CN111072704B - 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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CN111072704B
CN111072704B CN201811212796.1A CN201811212796A CN111072704B CN 111072704 B CN111072704 B CN 111072704B CN 201811212796 A CN201811212796 A CN 201811212796A CN 111072704 B CN111072704 B CN 111072704B
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grease
group
formula
hydrogen
base oil
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CN111072704A (en
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刘欣阳
庄敏阳
何懿峰
刘中其
姜靓
孙洪伟
段庆华
郑会
刘大军
刘伟
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
    • C07F7/0816—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring comprising Si as a ring atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
    • C07F7/083—Syntheses without formation of a Si-C bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M139/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00
    • C10M139/04—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00 having a silicon-to-carbon bond, e.g. silanes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/141—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings monocarboxylic
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Lubricants (AREA)

Abstract

The invention provides a silole derivative, a preparation method and application thereof, and photoluminescent grease containing the silole derivative. The silole derivative has 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
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 grease has great difficulty, the residual quantity of the grease is difficult to directly observe by naked eyes in many cases, and if the grease can emit high-intensity fluorescence, the grease is greatly helpful to the observation of the residual quantity of the grease.
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 aggregation state, strong interactions between molecules lead to an enhancement of the non-radiative decay process of the excited state, with a significant decrease in fluorescence quantum yield. In the practical application process, the practical application of the organic light-emitting material is limited to a great extent by the aggregate fluorescence quenching effect. In recent years, researches show that some compounds show properties opposite to those of the traditional organic light-emitting 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 light-emitting materials in a solid state or at a high concentration.
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 BDA0001832809810000011
in the formula (I), each R is independently selected from hydrogen and C1-6Straight or branched chain hydrocarbon radicals (preferably hydrogen, C)1-4A linear or branched alkyl group), each x is independently selected from an integer between 0 and 5; r is 1、R2Are the same or different from each other and are each independently selected from hydrogen, C1-6A linear or branched alkyl group; r is3、R4、R5、R3’、R4’、R5' same or different from each other, each independently selected from hydrogen, C1-300Straight or branched chain hydrocarbon radical (preferably C)1-10A linear or branched hydrocarbon radical or a polyolefin radical having a number average molecular weight Mn of 300-3000), a radical of the formula (II) and a radical of the formula (III), with the proviso that R3、R4、R5Wherein at least one group is a group of formula (II), R3’、R4’、R5' wherein at least one group is a group represented by the formula (II) or (III);
Figure BDA0001832809810000021
wherein R is6Is hydrogen, C1-6Straight or branched chain hydrocarbon radicals (preferably hydrogen, C)1-4Straight or branched alkyl), R7Is hydrogen, C1-6Straight or branched chain hydrocarbon radicals (preferably hydrogen, C)1-4Straight or branched chain alkyl).
Silole derivatives which may be mentioned according to the invention include one or more of the following compounds:
Figure BDA0001832809810000022
the preparation method of the silole derivative comprises the step of reacting the silole compound shown in the formula (IV) with the alkyne compound shown in the formula (V),
Figure BDA0001832809810000023
in formula (IV), each R is independently selected from hydrogen, C1-6Straight or branched chain hydrocarbon radicals (preferably hydrogen, C)1-4A straight chain or branched alkyl group), each x 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; in the formulae (IV) and (V), R 1、R2Are the same or different from each other and are each independently selected from hydrogen, C1-6A linear or branched alkyl group; r is3、R4、R5Are the same or different from each other and are each independently selected from hydrogen, C1-300Straight or branched chain hydrocarbon radical (preferably C)1-10A linear or branched hydrocarbon radical or a polyolefin radical having a number average molecular weight Mn of 300-3000), a radical of the formula (II) and a radical of the formula (III), with the proviso that R3、R4、R5At least one group is a group represented by formula (II);
Figure BDA0001832809810000031
wherein R is6Is hydrogen, C1-6Straight or branched chain hydrocarbon radicals (preferably hydrogen, C)1-4Straight or branched alkyl), R7Is hydrogen, C1-6Straight or branched chain hydrocarbon radicals (preferably hydrogen, C)1-4Straight or branched chain alkyl).
Silole compounds of formula (IV) include:
Figure BDA0001832809810000032
the acetylene compounds represented by the formula (V) include:
Figure BDA0001832809810000033
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 BDA0001832809810000034
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 copper halide, iron halide and zinc halide, for example, one or more of copper chloride, cuprous chloride, copper bromide, cuprous bromide, copper iodide, cuprous iodide, ferric chloride, ferrous chloride, ferric bromide, ferrous bromide, ferric iodide, ferrous iodide, zinc chloride, zinc chlorite, zinc bromide, zinc iodide and zinc iodide may be used, and more preferably one or more of copper chloride, cuprous chloride, copper bromide, cuprous bromide, copper iodide and cuprous iodide.
According to the present invention, preferably, the hydrocarbyl phosphine compound has the structure
Figure BDA0001832809810000041
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 diphenyl butyl phosphine.
According to the invention, the amount of the catalyst added is preferably 1% to 20% of the amount of the silole compound represented by formula (IV).
According to the invention, a solvent is preferably 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 addition amount of the solvent is preferably 10-500 times of the mass of the silole compound.
According to the invention, the reaction is preferably carried out under an inert gas blanket, most preferably under a nitrogen blanket.
According to the present invention, in the reaction, the molar ratio between the silole compound represented by the formula (IV) and the acetylene compound represented by the formula (V) 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.
According to the invention, the product of the reaction is preferably subjected to a purification treatment. The purification treatment may be carried out by one or more methods of filtration, washing with water, distillation, column chromatography and recrystallization, and is not particularly limited. When the product of the reaction is purified by a column chromatography method, dichloromethane and/or methanol are preferably used as an eluent, a mixed solvent of dichloromethane and methanol is more preferably used as an eluent, and the volume ratio of the dichloromethane to the methanol is preferably 5-50: 1.
The silole derivative disclosed by the invention 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 0.0005 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 thickener comprises one or more of a polyurea thickener, a lithium-based thickener, a composite lithium-based thickener, a calcium-based thickener and a composite aluminum-based thickener, preferably the polyurea thickener, the lithium-based thickener, the composite lithium-based thickener and the composite aluminum-based thickener, and most preferably the lithium-based thickener.
The lubricating base oil can be one or more of mineral oil, vegetable oil and synthetic oil, and 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 present invention, it is preferable that the silole derivative is dissolved in a solvent and then mixed with a lubricating base oil and a thickener to be refined. The solvent is preferably toluene and/or xylene. The silole derivative accounts for 0.1-50% of the mass of the solvent, and preferably 0.5-20%. The solvent may be distilled off during the refining.
The thickening agent can be a soap-based thickening agent or a non-soap-based thickening agent. The soap-based thickener is preferably a metal soap, which can be a single metal soap or a composite metal soap, and the metal can be one or more of lithium, sodium, calcium, aluminum, zinc, potassium, barium, lead and manganese. The non-soap-based grease thickener is preferably one or more of graphite, carbon black, asbestos, polyurea, 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, the amine and the 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, such as one or more of octadecylamine, cyclohexylamine, aniline; the isocyanate is C 2-C20The isocyanate of (b) may be Toluene Diisocyanate (TDI) and/or 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 the 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 small molecular acid in a reaction kettle, heating to 40-90 deg.C, addingThe silole derivative is prepared by mixing and heating the other part of lubricating base oil and an aluminum alkoxide compound to 40-100 ℃, adding the mixture into a 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 to cool 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 (red fluorescence) and oxidation resistance, and can be used for relevant mechanical equipment in the electrical appliance industry, the metallurgical industry, the food industry, the paper industry, the automobile industry and the aircraft industry.
Detailed Description
The raw material sources are as follows:
chemical reagents such as 1, 1-dimethyl-2, 5-dibromo-3, 4-diphenylsilole, 4- (dicyanovinyl) phenylacetylene, cuprous iodide, triphenylphosphine, palladium tetratriphenylphosphine, octadecylamine, MDI, 12-hydroxystearic acid, lithium hydroxide monohydrate, stearic acid, benzoic acid, aluminum isopropoxide trimer, tetrahydrofuran, triethylamine, dichloromethane, methanol, toluene and the like were obtained from Bailingwei reagent, ImmunoKai reagent or Sigma reagent, analytically pure, and PAO10 base oil was obtained from Exxon Mobil.
The test methods used were as follows:
the method comprises a grease wide temperature range dropping point measuring method GB/T3498, a grease and petroleum cone penetration measuring method GB/T269, a grease steel mesh oil separation measuring method SH/T0324, a grease extreme pressure performance measuring method SH/T0202, a grease anti-wear performance measuring method SH/T0204 and a grease copper sheet corrosion test method GB/T7326.
Example 1
To a 100mL Schlenk reaction vessel were added 420mg (1mmol) of 1, 1-dimethyl-2, 5-dibromo-3, 4-diphenylsilole, 534mg (3mmol) of 4- (dicyanovinyl) phenylacetylene, 19mg (0.1mmol) of cuprous iodide, and 26mg (0.1mmol) of triphenylphosphine. 23mg (0.02mmol) of palladium tetrakistriphenylphosphine, 30mL tetrahydrofuran/triethylamine (2/1, v/v) were added under nitrogen and reacted at 25 ℃ 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 360mg of a red solid product with a yield of 59%. The nuclear magnetic results are:1H NMR(400MHz,CDCl3),δ(TMS,ppm)：7.79(s,2H),7.51(d,4H),7.35(d,4H),7.12–6.85(m,10H),0.49(s,6H)MS(MALDI-TOF):m/z calcd:614.2[M]+614.1 for found. An exemplary reaction scheme is shown below.
Figure BDA0001832809810000071
Example 2
Mixing 145 g of PAO10 base oil and 44.39 g of octadecylamine in a reaction kettle, heating to 60 ℃, dissolving 2.5 g of 1, 1-dimethyl-2, 5- (dicyanovinylphenylethynyl) -3, 4-diphenylsilole in 25 g of toluene, adding into the reaction kettle, mixing 145 g of PAO10 base oil and 20.61 g of MDI, heating to 60 ℃, adding into the reaction kettle after all the MDI is dissolved, heating to 80 ℃, reacting for 30min, continuously heating to 210 ℃, adding 145 g of PAO10 base oil, cooling to about 100 ℃, and grinding.
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, and the mixture is cooled to about 100 ℃ and ground.
Comparative example 2
Mixing 145 g of PAO10 base oil and 44.39 g of octadecylamine in a reaction kettle, heating to 60 ℃, mixing 145 g of PAO10 base oil and 20.61 g of MDI, heating to 60 ℃, adding the mixture into the reaction kettle after the MDI is completely dissolved, heating to 80 ℃, reacting for 30min, continuing heating to 210 ℃, adding 145 g of PAO10 base oil, cooling to about 100 ℃, adding 2.5 g of 1, 1-dimethyl-2, 5- (dicyanovinylphenylethynyl) -3, 4-diphenylsilole, and grinding.
The greases of example 2 and comparative examples 1 and 2 were subjected to physical and chemical property tests, and the test results are shown in table 1.
TABLE 1 test results
Test item Example 2 Comparative example 1 Comparative example 2
Soap amount% 13 13 13
Dropping Point/. degree.C 284 282 283
Appearance of the product Brown colour Brown colour Brown colour
Penetration/0.1 mm 260 260 261
PB/kgf 80 50 63
PD/kgf 250 200 250
Abrasive grain diameter/mm 0.51 0.69 0.55
Steel mesh oil separation, 100 ℃,24 h/%) 3.9 4.1 3.9
Under the irradiation of ultraviolet lamp Red fluorescence Do not emit light Red fluorescence
Example 3
Mixing 300 g of PAO10 base oil and 39.21 g of 12-hydroxystearic acid in a reaction kettle, heating to 85 ℃, dissolving 2.5 g of 1, 1-dimethyl-2, 5- (dicyanovinylphenylethynyl) -3, 4-diphenylsilole in 25 g of toluene, adding into the reaction kettle, mixing 6.06 g of lithium hydroxide monohydrate and 40 g of distilled water, heating to 95 ℃, adding into the reaction kettle after the lithium hydroxide is completely dissolved, heating to 210 ℃ after heating to remove water, adding 160 g of PAO10 base oil, cooling and grinding.
Comparative example 3
Mixing 300 g of PAO10 base oil and 39.21 g of 12-hydroxystearic acid in a reaction kettle, heating to 85 ℃, mixing 6.06 g of lithium hydroxide monohydrate with 40 g of distilled water, heating to 95 ℃, adding the mixture into the reaction kettle after the lithium hydroxide is completely dissolved, heating to 210 ℃ after removing water by heating, adding 160 g of PAO10 base oil, cooling and grinding.
The greases of example 3 and comparative example 3 were tested for physical and chemical properties, and the results are shown in table 2.
TABLE 2 test results
Test item Example 3 Comparative example 3
Soap content% 8 8
Dropping Point/. degree.C 202 197
Appearance of the product White colour White colour
Penetration/0.1 mm 266 271
PB/kgf 80 50
PD/kgf 250 200
Abrasion spot diameter/mm 0.48 0.62
Steel mesh oil separation, 100 ℃,24 h/%) 4.2 4.3
Under the irradiation of ultraviolet lamp Red fluorescence Do not emit light
Example 4
Mixing 200 g of PAO10 base oil, 32.5 g of stearic acid and 14 g of benzoic acid in a reaction kettle, heating to 90 ℃, dissolving 2.5 g of 1, 1-dimethyl-2, 5- (dicyanovinylphenylethynyl) -3, 4-diphenylsilole in 25 g of toluene, adding into the reaction kettle, mixing 100 g of PAO10 base oil and 32 g of aluminum isopropoxide trimer, heating until the aluminum isopropoxide trimer is completely dissolved, adding into the reaction kettle, continuously heating to 210 ℃, reacting for 30 minutes, adding 150 g of PAO10 base oil, cooling, and grinding.
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 ground after cooling.
The greases of example 4 and comparative example 4 were tested for physical and chemical properties, and the results are shown in table 3. TABLE 3 test results
Test items Example 4 Comparative example 4
Soap amount% 10 10
Dropping Point/. degree.C 275 269
Appearance of the product Yellow colour Yellow colour
Penetration/0.1 mm 258 266
PB/kgf 63 50
PD/kgf 250 200
Abrasion spot diameter/mm 0.55 0.71
Steel mesh oil separation, 100 ℃,24 h/%) 3.8 3.8
Under the irradiation of ultraviolet lamp Red fluorescence Does not emit light

Claims (18)

1. A silole derivative having the structure:
Figure FDA0003557783350000011
in the formula (I), each R is independently selected from hydrogen and C1-6A straight chain or branched chain alkyl group, each x is independently selected from an integer between 0 and 5; 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、R5、R3’、R4’、R5' same or different from each other, each independently selected from hydrogen, C1-10A linear or branched hydrocarbon group, a group of formula (II) and a group of formula (III), provided that R3、R4、R5Wherein at least one group is a group of formula (II), R3’、R4’、R5' wherein at least one group is of the formula (II)) Or is a group represented by (III);
Figure FDA0003557783350000012
wherein R is6Is hydrogen, C1-6Straight-chain or branched hydrocarbon radicals, R7Is hydrogen, C1-6A straight or branched chain hydrocarbon group.
2. The silole derivative according to claim 1, wherein each R is independently selected from hydrogen, C1-4A linear or branched alkyl group; wherein R is6Is hydrogen, C1-4Straight or branched alkyl, R7Is hydrogen, C1-4Straight or branched chain alkyl.
3. Silole derivatives according to claim 1, characterized in that they are selected from one or more of the following compounds:
Figure FDA0003557783350000013
4. A process for producing the silole derivative according to any one of claims 1 to 3, which comprises reacting a silole compound represented by the formula (IV) with an acetylene compound represented by the formula (V),
Figure FDA0003557783350000021
in formula (IV), each R is independently selected from hydrogen, C1-6A straight chain or branched chain alkyl group, each x is independently selected from an integer between 0 and 5; each group X, equal to or different from each other, is independently selected from F, Cl, Br, I, OH; in the formulae (IV) and (V), 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 C1-10A linear or branched hydrocarbon group, a group of formula (II) and a group of formula (III), provided that R3、R4、R5At least one group is a group represented by the formula (II);
Figure FDA0003557783350000022
wherein R is6Is hydrogen, C1-6Straight-chain or branched hydrocarbon radicals, R7Is hydrogen, C1-6A straight or branched chain hydrocarbon group.
5. The process according to claim 4, wherein in formula (IV), each R is independently selected from hydrogen, C1-4A linear or branched alkyl group; each group X is independently selected from Cl or Br; r6Is hydrogen, C1-4Straight or branched alkyl, R7Is hydrogen, C1-4Straight or branched chain alkyl.
6. The method according to claim 4, wherein the silole compound of formula (IV) is selected from one or more of the following compounds:
Figure FDA0003557783350000023
The alkyne compound shown in the formula (V) is selected from one or more of the following compounds:
Figure FDA0003557783350000024
7. a process according to claim 4, wherein a catalyst is added to the reaction, said catalyst being one or more of a metal phosphine complex, a metal halide and a hydrocarbyl phosphine compound.
8. The process according to claim 4, 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.
9. The process according to claim 4, wherein in the reaction, the molar ratio between the silole compound of formula (IV) and the alkyne compound of formula (V) is 1: 1-6; the reaction temperature is 0-50 ℃.
10. Use of the silole derivative according to any of claims 1 to 3 or prepared 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; 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.
12. The grease of claim 11 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.
13. A method of preparing a grease according to claim 11 or 12 comprising: mixing lubricating base oil, thickener and silole derivative, refining, and grinding into grease.
14. The method of claim 13, wherein the refining operation is carried out at a temperature of 160 to 240 ℃; the refining operation time is 10-240 min.
15. The method of claim 13, wherein the silole derivative is dissolved in a solvent and then mixed with a lubricating base oil and a thickener for refining.
16. The method of claim 13, wherein the grease is a polyurea grease prepared by a method comprising: mixing part of lubricating base oil, 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.
17. The method of claim 13, wherein the grease is a lithium-based grease prepared by a method comprising: 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 190-.
18. The method of claim 13, wherein the grease is a complex aluminum-based grease prepared by a method comprising: 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 the 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.
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Citations (1)

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JP2003226871A (en) * 2002-02-04 2003-08-15 Matsushita Electric Ind Co Ltd Luminescent element material and luminescent element, and device produced by using the material

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JP2003226871A (en) * 2002-02-04 2003-08-15 Matsushita Electric Ind Co Ltd Luminescent element material and luminescent element, and device produced by using the material

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A Controlled, Iterative Synthesis and the Electronic Properties of Oligo[(p-phenyleneethynylene)-alt-(2,5-siloleneethynylene)]s;Andrew J.Boydston，et al.;《J.AM.CHEM.SOC.》;20040731;第126卷(第33期);第10350-10354页 *
Improving Quantum Efficiencies of Siloles and Silole-Derived Butadiene Chromophores through Structural Tuning;Andrew J.Boydston，et al.;《Angew.Chem.Int.Ed.》;20041231;第43卷;第6336-6338页 *
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