CN111100158B - 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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CN111100158B
CN111100158B CN201811268734.2A CN201811268734A CN111100158B CN 111100158 B CN111100158 B CN 111100158B CN 201811268734 A CN201811268734 A CN 201811268734A CN 111100158 B CN111100158 B CN 111100158B
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grease
silole
silole derivative
base oil
independently selected
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CN111100158A (en
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刘欣阳
庄敏阳
孙洪伟
段庆华
刘中其
何懿峰
郑会
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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
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—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 System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/0825—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
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/06—Well-defined aromatic compounds
    • 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
    • C10M2207/02—Hydroxy compounds
    • C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
    • 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
    • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
    • C10M2207/124—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms containing hydroxy groups; Ethers thereof
    • C10M2207/1245—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms containing hydroxy groups; Ethers thereof 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • 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

Abstract

The invention provides a silole derivative, a preparation method and application thereof, and photoluminescent grease containing the silole derivative. The silole derivative has the structure as follows:

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 luminescent 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. Polyphenylsilole is a typical AIE compound, and researchers have used it in many research fields such as light emitting devices, fluorescent probes, biological imaging in recent decades.
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, transportation industry, aerospace industry, 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.
The silole derivative has the structure as follows:
Figure BDA0001845514620000011
in the general formula (I), each R is independently selected from hydrogen and C1-6A straight chain or branched chain alkyl, each n is independently selected from an integer between 0 and 5; r is1、R2Are the same or different from each other and are each independently selected from hydrogen and C1-6A linear or branched alkyl group; r3、R4、R5、R3’、R4’、R5' same or different from each other, each independently selected from hydrogen, C1-300Straight or branched alkyl (preferably C)1-10A linear or branched alkyl group or a polyolefin group having a number average molecular weight Mn of 300-3000), a group of the formula (II), with the proviso that R3、R4、R5Wherein at least one group is a group of the formula (II), R 3’、R4’、R5' wherein at least one group is a group represented by the general formula (II);
Figure BDA0001845514620000021
each radical RaAre the same or different from each other and are each independently selected from hydrogen, C1-20Straight or branched chain alkyl (preferably selected from C)1-10Straight or branched alkyl) and a group of the formula (II); each radical RbAre the same or different from each other and are each independently selected from hydrogen and C1-20Straight-chain or branched alkyl and a group of the formula (II).
R3、R5Preferably a group of the formula (II); r3’、R5' preferably a group represented by the general formula (II); r4、R4' preferably hydrogen or a group represented by the formula (II).
Examples of the silole derivative include one or more of the following compounds:
Figure BDA0001845514620000022
the method for preparing silole derivative comprises the step of reacting silole compound shown in general formula (III) with alkyne compound shown in general formula (IV),
Figure BDA0001845514620000023
in the general formula (III), each R is independently selected from hydrogen and C1-6A straight chain or branched chain alkyl, wherein each n is independently selected from an integer between 0 and 5; each group X, equal to or different from each other, is independently selected from F, Cl, Br, I, OH, preferably Cl or Br; r1、R2Are the same or different from each other and are each independently selected from hydrogen and C1-6A linear or branched alkyl group; r3、R4、R5Are the same or different from each other and are each independently selected from hydrogen and C 1-300Straight or branched chain alkyl (preferably C)1-10A linear or branched alkyl group or a polyolefin group having a number average molecular weight Mn of 300-3000), a group of the formula (V), with the proviso that R3、R4、R5At least one group is a group represented by the general formula (V);
Figure BDA0001845514620000031
each radical RaAre the same or different from each other and are each independently selected from hydrogen, C1-20Straight or branched chain alkyl (preferably selected from C)1-10Straight or branched chain alkyl); each radical RbAre the same or different from each other and are each independently selected from hydrogen and C1-20Straight or branched chain alkyl.
Silole compounds of formula (III) include:
Figure BDA0001845514620000032
the alkyne compounds of formula (IV) include:
Figure BDA0001845514620000033
a catalyst is preferably added in 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 BDA0001845514620000034
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 compoundIs structured as
Figure BDA0001845514620000041
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 invention, the amount of the catalyst added is preferably from 0.1% to 100% (preferably from 1% to 20%) of the amount of the silole compound of the formula (III) expressed by the substance.
In the reaction, the molar ratio between the silole compound represented by the general formula (III) and the acetylene compound represented by the general formula (IV) is preferably 1: 1 to 6, most preferably 1: 2 to 4.
The reaction temperature is 0-50 ℃, and preferably 15-35 ℃.
The reaction time is 12-96 h, preferably 24-72 h.
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, imaging parts, 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 0.0005 to 5 percent of the total mass of the lubricating grease, and preferably accounts for 0.001 to 1 percent; the thickening agent accounts for 5-30% of the total mass of the lubricating grease, preferably 10-20%; the lubricating base oil constitutes the main component of the grease.
The thickening agent comprises one or more of a polyurea thickening agent, a calcium-based thickening agent and a composite aluminum-based thickening agent, and the polyurea thickening agent and the composite aluminum-based thickening agent are preferred.
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.
According to the production method 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 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, and can be a single metal soap or a composite metal soap, and the metal can be one or more of 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 lubricating grease comprises polyurea lubricating grease or composite aluminum-based lubricating grease, wherein the thickening agent contained in the lubricating grease is a polyurea thickening agent or a composite aluminum-based thickening agent respectively.
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 the reaction is completed, 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, e.g. octadecylamine, cyclohexylamineOne or more of 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 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 C 12-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 (3) 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.
The lubricating grease has excellent photoluminescence performance, oxidation resistance and anti-foaming performance, and can be used on 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 raw material sources are as follows: chemical reagents such as 1, 1-dimethyl-2, 5-dibromo-3, 4-diphenylsilole, 3, 5-bis (dimethylamino) phenylacetylene, 3, 5-bis (diethylamino) phenylacetylene, 3, 5-bis (dipropylamino) phenylacetylene, cuprous iodide, triphenylphosphine, palladium tetratriphenylphosphine, octadecylamine, MDI, stearic acid, benzoic acid, aluminum isopropoxide trimer, tetrahydrofuran, triethylamine, dichloromethane, methanol, toluene, etc. are available from carbofuran reagent, enooka reagent, or sigma reagent; PAO10 base oil was from exxon mobil corporation.
Example 1
A100 mL Schlenk flask was charged with 420mg (1mmol) of 1, 1-dimethyl-2, 5-dibromo-3, 4-diphenylsilol, 733mg (3mmol) of 3, 5-bis (diethylamino) phenylacetylene, 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 under nitrogen protection to react at room temperature for 48 hours. After the reaction was completed, the product was separated and purified by column chromatography using a dichloromethane/methanol (20/1, v/v) mixed solvent as an eluent by filtration and spin-drying of the filtrate to obtain 460mg of a yellow solid product in a yield of 62%. The nuclear magnetic result of the product is as follows:1H NMR(400MHz,CDCl3),δ(TMS,ppm):7.11–6.85(m,10H),6.57(m,4H),6.36(m,2H),3.43(m,16H),1.27(m,24H),0.49(s,6H)；MS(MALDI-TOF):m/z calcd:746.5[M]+,found:746.5。
the reaction equation for example 1 is as follows:
Figure BDA0001845514620000061
a100 mL Schlenk reaction flask was charged with 420mg (1mmol) of 1, 1-dimethyl-2, 5-dibromo-3, 4-diphenylsilol, 901mg (3mmol) of 3, 5-bis (dipropylamino) phenylacetylene, 19mg (0.1mmol) of cuprous iodide, 26mg (0.1mmol) of triphenylphosphine, 23mg (0.02mmol) of palladium tetratriphenylphosphine and 30mL of tetrahydrofuran/triethylamine (2/1, v/v) under nitrogen, and reacted at room temperature for 48 hours. After the reaction was completed, the reaction mixture 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 507mg of a yellow solid product with a yield of 59%. The nuclear magnetic result of the product is as follows: 1H NMR(400MHz,CDCl3),δ(TMS,ppm):7.12–6.84(m,10H),6.55(m,4H),6.34(m,2H),3.42(m,16H),1.62(m,16H),0.83(m,24H),0.49(s,6H)；MS(MALDI-TOF):m/z calcd:858.6[M]+,found:858.6。
The reaction equation for example 2 is as follows:
Figure BDA0001845514620000071
to a 100mL Schlenk reaction flask were added 420mg (1mmol) of 1, 1-dimethyl-2, 5-dibromo-3, 4-diphenylsilole, 565mg (3mmol) of 3, 5-bis (dimethylamino) phenylacetylene, 19mg (0.1mmol) of cuprous iodide, 26mg (0.1mmol) of triphenylphosphine, and under nitrogen, 23mg (0.02mmol) of palladium tetratriphenylphosphine, 30mL of tetrahydrofuran/triethylamine (2/1, v/v) were added and reacted at room temperature for 48 hours. After the reaction was completed, the product was separated and purified by column chromatography using a dichloromethane/methanol (20/1, v/v) mixed solvent as an eluent by filtration and spin-drying of the filtrate to obtain 406mg of a yellow solid product in a yield of 64%. The nuclear magnetic result of the product is as follows:1H NMR(400MHz,CDCl3),δ(TMS,ppm):7.10–6.84(m,10H),6.55(m,4H),6.35(m,2H),3.12(m,24H),0.49(s,6H)；MS(MALDI-TOF):m/z calcd:634.4[M]+,found:634.4。
the reaction equation for example 3 is as follows:
Figure BDA0001845514620000072
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, 1-dimethyl-2, 5-bis (3, 5-diethylaminophenylethynyl) -3, 4-diphenyl silole is dissolved in 5 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 ℃, added into the reaction kettle after all MDI is dissolved, heated to 80 ℃ for reaction for 30min, continuously heated to 210 ℃, 145 g of PAO10 base oil is added, and the base oil is cooled to about 100 ℃ and 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, 2.5 g of 1, 1-dimethyl-2, 5-bis (3, 5-dipropylaminophenylethynyl) -3, 4-diphenyl silole is dissolved in 5 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 ℃, added into the reaction kettle after all MDI is dissolved, heated to 80 ℃ for reaction for 30min, continuously heated to 210 ℃, 145 g of PAO10 base oil is added, and the mixture is cooled to about 100 ℃ and ground into grease.
Example 6
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, 1-dimethyl-2, 5-bis (3, 5-dimethylaminophenylethynyl) -3, 4-diphenyl silole is dissolved in 5 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 ℃, added into the reaction kettle after all MDI is dissolved, heated to 80 ℃ for reaction for 30min, continuously heated to 210 ℃, 145 g of PAO10 base oil is added, and the base oil is cooled to about 100 ℃ and 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 raised to 80 ℃ for reaction for 30min, the temperature is continuously raised to 210 ℃, 145 g of PAO10 base oil is added to be cooled to about 100 ℃ and is ground into grease.
Comparative example 2
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 raised to 80 ℃ for reaction for 30min, the temperature is continuously raised to 210 ℃, 145 g of PAO10 base oil is added to be cooled to about 100 ℃, 2.5 g of 1, 1-dimethyl-2, 5-bis (3, 5-diethylaminophenylethynyl) -3, 4-diphenylsilole is added and ground into grease.
The greases of example 4, example 5 and example 6, and comparative example 1 and comparative example 2 were subjected to performance evaluation, the evaluation methods include GB/T3498, GB/T269, SH/T0325, SH/T0719 and SH/T0324, and the evaluation results are shown in Table 1.
TABLE 1
Figure BDA0001845514620000091
Example 7
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, 10 mg of 1, 1-dimethyl-2, 5-bis (3, 5-diethylaminophenylethynyl) -3, 4-diphenyl silole is dissolved in 5 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.
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, 10 mg of 1, 1-dimethyl-2, 5-bis (3, 5-dipropylaminophenylethynyl) -3, 4-diphenyl silole is dissolved in 5 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.
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, 10 mg of 1, 1-dimethyl-2, 5-bis (3, 5-dimethylaminophenylethynyl) -3, 4-diphenyl silole is dissolved in 5 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 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 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 of example 7, example 8, example 9 and comparative example 3 were evaluated for performance in the same manner as described above, and the evaluation results are shown in table 2.
TABLE 2 analytical results
Lubricating grease Example 7 Example 8 Example 9 Comparative example 3
Soap amount/% 10 10 10 10
Dropping Point/. degree.C 278 273 274 269
Appearance of the product Yellow colour Yellow colour Yellow colour Yellow colour
Penetration/0.1 mm 260 262 261 266
Oxidation induction period of 200 deg.C/min 96 88 102 28
Steel mesh oil separation, 100 ℃,24 h/%) 3.7 3.9 3.8 3.8
Under the irradiation of ultraviolet lamp Yellow fluorescence Yellow fluorescence Yellow fluorescence Does not emit light

Claims (14)

1. A silole derivative having the structure:
Figure FDA0003611860430000011
in the general formula (I), each R is independently selected from hydrogen and C1-6A straight chain or branched chain alkyl, wherein each n is independently selected from an integer between 0 and 5; r1、R2Are the same or different from each other and are each independently selected from hydrogen and C1-6A linear or branched alkyl group; r4、R4' is selected from hydrogen, R3、R5Is a group of the formula (II), R3’、R5' is a group represented by the general formula (II);
Figure FDA0003611860430000012
each radical RaAre the same or different from each other and are each independently selected from C1-20A linear or branched alkyl group; each radical RbAre the same or different from each other and are each independently selected from C1-20Straight or branched chain alkyl.
2. The silole derivative according to claim 1, characterized in that it comprises one or more of the following compounds:
Figure FDA0003611860430000013
3. A method for producing a silole derivative, comprising the step of reacting a silole compound represented by the general formula (III) with an acetylene compound represented by the general formula (IV),
Figure FDA0003611860430000014
in the general formula (III), each R is independently selected from hydrogen and C1-6A straight chain or branched chain alkyl, wherein each n is independently selected from an integer between 0 and 5; each group X, equal to or different from each other, is independently selected from F, Cl, Br, I, OH; r1、R2Are the same or different from each other and are each independently selected from hydrogen and C1-6A linear or branched alkyl group; r4Selected from hydrogen, R3、R5Is a group of the formula (V);
Figure FDA0003611860430000021
each radical RaAre the same or different from each other and are each independently selected from C1-20A linear or branched alkyl group; each radical RbAre the same or different from each other and are each independently selected from C1-20Straight or branched chain alkyl.
4. A method according to claim 3, wherein the silole compound of formula (III) comprises:
Figure FDA0003611860430000022
the acetylene compounds represented by the general formula (IV) include:
Figure FDA0003611860430000023
5. the process according to claim 3, wherein a catalyst is added to the reaction, the catalyst being selected from one or more of a metal phosphine complex, a metal halide and a hydrocarbyl phosphine compound.
6. A process according to claim 3, wherein a catalyst is added to the reaction, said catalyst being selected from the group consisting of metal phosphine complexes, mixtures of metal halides and hydrocarbyl phosphine compounds, in a molar ratio of 1: 0.1-10: 0.1 to 10.
7. A process according to claim 3, characterized in that in the reaction the molar ratio between the silole compound of formula (III) and the alkyne compound of formula (IV) is 1: 1-6; the reaction temperature is 0-50 ℃.
8. A process according to claim 3, characterized in that in the reaction the molar ratio between the silole compound of formula (III) and the alkyne compound of formula (IV) is 1: 2-4; the reaction temperature is 15-35 ℃.
9. Use of the silole derivative of claim 1 or 2 or of the silole derivative obtainable by the process of any one of claims 3 to 8 in light-emitting components and devices, fluorescent probes, imaging components, lubricating oils and greases.
10. A grease comprising the silole derivative of claim 1 or 2 or the silole derivative prepared by the method of any one of claims 3 to 8, a thickener and a lubricating base oil; the silole derivative accounts for 0.0005 to 5 percent of the total mass of the lubricating 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.
11. The grease of claim 10 wherein the silole derivative is present at a level of from 0.001% to 1% by weight of the total grease; the thickening agent accounts for 10-20% of the total mass of the lubricating grease.
12. The grease of claim 10 wherein the grease comprises a polyurea grease or a complex aluminum-based grease and wherein the thickener comprises a polyurea thickener or a complex aluminum-based thickener, respectively.
13. A method of making a grease of claim 10 comprising: mixing lubricating base oil, thickener and silole derivative, refining, and grinding into grease.
14. A method of preparing a grease according to claim 12,
the preparation method of the polyurea lubricating grease comprises the following steps: mixing part of lubricating base oil, the silole derivative as defined in claim 1 or 2 or the silole derivative prepared by the method as defined in any one of claims 3 to 8, amine and isocyanate, reacting at 65-95 ℃ for 10-60min, continuously heating to 190-220 ℃ after the reaction is completed, carrying out high-temperature refining, adding the rest base oil, cooling to 60-120 ℃, and grinding into grease;
the preparation method of the composite aluminum-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 40-90 ℃, adding the silole derivative of claim 1 or 2 or the silole derivative prepared by the method of any one of claims 3-8, 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.
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