CN111100742B - Composite lithium-based lubricating grease and preparation method thereof - Google Patents

Composite lithium-based lubricating grease and preparation method thereof Download PDF

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CN111100742B
CN111100742B CN201811268016.5A CN201811268016A CN111100742B CN 111100742 B CN111100742 B CN 111100742B CN 201811268016 A CN201811268016 A CN 201811268016A CN 111100742 B CN111100742 B CN 111100742B
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lithium
grease
alkyl group
lithium complex
reaction
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CN111100742A (en
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刘欣阳
庄敏阳
郑会
孙洪伟
何懿峰
刘中其
姜靓
段庆华
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
    • 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
    • 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
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/38—Heterocyclic nitrogen compounds
    • C10M133/44—Five-membered ring containing nitrogen and carbon only
    • 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
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/38—Heterocyclic nitrogen compounds
    • C10M133/48—Heterocyclic nitrogen compounds the ring containing both nitrogen and 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
    • 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
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • 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
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
    • 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
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
    • 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
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/223—Five-membered rings containing nitrogen and carbon only
    • 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
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and 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
    • 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)
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  • 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 composite lithium-based lubricating grease and a preparation method thereof. The composite lithium-based lubricating grease comprises benzoazacyclo derivative, a composite lithium-based thickening agent, optional additives and lubricating base oil; the benzoazacyclo derivative accounts for 0.0005 to 5 percent of the total mass of the lubricating grease; the composite lithium-based thickening agent accounts for 5-30% of the total mass of the lubricating grease; the optional additive accounts for 0-20% of the total mass of the lubricating grease; the lubricating base oil constitutes the main component of the grease. The lithium-based lubricating grease disclosed by the invention can emit orange yellow light under the irradiation of ultraviolet light, has excellent photoluminescence performance and wear resistance, and can be applied to relevant mechanical equipment in the electrical appliance industry, the metallurgical industry, the food industry, the paper industry, the automobile industry and the aircraft industry.

Description

Composite lithium-based lubricating grease and preparation method thereof
Technical Field
The invention relates to lubricating grease, in particular to composite lithium-based lubricating grease with a light-emitting 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 and electronic information industry.
Under some dark working conditions, the monitoring of the lubricating grease has great difficulty, the residual quantity of the lubricating grease is difficult to directly observe by naked eyes in many cases, and if the lubricating grease can emit high-intensity fluorescence, the monitoring of the content of the lubricating grease is greatly facilitated. However, the current report of the luminescent grease is rare.
Traditional organic chromophores generally have strong luminescence at low concentrations, and weak or even no luminescence at high concentrations or in solid states, exhibiting an aggregate fluorescence quenching effect. This is because in the aggregate state, the strong intermolecular interactions lead to an enhancement of the non-radiative decay process of the excited state, with a significant decrease in fluorescence quantum yield. In the practical application process, the practical application of the organic light-emitting material is limited to a great extent by the aggregate fluorescence quenching effect. In recent years, research shows that some compounds show the opposite properties to the traditional organic luminescent compounds, not only do not have aggregation fluorescence quenching effect, but also show Aggregation Induced Emission (AIE) properties, and the appearance of the aggregation induced emission compounds provides a new solution for the application of organic luminescent materials in a solid state or at high concentration.
The composite lithium-based lubricating grease is high-temperature multi-effect lubricating grease developed in the 60 th of the 20 th century, has a higher dropping point than that of the lithium-based lubricating grease, is suitable for being used at high temperature, and has good colloid stability, shear stability, water resistance and long service life. In recent years, composite lithium grease has been greatly developed at home and abroad. For example, US3681242, US3929651, US3711407, CN1052890A, CN1052891A, CN1055384A and CN101705141A report the composition and preparation method of the lithium complex grease, which is compounded by adopting two components of 12-hydroxy lithium stearate and binary acid or boric acid and lithium salt of salicylic acid.
Disclosure of Invention
The invention provides a composite lithium-based lubricating grease and a preparation method thereof.
The composite lithium-based lubricating grease comprises benzoazacyclo derivative, a composite lithium-based thickening agent, optional additives and lubricating base oil; the benzoazacyclo derivative accounts for 0.0005 to 5 percent (preferably 0.001 to 1 percent) of the total mass of the lubricating grease; the composite lithium-based thickening agent accounts for 5-30% (preferably 10-20%) of the total mass of the lubricating grease; the optional additive accounts for 0-20% (preferably 1-10%) of the total mass of the lubricating grease; the lubricating base oil constitutes the main component of the grease; the structure of the benzo nitrogen heterocyclic derivative is as follows:
Figure BDA0001845339050000021
wherein A is S, O or NR, R is hydrogen or C1～6An alkyl group; each RaRadical, each RbRadical, each RcThe radicals, equal to or different from each other, are each independently selected from C1～6Straight or branched alkyl (preferably C)1～4Straight or branched chain alkyl); x is an integer of 0 to 4 (preferably 0 or 1), y is an integer of 0 to 3 (preferably 0 or 1), and z is an integer of 0 to 4 (preferably 0 or 1).
The benzo nitrogen heterocyclic derivative comprises one or more of the following compounds:
Figure BDA0001845339050000022
the preparation method of the benzo nitrogen heterocyclic derivative comprises the step of reacting the benzo nitrogen heterocyclic compound shown in the general formula (II) with the alkyne compound shown in the general formula (III),
Figure BDA0001845339050000023
in the general formula (II), the A group is S, O or NR, R is hydrogen or C1～6An alkyl group; the group X is F, Cl, Br, I, OH (preferably Cl or Br); each RaRadical, each RbThe radicals, equal to or different from each other, are each independently selected from C1～6Straight or branched alkyl (preferably C)1～4Straight or branched chain alkyl); x is an integer of 0 to 4 (preferably 0 or 1), and y is an integer of 0 to 3 (preferably 0 or 1); in the general formula (III), each RcThe radicals, equal to or different from each other, are each independently selected from C1～6Straight or branched alkyl (preferably C)1～4Straight or branched chain alkyl); z is an integer of 0 to 4 (preferably 0 or 1).
Benzazepine compounds of the general formula (II) include:
Figure BDA0001845339050000031
the acetylene compounds represented by the general formula (III) include:
Figure BDA0001845339050000032
according to the invention, in the reaction, the molar ratio between the benzoazacyclic compound represented by the general formula (II) and the alkyne compound represented by the general formula (III) is preferably 1 to 3: 1, most preferably 1 to 2: 1; the reaction temperature is 0-50 ℃, and preferably 15-35 ℃; the reaction time is preferably 12-96 h, and more preferably 24-72 h; the reaction is preferably carried out under an inert gas (preferably nitrogen) blanket.
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 BDA0001845339050000041
Wherein M is Pd, Ru or Rh, L is selected from PPh3Ph, F, Cl, Br, I. The metal phosphine complex can be one or more of tetrakis (triphenylphosphine) palladium, tris (triphenylphosphine) palladium chloride, bis (triphenylphosphine) palladium dichloride, (triphenylphosphine) palladium trichloride, tetrakis (triphenylphosphine) ruthenium, tris (triphenylphosphine) ruthenium chloride, bis (triphenylphosphine) ruthenium dichloride, (triphenylphosphine) ruthenium trichloride, tetrakis (triphenylphosphine) rhodium, tris (triphenylphosphine) rhodium chloride, bis (triphenylphosphine) rhodium dichloride and (triphenylphosphine) rhodium trichloride, and preferably one or more of tetrakis (triphenylphosphine) palladium, tris (triphenylphosphine) palladium chloride, bis (triphenylphosphine) palladium dichloride and (triphenylphosphine) palladium trichloride.
According to the present invention, preferably, the metal halide may be one or more of a copper halide, an iron halide and a zinc halide, for example, one or more of copper chloride, cuprous chloride, copper bromide, cuprous bromide, copper iodide, cuprous iodide, ferric chloride, ferrous chloride, ferric bromide, ferrous bromide, ferric iodide, ferrous iodide, zinc chloride, zinc bromide, zinc iodide and zinc iodide may be used, and more preferably one or more of copper chloride, cuprous chloride, copper bromide, cuprous bromide, copper iodide and cuprous iodide.
According to the present invention, preferably, the hydrocarbyl phosphine compound has the structure
Figure BDA0001845339050000042
Wherein each R is independently selected from C6～C10Aryl and C1～C6Wherein at least one R is C6～C10Aryl group of (1). Said C is6～C10The aryl group of (a) may be selected from phenyl, naphthyl; said C is1～C6Straight or branched chain ofThe alkyl group 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 0.1-100% of the mass of the benzoazacyclo compound shown in formula (II).
According to the invention, a solvent may or may not be added to the reaction, preferably a solvent is added. The solvent is preferably furan or C1～6Chlorinated alkane of (C)1～6Alkyl amine (more preferably furan, C)1～4Chlorinated alkane of (C)1～4The alkylamine of (b) may be, for example, one or more of tetrahydrofuran, chloroform, methylene chloride, methyl chloride, trimethylamine, triethylamine and tripropylamine.
According to the invention, the product of the reaction is preferably subjected to a purification treatment. The purification treatment is preferably a recrystallization method and/or a column chromatography method. The recrystallization method is to separate and purify the product by using a solvent through a recrystallization method; the solvent is preferably one or more of benzene, toluene, xylene and hexane (more preferably a mixed solvent of toluene and n-hexane, and the mass ratio of the toluene to the n-hexane is 1: 0.1-10). The column chromatography method is to separate and purify a product by using an eluant through column chromatography; the eluent is preferably C1～6Chlorinated alkane of (C)1～6The alcohol(s) (more preferably a mixed solution of dichloromethane and methanol, in a volume ratio of 1: 0.05-10). According to the invention, the process for the preparation of benzazepine compounds of the general formula (II) preferably comprises the step of reacting a compound of the general formula (IV) with a compound of the general formula (V),
Figure BDA0001845339050000051
in the general formula (IV), A is S, O or NR, R is hydrogen or C1～6An alkyl group; each RaThe radicals, equal to or different from each other, are each independently selected from C1～6Straight chain orBranched alkyl radical (preferably C)1～4Straight or branched chain alkyl); x is an integer between 0 and 4 (preferably 0 or 1); in formula (V), the group X is F, Cl, Br, I, OH (preferably Cl or Br); each RbThe radicals, equal to or different from each other, are each independently selected from C1～6Straight or branched alkyl (preferably C)1～4Straight or branched chain alkyl); y is an integer of 0 to 3 (preferably 0 or 1).
According to the present invention, preferably, in the method for producing a benzazepine compound represented by the general formula (II), the molar ratio between the compound represented by the general formula (IV) and the compound represented by the general formula (V) is preferably 0.5 to 2: 1, most preferably 0.9 to 1.1: 1. the temperature for the reaction of the compound represented by the general formula (IV) and the compound represented by the general formula (V) is 80-240 ℃ (preferably 140-180 ℃); the reaction time is preferably 2-24 h (more preferably 4-12 h); the reaction is preferably carried out under the protection of an inert gas (preferably nitrogen); a solvent is preferably added in the reaction, and the solvent is preferably one or more of polyphosphoric acid, dimethyl sulfoxide, dimethylformamide and 1, 4-dioxane (more preferably polyphosphoric acid). The solvent may be removed by a technique known in the art, and is not particularly limited.
The benzo nitrogen heterocyclic ring derivative has excellent photoluminescence performance, can emit orange yellow light under ultraviolet irradiation, and can be applied to light-emitting parts and devices, fluorescent probes, biological imaging, lubricating oil and lubricating grease.
According to the invention, the composite lithium-based thickening agent is a thickening agent formed by the reaction of composite acid and lithium hydroxide. The complex acid comprises C12～20Fatty acids and C2～11The organic acid of (1), the C12～20The fatty acid can be one or more selected from lauric acid, myristic acid, palmitic acid, stearic acid and 12-hydroxystearic acid, and C2～11The organic acid of (a) may be selected from one or more of acetic acid, propionic acid, oxalic acid, adipic acid, azelaic acid, sebacic acid, terephthalic acid. The molar ratio of the composite acid (calculated by carboxyl) to the lithium hydroxide is 1: 0.5 to 2 (preferably 1: 0.8 to 1.2).
According to the invention, the lubricating base oil can be one or more of mineral oil, vegetable oil and synthetic oil, preferably mineral oil and/or synthetic oil, such as 150SN, 500SN, PAO8 and PAO 10.
According to the present invention, the optional additives include one or more of antioxidants, rust inhibitors and extreme pressure anti-wear agents. The antioxidant, the rust preventive agent and the extreme pressure antiwear agent may be any of known antioxidants, antiwear agents, rust preventive agents and extreme pressure agents, and are not particularly limited. The antioxidant is preferably an amine antioxidant and/or a phenol antioxidant, and for example, diphenylamine or 2, 6-di-tert-butylphenol can be used. The rust inhibitor is preferably sulfonate, and for example, barium dinonylnaphthalene sulfonate and barium petroleum sulfonate can be selected. The extreme pressure antiwear agent is preferably one or more of dialkyl dithiocarbamate, aminothioester and phosphate, for example, zinc dialkyl dithiocarbamate can be selected.
The preparation method of the composite lithium-based lubricating grease comprises the following steps: mixing lubricating base oil, lithium-based thickening agent and thiazole 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 thiazole derivative and the thickener may be mixed and refined, or part of the lubricating base oil, part of the thiazole derivative and the thickener may be mixed and refined, and then mixed with the rest of the lubricating base oil and the rest of the thiazole derivative.
According to the preparation method of the lithium complex grease of the present invention, preferably, the preparation method of the lithium complex grease comprises: mixing and heating all or part of lubricating base oil and the composite acid in a reaction kettle, heating to 40-90 ℃, adding the aqueous solution of the thiazole derivative and the lithium hydroxide, heating to remove water, continuously heating to 190-220 ℃ for high-temperature refining, cooling to 60-120 ℃ or adding the rest of lubricating base oil, cooling to 60-120 ℃, adding an optional additive, and grinding into grease. The fatty acid is C12～C20Fatty acid and/or C12～C20The hydroxy fatty acid may be selected from lauric acid, myristic acid, palmitic acid, and stearic acidOne or more of fatty acid and 12-hydroxystearic acid. The concentration of the aqueous solution of lithium hydroxide is 5-30%, preferably 10-20%. The molar ratio of the lithium hydroxide in the aqueous solution of the lithium hydroxide to the fatty acid is 0.3-3: 1, preferably 0.5 to 2: 1. the time for high-temperature refining is preferably 5-240 min, and more preferably 10-60 min.
According to the method for preparing the lithium complex grease of the present invention, the thiazole derivative is preferably dissolved in a solvent in advance, and the solvent is preferably an aromatic hydrocarbon solvent such as benzene, toluene, xylene. The thiazole derivative is preferably present in an amount of 1 to 20% by mass based on the mass of the solvent.
The composite lithium-based lubricating grease disclosed by the invention can emit orange yellow light under the irradiation of ultraviolet light, has excellent photoluminescence performance and wear 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 main raw materials used are as follows:
chemical reagents such as polyphosphoric acid, o-aminothiophenol, sodium hydroxide bromosalicylate, sodium carbonate, 4- (dicyanovinyl) phenylacetylene, cuprous iodide, triphenylphosphine, palladium tetratriphenylphosphine, 1, 4-dioxane, 12-hydroxystearic acid, sebacic acid, lithium hydroxide monohydrate, tetrahydrofuran, triethylamine, dichloromethane, methanol, toluene and the like are from the company Bailingwei reagent, the company enokay reagent or the company Sigma reagent, and the analytical purity is high; the PAO10 base oil was obtained from Exxon Mobil.
Example 1
200mL of polyphosphoric acid (PPA), 0.2mol of o-aminosulfol and 0.2mol of p-bromosalicylic acid are added into a 500mL three-neck 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, and oven drying at 60 deg.C in vacuum oven to obtain 2- (2'-hydroxy-4-bromophenyl) benzothiazole, 54% yield. The nuclear magnetic results are:1H NMR(400MHz,DMSO-d6),δ(TMS,ppm):11.71(s,1H),8.02(d,1H),7.88(d,1H),7.62(d,1H),7.45(m,1H),7.33(m,1H),6.24(d,1H),6.15(d,1H,),5.95(s,2H).MS(ESI-TOF):304.95([M+H]+)。
the reaction formula of example 1 is as follows:
Figure BDA0001845339050000071
example 2
A100 mL Schlenk flask was charged with 10mmol of 2- (2' -hydroxy-4-bromophenyl) benzothiazole, 30mmol of 4- (dicyanovinyl) phenylacetylene, 1mmol of cuprous iodide, and 1mmol of triphenylphosphine. 0.2mmol of tetratriphenylphosphine palladium, 50mL of tetrahydrofuran/triethylamine (2/1, v/v) were added under nitrogen, and the mixture was reacted at room temperature for 48 hours. After the reaction is finished, filtering, drying the filtrate by spinning, and separating and purifying the product by column chromatography by using a dichloromethane/methanol (20/1, v/v) mixed solvent as an eluent to obtain the 2- (2 '-hydroxy-4' -dicyanovinylphenyl alkynyl) benzothiazole, wherein the yield of the yellow solid product is 57%. The nuclear magnetic results are:1H NMR(400MHz,CDCl3),δ(TMS,ppm):11.71(s,1H),8.02(d,1H),7.98(d,1H),7.78(s,1H),7.62(d,2H),7.58(d,1H),7.45(m,1H),7.35(d,2H),7.33(m,1H),6.24(d,1H),6.15(d,1H,).MS(MALDI-TOF):m/z calcd:403.1[M]+,found:403.1。
the reaction formula of example 2 is as follows:
Figure BDA0001845339050000081
example 3
Mixing and heating 50 g of 500SN base oil, 10 g of 12-hydroxystearic acid and 3.3 g of sebacic acid in a reaction kettle to 85 ℃, dissolving 0.5g of 2- (2 '-hydroxy-4' -dicyanovinylphenyl alkynyl) benzothiazole in 10 g of toluene, adding the mixture into the reaction kettle, mixing and heating 2.8 g of lithium hydroxide monohydrate and 18 g of distilled water to 95 ℃, dropwise adding the mixture into the reaction kettle after all the lithium hydroxide is dissolved for saponification reaction for 20min, stirring and heating to 110 ℃ and 150 ℃ for dehydration and debenzolization, then continuously heating to 210 ℃ for refining at high temperature for 10min, adding 36.5 g of 500SN base oil, cooling to 110 ℃, adding 0.5g of diphenylamine and 0.5g of barium petroleum sulfonate, cooling to room temperature and grinding into grease.
Example 4
Mixing and heating 50 g of 500SN base oil, 10 g of 12-hydroxystearic acid and 3.3 g of sebacic acid in a reaction kettle to 85 ℃, dissolving 1g of 2- (2 '-hydroxy-4' -dicyanovinylphenyl alkynyl) benzothiazole in 10 g of toluene, adding the mixture into the reaction kettle, mixing and heating 2.8 g of lithium hydroxide monohydrate and 18 g of distilled water to 95 ℃, dropwise adding the mixture into the reaction kettle after the lithium hydroxide is completely dissolved for saponification reaction for 20min, stirring and heating to 110 ℃ and 150 ℃ for dehydration and benzene removal, then continuously heating to 210 ℃ for high-temperature refining for 10min, adding 36.5 g of 500SN base oil, cooling to 110 ℃, adding 0.5g of diphenylamine and 0.5g of barium petroleum sulfonate, cooling to room temperature, and grinding into grease.
Example 5
Mixing 50 g of PAO10 base oil, 10 g of 12-hydroxystearic acid and 3.3 g of sebacic acid in a reaction kettle, heating to 85 ℃, dissolving 0.5g of 2- (2 '-hydroxy-4' -dicyanovinylphenyl alkynyl) benzothiazole in 10 g of toluene, adding the mixture into the reaction kettle, mixing and heating 2.8 g of lithium hydroxide monohydrate and 18 g of distilled water to 95 ℃, dropwise adding the mixture into the reaction kettle after the lithium hydroxide is completely dissolved, performing saponification for 20min, stirring and heating to 110 ℃ and 150 ℃ for dehydration and benzene removal, continuously heating to 210 ℃, performing high-temperature refining for 10min, adding 36.5 g of PAO10 base oil, cooling to 110 ℃, adding 0.5g of diphenylamine and 0.5g of barium petroleum sulfonate, cooling to room temperature, and grinding into grease.
Example 6
Mixing 50 g of PAO10 base oil, 10 g of 12-hydroxystearic acid and 3.3 g of sebacic acid in a reaction kettle, heating to 85 ℃, dissolving 1g of 2- (2 '-hydroxy-4' -dicyanovinylphenyl alkynyl) benzothiazole in 10 g of toluene, adding the mixture into the reaction kettle, mixing 2.8 g of lithium hydroxide monohydrate and 18 g of distilled water, heating to 95 ℃, dropwise adding the mixture into the reaction kettle after the lithium hydroxide is completely dissolved, performing saponification for 20min, stirring, heating to 110 ℃ and 150 ℃, performing dehydration and debenzolization, continuously heating to 210 ℃, performing high-temperature refining for 10min, adding 36.5 g of PAO10 base oil, cooling to 110 ℃, adding 0.5g of diphenylamine and 0.5g of barium petroleum sulfonate, cooling to room temperature, and grinding into grease.
Example 7
50 g of PAO10 base oil, 10 g of 12-hydroxystearic acid and 3.3 g of sebacic acid are mixed and heated to 85 ℃ in a reaction kettle, 2.8 g of lithium hydroxide monohydrate and 18 g of distilled water are mixed and heated to 95 ℃, after lithium hydroxide is completely dissolved, the mixture is dripped into the reaction kettle for saponification reaction for 20min, the mixture is stirred and heated to 110 ℃ and 150 ℃ for dehydration and debenzolization, then the mixture is continuously heated to 210 ℃ for refining at high temperature for 10min, 36.5 g of PAO10 base oil is added, diphenylamine 0.5g, barium petroleum sulfonate 0.5g and 2- (2 '-hydroxy-4' -dicyanovinylphenyl alkynyl) benzothiazole 1g are added after cooling to 110 ℃, and the mixture is ground into grease after cooling to room temperature.
Comparative example 1
Mixing and heating 50 g of 500SN base oil, 10 g of 12-hydroxystearic acid and 3.3 g of sebacic acid in a reaction kettle to 85 ℃, mixing and heating 2.8 g of lithium hydroxide monohydrate and 18 g of distilled water to 95 ℃, dropwise adding the mixture into the reaction kettle for saponification for 20min after the lithium hydroxide is completely dissolved, stirring and heating to 110 ℃ and 150 ℃ for dehydration and debenzolization, then continuously heating to 210 ℃ for high-temperature refining for 10min, adding 36.5 g of PAO10 base oil, cooling to 110 ℃, adding 0.5g of diphenylamine, 0.5g of barium petroleum sulfonate and 1g of dialkyl dithiocarbamate, cooling to room temperature, and grinding into grease.
Comparative example 2
Mixing 50 g of PAO10 base oil, 10 g of 12-hydroxystearic acid and 3.3 g of sebacic acid in a reaction kettle, heating to 85 ℃, mixing 2.8 g of lithium hydroxide monohydrate and 18 g of distilled water, heating to 95 ℃, dropwise adding the mixture into the reaction kettle after the lithium hydroxide is completely dissolved for saponification reaction for 20min, stirring, heating to 110 ℃ and 150 ℃ for dehydration and debenzolization, then continuously heating to 210 ℃ for high-temperature refining for 10min, adding 36.5 g of PAO10 base oil, cooling to 110 ℃, adding 0.5g of diphenylamine, 0.5g of barium petroleum sulfonate and 1g of dialkyl dithiocarbamate, cooling to room temperature, and grinding into grease.
The greases of examples 3-7 and comparative examples 1-2 were respectively subjected to performance evaluation by 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 evaluation of grease Properties
Figure BDA0001845339050000101

Claims (19)

1. A complex lithium-based lubricating grease comprises benzoazacyclo derivative, complex lithium-based thickener, optional additive and lubricating base oil; the benzoazacyclo derivative accounts for 0.0005-5% of the total mass of the lubricating grease; the composite lithium-based thickening agent accounts for 5-30% of the total mass of the lubricating grease; the optional additive accounts for 0-20% of the total mass of the lubricating grease; the lubricating base oil constitutes the main component of the grease; the benzoazacyclo derivative has the structure as follows:
Figure 296719DEST_PATH_IMAGE001
（I）
wherein A is S, O or NR, R is hydrogen or C1~6An alkyl group; each RaRadical, each RbRadical, each RcThe radicals, equal to or different from each other, are each independently selected from C1~6A linear or branched alkyl group; x is an integer of 0 to 4, y is an integer of 0 to 3, and z is an integer of 0 to 4.
2. The lithium complex grease of claim 1 wherein the benzoazacyclo derivative is present in an amount of 0.001% to 1% by weight of the total grease; the composite lithium-based thickening agent accounts for 10-20% of the total mass of the lubricating grease; the optional additive accounts for 1-10% of the total mass of the lubricating grease; each RaRadical, each RbRadical, each RcEach independently selected from C1~4A linear or branched alkyl group; x is 0 or 1, y is 0 or 1, zIs 0 or 1.
3. The lithium complex grease of claim 1 wherein the benzazepine derivative comprises one or more of the following compounds:
Figure 90232DEST_PATH_IMAGE002
。
4. the lithium complex grease according to claim 1 wherein the benzoazacyclo derivative is prepared by a process comprising the step of reacting a benzoazacyclo compound represented by the general formula (II) with an acetylene compound represented by the general formula (III),
Figure 536125DEST_PATH_IMAGE003
（II），
Figure 680668DEST_PATH_IMAGE004
（III），
in the general formula (II), A is S, O or NR, R is hydrogen or C1~6An alkyl group; the group X is F, Cl, Br, I, OH; each RaRadical, each RbThe radicals, equal to or different from each other, are each independently selected from C1~6A linear or branched alkyl group; x is an integer between 0 and 4, and y is an integer between 0 and 3; in the general formula (III), each RcThe radicals, equal to or different from each other, are each independently selected from C1~6A linear or branched alkyl group; z is an integer of 0 to 4.
5. The lithium complex grease according to claim 4 characterized in that in formula (II), the group X is Cl or Br; each RaRadical, each RbEach independently selected from C1~4A linear or branched alkyl group; x is 0 or 1, y is 0 or 1; in the general formula (III), each RcEach independently selected from C1~4A linear or branched alkyl group; z is0 or 1.
6. The lithium complex grease according to claim 4 wherein the benzoazacyclic compound of formula (II) comprises:
Figure 745576DEST_PATH_IMAGE005
Figure 737802DEST_PATH_IMAGE006
Figure 38420DEST_PATH_IMAGE007
Figure 998155DEST_PATH_IMAGE008
Figure 866754DEST_PATH_IMAGE009
Figure 447908DEST_PATH_IMAGE010
；
the alkyne compounds of formula (III) include:
Figure DEST_PATH_IMAGE011
。
7. the lithium complex grease according to claim 4 wherein the molar ratio of the benzoazacyclo compound of formula (II) to the alkyne compound of formula (III) in the reaction is 1 to 3: 1; the reaction temperature is 0-50 ℃; the reaction time is 12-96 h; the reaction is carried out under the protection of inert gas.
8. The lithium complex grease according to claim 4 wherein the molar ratio of the benzoazacyclo compound of formula (II) to the alkyne compound of formula (III) in the reaction is 1 to 2: 1; the reaction temperature is 15-35 ℃; the reaction time is 24-72 h; the reaction was carried out under nitrogen protection.
9. The lithium complex grease according to claim 4 wherein a catalyst is added to the reaction, the catalyst being one or more of a metal phosphine complex, a metal halide and a hydrocarbyl phosphine compound.
10. The lithium complex grease according to claim 4 wherein a catalyst is added in the reaction, the catalyst being a mixture of a metal phosphine complex, a metal halide and a hydrocarbyl phosphine compound, the molar ratio of the three being 1: 0.1-10: 0.1 to 10.
11. The lithium complex grease according to claim 4 wherein the process for preparing the benzazepine compound represented by the general formula (II) comprises the step of reacting the compound represented by the general formula (IV) with the compound represented by the general formula (V),
Figure 173287DEST_PATH_IMAGE012
（IV），
Figure DEST_PATH_IMAGE013
（V），
in the general formula (IV), A is S, O or NR, R is hydrogen or C1~6An alkyl group; each RaThe radicals, equal to or different from each other, are each independently selected from C1~6A linear or branched alkyl group; x is an integer between 0 and 4; in the general formula (V), the group X is F, Cl, Br, I, OH; each RbThe radicals, equal to or different from each other, are each independently selected from C1~6A linear or branched alkyl group; y is an integer of 0 to 3.
12. The lithium complex grease according to claim 11 wherein in formula (IV), each R isaEach independently selected from C1~4A linear or branched alkyl group; x is 0 or 1; in the formula (V), the group X is Cl or Br; each RbEach independently selected from C1~4A linear or branched alkyl group; y is 0 or 1.
13. The lithium complex grease as claimed in any one of claims 1 to 12 wherein the lithium complex thickener is a thickener obtained by reacting a complex acid with lithium hydroxide.
14. The lithium complex grease of claim 13 wherein said complex acid comprises C12~20Fatty acids and C2~11The organic acid of (1).
15. The lithium complex grease as claimed in any one of claims 1 to 12 wherein the optional additives include one or more of antioxidants, rust inhibitors and extreme pressure anti-wear agents.
16. The method for preparing the lithium complex grease according to any one of claims 1 to 15, comprising: mixing lubricating base oil, lithium-based thickening agent and benzoazacyclo derivative, refining, and grinding into grease.
17. The method of preparing a lithium complex grease according to claim 16 wherein the method of preparing the lithium complex grease comprises: mixing and heating all or part of lubricating base oil and the composite acid described in claim 13 in a reaction kettle, heating to 40-90 ℃, adding a water solution of benzo-nitrogen heterocyclic derivative and lithium hydroxide, heating to remove water, continuously heating to 190-220 ℃ for high-temperature refining, then cooling to 60-120 ℃ or adding the rest lubricating base oil, cooling to 60-120 ℃, adding an optional additive, and grinding into grease.
18. The method of preparing a lithium complex grease according to claim 16 wherein the benzazepine derivative is dissolved in a solvent in advance.
19. The method of preparing a lithium complex grease according to claim 18 wherein the solvent is an aromatic hydrocarbon solvent.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001348589A (en) * 2000-06-08 2001-12-18 Minebea Co Ltd Fluorescent grease and bearing as its application
JP2008115237A (en) * 2006-11-02 2008-05-22 Chugoku Electric Power Co Inc:The Corrosion resistant grease composition and corrosion resistant overhead wire
CN103214428A (en) * 2013-04-16 2013-07-24 浙江大学 Benzothiazole-cyanophenyl compound serving as hydrazine fluorescence probe as well as preparation method and application method of benzothiazole-cyanophenyl compound

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030144159A1 (en) * 2000-06-08 2003-07-31 Motoharu Akiyama Fluorescent grease and bearings having the same therein

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001348589A (en) * 2000-06-08 2001-12-18 Minebea Co Ltd Fluorescent grease and bearing as its application
JP2008115237A (en) * 2006-11-02 2008-05-22 Chugoku Electric Power Co Inc:The Corrosion resistant grease composition and corrosion resistant overhead wire
CN103214428A (en) * 2013-04-16 2013-07-24 浙江大学 Benzothiazole-cyanophenyl compound serving as hydrazine fluorescence probe as well as preparation method and application method of benzothiazole-cyanophenyl compound

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