CN111072703B - 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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CN111072703B
CN111072703B CN201811212645.6A CN201811212645A CN111072703B CN 111072703 B CN111072703 B CN 111072703B CN 201811212645 A CN201811212645 A CN 201811212645A CN 111072703 B CN111072703 B CN 111072703B
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compound
general formula
silole
grease
formula
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CN111072703A (en
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刘欣阳
庄敏阳
刘显秋
魏克成
孙洪伟
何懿峰
李茂森
郑会
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
    • 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
    • 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
    • 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)
  • 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 emit light strongly at low concentrations, but emit light weakly or even not at high concentrations or in a solid state, and exhibit 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 number of research fields such as light emitting devices, fluorescent probes, bio-imaging, etc.
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 lubricating grease containing the silole derivative.
The silole derivative has a structure shown in a general formula (I):
Figure GDA0003624007640000011
in the general formula (I), each R1Each independently selected from hydrogen and C1-6Straight or branched alkyl, C6-10An aryl group; each R is2Each independently selected from C1-6A linear or branched alkylene group; each R is independently selected from hydrogen and C1-6A linear or branched alkyl group; x is an integer between 0 and 5; y is an integer of 0 to 4.
Silole derivatives according to the invention, preferably each R1Each independently selected from hydrogen and C1-4Straight or branched chain alkyl, phenyl; each R is2Each independently selected from C1-4A linear or branched alkylene group; each R is independently selected from hydrogen and C1-4A linear or branched alkyl group; x is an integer of 0 to 3; y is 0, 1 or 2.
According to the present invention, the silole derivatives that may be mentioned include one or more of the following compounds:
Figure GDA0003624007640000021
the method for producing a silole derivative according to the present invention comprises a step of reacting a silole compound represented by general formula (II), a phenol compound represented by general formula (III), and a compound represented by general formula (IV),
Figure GDA0003624007640000022
in the general formula (II), R1Selected from hydrogen, C1-6Straight or branched alkyl, C6-10An aryl group; each R is independently selected from hydrogen and C1-6A linear or branched alkyl group; x is an integer of 0 to 5;
in the general formula (III), R is selected from hydrogen and C1-6A linear or branched alkyl group; y is an integer of 0 to 4; x is selected from F, Cl, Br and I;
in the general formula (IV), each R2Each independently selected from C1-6A linear or branched alkylene group; x' is selected from F, Cl, Br, I and OH.
According to the preparation process of the present invention, preferably, in the general formula (II), R1Selected from hydrogen, C1-4Straight or branched chain alkyl, phenyl; each R is independently selected from hydrogen and C1-4A linear or branched alkyl group; x is an integer between 0 and 3; in the general formula (III), R is selected from hydrogen and C1-4A linear or branched alkyl group; y is 0, 1 or 2; x is selected from Cl, Br, I and OH; in the general formula (IV), each R2Each independently selected from C1-4A linear or branched alkylene group; x' is selected from Cl, Br, I and OH.
According to the production method of the present invention, preferably, the silole compound represented by the general formula (II) includes specific compounds as shown below:
Figure GDA0003624007640000023
according to the production method of the present invention, preferably, the phenol compound represented by the general formula (III) includes specific compounds shown below:
Figure GDA0003624007640000031
according to the production method of the present invention, preferably, the compound represented by the general formula (IV) includes specific compounds shown below:
Figure GDA0003624007640000032
according to the production method of the present invention, preferably, in the reaction, the molar ratio of the silole compound represented by the general formula (II) to the phenol compound represented by the general formula (III) or the compound represented by the general formula (IV) is preferably 1: 0.5-5: 0.2 to 5, most preferably 1: 0.8-3: 0.3 to 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 of the invention, the longer the reaction time is, the higher the conversion rate is, and generally, the time is 6-96 h, preferably 12-72 h.
According to the production method of the present invention, preferably, a solvent is added to 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 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.
According to the production method of the present invention, it is preferable that the silole compound represented by the general formula (II) is reacted with the phenol compound represented by the general formula (III) and then the reaction product is reacted with the compound represented by the general formula (IV).
According to the production method of the present invention, preferably, in the reaction of the silole compound represented by the general formula (II) and the phenol compound represented by the general formula (III), the molar ratio between the silole compound represented by the general formula (II) and the phenol compound represented by the general formula (III) is preferably 1: 0.5 to 5, more preferably 1: 0.8 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 production method of the present invention, a catalyst is preferably added in the reaction of the silole compound represented by the general formula (II) and the phenol compound represented by the general formula (III). 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: 0.1-10: 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 GDA0003624007640000041
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 preparation method of 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 selected, and more preferably one or more of copper chloride, cuprous chloride, copper bromide, cuprous bromide, copper iodide and cuprous iodide.
According to the production method of the present invention, preferably, the hydrocarbyl phosphine compound has a structure of
Figure GDA0003624007640000042
Wherein each R is independently selected from C6～C10Aryl and C1～C6Wherein at least one R is C6～C10Aryl group of (2). 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, in the reaction of the silole compound represented by the general formula (II) with the phenol compound represented by the general formula (III), the amount of the catalyst to be added is preferably 1% to 100% of the amount of the silole compound represented by the general formula (II) in terms of substance.
According to the production method of the present invention, preferably, in the reaction of the reaction product of the silole compound represented by the general formula (II) with the phenol compound represented by the general formula (III) and the compound represented by the general formula (IV), the molar ratio between the silole compound represented by the general formula (II) and the compound represented by the general formula (IV) is preferably 1: 0.5 to 5, more preferably 1: 0.8 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 production method of the present invention, it is preferable to add a catalyst to the reaction of the silole compound represented by the general formula (II) with the phenol compound represented by the general formula (III) and the compound represented by the general formula (IV). The catalyst is preferably a hydrocarbyl phosphine compound and/or an azo compound, more preferably a mixture of the hydrocarbyl phosphine compound and the azo compound, and the molar ratio of the hydrocarbyl phosphine compound to the azo compound is preferably 1: 0.1 to 10, more preferably 1: 0.2 to 5. The hydrocarbyl phosphine compound preferably has the structure
Figure GDA0003624007640000051
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 diphenyl butyl phosphine. The preferable structure of the azo compound is as follows:
Figure GDA0003624007640000052
wherein each R' is the same or different from each other and is independently selected from hydrogen and C1-6Straight or branched alkyl, C3-10Cycloalkyl radical, C6-10Aryl and C1-6An alkoxy group. The azo compound may preferably be one or more selected from dimethyl azodicarboxylate, diethyl azodicarboxylate, dipropyl azodicarboxylate and dibutyl azodicarboxylate.
According to the production method of the present invention, in the reaction of the reaction product of the silole compound represented by the general formula (II) with the phenol compound represented by the general formula (III) and the compound represented by the general formula (IV), the amount of the catalyst to be added is preferably 1% to 100% of the amount of the silole compound represented by the general formula (II).
The silole derivative has excellent photoluminescence performance, 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.
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 oxidation resistance.
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 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).
Lithium-based lubricants of the inventionA method of making a lipid comprising: 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 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
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, p-iodophenol, cuprous iodide, triphenylphosphine, palladium tetratriphenylphosphine, diethyl azodicarboxylate, 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 Bailingwei reagent company, Imokay 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, 264mg (1.2mmol) of p-iodophenol, 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 placed in a 100mL Schlenk reaction flask and reacted at room temperature for 48 hours. After the reaction was completed, filtration was performed and the filtrate was spin-dried, and the product was isolated and purified by column chromatography using a mixed solvent of dichloromethane/petroleum ether (1/1, v/v) as an eluent, to obtain 430mg of a yellow solid product in a yield of 74%. The nuclear magnetic result of the product is as follows:1H NMR(400MHz,CDCl3),δ(TMS,ppm):7.74(m,2H),7.36(m,3H),7.15–6.85(m,24H)；MS(MALDI-TOF):m/zcalcd:578.2[M]+,found:578.2。
the reaction formula of example 1 is as follows:
Figure GDA0003624007640000081
example 2
Into a 100mL reaction vessel were charged 1158mg (2mmol) of 1- (4-hydroxyphenylalkynyl) -1,2,3,4, 5-pentaphenylsilole, 178mg (1mmol) of thiodipropionic acid, 630mg (2.4mmol) of triphenylphosphine, 30mL of tetrahydrofuran, and 418mg (2.4mmol) of diethyl azodicarboxylate slowly added dropwise at 0 ℃ and then reacted at room temperature for 18 hours. After the reaction was complete, it was filtered and the filtrate was spin-dried, washed with dichloromethane/petroleum ether (1/2,v/v) the product was separated and purified by column chromatography using the mixed solvent as an eluent to obtain 960mg of a yellow solid product with a yield of 78%. The nuclear magnetic result of the product is as follows:1H NMR(400MHz,CDCl3),δ(TMS,ppm):7.72(m,4H),7.35(m,6H),7.13–6.85(m,48H),2.92(m,4H),2.78(m,4H)；MS(MALDI-TOF):m/zcalcd:1298.4[M]+,found:1298.4。
the reaction formula of example 2 is as follows:
Figure GDA0003624007640000082
example 3
425mg (1mmol) of 1-methyl-1-alkynyl-2, 3,4, 5-tetraphenylsilole, 264mg (1.2mmol) of p-iodophenol, 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) were added to a 100mL Schlenk reaction flask and reacted at room temperature for 48 hours under nitrogen. After the reaction is finished, filtering is carried out, the filtrate is dried in a spinning mode, and the product is separated and purified by column chromatography by taking a dichloromethane/petroleum ether (1/1, v/v) mixed solvent as an eluent, so that 400mg of a yellow solid product is obtained, and the yield is 78%. The nuclear magnetic result of the product is as follows:1H NMR(400MHz,CDCl3),δ(TMS,ppm):7.15–6.85(m,24H),0.22(s,3H)；MS(MALDI-TOF):m/zcalcd:516.2[M]+,found:516.2。
the reaction formula for example 3 is shown below:
Figure GDA0003624007640000091
example 4
949mg (2mmol) of 1- (4-hydroxyphenylalkynyl) -1,2,3,4, 5-pentaphenylsilol, 178mg (1mmol) of thiodipropionic acid, 630mg (2.4mmol) of triphenylphosphine and 30mL of tetrahydrofuran are placed in a 100mL reaction flask, and 418mg (2.4mmol) of diethyl azodicarboxylate is slowly added dropwise at 0 ℃ and the reaction is carried out at room temperature for 18 hours. After the reaction is finished, filtering and spin-drying the filtrate, and eluting by using a dichloromethane/petroleum ether (1/2, v/v) mixed solventThe product was isolated and purified by column chromatography to give 870mg of a yellow solid, 74% yield. The nuclear magnetic result of the product is as follows:1H NMR(400MHz,CDCl3),δ(TMS,ppm):7.13–6.85(m,48H),2.92(m,4H),2.78(m,4H),0.22(s,6H)；MS(MALDI-TOF):m/z calcd:1174.4[M]+,found:1174.4。
the reaction formula of example 4 is as follows:
Figure GDA0003624007640000092
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 di (4- (1,2,3,4, 5-pentaphenylsiloyl alkynyl)) phenyl thiodipropionate 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 ℃ until all MDI was dissolved, then added to the reaction kettle, heated to 80 ℃ for reaction for 30min, heated to 210 ℃ continuously, 145 g of PAO10 base oil was added, and ground to about 100 ℃ to form a fat which was cooled.
Example 6
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 di (4- (1-methyl-2, 3,4, 5-tetraphenylsilolopyrrolyl) phenyl thiodipropionate prepared in example 4 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 30min, the temperature was raised to 210 ℃ continuously, 145 g of PAO10 base oil was added 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 30min, the temperature is continuously increased to 210 ℃, 145 g of PAO10 base oil is added, the mixture is cooled to about 100 ℃ and is ground into grease.
Comparative example 2
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 all MDI was dissolved, heated to 80 ℃ to react for 30min, continuously heated to 210 ℃, 145 g of PAO10 base oil was added to cool to about 100 ℃, 2.5 g of di (4- (1,2,3,4, 5-pentaphenylsiloyl alkynyl) phenyl thiodipropionate prepared in example 2 was added to the mixture, and the mixture was ground into grease.
The greases of examples 5-6 and comparative examples 1-2 were subjected to performance evaluation, the evaluation methods are 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 GDA0003624007640000101
Example 7
300 g of PAO10 base oil and 39.21 g of 12-hydroxystearic acid were mixed and heated to 85 ℃ in a reaction vessel, 2.5 g of bis (4- (1,2,3,4, 5-pentaphenylthiapyrrolyl) phenyl thiodipropionate prepared in example 2 was dissolved in 10 g of toluene and added to the reaction vessel, 6.06 g of lithium hydroxide monohydrate was mixed with 40 g of distilled water and heated to 95 ℃ and added to the reaction vessel after all the lithium hydroxide was dissolved, heating to 210 ℃ after removal of water was carried out, 160 g of PAO10 base oil was added, and the mixture was cooled and ground to a fat.
Example 8
300 g of PAO10 base oil and 39.21 g of 12-hydroxystearic acid were mixed and heated to 85 ℃ in a reaction vessel, 2.5 g of bis (4- (1-methyl-2, 3,4, 5-tetraphenylthiapyrrolyl) alkynyl) phenyl thiodipropionate obtained in example 4 were dissolved in 10 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 ℃ and added to the reaction vessel after all the lithium hydroxide had dissolved, the temperature was raised to 210 ℃ after the water removal by heating, 160 g of PAO10 base oil was added, and the mixture was cooled and ground to grease.
Comparative example 3
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 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 7, example 8 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 2.
TABLE 2 evaluation results
Figure GDA0003624007640000111
Example 9
200 g of PAO10 base oil, 32.5 g of stearic acid and 14 g of benzoic acid were mixed and heated to 90 ℃ in a reaction kettle, 2.5 g of bis (4- (1,2,3,4, 5-pentaphenylsilolopyrrolyl) phenyl thiodipropionate prepared in example 2 was dissolved in 10 g of toluene and added to the reaction kettle, 100 g of PAO10 base oil and 32 g of aluminum isopropoxide trimer were mixed and heated, after all of the aluminum isopropoxide trimer was dissolved, the mixture was added to the reaction kettle, the temperature was further raised to 210 ℃ for reaction for 30 minutes, 150 g of PAO10 base oil was added, and the mixture was cooled and ground into grease.
Example 10
200 g of PAO10 base oil, 32.5 g of stearic acid and 14 g of benzoic acid were mixed and heated to 90 ℃ in a reaction vessel, 2.5 g of bis (4- (1-methyl-2, 3,4, 5-tetraphenylsilolopyrrolyl) phenyl thiodipropionate obtained in example 4 was dissolved in 10 g of toluene and added to the reaction vessel, 100 g of PAO10 base oil and 32 g of aluminum isopropoxide trimer were mixed and heated, after all of the aluminum isopropoxide trimer was dissolved, the mixture was added to the reaction vessel, the temperature was further raised to 210 ℃ for reaction for 30 minutes, 150 g of PAO10 base oil was added, and the mixture was cooled and ground to fat.
Comparative example 4
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 tripolymer are mixed and heated, the mixture is added into the reaction kettle after the aluminum isopropoxide tripolymer 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.
The greases (both in appearance, yellow) of examples 9 to 10 and comparative example 4 were evaluated for performance in the same manner as described above, and the evaluation results are shown in table 3.
TABLE 3 evaluation results
Assessment item Example 9 Example 10 Comparative example 4
Soap content% 10 10 10
Dropping Point/. degree.C 276 275 269
Penetration/0.1 mm 264 266 266
Oxidation induction period of 200 deg.C/min 130 132 28
Oxidation stability, 99 ℃,100h/MPa 0.006 0.006 0.050
Steel mesh oil separation, 100 ℃,24 h/%) 3.7 3.7 3.8
Under the irradiation of ultraviolet lamp Yellow green fluorescence Yellow green fluorescence Does not emit light

Claims (25)

1. A silole derivative has a structure shown in a general formula (I):
Figure FDA0003624007630000011
in the general formula (I), each R1Each independently selected from hydrogen and C1-6Straight or branched alkyl, C6-10An aryl group; each R is2Each independently selected from C1-6A linear or branched alkylene group; each R is independently selected from hydrogen and C1-6A linear or branched alkyl group; x is an integer between 0 and 5; y is an integer of 0 to 4.
2. Silole derivatives according to claim 1, characterized in that each R is1Each independently selected from hydrogen, C1-4Straight or branched chain alkyl, phenyl; each R is2Each independently selected from C1-4A linear or branched alkylene group; each R is independently selected from hydrogen and C1-4A linear or branched alkyl group; x is an integer between 0 and 3; y is 0, 1 or 2.
3. The silole derivative according to claim 1, characterized in that it comprises one or more of the following compounds:
Figure FDA0003624007630000012
4. a method for producing the silole derivative according to any one of claims 1 to 3, which comprises reacting a silole compound represented by the general formula (II) with a phenol compound represented by the general formula (III) or a compound represented by the general formula (IV),
Figure FDA0003624007630000013
in the general formula (II), R1Selected from hydrogen, C1-6Straight or branched alkyl, C6-10An aryl group; each R is independently selected from hydrogen and C1-6A linear or branched alkyl group; x is an integer of 0 to 5;
in the general formula (III), R is selected from hydrogen and C1-6A linear or branched alkyl group; y is an integer of 0 to 4; x is selected from F, Cl, Br and I;
in the general formula (IV), each R2Each independently selected from C1-6A linear or branched alkylene group; x' is selected from F, Cl, Br, I and OH.
5. A process according to claim 4, wherein in formula (II), R1Selected from hydrogen, C1-4Straight or branched chain alkyl, phenyl; each R is independently selected from hydrogen and C1-4A linear or branched alkyl group; x is 0 to 3An integer of (d) m; in the general formula (III), R is selected from hydrogen and C1-4A linear or branched alkyl group; y is 0, 1 or 2; x is selected from Cl, Br and I; in the general formula (IV), each R2Each independently selected from C1-4A linear or branched alkylene group; x' is selected from Cl, Br, I and OH.
6. The method according to claim 4, wherein the silole compound of formula (II) comprises the following specific compounds:
Figure FDA0003624007630000021
the phenol compounds represented by the general formula (III) include specific compounds shown below:
Figure FDA0003624007630000022
the compounds represented by the general formula (IV) include specific compounds shown below:
Figure FDA0003624007630000023
7. the process according to claim 4, wherein in the reaction, the molar ratio of the silole compound of the formula (II) to the phenol compound of the formula (III) to the compound of the formula (IV) is 1: 0.5-5: 0.2 to 5; the reaction temperature is 0-50 ℃.
8. The process according to claim 4, wherein the silole compound represented by the general formula (II) is reacted with the phenol compound represented by the general formula (III), and the reaction product is reacted with the compound represented by the general formula (IV).
9. The process according to claim 8, wherein in the reaction of the silole compound of formula (II) with the phenol compound of formula (III), the molar ratio between the silole compound of formula (II) and the phenol compound of formula (III) is 1: 0.5 to 5; the reaction temperature is 0-50 ℃.
10. The method according to claim 8, wherein a catalyst is added to the reaction of the silole compound represented by the general formula (II) with the phenol compound represented by the general formula (III), and the catalyst is one or more of a metal phosphine complex, a metal halide and a hydrocarbyl phosphine compound.
11. The process according to claim 8, wherein a catalyst is added to the reaction of the silole compound of the formula (II) with the phenol compound of the formula (III), 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: 0.1-10: 0.1 to 10.
12. The method of claim 11, wherein the metal phosphine complex has the structure
Figure FDA0003624007630000031
Wherein M is Pd, Ru or Rh, L is selected from PPh3Ph, F, Cl, Br, I; one or more selected from the group consisting of copper halides, iron halides, and zinc halides;
the structure of the hydrocarbyl phosphine compound is
Figure FDA0003624007630000032
Wherein each R is independently selected from C6～C10Aryl and C1～C6Wherein at least one R is C6～C10Aryl group of (2).
13. The process according to claim 8, wherein in the reaction of the reaction product of the silole compound of the formula (II) with the phenol compound of the formula (III) and the compound of the formula (IV), the molar ratio of the silole compound of the formula (II) to the compound of the formula (IV) is 1: 0.2 to 5; the reaction temperature is 0-50 ℃.
14. The process according to claim 8, wherein a catalyst is added to the reaction of the reaction product of the silole compound represented by the general formula (II) with the phenol compound represented by the general formula (III) and the compound represented by the general formula (IV), and the catalyst is a hydrocarbyl phosphine compound and/or an azo compound.
15. The process according to claim 8, wherein a catalyst which is a mixture of a hydrocarbylphosphine compound and an azo compound is added to the reaction of the reaction product of the silole compound of the general formula (II) with the phenol compound of the general formula (III) and the compound of the general formula (IV) in a molar ratio of 1: 0.1 to 10.
16. A process according to claim 14, wherein the hydrocarbyl phosphine compound has the structure
Figure FDA0003624007630000033
Wherein each R is independently selected from C6～C10Aryl and C1～C6Wherein at least one R is C6～C10Aryl of (a); the azo compound has the structure as follows:
Figure FDA0003624007630000034
wherein each R' is the same or different from each other and is independently selected from hydrogen and C1-6Straight or branched alkyl, C3-10Cycloalkyl radical, C6-10Aryl and C1-6An alkoxy group.
17. Use of the silole derivative according to any of claims 1 to 3 or the silole derivative prepared according to any of claims 4 to 16 in light-emitting components and devices, fluorescent probes, bio-imaging, lubricating oils and greases.
18. 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 16, a thickener and a lubricating base oil.
19. The grease of claim 18 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.
20. The grease of claim 18 wherein the thickener comprises one or more of a polyurea thickener, a lithium-based thickener, a lithium complex-based thickener, a calcium-based thickener, and a aluminum complex-based thickener.
21. A method of preparing a grease as claimed in any one of claims 18 to 20 comprising: mixing lubricating base oil, thickener and silole derivative, refining, and grinding into grease.
22. A method for preparing a grease as claimed in any one of claims 18 to 20, 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.
23. A method for preparing a grease as claimed in any one of claims 18 to 20, 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.
24. The method for preparing the grease as claimed in any one of claims 18 to 20, wherein the grease is a complex aluminum-based grease, and the method for preparing the same 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.
25. A method for preparing a grease as claimed in any one of claims 21 to 24, wherein the silole derivative is dissolved in a solvent in advance, and the solvent is an aromatic hydrocarbon solvent.
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