CN112760157B - 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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CN112760157B
CN112760157B CN201910997459.6A CN201910997459A CN112760157B CN 112760157 B CN112760157 B CN 112760157B CN 201910997459 A CN201910997459 A CN 201910997459A CN 112760157 B CN112760157 B CN 112760157B
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grease
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radicals
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CN112760157A (en
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庄敏阳
郑会
刘显秋
刘欣阳
刘中其
刘伟
姜靓
孙洪伟
何懿峰
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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
    • C10M169/04—Mixtures of base-materials and additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/094—Esters of phosphoric acids with arylalkanols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/11—Esters of phosphoric acids with hydroxyalkyl compounds without further substituents on alkyl
    • 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
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/0206—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M2207/127—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 polycarboxylic
    • C10M2207/1276—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 polycarboxylic used as thickening agent
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/16—Naphthenic acids
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/74—Recovery of fats, fatty oils, fatty acids or other fatty substances, e.g. lanolin or waxes

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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)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Lubricants (AREA)

Abstract

The invention provides a composite lithium-based lubricating grease and a preparation method thereof. The lithium complex grease comprises the following components: (a) an additive; (b) a complex lithium-based thickener; (c) a lubricating base oil; wherein the additive is a mixture of a phosphorus-containing compound, a rust inhibitor and an oiliness agent; the structure of the phosphorus-containing compound is as follows:

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 biodegradability.
Background
The lubricating grease is a necessary working medium in the normal operation of mechanical equipment and the manufacturing and processing process of materials, and the demand of the lubricating grease is more and more increased along with the rapid development of the industry. During the storage, transportation and use of the lubricating grease, various environmental pollution conditions such as leakage, overflow and improper discharge inevitably occur. Although the acute toxicity of the grease to organisms is very small, the grease entering the environment seriously pollutes the land, rivers and lakes due to poor biodegradability, and the grease is not easy to recycle like the lubricating oil, so the research on the grease with biodegradability becomes a breakthrough for solving the problem of ecological environment.
In recent years, the influence of waste and leaked lubricating grease on the environment has attracted much attention, and in order to solve the problem, the lubricating grease is mainly prepared by using biodegradable vegetable oil and ester synthetic oil, or the lubricating grease is prepared by using vegetable oil, ester oil and poly-alpha-olefin mixed oil as base oil, such as the biodegradable lubricating grease reported in CN 1504552A and CN 103265999A; at present, lubricating grease with degradation performance and taking mineral oil or poly-alpha-olefin as a main base oil component is not common.
Disclosure of Invention
The invention provides a composite lithium-based lubricating grease and a preparation method thereof.
The composite lithium-based lubricating grease comprises the following components:
(a) an additive; (b) a complex lithium-based thickener; (c) a lubricating base oil; wherein the additives include a phosphorus-containing compound, a rust inhibitor, and an oiliness agent; the structure of the phosphorus-containing compound is as follows:
Figure BDA0002240216500000011
in the formula I, n is an integer of 0-50 (preferably an integer of 0-20, more preferably an integer of 0-10);
n + 1R groups, equal to or different from each other, are each independently selected from trivalent C1～C30Is preferably trivalent C1～C10Alkyl, more preferably trivalent C1～C4Alkyl groups); rbThe radicals being H or C1～C10Is preferably H or C1～C6Straight or branched alkyl of (2), more preferably H or C1～C4Linear or branched alkyl groups of (a);
each R is0The radicals, equal to or different from each other, are each independently selected from H, C1～C30And a hydrocarbon group of
Figure BDA0002240216500000021
(preferably each independently selected from H, C1～C10Straight or branched alkyl and
Figure BDA0002240216500000022
more preferably each independently selected from H, C1～C4And linear or branched alkyl and
Figure BDA0002240216500000023
and at least one of R0Is composed of
Figure BDA0002240216500000024
) Wherein x is an integer of 0 to 5 (preferably 0 to 4, more preferably 0, 1, 2 or 3), and y is an integer of 1 to 5 (preferably 1 to E)4, more preferably 1, 2 or 3), x R1The radicals, equal to or different from each other, are each independently selected from H, C1～C30Is preferably selected from C1～C10And C is a straight or branched alkyl group6～C10More preferably selected from C1～C4Straight or branched chain alkyl groups of (b), benzyl and phenyl); ar group is C3～C30Cyclic group (preferably C)6～C15More preferably a benzene ring, a naphthalene ring or an anthracene ring), R2The radicals being single bonds or C1～C10Alkylene (preferably a single bond or C)1～C6More preferably a single bond or C1～C4Alkylene groups of (a);
each A group, which may be the same or different from each other, is independently selected from
Figure BDA0002240216500000025
OH、C1～C30Is preferably C1～C10Straight or branched alkyl of (2), more preferably C1～C4Straight or branched alkyl group of), C1～C30Alkoxy (preferably C)1～C10More preferably C1～C4Linear or branched alkoxy) and H, wherein at least one A group is
Figure BDA0002240216500000026
X is O or S, a is 0 or 1, R' is selected from C1～C30Is preferably C1～C10Straight or branched alkyl of (2), more preferably C1～C4Straight or branched alkyl group of (2), benzyl, phenyl,
Figure BDA0002240216500000027
R' is selected from C1～C30Is preferably C1～C10Straight or branched alkyl of (2), more preferably C1～C4Straight or branched alkyl group of), C1～C30Alkoxy (preferably C)1～C10More preferably C1～C4Linear or branched alkoxy) of (2), wherein each R is0、R、RbN is as defined above;
optionally including the products of partial or total condensation dehydration reaction between NH and COOH present in the compounds of formula (I).
Among the compounds of formula (I), preferably
Figure BDA0002240216500000031
In the group, Ar is preferably a benzene ring, x is preferably 2, and OH is preferably located at R2Para to the radical, two R1Preferably in each of the two ortho-positions to OH, two R1Each independently selected from C1～C4Preferably selected from tert-butyl.
In the compounds of formula (I), preferably, each A group is independently selected from
Figure BDA0002240216500000032
OH、C1～C10Straight or branched alkyl of (2), C1～C10And H, more preferably, each A group is independently selected from
Figure BDA0002240216500000033
OH、C1～C4Straight or branched alkyl of (2), C1～C4And H.
According to the invention, the phosphorus-containing compound comprises one or more of the following compounds:
Figure BDA0002240216500000034
according to the present invention, the process for producing the phosphorus-containing compound comprises:
the step (1): reacting a compound shown in a formula (II) and/or an inorganic acid salt thereof with a compound shown in a formula (III), and collecting a product in the step (1);
Figure BDA0002240216500000035
in the formula (II), n is an integer of 0 to 50 (preferably an integer of 0 to 20, more preferably an integer of 0 to 10); n + 1R groups, equal to or different from each other, are each independently selected from trivalent C1～C30Is preferably trivalent C1～C10Alkyl, more preferably trivalent C1～C4Alkyl groups); rbGroup H, C1～C10Is preferably H or C1～C6Straight or branched alkyl of (2), more preferably H or C1～C4Linear or branched alkyl groups of) and benzyl; each R is0' the groups, which are identical or different from one another, are each independently selected from H, C1～C30Is preferably each independently selected from H, C1～C10More preferably each independently selected from H, C1～C4Wherein x is an integer of 0 to 5 (preferably an integer of 0 to 4, more preferably 0, 1, 2 or 3), y is an integer of 1 to 5 (preferably an integer of 1 to 4, more preferably 1, 2 or 3), and x R are1The radicals, equal to or different from each other, are each independently selected from H, C1～C30Is preferably selected from H, C1～C10More preferably selected from H, C1～C4Straight or branched alkyl group) Ar group is C3～C30Cyclic group (preferably C)6～C15More preferably a benzene ring, a naphthalene ring or an anthracene ring), R2The radicals being single bonds or C1～C10Alkylene (preferably a single bond or C)1～C6More preferably a single bond or C1～C4Alkylene groups of (a);
each A 'group, equal to or different from each other, is independently selected from OA' ", C1～C30Is preferably C1～C10Straight or branched chain ofAlkanyl radical, more preferably C1～C4Straight or branched alkyl group of), C1～C30Alkoxy (preferably C)1～C10More preferably C1～C4Linear or branched alkoxy) and H, a ' "is selected from F, Cl, Br, I, H, wherein at least one a ' group is OA '"; the structure of the inorganic acid salt of the compound shown as the formula (II) is
Figure BDA0002240216500000041
Wherein M is an inorganic acid group, j is an absolute value of the charge number of the inorganic acid group, z is an integer of 1 to 10 (preferably an integer of 1 to 3), and the other groups are as defined in formula (II) (the inorganic acid salt of the compound of formula (II) is preferably a hydrochloride thereof, a nitrate thereof, or a sulfate thereof, and most preferably a hydrochloride thereof);
in formula (III), X is O or S, a is 0 or 1, each R '"is the same or different from each other and is independently selected from A'", C1～C30Is preferably C1～C10Straight or branched alkyl, benzyl or phenyl of (2), more preferably C1～C4Straight or branched alkyl groups of (a), benzyl or phenyl;
and optionally (2) a step of: reacting the product obtained in the step (1) with a compound shown as a formula (IV), and collecting the product obtained in the step (2);
Figure BDA0002240216500000042
wherein x is an integer of 0 to 5 (preferably an integer of 0 to 4, more preferably 0, 1, 2 or 3), y is an integer of 1 to 5 (preferably an integer of 1 to 4, more preferably 1, 2 or 3), and x R are1The radicals, equal to or different from each other, are each independently selected from H, C1～C30Is preferably selected from H, C1～C10More preferably selected from H, C1～C4Straight-chain or branched alkyl groups) Ar is C3～C30Cyclic group of (III)C selection6～C15More preferably a benzene ring, a naphthalene ring or an anthracene ring), R2The radicals being single bonds or C1～C10Alkylene (preferably a single bond or C)1～C6More preferably a single bond or C1～C4Alkylene) of (a), X' is F, Cl, Br, I or OH (preferably Cl, Br).
According to the preparation method of the phosphorus-containing compound, the inorganic acid salt of the compound shown in the formula (II) can be obtained by performing salt-forming reaction on the compound shown in the formula (II) and an inorganic acid.
According to the method for producing the phosphorus-containing compound of the present invention, the compound represented by the formula (II) and/or the inorganic acid salt thereof may be one or more selected from an amino acid, a condensate of an amino acid (partial condensation or total condensation), an inorganic salt of an amino acid, and an inorganic salt of a condensate of an amino acid (partial condensation or total condensation). The compound shown in the formula (II) and/or the inorganic acid salt thereof can be selected from one or more of the following specific compounds: l-serine and/or L-serine ester hydrochloride, L-leucine and/or L-leucine ester hydrochloride, L-isoleucine and/or L-isoleucine ester hydrochloride, glycine and/or glycine ester hydrochloride, L-phenylalanine and/or L-phenylalanine ester hydrochloride, L-valine and/or L-valine ester hydrochloride.
According to the preparation method of the phosphorus-containing compound, the compound shown in the formula (III) can be selected from phosphorous acid and/or phosphorous acid ester, and specific compounds which can be cited comprise one or more of phosphorous acid, dimethyl phosphite, diethyl phosphite, dipropyl phosphite, diisopropyl phosphite, di-n-butyl phosphite, diisobutyl phosphite, di-tert-butyl phosphite, 2-ethylhexyl phosphite, dibenzyl phosphite and diphenyl phosphite.
According to the preparation method of the phosphorus-containing compound, in the step (1), the equivalent ratio of the compound shown in the formula (II) and/or the inorganic acid salt thereof (calculated as OA') to the compound shown in the formula (III) (calculated as P-H) is preferably 1: 5-5: 1, and more preferably 1: 3-3: 1; the reaction temperature is preferably-40-80 ℃, and more preferably-20-40 ℃; the reaction time is generally as long as possible, and is preferably 0.5 to 30 hours, more preferably 1 to 8 hours, in order to improve the reaction efficiency.
According to the preparation method of the phosphorus-containing compound, in the step (1), a solvent may be added or may not be added in the reaction of the compound represented by the formula (II) and/or the inorganic acid salt thereof and the compound represented by the formula (III), and the solvent is preferably added. The solvent is preferably one or more of a protic solvent, a hydrocarbon solvent and a furan-based solvent, and for example, one or more of n-hexane, benzene, toluene, tetrahydrofuran, dichloromethane, methanol, ethanol, isopropanol and water may be used, and more preferably, a protic solvent, for example, one or more of methanol, ethanol, isopropanol and water may be used. The amount of the solvent to be added is not particularly limited, and is preferably such that the reaction is smoothly progressed.
According to the preparation method of the phosphorus-containing compound, in the step (1), in the reaction between the compound shown in the formula (II) and/or the inorganic acid salt thereof and the compound shown in the formula (III), a catalyst can be added or not be added, and the catalyst is preferably added. The catalyst may be a phase transfer catalyst which may be selected from quaternary ammonium salts and/or crown ethers, preferably tetraalkylammonium halides, for example one or more of tetrabutylammonium bromide, trioctylammonium chloride, cetyltrimethylammonium bromide, triethylbenzylammonium chloride and 18-crown-6, more preferably tetrabutylammonium bromide. The adding amount of the catalyst is preferably 0.1-10% of the mass of the compound shown in the formula (II) and/or the inorganic acid salt thereof.
According to the method for preparing the phosphorus-containing compound of the present invention, in the step (1), a chloride is preferably added when the compound represented by the formula (II) and/or the inorganic acid salt thereof reacts with the compound represented by the formula (III). The chloride is preferably an aqueous solution of hypochlorite, preferably one or more of sodium hypochlorite, potassium hypochlorite and calcium hypochlorite, and/or chlorinated alkane, preferably chlorinated methane, for example, one or more of carbon monochloride, carbon dichloride, carbon trichloride and carbon tetrachloride can be selected. The chloride is preferably an aqueous solution of hypochlorite, preferably having a concentration of 5% to 80%, more preferably an aqueous solution of sodium hypochlorite. The addition amount of the chloride is preferably 30-100 mL/100mmol of the compound shown in the formula (II) and/or the inorganic acid salt thereof.
According to the preparation method of the phosphorus-containing compound, in the step (1), the reaction between the compound shown in the formula (II) and/or the inorganic acid salt thereof and the compound shown in the formula (III) is preferably carried out under the condition that the pH value is 8-10 (preferably 8.5-9.5). The PH may be adjusted by adding an alkaline medium, preferably an alkaline solution, preferably an aqueous solution of one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide and calcium hydroxide.
According to the preparation method of the phosphorus-containing compound, in the step (1), after the reaction of the compound represented by the formula (II) and/or the inorganic acid salt thereof and the compound represented by the formula (III), the reaction product is subjected to an optional extraction operation, an optional drying operation and an optional ultrasonic operation.
The reaction product is preferably subjected to an extraction operation using a solvent, and more preferably, the reaction product is subjected to an extraction operation using a solvent in an acidic environment. The solvent is preferably one or more selected from ether solvents, ester solvents, alkyl chloride solvents and hydrocarbon solvents, and for example, one or more selected from petroleum ether, diethyl ether, ethyl acetate, dichloromethane, chloroform and toluene may be used. The extraction operation is preferably performed for 1 to 3 times. The acid environment is obtained by adding acid liquor to adjust the pH value of a system in which a reaction product is positioned, wherein the pH value is preferably 2-5, and more preferably 2.5-3.5; the acid solution is preferably one or more of hydrochloric acid, acetic acid, nitric acid and sulfuric acid, and the concentration of the acid solution is preferably 1-10 mol/L. Preferably, an inorganic salt is added while the extraction is performed to improve extraction efficiency. The inorganic salt is preferably one or more of sodium chloride, potassium chloride, sodium sulfate and potassium sulfate.
The drying operation is preferably carried out on the reaction product by adding a drying agent. The desiccant can be anhydrous magnesium chloride and/or anhydrous sodium sulfate.
The reaction product is preferably subjected to an ultrasonic operation, more preferably, the ultrasonic operation is performed in the presence of a solvent, preferably one or more of furan-based solvents, haloalkane solvents, ketone solvents, ester solvents and nitrile solvents, for example, one or more of tetrahydrofuran, dichloromethane, chloroform, acetone, ethyl acetate and acetonitrile may be selected, and more preferably, one or more of tetrahydrofuran, dichloromethane and acetonitrile may be selected. The time of the ultrasonic operation is preferably 1-10 hours, and more preferably 2-8 hours.
According to the preparation method of the phosphorus-containing compound, in the step (1), after the compound shown in the formula (II) and/or the inorganic acid salt thereof is reacted with the compound shown in the formula (III), the reaction product obtained in the step (1) is subjected to further purification operation. The purification operation includes one or more of drying, evaporation, washing, distillation, recrystallization, and centrifugation methods known in the art.
According to the method for preparing the phosphorus-containing compound of the present invention, in the optional step (2), the structural compound represented by the formula (IV) can be prepared by a method known in the art, and is not particularly limited. The compound shown in the formula (IV) can be selected from one or more of the following specific compounds: 3, 5-bis (tert-butyl) -4-hydroxyphenylacetyl chloride, 3, 5-bis (tert-butyl) -4-hydroxyphenylpropionyl chloride, p-hydroxyphenylacetyl chloride, 3-hydroxyphenylacetyl chloride, 2-hydroxyphenylacetyl chloride, 3, 4-dihydroxyphenylacetyl chloride, 3, 5-dihydroxyphenylacetyl chloride, 3-methyl-4-hydroxyphenylacetyl chloride, 3, 5-dimethyl-4-hydroxyphenylacetyl chloride, 2, 4-dihydroxyphenylpropionyl chloride, 3, 4-dihydroxyphenylpropionyl chloride, 2-hydroxy-naphthylacetyl chloride.
According to the preparation method of the phosphorus-containing compound, in the optional step (2), the reaction equivalent ratio of the compound shown in the formula (IV) (calculated by X') and the reaction product (calculated by NH) in the step (1) is preferably 5: 1-1: 5, and more preferably 1: 2-2: 1; the reaction temperature is preferably-40 to 60 ℃, and more preferably-20 to 20 ℃; the reaction time is generally as long as possible, and in order to improve the reaction efficiency, the reaction time is preferably 1 to 20 hours, more preferably 3 to 8 hours.
According to the preparation method of the phosphorus-containing compound, in the optional step (2), a solvent can be added or not added in the reaction between the compound (calculated as X') shown in the formula (IV) and the reaction product (calculated as NH in the reaction product) in the step (1), and the solvent is preferably added. The solvent is preferably one or more of protic solvents, ether solvents, ester solvents, chloroalkane solvents, furan solvents, ketone solvents, and hydrocarbon solvents, and may be selected from, for example, water, methanol, ethanol, isopropanol, dichloromethane, chloroform, diethyl ether, tetrahydrofuran, ethyl acetate, acetone, and toluene, and more preferably one or more of water, ethanol, diethyl ether, tetrahydrofuran, and acetone. The amount of the solvent to be added is not particularly limited, as long as the reaction is promoted to proceed smoothly.
According to the preparation method of the phosphorus-containing compound, in the optional step (2), after the reaction between the compound shown in the formula (IV) (calculated as X') and the reaction product (calculated as NH in the reaction product) in the step (1), the reaction product in the step (2) is washed to improve the purity of the reaction product. Preferably, the reaction product of the step (2) is washed with an acid solution. The acid solution is preferably one or more of hydrochloric acid, sulfuric acid and nitric acid, and the concentration of the acid solution is preferably 1-12 mol/L. According to the process for the preparation of the phosphorus compound of the present invention, in the optional step (2), after the reaction between the compound represented by the formula (IV) (in terms of X') and the reaction product of the step (1) (in terms of NH therein), the reaction product of the step (2) is subjected to a further purification operation. The purification operations include one or more of washing, distillation, recrystallization, and centrifugation methods known in the art.
According to the present invention, the phosphorus-containing compound has very excellent biodegradability and antioxidant property, and is particularly suitable for promoting biodegradation of a lubricating grease product.
According to the invention, preferably, the additive accounts for 0.1-5% of the lithium complex grease; the composite lithium-based thickening agent accounts for 4-30% of the composite lithium-based lubricating grease; the lubricating base oil accounts for 65-95% of the composite lithium-based lubricating grease; more preferably, the additive accounts for 0.2% -2% of the lithium complex grease; the composite lithium-based thickening agent accounts for 8-25% of the composite lithium-based lubricating grease; the lubricating base oil accounts for 73-90% of the lithium complex grease.
According to the invention, among the additives, the rust inhibitor is preferably naphthenate and/or sulfonate, for example, one or more of zinc naphthenate, barium petroleum sulfonate and barium dinonylnaphthalene sulfonate can be selected; the oiliness agent is preferably benzotriazole fatty amine.
According to the invention, the weight ratio of the phosphorus-containing compound, the rust inhibitor and the oiliness agent is preferably 1: 0.1-10: 0.01 to 5, more preferably 1: 0.5-2: 0.1 to 2.
According to the invention, the composite lithium-based thickener is prepared by reacting acid with lithium hydroxide. The acid is a mixed acid of fatty acid and auxiliary acid, and the fatty acid is preferably selected from C12-C20Fatty acids and/or hydroxy fatty acids, which may be one or more of lauric acid, myristic acid, palmitic acid, oleic acid, stearic acid and 12-hydroxystearic acid, more preferably 12-hydroxystearic acid and/or stearic acid; the auxiliary acid is preferably selected from one or more of acetic acid, propionic acid, butyric acid, valeric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, terephthalic acid, phosphoric acid and boric acid, more preferably sebacic acid and/or azelaic acid. The molar ratio of the fatty acid to the auxiliary acid is preferably 2-0.1: 2, more preferably 1.5-0.5: 2.
According to the present invention, the lubricating base oil may be one or more of mineral oil, vegetable oil and synthetic oil, and the mineral oil may be one or more of paraffin-based base oil, intermediate-based base oil, naphthenic base oil; the vegetable oil can be one or more of castor oil, rapeseed oil, peanut oil and soybean oil; the synthetic oil can be one or more of poly alpha-olefin oil, ester oil, fluorine oil and silicone oil; the lubricating base oil preferably has a kinematic viscosity of 5-60mm at 100 DEG C2A lubricating base oil of which the kinematic viscosity at 100 ℃ is from 10 to 30mm is most preferred2(ii) lubricating base oil per s.
The preparation method of the lubricating grease comprises the following steps: the composite lithium-based thickening agent and part of lubricating base oil in any one aspect are refined at the constant temperature of 230 ℃ at 180 ℃, cooled, added with the additive in any one aspect and the rest of the lubricating base oil, and ground into grease. The refining time is preferably 1 to 25 minutes.
According to the preparation method of the lubricating grease, the composite lithium-based thickening agent is preferably obtained by saponification reaction of peracid and lithium hydroxide. The lithium-based thickener obtained by saponification can be directly used in the subsequent preparation method. The saponification reaction temperature is preferably 60 to 180 ℃, more preferably 70 to 160 ℃. The time of the saponification reaction is preferably 30 to 300min, more preferably 50 to 240 min.
According to the method for preparing the grease of the present invention, water is preferably added in the saponification reaction. The water can directly participate in the saponification reaction, and can also participate in the saponification reaction after being mixed with the lithium hydroxide into a solution.
The composite lithium-based lubricating grease disclosed by the invention has excellent biodegradability, and has good colloid stability, excellent mechanical stability and excellent oxidation resistance while environment friendliness is ensured. The composite lithium-based lubricating grease disclosed by the invention can be used under severe working conditions of high temperature, high speed, high load, much water and the like.
Detailed Description
The process of the present invention is illustrated below by means of specific examples, but the present invention is not limited thereto.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
Synthesis of O-dimethyloxyphosphoryl-N-3, 5-bis (tert-butyl) -4-hydroxyphenylpropionyl-L-serine
(1) L-serine (represented by formula ii-a) (100mmol, 10.5g) and 40mL of water were sequentially added to the reactor, the temperature was reduced to 0 ℃, pH was adjusted to 9.0 with sodium hydroxide, dimethyl phosphite (represented by formula iii-a) (130mmol, 14.3g) and tetrabutylammonium bromide (1mmol, 0.32g) were added, and 50mL of a 12% sodium hypochlorite solution was added dropwise with stirring. After 4 hours of reaction, the mixture was extracted with ether 2 times, the aqueous layer was adjusted to pH 3 with hydrochloric acid, 8g of sodium chloride was added, extraction was performed with ethyl acetate 2 times, the organic phases were combined, dried over anhydrous magnesium chloride, and the solvent was distilled off under reduced pressure to give a colorless oil. Dissolving the colorless oily substance in 60mL acetonitrile, performing ultrasonic treatment for 5 hours at room temperature, and filtering to obtain a white solid;
(2) the above white solid (47.6mmol, 10.2g), 40mL acetone, 20mL water, sodium hydroxide (95.2mmol, 10g) was cooled to 0 deg.C and 3, 5-bis (tert-butyl) -4-hydroxyphenylacryloyl chloride (47.6mmol, 14.1g) was added. After 5 hours of reaction, using 6 mol/L hydrochloric acid solution to acidify until the pH value is 2, a large amount of white solid appears, filtering, washing a filter cake with water and petroleum ether, and obtaining the reaction product of the step (2), wherein the structure and the exemplary reaction formula are shown as follows, and the structure of the reaction product of the step (2) is the formula I-a in the exemplary reaction formula.
Figure BDA0002240216500000101
Wherein the preparation method of the 3, 5-bis (tert-butyl) -4-hydroxy phenylpropionyl chloride in the step (2) comprises the following steps: 3, 5-bis (tert-butyl) -4-hydroxyphenylpropionic acid (81mmol, 22.5g) was dissolved in 150mL of chloroform, thionyl chloride (124mmol, 14.8g) was added, refluxed for 4 hours, and the solvent and excess thionyl chloride were removed by rotary evaporation to give a pale yellow solid (i.e., 3, 5-bis (tert-butyl) -4-hydroxyphenylacryloyl chloride).
The results of confirming the structure of the reaction product of the step (2) are as follows:1H NMR(400MHz,CDCl3)δ12.19(br,1H),8.71(s,1H),6.96(s,2H),5.97(br,1H),4.66(d,J＝6.4Hz,2H),4.07(t,J＝6.8Hz,1H),3.79(s,6H),2.87(t,J＝6.8Hz,2H),2.49(t,J＝6.8Hz,2H),1.31(s,18H)；HRMS(FT-ICRMS)calcd for C22H35NO8P-(M-H):472.2106,found:472.2109.
the compound synthesized by the structural identification is confirmed to be a target compound O-dimethyloxyphosphoryl-N-3, 5-bis (tert-butyl) -4-hydroxyphenylpropionyl-L-serine (shown as a structural formula I-a).
Example 2
Synthesis of O-diisopropyloxyphosphoryl-N-3, 5-bis (tert-butyl) -4-hydroxyphenylpropionyl-L-serine
(1) L-serine (represented by formula ii-a) (100mmol, 10.5g) and 40mL of water were sequentially added to a reactor, the temperature was reduced to 0 ℃, pH was adjusted to 9.0 with sodium hydroxide, diisopropyl phosphite (represented by formula iii-b) (130mmol, 21.7g) and tetrabutylammonium bromide (1mmol, 0.32g) were added, and 50mL of a 12% sodium hypochlorite solution was added dropwise with stirring. After 4 hours of reaction, the mixture was extracted with ether 2 times, the aqueous layer was adjusted to pH 3 with hydrochloric acid, 8g of sodium chloride was added, extraction was performed with ethyl acetate 2 times, the organic phases were combined, dried over anhydrous magnesium chloride, and the solvent was distilled off under reduced pressure to give a colorless oil. Dissolving the colorless oily substance in 60mL of acetonitrile, performing ultrasonic treatment at room temperature for 5 hours, and filtering to obtain a white solid;
(2) the white solid (47.6mmol, 12.8g), 40mL acetone, 20mL water, sodium hydroxide (95.2mmol, 10g) was cooled to 0 deg.C and 3, 5-bis (tert-butyl) -4-hydroxyphenylacryloyl chloride (47.6mmol, 14.1g) was added. After 5 hours of reaction, using 6 mol/L hydrochloric acid solution to acidify until the pH value is 2, generating a large amount of white solid, filtering, washing a filter cake with water and petroleum ether, and obtaining the reaction product of the step (2), wherein the structure and the exemplary reaction formula are shown as follows, and the structure of the reaction product of the step (2) is the formula I-b in the exemplary reaction formula.
Figure BDA0002240216500000111
Wherein the preparation method of the 3, 5-bis (tert-butyl) -4-hydroxy phenylpropyl chloride in the step (2) comprises the following steps: 3, 5-bis (tert-butyl) -4-hydroxyphenylpropionic acid (81mmol, 22.5g) was dissolved in 150mL of chloroform, thionyl chloride (124mmol, 14.8g) was added, reflux was carried out for 4 hours, and the solvent and excess thionyl chloride were removed by rotary evaporation to give a pale yellow solid (i.e., 3, 5-bis (tert-butyl) -4-hydroxyphenylacryloyl chloride).
The results of confirming the structure of the reaction product of the step (2) are as follows:1H NMR(400MHz,CDCl3)δ12.10(br,1H),8.55(s,1H),6.88(s,2H),5.85(br,1H),4.61(d,J＝6.4Hz,2H),4.09(t,J＝6.8Hz,1H),3.99-3.89(m,2H),2.81(t,J＝6.8Hz,2H),2.44(t,J＝6.8Hz,2H),1.31(s,18H),1.25(s,12H)；HRMS(FT-ICRMS)calcd for C26H43NO8P-(M-H):528.2732,found:528.2737.
the compound synthesized by the structural identification is confirmed to be a target compound O-diisopropyl oxyphosphoryl-N-3, 5-bis (tert-butyl) -4-hydroxybenzoyl-L-serine (shown as a structural formula I-b).
Example 3
Synthesis of O-Diphenylmethyloxyphosphoryl-N-3, 5-bis (tert-butyl) -4-hydroxyphenylpropionyl-L-serine
(1) L-serine (represented by formula ii-a) (100mmol, 10.5g) and 40mL of water were sequentially added to the reactor, the temperature was reduced to 0 ℃, pH was adjusted to 9.0 with sodium hydroxide, dibenzyl phosphite (represented by formula iii-c) (130mmol, 34.0g) and tetrabutylammonium bromide (1mmol, 0.32g) were added, and 50mL of a 12% sodium hypochlorite solution was added dropwise with stirring. After 4 hours of reaction, the mixture was extracted with ether 2 times, the aqueous layer was adjusted to pH 3 with hydrochloric acid, 8g of sodium chloride was added, extracted with ethyl acetate 2 times, the organic phases were combined, dried over anhydrous magnesium chloride, and the solvent was distilled off under reduced pressure to give a colorless oil. Dissolving the colorless oily substance in 60mL of acetonitrile, performing ultrasonic treatment at room temperature for 5 hours, and filtering to obtain a white solid;
(2) the white solid (47.6mmol, 17.4g), 40mL acetone, 20mL water, sodium hydroxide (95.2mmol, 10g) was cooled to 0 deg.C and 3, 5-bis (tert-butyl) -4-hydroxyphenylacryloyl chloride (47.6mmol, 14.1g) was added. After 5 hours of reaction, acidifying with 6 mol/L hydrochloric acid solution until the pH value is 2, generating a large amount of white solid, filtering, washing a filter cake with water and petroleum ether, and obtaining the reaction product of the step (2), wherein the structure and the example reaction formula are shown as follows, and the structure of the reaction product of the step (2) is the formula I-c in the example reaction formula.
Figure BDA0002240216500000121
Wherein the preparation method of the 3, 5-bis (tert-butyl) -4-hydroxy phenylpropionyl chloride in the step (2) comprises the following steps: 1) 3, 5-bis (tert-butyl) -4-hydroxyphenylpropionic acid (81mmol, 22.5g) was dissolved in 150mL of chloroform, thionyl chloride (124mmol, 14.8g) was added, refluxed for 4 hours, and the solvent and excess thionyl chloride were removed by rotary evaporation to give a pale yellow solid (i.e., 3, 5-bis (tert-butyl) -4-hydroxyphenylacryloyl chloride).
The results of confirming the structure of the reaction product of the step (2) are as follows:1H NMR(400MHz,CDCl3)δ12.27(br,1H),8.64(s,1H),7.55-7.26(m,10H),6.91(s,2H),5.71(br,1H),5.17(s,4H),4.61(d,J＝6.4Hz,2H),4.01(t,J＝6.8Hz,1H),2.81(t,J＝6.8Hz,2H),2.44(t,J＝6.8Hz,2H),1.32(s,18H)；HRMS(FT-ICRMS)calcd for C34H43NO8P-(M-H):624.2732,found:624.2730.
the compound synthesized by the structural identification is confirmed to be a target compound O-diphenylmethoxy phosphoryl-N-3, 5-bi (tertiary-butyl) -4-hydroxybenzenepropionyl-L-serine (shown as a structural formula I-c).
Example 4
Synthesis of O-dimethyloxyphosphoryl-N-3, 5-bis (tert-butyl) -4-hydroxyphenylpropionyl-L-serine methyl ester
(1) To the reactor were added L-serine methyl ester hydrochloride (represented by formula ii-b) (100mmol, 15.5g) and 40mL of water in this order, the temperature was reduced to 0 ℃, pH was adjusted to 9.0 with sodium hydroxide, dimethyl phosphite (represented by formula iii-a) (130mmol, 14.3g) and tetrabutylammonium bromide (1mmol, 0.32g) were added, and 50mL of a 12% sodium hypochlorite solution was added dropwise with stirring. After 4 hours of reaction, the mixture was extracted with ether 2 times, the aqueous layer was adjusted to pH 3 with hydrochloric acid, 8g of sodium chloride was added, extraction was performed with ethyl acetate 2 times, the organic phases were combined, dried over anhydrous magnesium chloride, and the solvent was distilled off under reduced pressure to obtain a white solid. Dissolving the white solid in 60mL of acetonitrile, performing ultrasonic treatment at room temperature for 5 hours, and filtering to obtain a white solid;
(2) the white solid (47.6mmol, 10.8g), 40mL acetone, 20mL water, sodium hydroxide (95.2mmol, 10g) was cooled to 0 deg.C and 3, 5-bis (tert-butyl) -4-hydroxyphenylacryloyl chloride (47.6mmol, 14.1g) was added. After 5 hours of reaction, using 6 mol/L hydrochloric acid solution to acidify until the pH value is 2, generating a large amount of white solid, filtering, washing a filter cake with water and petroleum ether, and obtaining the reaction product of the step (2), wherein the structure and the exemplary reaction formula are shown as follows, and the structure of the reaction product of the step (2) is the formula I-d in the exemplary reaction formula.
Figure BDA0002240216500000131
Wherein the preparation method of the 3, 5-bis (tert-butyl) -4-hydroxy phenylpropionyl chloride in the step (2) comprises the following steps: 3, 5-bis (tert-butyl) -4-hydroxyphenylpropionic acid (81mmol, 22.5g) was dissolved in 150mL of chloroform, thionyl chloride (124mmol, 14.8g) was added, refluxed for 4 hours, and the solvent and excess thionyl chloride were removed by rotary evaporation to give a pale yellow solid (i.e., 3, 5-bis (tert-butyl) -4-hydroxyphenylacryloyl chloride).
The results of confirming the structure of the reaction product of the step (2) are as follows:1H NMR(400MHz,CDCl3)δ8.54(s,1H),6.91(s,2H),5.77(br,1H),4.60(d,J＝6.4Hz,2H),4.11(t,J＝6.8Hz,1H),3.73(s,6H),3.61(s,3H),2.80(t,J＝6.8Hz,2H),2.52(t,J＝6.8Hz,2H),1.35(s,18H)；HRMS(FT-ICRMS)calcd for C23H37NO8P-(M-H):486.2262,found:486.2268.
the compound synthesized by the structural identification is confirmed to be a target compound O-dimethyloxyphosphoryl-N-3, 5-bis (tert-butyl) -4-hydroxyphenylpropionyl-L-serine methyl ester (shown as a structural formula I-d).
Example 5 preparation of lithium complex grease
The raw materials used include: PAO 41015 g (viscosity at 100 ℃ C. of 3.9 mm)2S); 24.67g of lithium hydroxide monohydrate; 89.46g of dodecahydroxystearic acid; azelaic acid 27.39 g; zinc naphthenate T7045.80g; benzotriazole fatty amine T4061.32g and phosphorus-containing compound I-a 10.75 g.
Firstly adding 455 g of PAO 4 base oil, 89.46g of 12-hydroxystearic acid and 27.39g of azelaic acid into a fat making kettle, uniformly stirring, heating to 85 ℃, adding a lithium hydroxide aqueous solution (containing 24.67g of lithium hydroxide monohydrate and 200 g of water) to perform saponification reaction for 120min, continuously heating to 130 ℃ for dehydration, adding 280 g of base oil, heating to 210 ℃, and performing high-temperature refining for 10 min; adding 280 g of PAO 4 base oil, cooling to 110 ℃, adding 5.80g of zinc naphthenate T704, 1.32g of benzotriazole fatty amine T406 and 10.75g of phosphorus-containing compound I-a, stirring uniformly, and grinding for 2 times by a three-roll machine to form grease. The product properties are shown in table 1.
Example 6 preparation of lithium complex grease
The raw materials used include: 500SN 965g (viscosity at 100 ℃ 11 mm)2S); 35.57g of lithium hydroxide monohydrate; 135g of dodecahydroxystearic acid; 40g of sebacic acid; zinc naphthenate T7045.87g; benzotriazole fatty amine T4061.04g and phosphorus-containing compound I-b 10.24 g.
Adding 435 g of 500SN base oil, 135g of 12-hydroxystearic acid and 40g of sebacic acid into a fat making kettle, uniformly stirring, heating to 88 ℃, adding a lithium hydroxide aqueous solution (containing 35.57g of lithium hydroxide monohydrate and 280 g of water) to perform saponification reaction for 90min, continuously heating to 150 ℃ for dehydration, adding 265 g of 500SN base oil, heating to 220 ℃ and performing high-temperature refining for 5 min; 265 g of 500SN base oil is added, the temperature is reduced to 100 ℃, 5.87g of zinc naphthenate T704, 1.04g of benzotriazole fatty amine T406 and 10.24g of phosphorus-containing compound I-b are added, the mixture is stirred uniformly and ground by a three-roller machine for 3 times to form grease. The product properties are shown in table 1.
Example 7 preparation of lithium complex grease
The raw materials used include: PAO 10775 g (viscosity 10mm at 100 ℃)2S); 14.6g of lithium hydroxide monohydrate; 54g of dodecahydroxystearic acid; 16g of azelaic acid; zinc naphthenate T7044.30g; benzotriazole fatty amine T4060.96g; 8.21g of phosphorus-containing compound I-c.
Firstly adding 355 g of PAO 10 base oil, 54g of 12-hydroxystearic acid and 16g of azelaic acid into a fat making kettle, uniformly stirring, heating to 90 ℃, adding a lithium hydroxide aqueous solution (containing 14.6g of lithium hydroxide monohydrate and 120 g of water) to carry out saponification reaction for 240min, continuously heating to 180 ℃, dehydrating, adding 210 g of PAO 10 base oil, heating to 220 ℃, carrying out high-temperature refining for 10min, adding 210 g of PAO 10 base oil, cooling to 120 ℃, adding 4.30g of zinc naphthenate T704, 0.96g of benzotriazole aliphatic amine T406 and 8.21g of phosphorus-containing compound I-c, uniformly stirring, and grinding for 3 times by a three-roll machine to form fat. The product properties are shown in table 1.
Example 8 preparation of lithium complex grease
The raw materials used include: 500SN 745g (viscosity at 100 ℃ of 11 mm)2S); 21.79g of lithium hydroxide monohydrate; twelve hydroxyl groups79.36g of stearic acid; 25.54g of sebacic acid; zinc naphthenate T7044.40g; benzotriazole fatty amine T4060.84g; 7.85g of phosphorus-containing compound I-d.
Firstly adding 335 g of 500SN base oil, 79.36g of 12-hydroxystearic acid and 25.54g of sebacic acid into a grease making kettle, uniformly stirring, heating to 75 ℃, adding a lithium hydroxide aqueous solution (containing 21.79g of lithium hydroxide monohydrate and 176 g of water) to perform saponification reaction for 130min, continuously heating to 125 ℃ for dehydration, adding 205 g of 500SN base oil, heating to 215 ℃ for high-temperature refining for 5 min; adding 205 g of 500SN base oil, cooling to 115 ℃, adding 4.40g of zinc naphthenate T704, 0.84g of benzotriazole aliphatic amine T406 and 7.85g of phosphorus-containing compounds I-d, stirring uniformly, and grinding by a three-roll machine for 3 times to form grease. The product properties are shown in table 1.
Comparative example 1 preparation of lithium complex grease
The raw materials used include: 500SN 745g (viscosity at 100 ℃ of 11 mm)2S); 21.79g of lithium hydroxide monohydrate; 79.36g of dodecahydroxystearic acid; 25.54g of sebacic acid; zinc naphthenate T70410.99g; benzotriazole fatty amine T4062.10g.
Firstly adding 335 g of 500SN base oil, 79.36g of 12-hydroxystearic acid and 25.54g of sebacic acid into a grease making kettle, uniformly stirring, heating to 75 ℃, adding a lithium hydroxide aqueous solution (containing 21.79g of lithium hydroxide monohydrate and 176 g of water) to perform saponification reaction for 130min, continuously heating to 125 ℃ for dehydration, adding 205 g of 500SN base oil, heating to 215 ℃ for high-temperature refining for 5 min; adding 205 g of 500SN base oil, cooling to 115 ℃, adding 10.99g of zinc naphthenate T704 and 2.10g of benzotriazole fatty amine T406, uniformly stirring, and grinding by a three-roll machine for 3 times to form grease. The product properties are shown in table 1.
The grease products of examples 5 to 8 and comparative example 1 were subjected to performance evaluation, and the evaluation results are shown in table 1.
Table 1 grease performance evaluation
Figure BDA0002240216500000161

Claims (21)

1. A composite lithium-based lubricating grease comprises the following components:
(a) an additive; (b) a complex lithium-based thickener; (c) a lubricating base oil; wherein the additive is a mixture of a phosphorus-containing compound, a rust inhibitor and an oiliness agent; the structure of the phosphorus-containing compound is as follows:
Figure FDA0003611900960000011
in formula I, n is 0; r group is selected from trivalent C1～C30A hydrocarbon group of (a); rbThe radicals being H or C1～C10A hydrocarbon group of (a); each R is0The radicals, equal to or different from each other, are each independently selected from H, C1～C30And a hydrocarbon group of
Figure FDA0003611900960000012
And at least one of R0Is composed of
Figure FDA0003611900960000013
Wherein x is 2, y is 1, and x R1The radicals, equal to or different from each other, are each independently selected from C1～C4Is a straight-chain or branched alkyl group of (A), Ar is a benzene ring, R2The radicals being single bonds or C1～C10An alkylene group of (a); OH at R2Para to the radical, two R1Respectively positioned at two ortho positions of OH;
a is a group selected from
Figure FDA0003611900960000014
X is O or S, a is 0 or 1, R' is selected from C1～C30A hydrocarbon group of (a); optionally including the products of partial or total condensation dehydration between NH and COOH present in the compounds of formula (I).
2. Grease according to claim 1, characterized in that in formula (I) the R group is chosen from trivalent C1～C10An alkyl group; rbThe radicals being H or C1～C6Straight or branched chain alkyl of (a);
R0the group is selected from H, C1～C10And linear or branched alkyl and
Figure FDA0003611900960000015
R2the radicals being single bonds or C1～C6An alkylene group of (a); r' is selected from C1～C10And C is a straight or branched alkyl group6～C10Aryl group of (1).
3. Grease according to claim 1, characterized in that in formula (I) the R group is chosen from trivalent C1～C4An alkyl group; rbThe radicals being H or C1～C4Linear or branched alkyl of (a);
R0the group is selected from H, C1～C4And linear or branched alkyl and
Figure FDA0003611900960000016
R2the radicals being single bonds or C1～C4An alkylene group of (a); r' is selected from C1～C4Linear or branched alkyl, benzyl and phenyl.
4. A grease lubricant according to claim 1, characterized in that, in the compound of formula (I), in
Figure FDA0003611900960000021
In the radical, two R1Selected from tertiary butyl groups.
5. The grease of claim 1, wherein the phosphorus-containing compound comprises one or more of the following compounds:
Figure FDA0003611900960000022
6. the grease of claim 1, wherein the process for preparing the phosphorus-containing compound comprises: the step (1): reacting a compound shown in a formula (II) and/or an inorganic acid salt thereof with a compound shown in a formula (III), and collecting a product in the step (1);
Figure FDA0003611900960000023
in formula (II), n is 0; r group is selected from trivalent C1～C30A hydrocarbon group of (a); r isbGroup H, C1～C10A hydrocarbon group of (a);
each R is0' the groups, which are identical or different from one another, are each independently selected from H, C1～C30A hydrocarbon group of (a);
the A ' group is selected from OA ' ", A '" is selected from F, Cl, Br, I, H, wherein at least one A ' group is OA ' ";
the structure of the inorganic acid salt of the compound shown as the formula (II) is
Figure FDA0003611900960000024
Wherein M is an inorganic acid radical, j is the absolute value of the charge number of the inorganic acid radical, z is an integer between 1 and 10, n is 0, and R group is selected from trivalent C1～C30A hydrocarbon group of RbGroup H, C1～C10A hydrocarbon group of (a); each R is0' the groups, which are identical or different from one another, are each independently selected from H, C1～C30A hydrocarbon group of (1); a ' group is selected from OA ' ″, A ' ″ is selected from F, Cl, Br, I, H;
in formula (III), X is O or S, a is 0 or 1, each R '"is the same or different from each other and is independently selected from A'", C1～C30A hydrocarbon group of (a);
step (2): reacting the product in the step (1) with a compound shown in a formula (IV), and collecting the product in the step (2);
Figure FDA0003611900960000031
wherein x is 2, y is 1, x R1The radicals, equal to or different from each other, are each independently selected from C1～C4A straight-chain or branched alkyl radical of (A), an Ar group a benzene ring, R2The radicals being single bonds or C1～C10Alkylene of (OH) at R2Para to the radical, two R1Respectively positioned at two ortho positions of OH; x' is F, Cl, Br, I or OH.
7. Grease according to claim 6, characterized in that the R groups are chosen from trivalent C1～C10An alkyl group; rbThe radicals being H or C1～C6Linear or branched alkyl of (a); each R is0' Each group is independently selected from H, C1～C10Linear or branched alkyl of (a); z is an integer between 1 and 3; each R 'is independently selected from A' and C1～C10Linear or branched alkyl, benzyl or phenyl; r1The radicals being selected from tert-butyl, R2The radicals being single bonds or C1～C6X' is Cl or Br.
8. Grease according to claim 6, characterized in that the R groups are chosen from trivalent C1～C4An alkyl group; rbThe radicals being H or C1～C4Linear or branched alkyl of (a); each R is0' Each group is independently selected from H, C1～C4Linear or branched alkyl of (a); each R 'is independently selected from A' and C1～C4Linear or branched alkyl, benzyl or phenyl; r2The radicals being single bonds or C1～C4An alkylene group of (a).
9. The grease lubricant according to claim 6, wherein the compound represented by the formula (II) and/or the inorganic acid salt thereof is one or more of an amino acid, a condensate of an amino acid, an inorganic salt of an amino acid, and an inorganic salt of a condensate of an amino acid.
10. Grease lubricant according to claim 6, characterized in that the compound of formula (II) and/or its salt of an inorganic acid is selected from one or more of the following specific compounds: l-serine and/or L-serine ester hydrochloride, L-leucine and/or L-leucine ester hydrochloride, L-isoleucine and/or L-isoleucine ester hydrochloride, glycine and/or glycine ester hydrochloride, L-phenylalanine and/or L-phenylalanine ester hydrochloride, and L-valine and/or L-valine ester hydrochloride.
11. Grease according to claim 6, characterized in that the compound of formula (III) is selected from phosphorous acid and/or phosphites.
12. A grease according to claim 6, wherein the compound of formula (III) is selected from one or more of phosphorous acid, dimethyl phosphite, dimethyl thiophosphite, diethyl phosphite, dipropyl phosphite, diisopropyl phosphite, di-n-butyl phosphite, diisobutyl phosphite, di-tert-butyl phosphite, (2-ethylhexyl) phosphite, dibenzyl phosphite and diphenyl phosphite.
13. The grease of claim 6, wherein in step (1), the compound of formula (II) and/or the inorganic acid salt thereof is calculated as OA' ", the compound of formula (III) is calculated as P-H, and the reaction equivalent ratio between the compound of formula (II) and/or the inorganic acid salt thereof and the compound of formula (III) is 1:5 to 5: 1; the reaction temperature is-40-80 ℃.
14. The grease of claim 6, wherein in step (1), the compound of formula (II) and/or the inorganic acid salt thereof is calculated as OA' ", the compound of formula (III) is calculated as P-H, and the reaction equivalent ratio between the compound of formula (II) and/or the inorganic acid salt thereof and the compound of formula (III) is 1:3 to 3: 1; the reaction temperature is-20-40 ℃.
15. The grease of claim 6, wherein in step (2), the compound represented by formula (IV) is selected from one or more of the following specific compounds: 3, 5-bis (tert-butyl) -4-hydroxyphenylacetyl chloride, 3, 5-bis (tert-butyl) -4-hydroxyphenylpropionyl chloride, p-hydroxyphenylacetyl chloride, 3-hydroxyphenylacetyl chloride, 2-hydroxyphenylacetyl chloride, 3, 4-dihydroxyphenylacetyl chloride, 3, 5-dihydroxyphenylacetyl chloride, 3-methyl-4-hydroxyphenylacetyl chloride, 3, 5-dimethyl-4-hydroxyphenylacetyl chloride, 2, 4-dihydroxyphenylpropionyl chloride, 3, 4-dihydroxyphenylpropionyl chloride, 2-hydroxy-naphthylacetyl chloride.
16. The grease of claim 6, wherein in step (2), the compound of formula (IV) is represented by X', the reaction product in step (1) is represented by NH, and the reaction equivalent ratio of the compound of formula (IV) to the reaction product in step (1) is 5:1 to 1: 5; the reaction temperature is-40-60 ℃.
17. The grease of claim 6, wherein in step (2), the compound represented by formula (IV) is calculated as X', the reaction product in step (1) is calculated as NH, and the reaction equivalent ratio of the compound represented by formula (IV) to the reaction product in step (1) is 1: 2-2: 1; the reaction temperature is-20 ℃.
18. Grease according to any of claims 1-17, characterized in that the additive comprises 0.1% to 5% of the lithium complex grease; the composite lithium-based thickening agent accounts for 4-30% of the composite lithium-based lubricating grease; the lubricating base oil accounts for 65-95% of the composite lithium-based lubricating grease.
19. Grease according to one of claims 1-17, characterized in that in the additive the rust inhibitor is a naphthenate and/or sulfonate; the oiliness agent is benzotriazole fatty amine.
20. Grease according to any of claims 1 to 17, characterized in that the weight ratio between the phosphorus-containing compound, the rust inhibitor and the oiliness agent is 1: 0.1-10: 0.01 to 5.
21. A method of preparing a grease according to any one of claims 1 to 20, comprising: refining the composite lithium-based thickening agent and part of the lubricating base oil at the constant temperature of 230 ℃ at 180 ℃, cooling, adding the additive and the rest of the lubricating base oil, and grinding into grease.
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