently selected from C 6 ～C 10 Aryl and C 1 ～C 6 Wherein at least one R is C 6 ～C 10 Aryl group of (2). Said C is 6 ～C 10 The aryl group of (a) may be selected from phenyl, naphthyl; said C is 1 ～C 6 The linear or branched alkyl group of (b) 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 invention, the amount of the catalyst added is preferably 1% to 20% of the amount of the silole compound of the formula (III).
According to the production method of the present invention, preferably, a solvent is added in the reaction. The solvent is preferably C 1 ～C 10 Examples of the organic amine and furan include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine and tetrahydrofuran, and most preferably C 1 ～C 10 The volume ratio of the organic amine to the furan is preferably 1:0.1 to 10. 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 distillation, evaporation, and column chromatography.
According to the preparation method of the present invention, preferably, the silole derivative of the present invention is isolated and purified by column chromatography, and a mixed solvent of dichloromethane/petroleum ether may be used as an eluent, and the volume ratio of dichloromethane to petroleum ether is preferably 1:0.5 to 5.
The silole derivative has excellent photoluminescence performance and oxidation resistance, can emit yellow green fluorescence under ultraviolet irradiation, and can be applied to light-emitting parts and devices, fluorescent probes, biological imaging, lubricating oil and lubricating grease.
In a third aspect, the present invention provides a grease.
The lubricating grease 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 thickener comprises one or more of a polyurea thickener, a lithium-based thickener, a composite lithium-based thickener, a calcium-based thickener and a composite aluminum-based thickener, preferably the polyurea thickener, the lithium-based thickener, the composite lithium-based thickener and the composite aluminum-based thickener, and most preferably the lithium-based thickener.
The lubricating base oil can be one or more of mineral oil, vegetable oil and synthetic oil, and is preferably mineral oil or synthetic oil.
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 ℃, preferably 180-220 ℃; the refining operation is preferably carried out for a time sufficient to form a grease, and is not particularly limited, and the refining operation may be completed when the temperature is raised to the refining temperature, or the refining operation may be carried out for a certain time while the temperature is raised to the refining temperature, and the refining operation is usually carried out for 10 to 240min, preferably 20 to 60min. 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 thickening agent can be a soap-based thickening agent or a non-soap-based thickening agent. The soap-based thickener is preferably a metal soap, which can be a single metal soap or a composite metal soap, and the metal can be one or more of lithium, sodium, calcium, aluminum, zinc, potassium, barium, lead and manganese. The non-soap-based grease thickener is preferably one or more of graphite, carbon black, asbestos, polyurea group, bentonite and organic clay.
The grease of the present invention is preferably polyurea grease, lithium-based grease and complex aluminum-based grease.
The preparation method of the polyurea lubricating grease comprises the following steps: mixing part of lubricating base oil, the silole derivative, the amine and the isocyanate, reacting for 10-60min at 65-95 ℃, continuously heating to 190-220 ℃ after the reaction is completed, refining at high temperature, adding the rest base oil, cooling to 60-120 ℃, and grinding into grease. The amine is C 2 ～C 20 Alkylamine and/or C 6 ～C 20 Aromatic amines, such as one or more of octadecylamine, cyclohexylamine, aniline; the isocyanate is C 2 ～C 20 The isocyanate of (3) may be one or more of Toluene Diisocyanate (TDI) and 4,4' -diphenylmethane diisocyanate (MDI).
The preparation method of the lithium-based lubricating grease comprises the following steps: mixing and heating 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, adding the rest lubricating base oil, cooling to 60-120 ℃, and grinding into grease. The fatty acid is C 12 ～C 20 Fatty acid and/or C 12 ～C 20 The hydroxy fatty acid can be one or more of lauric acid, palmitic acid, stearic acid and 12-hydroxystearic acid.
The preparation method of the composite lithium-based lubricating grease comprises the following steps: mixing and heating part of base oil, fatty acid and micromolecule acid in a reaction kettle, heating to 40-100 ℃, adding the silole derivative, mixing and heating water and lithium hydroxide monohydrate to 40-100 ℃, adding the mixture into the reaction kettle after the lithium hydroxide monohydrate is completely dissolved, continuously heating to 190-220 ℃ for high-temperature refining, adding the rest lubricating base oil, cooling to 60-120 ℃, and grinding into grease. The fatty acid is C 12 ～C 20 Fatty acid and/or C 12 ～C 20 Hydroxy fatty acid, which can be one or more of lauric acid, palmitic acid, stearic acid and 12-hydroxystearic acid; the small molecular acid is C 2 ～C 11 The organic acid of (2) can be one or more of acetic acid, propionic acid, oxalic acid, adipic acid, azelaic acid, sebacic acid and terephthalic acid.
The preparation method of the composite aluminum-based lubricating grease comprises the following steps: mixing and heating part of base oil, fatty acid and micromolecular acid in a reaction kettle, heating to 40-90 ℃, adding the silole derivative, mixing and heating the other part of lubricating base oil and an aluminum alkoxide compound to 40-100 ℃, and waiting for the aluminum alkoxide compoundAdding the mixture into a reaction kettle after the mixture is completely dissolved, continuously heating to 190-220 ℃ for high-temperature refining, adding the rest lubricating base oil to cool to 60-120 ℃, and grinding into grease. The fatty acid is C 12 ～C 20 Fatty acid and/or C 12 ～C 20 Hydroxy fatty acid, which can be one or more of lauric acid, palmitic acid, stearic acid and 12-hydroxystearic acid; the small molecular acid is C 2 ～C 11 The organic acid of (2) can be one or more of acetic acid, propionic acid, oxalic acid, adipic acid, azelaic acid, sebacic acid and terephthalic acid; the aluminium alkoxide compound is preferably selected from aluminium isopropoxide, aluminium isopropoxide dimer, aluminium isopropoxide trimer.
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 applied to 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
In the context of the present specification, the term "single bond" is sometimes used in the definition of a group. By "single bond" is meant that the group is absent. For example, assume the formula-CH 2 -A-CH 3 Wherein the group a is defined as being selected from the group consisting of a single bond and a methyl group. In this connection, if A is a single bond, this means that the group A is absent, in which case the formula is correspondingly simplified to-CH 2 -CH 3 。
In the context of the present specification, the expression "number + valence + group" or the like refers to a group obtained by removing the number of hydrogen atoms represented by the number from the basic structure (such as a chain, a ring or a combination thereof, etc.) to which the group corresponds, and preferably refers to a group obtained by removing the number of hydrogen atoms represented by the number from a carbon atom (preferably a saturated carbon atom and/or a non-identical carbon atom) contained in the structureThe resulting group. For example, "3-valent straight or branched alkyl" refers to a group obtained by removing 3 hydrogen atoms from a straight or branched alkane (i.e., the base chain to which the straight or branched alkyl corresponds), and "2-valent straight or branched heteroalkyl" refers to a group obtained by removing 2 hydrogen atoms from a straight or branched heteroalkane (preferably from a carbon atom contained in the heteroalkane, or further, from a non-identical carbon atom). For example, the 2-valent propyl group may be-CH 2 -CH 2 -CH 2 -*、
Figure BDA0002214528300000071
The 3-valent propyl group may be
Figure BDA0002214528300000081
The 4-valent propyl group can be->
Figure BDA0002214528300000082
Wherein represents a binding end in the group that may be bonded to other groups.
The main raw materials used in the invention are as follows:
chemical reagents such as 1-alkynyl-1, 2,3,4, 5-pentaphenylsilole, 1-methyl-1-alkynyl-2, 3,4, 5-tetraphenylsilole, 4-bromomethyl-2, 6-di-t-butyl, cuprous iodide, triphenylphosphine, palladium tetratriphenylphosphine, octadecylamine, MDI, 12-hydroxystearic acid, stearic acid, benzoic acid, lithium hydroxide monohydrate, aluminum isopropoxide trimer, tetrahydrofuran, triethylamine, dichloromethane, petroleum ether, etc. are available from carbofuran, enokay reagent, or sigma reagent; the PAO10 base oil was obtained from Exxon Mobil.
Example 1
A100 mLSchlenk reaction flask was charged with 1mmol of 1-alkynyl-1, 2,3,4, 5-pentaphenylsilole, 1.2mmol of 4-bromomethyl-2, 6-di-t-butyl-p-cresol, 0.1mmol of cuprous iodide, 0.1mmol of triphenylphosphine, and 0.02mmol of palladium tetratriphenylphosphine and 30mL of tetrahydrofuran/triethylamine (2/1, v/v) under nitrogen protection, and reacted at room temperature for 48 hours. After the reaction is finished, filtering and spin-drying the filtrate, and taking dichloromethane/petroleum ether (1/2, v/v) mixed solvent as eluentThe product was isolated and purified by column chromatography to give a yellow solid product in 75% yield. The mass spectrum result of the product is as follows: MS (MALDI-TOF): m/z calcd:704.3[ M ]] + ,found:704.3。
The reaction formula for example 1 is shown below:
Figure BDA0002214528300000083
example 2
A100-mL Schlenk reaction flask was charged with 1mmol of 1-methyl-1-alkynyl-2, 3,4, 5-tetraphenylsilole, 1.2mmol of 4-bromomethyl-2, 6-di-t-butyl-p-cresol, 0.1mmol of cuprous iodide, 0.1mmol of triphenylphosphine, and 0.02mmol of palladium tetratriphenylphosphine and 30mL of tetrahydrofuran/triethylamine (2/1, v/v) under nitrogen protection, and reacted at room temperature for 48 hours. After the reaction is finished, filtering and spin-drying the filtrate, and separating and purifying the product by column chromatography with a dichloromethane/petroleum ether (1/2, v/v) mixed solvent as an eluent to obtain a yellow solid product with the yield of 77%. The mass spectrum result of the product is as follows: MS (MALDI-TOF) m/z calcd 642.3[ M ]] + ,found:642.3。
The reaction formula of example 2 is as follows:
Figure BDA0002214528300000091
example 3
145 g of PAO10 base oil and 44.39 g of octadecylamine are mixed and heated to 60 ℃ in a reaction kettle, 2.5 g of 1- (methyl-2, 6-di-tert-butyl-p-cresol) -1,2,3,4, 5-pentaphenyl silole prepared in example 1 is dissolved in 25 g of toluene and added into the reaction kettle, 145 g of PAO10 base oil and 20.61 g of MDI are mixed and heated to 60 ℃, the mixture is added into the reaction kettle after all MDI is dissolved, the temperature is increased to 80 ℃ for reaction for 30 minutes, the temperature is continuously increased to 210 ℃, 145 g of PAO10 base oil is added and cooled to about 100 ℃, and the mixture is ground into grease.
Example 4
145 g of PAO10 base oil and 44.39 g of octadecylamine were mixed and heated to 60 ℃ in a reaction kettle, 145 g of PAO10 base oil and 20.61 g of MDI were mixed and heated to 60 ℃, added to the reaction kettle after MDI was completely dissolved, heated to 80 ℃ to react for 30 minutes, continuously heated to 210 ℃, 145 g of PAO10 base oil was added to cool to about 100 ℃, 2.5 g of 1- (methyl-2, 6-di-t-butyl-p-cresol) -1,2,3,4, 5-pentaphenyl silole prepared in example 1 was added, and ground into grease.
Example 5
145 g of PAO10 base oil and 44.39 g of octadecylamine were mixed and heated to 60 ℃ in a reaction kettle, 2.5 g of 1-methyl-1- (methyl-2, 6-di-tert-butyl-p-cresol) -2,3,4, 5-tetraphenylsilole prepared in example 2 was dissolved in 25 g of toluene and added to the reaction kettle, 145 g of PAO10 base oil and 20.61 g of MDI were mixed and heated to 60 ℃ and added to the reaction kettle after all MDI was dissolved, the temperature was raised to 80 ℃ for reaction for 30 minutes, the temperature was further raised to 210 ℃, 145 g of PAO10 base oil was added to 100 ℃ and cooled to about 100 ℃ and ground to grease.
Comparative example 1
145 g of PAO10 base oil and 44.39 g of octadecylamine are mixed and heated to 60 ℃ in a reaction kettle, 145 g of PAO10 base oil and 20.61 g of MDI are mixed and heated to 60 ℃, the mixture is added into the reaction kettle after the MDI is completely dissolved, the temperature is increased to 80 ℃ for reaction for 30 minutes, the temperature is continuously increased to 210 ℃, 145 g of PAO10 base oil is added to be cooled to about 100 ℃, and the mixture is ground into grease.
The greases of example 3, example 4, example 5 and comparative example 1 were evaluated for performance according to GB/T3498, GB/T269, SH/T0719, SH/T0325 and SH/T0324, and the evaluation results are shown in Table 1.
TABLE 1 evaluation results
Figure BDA0002214528300000101
Example 6
300 g of PAO10 base oil and 39.21 g of 12-hydroxystearic acid were mixed in a reaction vessel and heated to 85 ℃, 2.5 g of 1- (methyl-2, 6-di-tert-butyl-p-cresol) -1,2,3,4, 5-pentaphenylsilole from example 1 was dissolved in 25 g of toluene and added to the reaction vessel, 6.06 g of lithium hydroxide monohydrate and 40 g of distilled water were mixed and heated to 95 ℃, added to the reaction vessel after all the lithium hydroxide was dissolved, heated to 210 ℃ after removal of water, added 160 g of PAO10 base oil, cooled and ground to a fat.
Example 7
300 g of PAO10 base oil and 39.21 g of 12-hydroxystearic acid were mixed in a reaction vessel and heated to 85 ℃, 2.5 g of 1-methyl-1- (methyl-2, 6-di-tert-butyl-p-cresol) -2,3,4, 5-tetraphenylsilole from example 2 was dissolved in 25 g of toluene and added to the reaction vessel, 6.06 g of lithium hydroxide monohydrate and 40 g of distilled water were mixed and heated to 95 ℃, the mixture was added to the reaction vessel after all the lithium hydroxide had been dissolved, the temperature was continuously raised to 210 ℃ after heating and dewatering, 160 g of PAO10 base oil was added, and the mixture was cooled and ground to a fat.
Comparative example 2
300 g of PAO10 base oil and 39.21 g of 12-hydroxystearic acid are mixed and heated to 85 ℃ in a reaction kettle, 6.06 g of lithium hydroxide monohydrate and 40 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, the temperature is continuously raised to 210 ℃ after heating and dewatering, 160 g of PAO10 base oil is added, and the mixture is cooled and ground into grease.
The greases of example 6, example 7 and comparative example 2 were subjected to performance evaluation, and the evaluation results are shown in table 2, in the same manner as described above.
TABLE 2 evaluation results
Lubricating grease Example 6 Example 7 Comparative example 2
Dropping Point/. Degree.C 200 200 197
Appearance of the product White colour White colour White colour
Penetration/(0.1 mm) 272 275 271
Oxidative induction period (200 deg.C)/min 100 105 25
Oxidation stability, pressure drop (99 ℃,100 h)/kPa 6 6 60
Steel mesh oil separation (100 ℃,24 h)/%) 4.3 4.4 4.3
Under the irradiation of ultraviolet lamp Yellow green fluorescence Yellow green fluorescence Does not emit light
Example 8
300 g of PAO10 base oil, 43.59 g of 12-hydroxystearic acid and 14.61g of sebacic acid are mixed and heated to 85 ℃ in a reaction kettle, 2.5 g of 1- (methyl-2, 6-di-tert-butyl-p-cresol) -1,2,3,4, 5-pentaphenylsilole prepared in example 1 is dissolved in 25 g of toluene and added into the reaction kettle, 13.37 g of lithium hydroxide monohydrate and 60 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, the temperature is continuously raised to 210 ℃ after the water is removed by heating, 160 g of PAO10 base oil is added, and the mixture is cooled and ground into grease.
Example 9
300 g of PAO10 base oil, 43.59 g of 12-hydroxystearic acid and 14.61g of sebacic acid were mixed and heated to 85 ℃ in a reaction kettle, 2.5 g of 1-methyl-1- (methyl-2, 6-di-tert-butyl-p-cresol) -2,3,4, 5-tetraphenyl silole obtained in example 2 was dissolved in 25 g of toluene and added to the reaction kettle, 13.37 g of lithium hydroxide monohydrate and 60 g of distilled water were mixed and heated to 95 ℃, added to the reaction kettle after all of the lithium hydroxide was dissolved, the temperature was continuously raised to 210 ℃ after heating and dehydration, 160 g of PAO10 base oil was added, and the mixture was cooled and ground into grease.
Comparative example 3
300 g of PAO10 base oil, 43.59 g of 12-hydroxystearic acid and 14.61g of sebacic acid are mixed and heated to 85 ℃ in a reaction kettle, 13.37 g of lithium hydroxide monohydrate and 60 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, the temperature is continuously raised to 210 ℃ after the water is removed by heating, 160 g of PAO10 base oil is added, and the mixture is cooled and ground into grease.
The greases of example 8, example 9 and comparative example 3 were evaluated for their properties according to the same evaluation method as described above, and the evaluation results are shown in Table 3.
TABLE 3 evaluation results
Lubricating grease Example 8 Example 9 Comparative example 3
Dropping Point/. Degree.C 305 298 299
Appearance of the product White colour White colour White colour
Penetration/(0.1 mm) 273 274 276
Oxidative induction period (200 deg.C)/min 108 103 18
Oxidation stability, pressure drop (99 ℃,100 h)/kPa 6 7 48
Steel mesh oil separation (100 ℃,24 h)/%) 3.7 3.8 3.7
Under the irradiation of ultraviolet lamp Yellow green fluorescence Yellow green fluorescence Does not emit light
Example 10
200 g of PAO10 base oil, 32.5 g of stearic acid and 14 g of benzoic acid are mixed and heated to 90 ℃ in a reaction kettle, 2.5 g of 1- (methyl-2, 6-di-tert-butyl-p-cresol) -1,2,3,4, 5-penta-phenyl silole prepared in example 1 is dissolved in 25 g of toluene and added into the reaction kettle, 100 g of PAO10 base oil and 32 g of aluminum isopropoxide trimer are mixed and heated, the mixture is added into the reaction kettle after the aluminum isopropoxide trimer is completely dissolved, the temperature is continuously increased to 210 ℃ for reaction for 30 minutes, 150 g of PAO10 base oil is added, and the mixture is cooled and ground into grease.
Example 11
200 g of PAO10 base oil, 32.5 g of stearic acid and 14 g of benzoic acid are mixed in a reaction kettle and heated to 90 ℃, 2.5 g of 1-methyl-1- (methyl-2, 6-di-tert-butyl-p-cresol) -2,3,4, 5-tetraphenylsilole prepared in example 2 is dissolved in 25 g of toluene and added into the reaction kettle, 100 g of PAO10 base oil and 32 g of aluminum isopropoxide trimer are mixed and heated, the mixture is added into the reaction kettle after the aluminum isopropoxide trimer is completely dissolved, the temperature is continuously raised to 210 ℃ for reaction for 30 minutes, 150 g of PAO10 base oil is added, and the mixture is cooled and ground into grease.
Comparative example 4
Mixing 200 g of PAO10 base oil, 32.5 g of stearic acid and 14 g of benzoic acid in a reaction kettle, heating to 90 ℃, mixing and heating 100 g of PAO10 base oil and 32 g of aluminum isopropoxide trimer, adding the mixture into the reaction kettle after the aluminum isopropoxide trimer is completely dissolved, continuously heating to 210 ℃ for reaction for 30 minutes, adding 150 g of PAO10 base oil, cooling and grinding into grease.
The greases of example 10, example 11 and comparative example 4 were subjected to performance evaluation, and the evaluation results are shown in table 4, in the same manner as described above.
TABLE 4 evaluation results
Lubricating grease Example 10 Example 11 Comparative example 4
Dropping Point/. Degree.C 272 271 269
Appearance of the product Yellow colour Yellow colour Yellow colour
Penetration/(0.1 mm) 268 266 266
Oxidative induction period (200 deg.C)/min 88 82 28
Oxidation stability, pressure drop (99 ℃,100 h)/kPa 10 12 50
Steel mesh oil separation (100 ℃,24 h)/% 3.8 3.5 3.8
Under the irradiation of ultraviolet lamp Yellow green fluorescence Yellow-green fluorescence Does not emit light

Claims (17)

1. Silole derivative, the structure of which is shown in formula (I):
Figure FDA0004043614150000011
wherein each R is 0 Are the same or different from each other and are each independently selected from hydrogen and C 1-4 Straight or branched chain alkyl, each x is independently selected from 0, 1,2, 3; the L' group is selected from phenyl and methyl;
n is 1;
the A group is selected from the group shown in formula (II),
Figure FDA0004043614150000012
in formula (II), each R' is selected from tert-butyl; each R is selected from H;
the group L is methylene.
2. The silole derivative according to claim 1, having the structure:
Figure FDA0004043614150000013
3. the method for producing a silole derivative according to claim 1, which comprises the step of reacting a silole compound represented by the formula (III) with a compound represented by the formula (IV),
Figure FDA0004043614150000021
in the formula (III), each R 0 Are the same or different from each other and are each independently selected from hydrogen and C 1-4 Straight or branched chain alkyl, each x is independently selected from 0, 1,2, 3; the L' group is selected from phenyl and methyl;
in formula (IV), X groups are Cl, br; n is 1; the A group is selected from the group shown in formula (V),
Figure FDA0004043614150000022
in formula (V), each R' is selected from t-butyl; each R is selected from H;
the group L is methylene.
4. The process according to claim 3, wherein the silole compound of the formula (III) is one or more compounds selected from the group consisting of:
Figure FDA0004043614150000023
the compound shown in the formula (IV) is selected from one or more of the following compounds:
Figure FDA0004043614150000024
5. the process according to claim 3, wherein the molar ratio between the silole compound of formula (III) and the compound of formula (IV) in the reaction is 1:0.5 to 5; the reaction temperature is 0-50 ℃.
6. The production method according to claim 3, wherein in the reaction, the molar ratio between the silole compound represented by the formula (III) and the compound represented by the formula (IV) is 1:0.8 to 1.2; the reaction temperature is 15-35 ℃.
7. The process according to claim 3, wherein the reaction is carried out under an inert gas atmosphere.
8. The process according to claim 3, wherein a catalyst is added to the reaction, and the catalyst is one or more of a metal phosphine complex, a metal halide and a hydrocarbyl phosphine compound.
9. The process according to claim 3, wherein a catalyst is added to the reaction, and the catalyst is a mixture of a metal phosphine complex, a metal halide and a hydrocarbyl phosphine compound, and the molar ratio of the three is 1:0.1 to 10:0.1 to 10.
10. Use of the silole derivatives according to claim 1 or 2 or prepared according to one of the claims 3 to 9 in lubricating oils and greases.
11. A grease comprising a silole derivative according to claim 1 or 2 or a silole derivative obtainable by a process according to any of claims 3 to 9, a thickener and a lubricating base oil.
12. The grease of claim 11 wherein the silole derivative is present in an amount of 0.01% to 5% of the total weight 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.
13. The grease of claim 11 wherein the silole derivative comprises from 0.05% to 1% 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.
14. The grease of claim 11 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.
15. A method of preparing a grease according to any one of claims 11 to 14 comprising: mixing lubricating base oil, thickener and silole derivative, refining, and grinding into grease.
16. The process according to claim 15, wherein the silole derivative is previously dissolved in a solvent selected from aromatic hydrocarbon solvents.
17. A method for preparing a grease according to any one of claims 11 to 14, wherein the grease is a polyurea grease, a lithium-based grease, a lithium complex grease, or a aluminum complex grease;
the preparation method of the polyurea lubricating grease comprises the following steps: mixing part of lubricating base oil, the silole derivative of claim 1 or 2 or the silole derivative prepared by the method of any one of claims 3 to 9, amine and isocyanate, reacting at 65 to 95 ℃ for 10 to 60min, continuously heating to 190 to 220 ℃ after the reaction is completed, refining at high temperature, adding the rest of the base oil, cooling to 60 to 120 ℃, and grinding into grease;
the above-mentionedThe preparation method of the lithium-based lubricating grease comprises the following steps: mixing and heating part of lubricating base oil and fatty acid in a reaction kettle, heating to 40-90 ℃, adding the silole derivative of claim 1 or 2 or the silole derivative prepared by the method of any one of claims 3-9 and aqueous solution of lithium hydroxide, heating to remove water, continuously heating to 190-220 ℃, refining at high temperature, adding the rest lubricating base oil, cooling to 60-120 ℃, and grinding into grease; the preparation method of the composite lithium-based lubricating grease comprises the following steps: mixing and heating part of lubricating base oil, fatty acid and micromolecular acid in a reaction kettle, heating to 40-90 ℃, adding the silole derivative of claim 1 or 2 or the silole derivative prepared by the method of one of claims 3-9 and aqueous solution of lithium hydroxide, heating to remove water, continuously heating to 190-220 ℃ for high-temperature refining, adding the rest lubricating base oil, cooling to 60-120 ℃, and grinding into grease; the fatty acid is C 12 ～C 20 Fatty acid and/or C 12 ～C 20 Hydroxy fatty acid, the small molecular acid is C 2 ～C 11 The organic acid of (4);
the preparation method of the composite aluminum-based lubricating grease comprises the following steps: mixing and heating part of base oil, fatty acid and micromolecular acid in a reaction kettle, heating to 40-90 ℃, adding the silole derivative of claim 1 or 2 or the silole derivative prepared by the method of any one of claims 3-9, mixing and heating the other part of lubricating base oil and the aluminum alkoxide compound to 40-100 ℃, adding the aluminum alkoxide compound into the reaction kettle after the aluminum alkoxide compound is completely dissolved, continuously heating to 190-220 ℃ for high-temperature refining, adding the rest lubricating base oil, cooling to 60-120 ℃, and grinding into grease; the fatty acid is C 12 ～C 20 Fatty acid and/or C 12 ～C 20 Hydroxy fatty acid, the small molecular acid is C 2 ～C 11 The organic acid of (1).
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