CN111072705A - 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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Publication number
CN111072705A
CN111072705A CN201811212797.6A CN201811212797A CN111072705A CN 111072705 A CN111072705 A CN 111072705A CN 201811212797 A CN201811212797 A CN 201811212797A CN 111072705 A CN111072705 A CN 111072705A
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grease
base oil
silole
general formula
silole derivative
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CN111072705B (en
Inventor
刘欣阳
何懿峰
魏克成
李茂森
刘显秋
郑会
孙洪伟
庄敏阳
刘伟
李朝宇
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • 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
    • 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
    • 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
    • C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
    • 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
    • C10M2205/0206—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/045—Polyureas; Polyurethanes
    • C10M2217/0456—Polyureas; Polyurethanes 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
    • C10M2219/06—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
    • 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
    • C10M2227/04—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 having a silicon-to-carbon bond, e.g. organo-silanes

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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 lubricating grease containing the silole derivative. The silole derivative has a structure shown in a general 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 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.
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 photoluminescent lubricating grease containing the silole derivative.
The silole derivative has a structure shown in a general formula (I):
Figure BDA0001832809260000011
in the general formula (I), each R is independently selected from hydrogen and C1-6A linear or branched alkyl group; each x is independently selected from an integer between 0 and 5; r1Selected from hydrogen, C1-6Straight or branched alkyl, C6-10An aryl group; r2Selected from single bond, C1-20Straight or branched chain alkylene.
According to the invention, preferably, in the general formula (I), each R is independently chosen from hydrogen, C1-4A linear or branched alkyl group; each x is independently selected from an integer between 0 and 3; r1Selected from hydrogen, C1-4Straight or branched chain alkyl, phenyl; r2Selected from single bond, C6-18Straight or branched chain alkylene.
According to the present invention, preferably, the silole derivatives that may be cited include one or more of the following compounds:
Figure BDA0001832809260000021
the method for producing a silole derivative according to the present invention comprises a step of reacting a silole compound represented by the general formula (II) with a compound represented by the general formula (III),
Figure BDA0001832809260000022
in the general formula (II), each R is independently selected from hydrogen and C1-6A linear or branched alkyl group; each x is independently selected from an integer between 0 and 5; r1Selected from hydrogen, C1-6Straight or branched alkyl, C6-10An aryl group; in the general formula (III), R2Selected from single bond, C1-20A linear or branched alkylene group; x is selected from F, Cl, Br and I.
According to the invention, preferably, in the general formula (II), each R is independently chosen from hydrogen, C1-4A linear or branched alkyl group; each x is independently selected from an integer between 0 and 3; r1Selected from hydrogen, C1-4Straight or branched chain alkyl, phenyl; in the general formula (III), R2Selected from single bond, C6-18A linear or branched alkylene group; x is selected from Cl, Br and I.
According to the present invention, preferably, the silole compound represented by the general formula (II) includes one or more of the following compounds:
Figure BDA0001832809260000023
according to the present invention, preferably, the compound represented by the general formula (III) includes one or more of the following compounds:
Figure BDA0001832809260000024
Figure BDA0001832809260000031
according to the production method of the present invention, preferably, in the reaction, the molar ratio between the silole compound represented by the general formula (II) and the compound represented by the general formula (III) is preferably 1: 0.5 to 5, most preferably 1: 0.8 to 1.2.
According to the preparation method provided by the invention, the reaction temperature is preferably 0-50 ℃, and preferably 15-35 ℃.
According to the preparation method provided by the invention, the reaction time is preferably 6-96 h, and preferably 12-72 h.
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, 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 present invention, preferably, the metal phosphine complex has the structure
Figure BDA0001832809260000032
Wherein M is Pd, Ru or Rh, L is selected from PPh3Ph, 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, and 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 a copper halide, an iron halide and a 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 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 BDA0001832809260000033
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 straight or branched alkyl group of (1) may be selected fromFrom 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 formula (II).
According to the production method of the present invention, preferably, a solvent is added in the reaction. The solvent is preferably C1～C10Examples of the organic amine and furan include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine and tetrahydrofuran, and most preferably C1～C10The 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 a method of distillation, evaporation, and column chromatography. Preferably, the silole derivative of the present invention is isolated and purified by column chromatography, and a mixed solvent of alkyl halide and petroleum ether (preferably a mixed solvent of dichloromethane and petroleum ether) can be used as an eluent, and the volume ratio of the alkyl halide to the petroleum ether is preferably 1: 0.5 to 5.
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.
The lubricating grease disclosed by the invention has excellent photoluminescence performance and antirust performance.
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 thickener can be a soap-based thickener or a non-soap-based thickener. The soap-based thickener is preferably a metal soap, and 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, amine and isocyanate, reacting at 65-95 ℃ for 10-60min, continuously heating to 190-220 ℃ after complete reaction, refining at high temperature, adding the rest base oil, cooling to 60-120 ℃, and grinding into grease. The amine is C2～C20Alkylamine and/or C6～C20Aromatic amines, such as one or more of octadecylamine, cyclohexylamine, aniline; the isocyanate is C2～C20The 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 C12～C20Fatty acid and/or C12～C20The 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 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 ℃, adding the mixture into the reaction kettle after the aluminum alkoxide compound is completely dissolved, continuously heating to 190-220 ℃ for high-temperature refining, adding the rest of lubricating base oil, cooling to 60-120 ℃, and grinding into grease. The fatty acid is C12～C20Fatty acid and/or C12～C20Hydroxy fatty acid, which can be one or more of lauric acid, palmitic acid, stearic acid and 12-hydroxystearic acid; the small molecular acid is C2～C11The 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 grease of the present invention may further contain an antioxidant, an antiwear agent, an extreme pressure agent, and a rust preventive agent, which are known in the art, and the amount thereof is not particularly limited, and the amount thereof is also in accordance with the conventional amount in the art.
The lubricating grease has excellent photoluminescence performance and antirust performance, 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
The main raw materials used are as follows:
1-alkynyl-1, 2,3,4, 5-pentaphenyl silole, 1-methyl-1-alkynyl-2, 3,4, 5-tetraphenyl silole, 8-bromooctanoic acid, 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 and other chemical reagents are from carbofuran reagent company, enokay reagent company or sigma reagent company, and are analytically pure; the PAO10 base oil was obtained from Exxon Mobil.
Example 1
487mg (1mmol) of 1-alkynyl-1, 2,3,4, 5-pentaphenylsilol, 268mg (1.2mmol) of 8-bromooctanoic acid, 19mg (0.1mmol) of cuprous iodide, 26mg (0.1mmol) of triphenylphosphine and 23mg (0.02mmol) of palladium tetratriphenylphosphine and 30mL of tetrahydrofuran/triethylamine (2/1, v/v) are added to a 100mL Schlenk reaction flask and reacted at room temperature for 48 hours. After the reaction was completed, the reaction solution was filtered, and the filtrate was spin-dried, and the product was isolated and purified by column chromatography using a mixed solvent of dichloromethane/methanol (20/1, v/v) as an eluent, to obtain 450mg of a yellow solid product with a yield of 72%. The nuclear magnetic result of the product is as follows:1HNMR(400MHz,CDCl3),δ(TMS,ppm):7.78(m,2H),7.34(m,3H),7.13–6.87(m,20H),2.55(m,2H),2.18(m,2H),1.54(m,2H),1.42(m,2H),1.32–1.26(m,6H)；MS(MALDI-TOF):m/z calcd:628.3[M]+,found:628.3。
the reaction formula of example 1 is as follows:
Figure BDA0001832809260000061
example 2
To a 100mL Schlenk reaction flask was added 425mg (1mmol) of 1-methyl-1-alkynyl-2,3,4, 5-tetraphenylsilole, 268mg (1.2mmol) of 8-bromooctanoic acid, 19mg (0.1mmol) of cuprous iodide, 26mg (0.1mmol) of triphenylphosphine, 23mg (0.02mmol) of palladium tetratriphenylphosphine, 30mL of tetrahydrofuran/triethylamine (2/1, v/v) under nitrogen protection, and reaction at room temperature for 48 hours. After the reaction was completed, the reaction solution was filtered, and the filtrate was spin-dried, and the product was isolated and purified by column chromatography using a mixed solvent of dichloromethane/methanol (20/1, v/v) as an eluent, to give 390mg of a yellow solid product with a yield of 69%. The nuclear magnetic result of the product is as follows:1H NMR(400MHz,CDCl3),δ(TMS,ppm):7.14–6.85(m,20H),2.56(m,2H),2.22(m,2H),1.55(m,2H),1.38(m,2H),1.33–1.26(m,6H),0.22(s,3H)；MS(MALDI-TOF):m/z calcd:566.3[M]+,found:566.3。
the reaction formula of example 2 is as follows:
Figure BDA0001832809260000071
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-1- (9-carboxyl nonynyl) -2,3,4, 5-tetraphenyl silole prepared in example 2 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 the MDI is dissolved, the temperature is increased to 80 ℃ for reaction for 30min, the temperature is continuously increased to 210 ℃, 145 g of PAO10 base oil is added and cooled to about 100 ℃,10 g of molybdenum dibutyldithiocarbamate is added and ground into grease.
Example 4
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- (9-carboxyl nonynyl) -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 the MDI is dissolved, the temperature is raised to 80 ℃ for reaction for 30min, the temperature is raised to 210 ℃, 145 g of PAO10 base oil is added to be cooled to about 100 ℃,10 g of molybdenum dibutyldithiocarbamate is added, and the mixture is ground into grease.
Example 5
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 30min, the temperature is continuously increased to 210 ℃, 145 g of PAO10 base oil is added to be cooled to about 100 ℃, 2.5 g of 1- (9-carboxyl nonynyl) -1,2,3,4, 5-pentaphenyl silole prepared in example 1 and 10g of molybdenum dibutyl dithiocarbamate are added, and the mixture is ground into 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 30min, the temperature is continuously increased to 210 ℃, 145 g of PAO10 base oil is added to be cooled to about 100 ℃,10 g of molybdenum dibutyldithiocarbamate is added, 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, GB/T7326 and SH/T0324, and the evaluation results are shown in Table 1.
TABLE 1 evaluation results
Figure BDA0001832809260000081
Example 6
300 g of PAO10 base oil and 39.21 g of 12-hydroxystearic acid were mixed and heated to 85 ℃ in a reaction kettle, 2.5 g of 1-methyl-1- (9-carboxynonynyl) -2,3,4, 5-tetraphenylthiapyrrole prepared in example 2 were dissolved in 25 g of toluene and added to the reaction kettle, 6.06 g of lithium hydroxide monohydrate and 40 g of distilled water were mixed and heated to 95 ℃ and added to the reaction kettle after all the lithium hydroxide was dissolved, the temperature was further raised to 210 ℃ after the water was removed by heating, 160 g of PAO10 base oil was added to about 100 ℃,10 g of molybdenum dibutyldithiocarbamate was added and the mixture was ground to a fat.
Example 7
300 g of PAO10 base oil and 39.21 g of 12-hydroxystearic acid are mixed and heated to 85 ℃ in a reaction kettle, 2.5 g of 1- (9-carboxyl nonynyl) -1,2,3,4, 5-pentaphenyl silole prepared in example 1 is dissolved in 25 g of toluene and added into the 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 the water is removed by heating, 160 g of PAO10 base oil is added to 100 ℃,10 g of molybdenum dibutyl dithiocarbamate is added and the mixture is ground into grease.
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 to be cooled to about 100 ℃,10 g of molybdenum dibutyldithiocarbamate is added, and the mixture is ground into grease.
The greases of example 6, example 7 and comparative example 2 were evaluated for their properties in the same manner as described above, and the results are shown in Table 2.
TABLE 2 evaluation results
Lubricating grease Example 6 Example 7 Comparative example 2
Soap content% 8 8 8
Dropping Point/. degree.C 199 200 197
Appearance of the product Yellow colour Yellow colour Yellow colour
Penetration/0.1 mm 270 269 271
Corrosion of copper sheet at 100 deg.C for 24 h/grade 1b 1b 2b
Steel mesh oil separation, 100 ℃,24 h/%) 4.1 4.3 4.3
Under the irradiation of ultraviolet lamp Yellow green fluorescence Yellow green fluorescence Does not emit light
Example 8
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-1- (9-carboxynonynyl) -2,3,4, 5-tetraphenylsilole prepared in example 2 are dissolved in 25 g of toluene and added to the reaction kettle, 100 g of PAO10 base oil and 32 g of aluminum isopropoxide trimer are mixed and heated, the aluminum isopropoxide trimer is completely dissolved and then added to the reaction kettle, the temperature is continuously raised to 210 ℃ for reaction for 30 minutes, 150 g of PAO10 base oil is added to about 100 ℃,10 g of molybdenum dibutyldithiocarbamate is added and the mixture is ground into grease.
Example 9
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- (9-carboxynonynyl) -1,2,3,4, 5-pentaphenylsilole prepared in example 1 is dissolved in 25 g of toluene and added to the reaction kettle, 100 g of PAO10 base oil and 32 g of aluminum isopropoxide trimer are mixed and heated, the aluminum isopropoxide trimer is added to the reaction kettle after being completely dissolved, the temperature is continuously raised to 210 ℃ for reaction for 30 minutes, 150 g of PAO10 base oil is added to be cooled to about 100 ℃,10 g of molybdenum dibutyldithiocarbamate is added and the mixture is ground into grease.
Comparative example 3
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, 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 to be cooled to about 100 ℃,10 g of molybdenum dibutyldithiocarbamate is added, and the mixture is 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
Example 8 Example 9 Comparative example 3
Soap content% 10 10 10
Dropping Point/. degree.C 273 272 269
Appearance of the product Yellow colour Yellow colour Yellow colour
Penetration/0.1 mm 265 266 266
Corrosion of copper sheet at 100 deg.C for 24 h/grade 1b 1b 2b
Steel mesh oil separation, 100 ℃,24 h/%) 3.8 3.8 3.8
Under the irradiation of ultraviolet lamp Yellow green fluorescence Yellow green fluorescence Does not emit light

Claims (18)

1. A silole derivative has a structure shown in a general formula (I):
Figure FDA0001832809250000011
in the general formula (I), each R is independently selected from hydrogen and C1-6A linear or branched alkyl group; each x is independently selected from an integer between 0 and 5; r1Selected from hydrogen, C1-6Straight or branched alkyl, C6-10An aryl group; r2Selected from single bond, C1-20Straight or branched chain alkylene.
2. Silole derivatives according to claim 1, characterized in that in formula (I) each R is independently selected from hydrogen, C1-4A linear or branched alkyl group; each x is independently selected from an integer between 0 and 3; r1Selected from hydrogen, C1-4Straight or branched chain alkyl, phenyl; r2Selected from single bond, C6-18Straight or branched chain alkylene.
3. The silole derivative according to claim 1, characterized in that it comprises one or more of the following compounds:
Figure FDA0001832809250000012
4. a process for producing a silole derivative, which comprises reacting a silole compound represented by the general formula (II) with a compound represented by the general formula (III),
Figure FDA0001832809250000013
in the general formula (II), each R is independently selected from hydrogen and C1-6A linear or branched alkyl group; each x is independently selected from an integer between 0 and 5; r1Selected from hydrogen, C1-6Straight or branched alkyl, C6-10An aryl group; in the general formula (III), R2Selected from single bond, C1-20A linear or branched alkylene group; x is selected from F, Cl, Br and I.
5. The process according to claim 4, wherein in the general formula (II), each R is independently selected from hydrogen, C1-4A linear or branched alkyl group; each x is independently selected from an integer between 0 and 3; r1Selected from hydrogen, C1-4Straight or branched chain alkyl, phenyl; in the general formula (III), R2Selected from single bond, C6-18A linear or branched alkylene group; x is selected from Cl, Br and I.
6. The method of claim 4, wherein the silole compound of formula (II) comprises one or more of the following compounds:
Figure FDA0001832809250000021
the compounds represented by the general formula (III) include one or more of the following compounds:
Figure FDA0001832809250000022
7. the process according to claim 4, wherein in the reaction, the molar ratio between the silole compound of formula (II) and the compound of formula (III) is 1: 0.5 to 5; the reaction temperature is 0-50 ℃.
8. The method according to claim 4, wherein a catalyst is added to the reaction (the catalyst is preferably one or more of a metal phosphine complex, a metal halide and a hydrocarbyl phosphine compound, and more preferably a mixture of a metal phosphine complex, a metal halide and a hydrocarbyl phosphine compound, and the molar ratio of the three is preferably 1: 0.1-10).
9. The method of claim 8, wherein the metal phosphine complex has the structure
Figure FDA0001832809250000023
Wherein M is Pd, Ru or Rh, L is selected from PPh3、Ph、F、Cl、Br、I；
The metal halide is selected from one or more of copper halide, iron halide and zinc halide;
the structure of the hydrocarbyl phosphine compound is
Figure FDA0001832809250000024
Wherein each R is independently selected from C6～C10Aryl and C1～C6Wherein at least one R is C6～C10Aryl group of (1).
10. Use of the silole derivative according to any of claims 1 to 3 or the silole derivative obtainable by the process according to any of claims 4 to 9 in light-emitting components and devices, fluorescent probes, bio-imaging, lubricating oils and greases.
11. A grease comprising the silole derivative according to any one of claims 1 to 3 or the silole derivative prepared by the method according to any one of claims 4 to 9, a thickener and a lubricating base oil.
12. The grease of claim 11 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.
13. 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.
14. A method of preparing a grease as claimed in any one of claims 11 to 13, comprising: mixing lubricating base oil, thickener and silole derivative, refining, and grinding into grease.
15. A method for preparing a grease according to any one of claims 11 to 13, wherein the grease is a polyurea grease, and the method comprises: mixing part of lubricating base oil, silole derivatives, amine and isocyanate, reacting at 65-95 ℃ for 10-60min, continuously heating to 190-220 ℃ after complete reaction, refining at high temperature, adding the rest base oil, cooling to 60-120 ℃, and grinding into grease.
16. A method for preparing a grease as claimed in any one of claims 11 to 13, wherein the grease is a lithium-based grease, and the method comprises: mixing and heating part of lubricating base oil and fatty acid in a reaction kettle, heating to 40-90 ℃, adding aqueous solution of 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.
17. A method for preparing a grease as claimed in any one of claims 11 to 13, wherein the grease is a composite aluminum-based grease, and the method comprises: mixing and heating part of base oil, fatty acid and micromolecular acid in a reaction kettle, heating to 40-90 ℃, adding a silole derivative, mixing and heating the other part of lubricating base oil and an aluminum alkoxide compound to 40-100 ℃, adding the mixture into the reaction kettle after the aluminum alkoxide compound is completely dissolved, continuously heating to 190-220 ℃ for high-temperature refining, adding the rest of lubricating base oil, cooling to 60-120 ℃, and grinding into grease.
18. A method for preparing a grease as claimed in any one of claims 11 to 17, wherein the silole derivative is dissolved in a solvent (preferably an aromatic hydrocarbon solvent).
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