CN111100091B - Benzothiazole derivative, preparation method and application thereof, and lubricating grease - Google Patents
Benzothiazole derivative, preparation method and application thereof, and lubricating grease Download PDFInfo
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- CN111100091B CN111100091B CN201811268000.4A CN201811268000A CN111100091B CN 111100091 B CN111100091 B CN 111100091B CN 201811268000 A CN201811268000 A CN 201811268000A CN 111100091 B CN111100091 B CN 111100091B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
- C07D277/66—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2 with aromatic rings or ring systems directly attached in position 2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- 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
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/32—Heterocyclic sulfur, selenium or tellurium compounds
- C10M135/36—Heterocyclic sulfur, selenium or tellurium compounds the ring containing sulfur and carbon with nitrogen or oxygen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/06—Mixtures of thickeners and additives
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- 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
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
- C10M2203/1025—Aliphatic fractions used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
- C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
- C10M2207/128—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof
- C10M2207/1285—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof used as thickening agents
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
- C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
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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)
- Lubricants (AREA)
Abstract
The invention provides a benzothiazole derivative, a preparation method and application thereof, and lubricating grease containing the benzothiazole derivative. The benzothiazole derivative of the invention has the structure as follows:
Description
Technical Field
The invention relates to a benzothiazole derivative, in particular to a benzothiazole derivative with an anti-oxygen property.
Background
Traditional organic chromophores generally have strong luminescence at low concentrations, and weak or even no luminescence at high concentrations or in solid states, exhibiting an aggregate fluorescence quenching effect. This is because in the aggregate state, the strong intermolecular interactions lead to an enhancement of the non-radiative decay process of the excited state, with a significant decrease in fluorescence quantum yield. In the practical application process, the practical application of the organic light-emitting material is limited to a great extent by the aggregate fluorescence quenching effect. In recent years, research shows that some compounds show the opposite properties to the traditional organic luminescent compounds, not only do not have aggregation fluorescence quenching effect, but also show Aggregation Induced Emission (AIE) properties, and the appearance of the aggregation induced emission compounds provides a new solution for the application of organic luminescent materials in a solid state or at high concentration. Polyphenylsilole is a typical AIE compound, and has been used in many research fields such as light emitting devices, fluorescent probes, and 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, the transportation industry, the aerospace industry, the electronic information industry and various military equipment.
Under some dark working conditions, the monitoring of the lubricating grease has great difficulty. At present, the related report of the luminescent grease is rarely seen.
Disclosure of Invention
The invention provides a benzothiazole derivative, a preparation method and application thereof, and lubricating grease containing the benzothiazole derivative.
The benzothiazole derivative has the structure as follows:
in the general formula (I), the radicals G, which are identical or different from one another, are each independently selected from the group consisting of-N (R) c ) 2 Wherein each radical R c Are the same or different from each other and are each independently selected from H,
(preferred is
Wherein each group R' is the same or different from each other and is independently selected from hydrogen, C 1-20 Straight or branched chain alkyl (preferably each independently selected from hydrogen and C) 1-10 Straight or branched chain alkyl); each radical R d Are the same or different from each other and are each independently selected from hydrogen and C 1-20 Straight or branched chain alkyl (preferably each independently selected from hydrogen and C) 1-10 Straight-chain or branched alkyl), where the radicals R are each 0 Are the same or different from each other and are each independently selected from hydrogen and C 1-20 Straight or branched alkyl, C 6-20 Aryl (preferably each independently selected from hydrogen, C) 1-10 Straight or branched alkyl, C 6-20 Phenylalkyl and C 6-20 Alkylphenyl radicals); each radical R a Are the same or different from each other and are each independently selected from hydrogen, hydroxy and C 1-20 Straight or branched chain alkyl (preferably each independently selected from hydrogen, hydroxy and C) 1-10 Straight or branched chain alkyl); each cyclic group
Identical to or different from each other, each independently selected from aromatic rings (preferably benzene, naphthalene, anthracene and phenanthrene rings, more preferably benzene rings); each radical R b Are the same or different from each other and are each independently selected from hydrogen, hydroxy and C 1-20 Straight or branched chain alkyl (preferably each independently selected from hydrogen, hydroxy and C) 1-10 Straight or branched chain alkyl); each x in the general formula (I) is the same or different from each other and is independently selected from an integer of 0 to 3 (preferably0.1 or 2); each y in the general formula (I) is the same or different from each other and is independently selected from an integer of 0 to 3 (preferably 0, 1 or 2); each z in the general formula (I), equal to or different from each other, is independently selected from 0 or a positive integer (preferably an integer of 0 to 8, more preferably 0, 1 or 2); each n in the general formula (I), which may be the same or different from each other, is independently selected from 0 or a positive integer (preferably an integer of 0 to 8, more preferably 0, 1, 2 or 3).
As described above
Preference is given to
More preferably
The benzothiazole derivatives of the present invention include one or more of the following compounds:
the preparation method of the benzothiazole derivative comprises the step of reacting a benzothiazole compound shown in a general formula (II) with one or more compounds in formulas (III-1) to (III-5),
in the general formula (II), the radicals R e Are the same or different from each other and are each independently selected from hydrogen and C 1-20 Straight or branched chain alkyl (preferably each independently selected from hydrogen and C) 1-10 Straight or branched alkyl), and at least one R e Is hydrogen; wherein each group X is independently selected from halogen, hydroxyl and hydrogen (preferably F, cl, br, I); wherein each group R' is the same or different from each other and is independently selected from hydrogen, C 1-20 Straight or branched chain alkyl (preferably each independently)Selected from hydrogen and C 1-10 Straight or branched chain alkyl); each radical R d Are the same or different from each other and are each independently selected from hydrogen, C 1-20 Straight or branched chain alkyl (preferably each independently selected from hydrogen and C) 1-10 Straight-chain or branched alkyl), where the radicals R are each 0 Are the same or different from each other and are each independently selected from hydrogen and C 1-20 Straight or branched alkyl, C 6-20 Aryl (preferably each independently selected from hydrogen, C) 1-10 Straight or branched alkyl, C 6-20 Phenylalkyl and C 6-20 Alkylphenyl radicals); each radical R a Are the same or different from each other and are each independently selected from hydrogen, hydroxy and C 1-20 Straight or branched chain alkyl (preferably each independently selected from hydrogen, hydroxy and C) 1-10 Straight or branched chain alkyl); each cyclic group
Identical to or different from each other, each independently selected from aromatic rings (preferably benzene, naphthalene, anthracene and phenanthrene rings, more preferably benzene rings); each radical R b Are the same or different from each other and are each independently selected from hydrogen, hydroxy and C 1-20 Straight or branched chain alkyl (preferably each independently selected from hydrogen, hydroxy and C) 1-10 Straight or branched chain alkyl); each x is the same or different from each other and is independently selected from an integer of 0 to 3 (preferably 0, 1 or 2); each y is the same or different from each other and is independently selected from an integer of 0 to 3 (preferably 0, 1 or 2); each z, equal to or different from each other, is independently selected from 0 or a positive integer (preferably an integer of 0 to 8, more preferably 0, 1 or 2); each n is the same or different from each other, and is independently selected from 0 or a positive integer (preferably an integer of 0 to 8, more preferably 0, 1, 2 or 3).
According to the preparation method of the present invention, alternatively, the benzothiazole compounds represented by the general formula (II) include:
according to the production method of the present invention, alternatively, the compound represented by the general formula (III-1) includes:
according to the production method of the present invention, alternatively, the compound represented by the general formula (III-2) includes:
according to the production method of the present invention, alternatively, the compound represented by the general formula (III-3) includes:
according to the preparation method of the present invention, alternatively, the compound represented by the general formula (III-4) includes:
according to the preparation method of the present invention, alternatively, the compound represented by the general formula (III-5) includes:
according to the production method of the present invention, alternatively, in the reaction, the molar ratio between the benzothiazole compound represented by the general formula (II) and the compounds represented by the formulae (III-1) to (III-5) is preferably 1:0.5 to 2, most preferably 1:0.8 to 1.2.
According to the preparation method of the invention, optionally, the temperature of the reaction is 0-50 ℃, preferably 15-35 ℃; the pressure of the reaction is 0-10 MPa, preferably 0.05-0.2 MPa; the reaction time is 6 to 96 hours, preferably 12 to 72 hours.
According to the production method of the present invention, preferably, in the benzothiazole compounds represented by the general formula (II) and the formula (III-1)) Adding a catalyst to the reaction of the compound of formula (III-5). The catalyst is preferably a carbodiimide compound and/or a benzotriazole compound, more preferably a mixture of the carbodiimide compound and the benzotriazole compound, and the molar ratio of the carbodiimide compound to the benzotriazole compound is preferably 1:0.1 to 10, more preferably 1:0.2 to 5. The preferable structure of the carbodiimide compound is as follows:
and salts thereof, wherein each R is independently selected from C 6 ～C 10 Aryl of, C 1 ～C 6 Straight or branched alkyl of (2), mono (C) 1 ～C 4 Alkyl) amino C 1 ～C 10 Alkyl, di (C) 1 ～C 4 Alkyl) amino C 1 ～C 10 An alkyl group. Said C is 6 ～C 10 Aryl of (b) is preferably selected from phenyl, naphthyl; said C is 1 ～C 6 The linear or branched alkyl group of (b) may be selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl or isohexyl; the sheet (C) 1 ～C 4 Alkyl) amino C 1 ～C 10 The alkyl group is preferably selected from the group consisting of methylaminoethyl, ethylaminoethyl, propylaminoethyl, methylaminopropyl, ethylaminopropyl, propylaminopropyl; said two (C) 1 ～C 4 Alkyl) amino C 1 ～C 10 The alkyl group is preferably selected from dimethylaminoethyl, diethylaminoethyl, dipropylaminoethyl, dimethylaminopropyl, diethylaminopropyl and dipropylaminopropyl. The above-mentioned
The salt is preferably one or more of a hydrochloride, a sulfate, a nitrate and a phosphate thereof, and more preferably a hydrochloride thereof. The carbodiimide compound can be selected from 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 1- (3-diethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 1- (3-dipropylaminopropyl) -3-ethylcarbodiimide hydrochloride. The carbodiimide-based compound is most preferably selected from
A hydrochloride salt wherein each R is independently selected from C 6 ～C 10 Aryl of, C 1 ～C 6 Straight or branched alkyl of (2), mono (C) 1 ～C 4 Alkyl) amino C 1 ～C 10 Alkyl, di (C) 1 ～C 4 Alkyl) amino C 1 ～C 10 Alkyl, and wherein at least one R is di (C) 1 ～C 4 Alkyl) amino C 1 ～C 10 An alkyl group. The preferable structure of the benzotriazole compound is as follows:
wherein R' is selected from hydrogen and C 1-6 Straight or branched alkyl, C 3-10 Cycloalkyl, C 6-10 Aryl and C 1-6 An alkoxy group; x is selected from F, cl, br, I and OH. The benzotriazole compound can be one or more of 1-hydroxybenzotriazole, 6-methyl-1-hydroxybenzotriazole and 7-methyl-1-hydroxybenzotriazole. The addition amount of the catalyst is preferably 1 to 200% of the silole derivative represented by the formula (II).
According to the preparation method of the invention, optionally, a solvent, preferably C, may or may not be added in the reaction, preferably a solvent is added 1 ～C 10 The organic amine, furan and sulfoxide of (b) can be selected from one or more of methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, tetrahydrofuran and dimethyl sulfoxide, and most preferably C 1 ～C 10 The organic amine and furan mixed solvent (the volume ratio of the two is preferably 1.1-10) or sulfoxide, and the addition amount of the solvent is preferably 10-500 times of the mass of the benzothiazole compound.
According to the preparation method of the present invention, optionally, the product of the reaction of the benzothiazole compound of the general formula (II) with one or more of the compounds of the formulae (III-1) to (III-5) may be extracted using one or more of washing, filtering, recrystallization and column chromatographyPurifying, preferably purifying the reaction product by adopting a column chromatography method, wherein an eluent in the column chromatography method is preferably methyl chloride and/or petroleum ether, the methyl chloride comprises methyl chloride, dichloromethane, trichloromethane and tetrachloromethane, the eluent is more preferably a mixture of methyl chloride and petroleum ether, and the volume ratio of the methyl chloride to the petroleum ether is preferably 1:0.1 to 10. The process for preparing the benzothiazole compounds of the formula (II) preferably comprises reacting
And
a step of reaction, wherein each group R e Are the same or different from each other and are each independently selected from hydrogen and C 1-20 Straight or branched chain alkyl (preferably each independently selected from hydrogen and C) 1-10 Straight or branched alkyl), and at least one R e Is hydrogen; wherein each group X is independently selected from halogen, hydroxyl and hydrogen (preferably F, cl, br, I); each radical R a Are the same or different from each other and are each independently selected from hydrogen, hydroxy and C 1-20 Straight or branched chain alkyl (preferably each independently selected from hydrogen, hydroxy and C) 1-10 Straight or branched chain alkyl); each cyclic group
Identical to or different from each other, each independently selected from aromatic rings (preferably benzene, naphthalene, anthracene and phenanthrene rings, more preferably benzene rings); each radical R b Are the same or different from each other and are each independently selected from hydrogen, hydroxy and C 1-20 Straight or branched chain alkyl (preferably each independently selected from hydrogen, hydroxy and C) 1-10 Straight or branched chain alkyl); each x is the same or different from each other and is independently selected from an integer of 0 to 3 (preferably 0, 1 or 2); each y is the same or different from each other and is independently selected from an integer of 0 to 3 (preferably 0, 1 or 2); each z is the same or different from each other, and is independently selected from 0 or a positive integer (preferably an integer of 0 to 8, more preferably 0, 1 or 2).
According to the preparation method of the invention, optionally, the
And with
The reaction temperature is preferably 140-180 ℃, the reaction pressure is preferably 0.05-0.2 MPa, the reaction time is preferably 2-24 h, and the molar ratio between the two is preferably 0.5-2: 1. in that
And
in the step of carrying out the reaction, a solvent may be added or not, preferably a solvent is added, the solvent is preferably one or more of polyphosphoric acid, dimethyl sulfoxide, dimethylformamide and 1,4-dioxane, most preferably polyphosphoric acid, and the amount of the solvent added is preferably polyphosphoric acid
5 to 100 times of the mass. The reaction product may be purified using any of these solvents, and the solvent may be removed by a method known in the art, and is not particularly limited.
The benzothiazole derivative disclosed by the invention has excellent antioxidant property and wear resistance, and can be applied to lubricating oil and lubricating grease.
The invention also provides lubricating grease which comprises the benzothiazole derivative, an optional lubricating grease additive, a thickening agent and lubricating base oil. The benzothiazole derivative accounts for 0.0005 to 5 percent of the total mass of the lubricating grease, preferably 0.001 to 1 percent; the grease additive accounts for 0 to 10 percent of the total mass of the grease, and preferably 0.1 to 5 percent; the thickening agent accounts for 5-30%, preferably 10-20% of the total mass of the lubricating grease; the lubricating base oil constitutes the main component of the grease.
The thickener comprises one or more of a polyurea thickener, a lithium-based thickener, a composite lithium-based thickener, a calcium-based thickener and a composite aluminum-based thickener, preferably the polyurea thickener, the lithium-based thickener, the composite lithium-based thickener and the composite aluminum-based thickener, and most preferably the lithium-based thickener.
The grease additives include antioxidants, anti-wear agents, rust preventives, extreme pressure agents, and the like, which are generally used in greases, and the kind and amount thereof may follow the conventional treatment methods in the art, without particular limitation. For example, the antioxidant can be amine antioxidant and/or phenol antioxidant, and the addition amount of the antioxidant can be 0-2%, preferably 0.1-1.5%; the extreme pressure agent can be one or more of dialkyl dithiocarbamate and aminothioester, and the addition amount of the extreme pressure agent can be 0-3%, preferably 0.1-2.5%; the antirust agent can be a sulfonate antirust agent, and the addition amount of the antirust agent can be 0-2%, preferably 0.1-1.5%; the antiwear agent can be phosphate antiwear agent, and the addition amount of the phosphate antiwear agent can be 0-3%, and preferably 0.1-2.5%.
The base oil may be one or more of mineral oil, vegetable oil and synthetic oil, preferably mineral oil and synthetic oil.
The preparation method of the lubricating grease comprises the following steps: mixing and refining lubricating base oil, a thickening agent, an optional lubricating grease additive and a benzothiazole derivative, and grinding into grease. The refining operation temperature is 160-240 ℃, preferably 190-220 ℃; the refining operation time is 10-240 min, preferably 20-60 min. All of the lubricating base oil, the benzothiazole derivative, and optionally the grease additive and the thickener may be mixed and refined, or part of the lubricating base oil and the thickener may be mixed and refined and then mixed with the rest of the lubricating base oil, the benzothiazole derivative, and optionally the grease additive.
The thickening agent can be a soap-based thickening agent or a non-soap-based thickening agent. The soap-based thickener is preferably a metal soap, which can be a single metal soap or a composite metal soap, and the metal can be one or more of lithium, sodium, calcium, aluminum, zinc, potassium, barium, lead and manganese. The non-soap-based grease thickener is preferably one or more of graphite, carbon black, asbestos, polyurea group, bentonite and organic clay.
The 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 benzothiazole derivatives and lithium hydroxide, heating to remove water, continuously heating to 190-220 ℃ for high-temperature refining, adding the rest lubricating base oil and optional lubricating grease additives, cooling to 60-120 ℃, and grinding into grease. The fatty acid is C 12 -C 20 Fatty acid and/or C 12 -C 20 The hydroxy fatty acid can be one or more of lauric acid, palmitic acid, stearic acid and 12-hydroxystearic acid.
The lubricating grease disclosed by the invention has excellent antioxidant performance and wear resistance.
Detailed Description
The main raw material sources are as follows:
chemical reagents such as polyphosphoric acid, o-aminothiophenol, p-aminosalicylic acid, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 1-hydroxybenzotriazole, 12-hydroxystearic acid, lithium hydroxide monohydrate, tetrahydrofuran, triethylamine, dichloromethane, 1,4-dioxane, dimethyl sulfoxide, diphenylamine and the like are from Bailingwei reagent company, imokay reagent company or Sigma reagent company, and are analytically pure; PAO10 base oil from Exxon Mobil, 500SN, 150BS base oil from SK; barium petroleum sulfonate, barium dinonylnaphthalene sulfonate, is available from pubic international (shanghai) trade, ltd, and molybdenum dialkyldithiocarbamate is available from van der balt (beijing) trade, ltd.
Example 1
200mL of polyphosphoric acid (PPA), 0.2mol of o-aminosulfol and 0.2mol of p-aminosalicylic acid are added to a 500mL three-necked flask, and the mixture is stirred and reacted for 6 hours at 160 ℃ under the protection of nitrogen. After the reactant is cooled, a large amount of ice water is used for diluting, 10% sodium hydroxide solution and saturated sodium carbonate solution are used for adjusting the reactant to be neutral, a large amount of solids are separated out, and a crude product is obtained by filtration. Dissolving the crude product with 1,4-dioxane, filtering to remove insoluble impurities, adding appropriate amount of water into the filtrate, collecting the precipitated solid, drying in vacuum oven at 60 deg.C,to obtain the 2- (2' -hydroxy-4-aminophenyl) benzothiazole with the yield of 59 percent and the melting point of 212 to 214 ℃. 1 H NMR (400MHz, DMSO-d 6) delta (ppm) results were: 11.71 (s, 1H, arOH), 8.02 (d, 1H, arH), 7.88 (d, 1H, arH), 7.62 (d, 1H, arH), 7.45 (m, 1H, arH), 7.33 (m, 1H, arH), 6.24 (d, 1H, arH), 6.15 (d, 1H, arH), 5.95 (s, 2H, arNH) 2 ).MS(ESI-TOF):243.0582([M+H] + )。
The reaction equation for example 1 is:
example 2
4mmol of 2-carboxyphenothiazine, 5.6mmol of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 4mmol of 1-hydroxyphenyltriazole and 50mL of dimethyl sulfoxide (DMSO) are added into a 250mL three-necked flask, and 10mL of a DMSO solution in which 4mmol of 2- (2' -hydroxy-4-aminophenyl) benzothiazole is dissolved is slowly added dropwise with stirring to react at room temperature for 24 hours. After the reaction is finished, washing with water, and then separating and purifying the crude product by using a column chromatography method by using dichloromethane/petroleum ether (2/1) as an eluent to obtain a white solid product, marked as HBT-1, wherein the yield is 83%. 1 H NMR (400MHz, DMSO-d 6), delta (TMS, ppm) results: 11.62 (s, 1H, arOH), 8.04 (d, 2H, arH), 7.78 (d, 1H, arH), 7.67 (d, 2H, arH), 7.48 (m, 2H, arH), 7.35 (m, 2H, arH), 7.33 (m, 1H, arH), 6.82 (d, 2H, arH), 6.23 (d, 1H, arH), 6.18 (d, 1H, arH), MS (MALDI-TOF): m/z calcd of 467.1[ m ], [ m/z ] m] + ,found:467.1。
The reaction equation for example 2 is:
example 3
4mmol of 4-diethylaminobenzoic acid, 5.6mmol of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 4mmol of 1-hydroxyphenyltriazole and 50mL of dimethyl sulfoxide (DMSO) are added into a 250mL three-necked flask, and 10mL of reaction solution dissolved with 4mmol of 2- (2' -hydroxy-4-aminophenyl) benzothia are slowly dropped into the reaction solution under stirringOxazole in DMSO was reacted at room temperature for 24 hours. After the reaction is finished, washing with water, and then separating and purifying the crude product by column chromatography with dichloromethane/petroleum ether (2/1) as an eluent to obtain a white solid product, which is marked as HBT-2, and the yield is 76%. 1 H NMR (400MHz, DMSO-d 6), delta (TMS, ppm) results were: 11.60 (s, 1H, arOH), 8.02 (d, 1H, arH), 7.76 (d, 1H, arH), 7.66 (d, 1H, arH), 7.48 (m, 1H, arH), 7.42 (d, 2H, arH), 7.35 (d, 2H, arH), 7.33 (m, 1H, arH), 6.24 (d, 1H, arH), 6.16 (d, 1H, arH), 3.39 (d, 4H), 1.26 (d, 6H). MS (MALDI-TOF): m/z calcd:417.2[ M ] M] + ,found:417.2。
The reaction equation for example 3 is:
example 4
4mmol of 4-dimethylamino benzoic acid, 5.6mmol of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 4mmol of 1-hydroxy phenylpropyltriazole and 50mL of dimethyl sulfoxide (DMSO) are added into a 250mL three-necked flask, and 10mL of DMSO solution in which 4mmol of 2- (2' -hydroxy-4-aminophenyl) benzothiazole is dissolved is slowly added dropwise into the reaction solution under stirring, and the reaction is carried out for 24 hours at room temperature. After the reaction is finished, washing with water, and then separating and purifying the crude product by using a column chromatography method by using dichloromethane/petroleum ether (2/1) as an eluent to obtain a white solid product, which is marked as HBT-3 and has the yield of 76%. 1 H NMRZ (400MHz, DMSO-d 6), delta (TMS, ppm) results are: 11.60 (s, 1H, arOH), 8.02 (d, 1H, arH), 7.76 (d, 1H, arH), 7.66 (d, 1H, arH), 7.48 (m, 1H, arH), 7.43 (d, 2H, arH), 7.36 (d, 2H, arH), 7.33 (m, 1H, arH), 6.24 (d, 1H, arH), 6.16 (d, 1H, arH), 3.14 (s, 6H) MS (MALDI-TOF): m/z calcd:389.1[ M ] M/TOF ]] + ,found:389.1。
The reaction equation for example 4 is:
example 5
Mixing 60 g of 500SN base oil and 7.84 g of 12-hydroxystearic acid in a reaction kettle, heating to 85 ℃, mixing 1.21 g of lithium hydroxide monohydrate and 8 g of distilled water, heating to 95 ℃, adding the mixture into the reaction kettle after the lithium hydroxide is completely dissolved, performing saponification reaction for 20min, stirring, heating to 110-150 ℃, dehydrating, continuously heating to 210 ℃, performing high-temperature refining for 10min, adding 32 g of 500SN base oil, cooling to 110 ℃, adding 0.5g of barium petroleum sulfonate and 3g of HBT-1, cooling to room temperature, and grinding for three times to form grease.
Example 6
Mixing 60 g of 150BS base oil and 7.84 g of 12-hydroxystearic acid in a reaction kettle, heating to 85 ℃, mixing 1.21 g of lithium hydroxide monohydrate and 8 g of distilled water, heating to 95 ℃, adding the mixture into the reaction kettle after the lithium hydroxide is completely dissolved, performing saponification reaction for 20min, stirring, heating to 110-150 ℃, dehydrating, continuously heating to 210 ℃, performing high-temperature refining for 10min, adding 32 g of 150BS base oil, cooling to 110 ℃, adding 0.5g of barium petroleum sulfonate and 3g of HBT-1, cooling to room temperature, and grinding for three times to form grease.
Example 7
Mixing 60 g of PAO10 base oil and 7.84 g of 12-hydroxystearic acid in a reaction kettle, heating to 85 ℃, mixing 1.21 g of lithium hydroxide monohydrate and 8 g of distilled water, heating to 95 ℃, adding the mixture into the reaction kettle after the lithium hydroxide is completely dissolved, carrying out saponification reaction for 20min, stirring, heating to 110-150 ℃ for dehydration, then continuously heating to 210 ℃ for high-temperature refining for 10min, adding 32 g of PAO10 base oil, cooling to 110 ℃, adding 0.5g of barium dinonylnaphthalene sulfonate and 3g of HBT-1, cooling to room temperature, and grinding for three times to form grease.
Comparative example 1
Mixing 60 g of 500SN base oil and 7.84 g of 12-hydroxystearic acid in a reaction kettle, heating to 85 ℃, mixing 1.21 g of lithium hydroxide monohydrate and 8 g of distilled water, heating to 95 ℃, adding the mixture into the reaction kettle after the lithium hydroxide is completely dissolved, carrying out saponification reaction for 20min, stirring, heating to 110-150 ℃, dehydrating, continuously heating to 210 ℃, carrying out high-temperature refining for 10min, adding 32 g of 500SN base oil, cooling to 110 ℃, adding 1g of diphenylamine, 0.5g of barium petroleum sulfonate and 2g of molybdenum dialkyldithiocarbamate, cooling to room temperature, and grinding for three times to form grease.
Comparative example 2
Mixing 60 g of 150BS base oil and 7.84 g of 12-hydroxystearic acid in a reaction kettle, heating to 85 ℃, mixing 1.21 g of lithium hydroxide monohydrate and 8 g of distilled water, heating to 95 ℃, adding the mixture into the reaction kettle after the lithium hydroxide is completely dissolved, carrying out saponification reaction for 20min, stirring, heating to 110-150 ℃ for dehydration, then continuously heating to 210 ℃ for high-temperature refining for 10min, adding 32 g of 150BS base oil, cooling to 110 ℃, adding 1g of diphenylamine, 0.5g of barium petroleum sulfonate and 2g of molybdenum dialkyldithiocarbamate, cooling to room temperature, and grinding for three times to form grease.
Comparative example 3
Mixing 60 g of PAO10 base oil and 7.84 g of 12-hydroxystearic acid in a reaction kettle, heating to 85 ℃, mixing 1.21 g of lithium hydroxide monohydrate and 8 g of distilled water, heating to 95 ℃, adding the mixture into the reaction kettle after the lithium hydroxide is completely dissolved, carrying out saponification reaction for 20min, stirring, heating to 110-150 ℃, dehydrating, then continuously heating to 210 ℃, carrying out high-temperature refining for 10min, adding 32 g of PAO10 base oil, cooling to 110 ℃, adding 1g of diphenylamine, 0.5g of barium dinonylnaphthalene sulfonate and 2g of molybdenum dialkyldithiocarbamate, cooling to room temperature, and grinding for three times to form grease.
The greases of examples 5-7 and comparative examples 1-3 were subjected to performance evaluation according to GB/T3498, GB/T269, SH/T0325, SH/T0324, SH/T0202, SH/T0204 and GB/T7326, and the evaluation results are shown in Table 1.
TABLE 1 grease Properties
Example 8
Mixing 60 g of 500SN base oil and 7.84 g of 12-hydroxystearic acid in a reaction kettle, heating to 85 ℃, mixing 1.21 g of lithium hydroxide monohydrate and 8 g of distilled water, heating to 95 ℃, adding the mixture into the reaction kettle after the lithium hydroxide is completely dissolved, performing saponification reaction for 20min, stirring, heating to 110-150 ℃, dehydrating, continuously heating to 210 ℃, performing high-temperature refining for 10min, adding 32 g of 500SN base oil, cooling to 110 ℃, adding 0.5g of barium petroleum sulfonate and 3g of HBT-2, cooling to room temperature, and grinding for three times to form grease.
Example 9
Mixing 60 g of 150BS base oil and 7.84 g of 12-hydroxystearic acid in a reaction kettle, heating to 85 ℃, mixing 1.21 g of lithium hydroxide monohydrate and 8 g of distilled water, heating to 95 ℃, adding the mixture into the reaction kettle after the lithium hydroxide is completely dissolved, performing saponification reaction for 20min, stirring, heating to 110-150 ℃, dehydrating, continuously heating to 210 ℃, performing high-temperature refining for 10min, adding 32 g of 150BS base oil, cooling to 110 ℃, adding 0.5g of barium petroleum sulfonate and 3g of HBT-2, cooling to room temperature, and grinding for three times to form grease.
Example 10
Mixing 60 g of PAO10 base oil and 7.84 g of 12-hydroxystearic acid in a reaction kettle, heating to 85 ℃, mixing 1.21 g of lithium hydroxide monohydrate and 8 g of distilled water, heating to 95 ℃, adding the mixture into the reaction kettle after the lithium hydroxide is completely dissolved, carrying out saponification reaction for 20min, stirring, heating to 110-150 ℃ for dehydration, then continuously heating to 210 ℃ for high-temperature refining for 10min, adding 32 g of PAO10 base oil, cooling to 110 ℃, adding 0.5g of barium dinonylnaphthalene sulfonate and 3g of HBT-2, cooling to room temperature, and grinding for three times to form grease.
Example 11
Mixing 60 g of 500SN base oil and 7.84 g of 12-hydroxystearic acid in a reaction kettle, heating to 85 ℃, mixing 1.21 g of lithium hydroxide monohydrate and 8 g of distilled water, heating to 95 ℃, adding the mixture into the reaction kettle after the lithium hydroxide is completely dissolved, performing saponification reaction for 20min, stirring, heating to 110-150 ℃, dehydrating, continuously heating to 210 ℃, performing high-temperature refining for 10min, adding 32 g of 500SN base oil, cooling to 110 ℃, adding 0.5g of barium petroleum sulfonate and 3g of HBT, cooling to room temperature, and grinding for three times to form grease.
Example 12
Mixing 60 g of 150BS base oil and 7.84 g of 12-hydroxystearic acid in a reaction kettle, heating to 85 ℃, mixing 1.21 g of lithium hydroxide monohydrate and 8 g of distilled water, heating to 95 ℃, adding the mixture into the reaction kettle after the lithium hydroxide is completely dissolved, performing saponification reaction for 20min, stirring, heating to 110-150 ℃, dehydrating, continuously heating to 210 ℃, performing high-temperature refining for 10min, adding 32 g of 150BS base oil, cooling to 110 ℃, adding 0.5g of barium petroleum sulfonate and 3g of HBT, cooling to room temperature, and grinding for three times to form grease.
Example 13
Mixing 60 g of PAO10 base oil and 7.84 g of 12-hydroxystearic acid in a reaction kettle, heating to 85 ℃, mixing 1.21 g of lithium hydroxide monohydrate and 8 g of distilled water, heating to 95 ℃, adding the mixture into the reaction kettle after the lithium hydroxide is completely dissolved, carrying out saponification reaction for 20min, stirring, heating to 110-150 ℃ for dehydration, then continuously heating to 210 ℃ for high-temperature refining for 10min, adding 32 g of PAO10 base oil, cooling to 110 ℃, adding 0.5g of barium dinonylnaphthalene sulfonate and 3g of HBT-3, cooling to room temperature, and grinding for three times to form grease.
The greases of examples 8-13 were evaluated for performance by methods including GB/T3498, GB/T269, SH/T0325, SH/T0324, SH/T0202, SH/T0204, GB/T7326, and the results are shown in Table 2.
TABLE 2 grease Properties
Claims (27)
1. A benzothiazole derivative having the structure:
in the general formula (I), the group G is selected from-N (R) c ) 2 Wherein each radical R c Each independently selected from H and
radical R d Selected from hydrogen, C 1-20 A linear or branched alkyl group; each radical R a Are the same or different from each other and are each independently selected from hydrogen, hydroxy and C 1-20 Straight or branched chain alkanesA base; each cyclic group
Selected from benzene rings; each radical R b Selected from hydroxyl; each x in the general formula (I) is the same or different from each other, and each x is independently selected from integers of 0 to 3; y in formula (I) is selected from 1; z in formula (I) is selected from 1;
in the group G, one R c Selected from H, another R c Is selected from
2. Benzothiazole derivative according to claim 1, characterized in that the radical R d Selected from hydrogen and C 1-10 A linear or branched alkyl group; each radical R a Each independently selected from hydrogen, hydroxy and C 1-10 A linear or branched alkyl group; each x in formula (I) is independently selected from 0, 1 or 2.
3. Benzothiazole derivatives according to claim 1, characterized in that
Is composed of
4. A benzothiazole derivative according to claim 1 wherein said benzothiazole derivative is the following:
5. a process for producing a benzothiazole derivative which comprises the step of reacting a benzothiazole compound represented by the general formula (II) with a compound represented by the formula (III-5),
each radical R e Selected from hydrogen; wherein the group X is selected from halogen or hydroxyl;
radical R d Selected from hydrogen, C 1-20 A linear or branched alkyl group; each radical R a Are the same or different from each other and are each independently selected from hydrogen, hydroxy and C 1-20 A linear or branched alkyl group; cyclic group
Selected from benzene rings; radical R b Selected from hydroxyl; each x is the same or different and is independently selected from an integer of 0 to 3; y is selected from 1; z is selected from 1.
6. The process according to claim 5, wherein the group X is selected from F, cl, br, I; r d Selected from hydrogen and C 1-10 A linear or branched alkyl group; each radical R a Each independently selected from hydrogen, hydroxy and C 1-10 A linear or branched alkyl group;
each x is independently selected from 0, 1 or 2.
7. The method of claim 5,
the benzothiazole compounds represented by the general formula (II) are:
the compound represented by the general formula (III-5) is:
8. the process according to claim 5, wherein in the reaction, the molar ratio between the benzothiazole compound of the general formula (II) and the compound of the formula (III-5) is 1:0.5 to 2.
9. The process according to claim 5, wherein in the reaction, the molar ratio between the benzothiazole compound represented by the general formula (II) and the compound represented by the formula (III-5) is 1:0.8 to 1.2.
10. The process according to claim 5, wherein the temperature of the reaction is 0 to 50 ℃; the pressure of the reaction is 0-10 MPa.
11. The process according to claim 5, wherein the temperature of the reaction is 15 to 35 ℃; the pressure of the reaction is 0.05-0.2 MPa.
12. The process according to claim 5, wherein a catalyst is added to the reaction of the benzothiazole compound of general formula (II) and the compound of formula (III-5).
13. The method according to claim 5, wherein a catalyst is added to the reaction between the benzothiazole compound represented by general formula (II) and the compound represented by formula (III-5), and the catalyst is a carbodiimide-based compound and/or a benzotriazole-based compound.
14. The method of claim 13, wherein the carbodiimide-based compound has the structure:
and salts thereof, wherein each R is independently selected from C 6 ～C 10 Aryl of (C) 1 ～C 6 Linear or branched alkyl, mono (C) 1 ～C 4 Alkyl) amino C 1 ～C 10 Alkyl, di (C) 1 ～C 4 Alkyl) amino C 1 ～C 10 An alkyl group; the structure of the benzotriazole compound is as follows:
wherein R' is selected from hydrogen and C 1-6 Straight or branched alkyl, C 3-10 Cycloalkyl, C 6-10 Aryl and C 1-6 An alkoxy group; x is selected from F, cl, br, I and OH.
15. The method of claim 14, wherein C is 6 ～C 10 Aryl of (a) is selected from phenyl, naphthyl; said C is 1 ～C 6 Is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl or isohexyl; the sheet (C) 1 ～C 4 Alkyl) amino C 1 ～C 10 The alkyl is selected from methylamino ethyl, ethylamino ethyl, propyl amino ethyl, methylamino propyl, ethyl amino propyl, propyl amino propyl; said two (C) 1 ～C 4 Alkyl) amino C 1 ～C 10 The alkyl group is selected from dimethylaminoethyl, diethylaminoethyl, dipropylaminoethyl, dimethylaminopropyl, diethylaminopropyl and dipropylaminopropyl.
16. The method of claim 14, wherein said method further comprises
The salt is one or more of hydrochloride, sulfate, nitrate and phosphate thereof.
17. A process according to claim 5, characterized in that a solvent is added to the reaction.
18. The method of claim 17, wherein the solvent is C 1 ～C 10 Organic amine, furan, sulfoxide.
19. The process according to claim 5, wherein the benzothiazole compounds of general formula (II) are prepared by a process comprising reacting
And
a step of reaction, in which each group R e Selected from hydrogen; wherein the group X is selected from halogen or hydroxyl; each radical R a Are the same or different from each other and are each independently selected from hydrogen, hydroxy and C 1-20 A linear or branched alkyl group; cyclic group
Selected from benzene rings; radical R b Selected from hydroxyl; each x is the same or different and is independently selected from an integer of 0 to 3; y is selected from 1; z is selected from 1.
20. The method of claim 19, wherein each group X is independently selected from F, cl, br, I; each radical R a Each independently selected from hydrogen, hydroxy and C 1-10 A linear or branched alkyl group; each x is independently selected from 0, 1 or 2.
21. Use of benzothiazole derivatives according to any of claims 1 to 4 and prepared according to the process of claims 5 to 20 in lubricating oils and greases.
22. A grease comprising a benzothiazole derivative according to any of claims 1 to 4 and a benzothiazole derivative obtainable according to a process of claims 5 to 20, optionally a grease additive, a thickener and a lubricating base oil.
23. The grease of claim 22 wherein the benzothiazole derivative comprises from 0.0005% to 5% of the total grease mass; the lubricating grease additive accounts for 0-10% 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.
24. The grease of claim 22 wherein the benzothiazole derivative is present in an amount of from 0.001% to 1% of the total mass of the grease; the lubricating grease additive accounts for 0.1-5% of the total mass of the lubricating grease; the thickening agent accounts for 10-20% of the total mass of the lubricating grease; the lubricating base oil constitutes the main component of the grease.
25. The grease of claim 22, wherein the thickener is 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; the base oil is one or more of mineral oil, vegetable oil and synthetic oil.
26. A method of preparing a grease of any of claims 22-25, comprising: mixing and refining lubricating base oil, a thickening agent, an optional lubricating grease additive and a benzothiazole derivative, and grinding into grease.
27. The method of claim 26, 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 an aqueous solution of benzothiazole derivatives and lithium hydroxide, heating to remove water, continuing heating to 190-220 ℃ for high-temperature refining, adding the rest of lubricating base oil and optional lubricating grease additives, cooling to 60-120 ℃, and grinding into grease.
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