CN112760161B - Anhydrous calcium-based lubricating grease and preparation method thereof - Google Patents

Anhydrous calcium-based lubricating grease and preparation method thereof Download PDF

Info

Publication number
CN112760161B
CN112760161B CN201910997453.9A CN201910997453A CN112760161B CN 112760161 B CN112760161 B CN 112760161B CN 201910997453 A CN201910997453 A CN 201910997453A CN 112760161 B CN112760161 B CN 112760161B
Authority
CN
China
Prior art keywords
formula
grease
group
compound
radicals
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201910997453.9A
Other languages
Chinese (zh)
Other versions
CN112760161A (en
Inventor
刘显秋
庄敏阳
李茂森
郑会
刘伟
李朝宇
何懿峰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Original Assignee
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Research Institute of Petroleum Processing, China Petroleum and Chemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to CN201910997453.9A priority Critical patent/CN112760161B/en
Publication of CN112760161A publication Critical patent/CN112760161A/en
Application granted granted Critical
Publication of CN112760161B publication Critical patent/CN112760161B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with 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
    • C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
    • 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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06—Metal compounds
    • C10M2201/062—Oxides; Hydroxides; Carbonates or bicarbonates
    • 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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/085—Phosphorus oxides, acids or salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/128—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof
    • C10M2207/1285—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof used as thickening agents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters

Landscapes

  • 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 anhydrous calcium-based lubricating grease and a preparation method thereof. The anhydrous calcium-based lubricating grease comprises the following components: (a) an additive; (b) an anhydrous calcium-based thickener; (c) a lubricating base oil; wherein the additive is a mixture of a phosphorus-containing compound, a sulfonate rust inhibitor, and an organo-molybdenum friction modifier; the structure of the phosphorus-containing compound is as follows:

Description

Anhydrous calcium-based lubricating grease and preparation method thereof
Technical Field
The invention relates to lubricating grease, in particular to anhydrous calcium-based lubricating grease with biodegradability.
Background
The 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 grease is 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 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 anhydrous calcium-based lubricating grease and a preparation method thereof.
The anhydrous calcium-based lubricating grease disclosed by the invention comprises the following components:
(a) an additive; (b) an anhydrous calcium-based thickener; (c) a lubricating base oil; wherein the additive comprises a mixture of a phosphorus-containing compound, a sulfonate rust inhibitor, and an organo-molybdenum friction modifier; the structure of the phosphorus-containing compound is as follows:
Figure BDA0002240218220000011
in formula I, 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); 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 BDA0002240218220000021
(preferably each independently selected from H, C1～C10And linear or branched alkyl and
Figure BDA0002240218220000022
more preferably each independently selected from H, C1～C4Straight or branched alkyl and
Figure BDA0002240218220000023
and at least one of R0Is composed of
Figure BDA0002240218220000024
) 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 C1～C10And C is a straight or branched alkyl group6～C10More preferably selected from C1～C4Linear or branched alkyl groups of (a), benzyl and phenyl); ar group is C3～C30Cyclic group (preferably C)6～C15OfAromatic ring group, more preferably benzene ring, naphthalene ring or 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 BDA0002240218220000025
OH、C1～C30A hydrocarbon group (preferably C)1～C10Straight or branched alkyl of (2), more preferably C1～C4Straight or branched alkyl group of), C1～C30Alkoxy (preferably C)1～C10More preferably C1～C4And H, wherein at least one A group is
Figure BDA0002240218220000026
X is O or S, a is 0 or 1, R' is selected from C1～C30A hydrocarbon group (preferably C)1～C10Straight or branched alkyl of (2), more preferably C1～C4Straight or branched alkyl group of (2), benzyl, phenyl,
Figure BDA0002240218220000027
R' is selected from C1～C30Is preferably C1～C10Straight or branched alkyl of (2), more preferably C1～C4Straight or branched alkyl 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 between NH and COOH present in the compounds of formula (I).
In the compounds of the formula (I), preferably
Figure BDA0002240218220000031
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 BDA0002240218220000032
OH、C1～C10Straight or branched alkyl of (2), C1～C10And H, more preferably, each A group is independently selected from
Figure BDA0002240218220000033
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 BDA0002240218220000034
according to the present invention, the method for preparing the phosphorus-containing compound comprises:
the (1) step: 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 BDA0002240218220000035
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); r isbGroup H, C1～C10(preferably H or C)1～C6More preferably H or C1～C4Straight or branched alkyl groups of) and benzyl; each R is0' the groups, equal to or different from each other, 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, which may be the same or different from each other, is independently selected from OA' ", C1～C30A hydrocarbon group (preferably C)1～C10Straight or branched alkyl of (2), more preferably C1～C4Straight or branched alkyl of) C1～C30Alkoxy (preferably C)1～C10More preferably C1～C4Linear or branched alkoxy groups) 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 BDA0002240218220000041
Wherein M is an inorganic acid group, j is the 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 (iv), 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 BDA0002240218220000042
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 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～C6Alkylene of (3), more preferably a single bond or C1～C4Alkylene) of (b), 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, and 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 reaction 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 the reaction time 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 of the invention, in the step (1), a solvent may be added or not 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 preferably, a solvent is 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, as long as the reaction is promoted to proceed smoothly.
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 addition 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 process for producing a 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 chloroalkane, preferably methyl chloride, 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 at a pH value of 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 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 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 1-3 times. The acid environment is obtained by adding acid liquor to adjust the pH value of a system where a reaction product is located, wherein the pH value is preferably 2-5, and more preferably 2.5-3.5; the acid solution is preferably one or more aqueous solutions 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 sonication, more preferably in the presence of a solvent, preferably one or more of furan-based solvents, haloalkane solvents, ketone-based solvents, ester-based solvents and nitrile-based solvents, for example, one or more of tetrahydrofuran, dichloromethane, chloroform, acetone, ethyl acetate and acetonitrile may be selected, more preferably one or more of tetrahydrofuran, dichloromethane and acetonitrile. The time of the ultrasonic operation is preferably 1-10 h, and more preferably 2-8 h.
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 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-40-60 ℃, and more preferably-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 step (1), and the solvent is preferably added. The solvent is preferably one or more selected from the group consisting of protic solvents, ether solvents, ester solvents, chlorinated alkane solvents, furan solvents, ketone solvents and hydrocarbon solvents, and for example, water, methanol, ethanol, isopropanol, dichloromethane, chloroform, diethyl ether, tetrahydrofuran, ethyl acetate, acetone and toluene may be selected, and more preferably one or more selected from the group consisting 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 by X') and the reaction product in the step (1) (calculated by NH), the reaction product in the step (2) is washed to improve the purity of the reaction product. Preferably, the reaction product of 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-containing 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 operation includes 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 present invention, preferably, the additive comprises 1% to 15% of the anhydrous calcium-based grease; the calcium-based thickening agent accounts for 3-35% of the anhydrous calcium-based lubricating grease; the lubricating base oil accounts for 60-95% of the anhydrous calcium-based lubricating grease; more preferably, the additive comprises 2% to 12% of the anhydrous calcium-based grease; the calcium-based thickening agent accounts for 5-30% of the anhydrous calcium-based lubricating grease; the lubricating base oil accounts for 65-90% of the anhydrous calcium-based lubricating grease.
According to the invention, the sulfonate antirust agent is preferably a barium sulfonate antirust agent, for example, barium petroleum sulfonate and/or alkyl substituted barium naphthalene sulfonate can be selected, and common commercial products comprise TLA-162, LZ67, Hitec 631; the organic molybdenum friction modifier is preferably sulfurMolybdenum thiophosphates and/or molybdenum dialkyldithiocarbamates, for example, and those commercially available include T351, Molyvan A, and,
Figure BDA0002240218220000081
MoDTP。
According to the invention, the weight ratio of the phosphorus-containing compound, the sulfonate rust inhibitor and the organic molybdenum friction modifier is preferably 1: 0.2-3.5: 0.5 to 10, more preferably 1: 0.5-2.5: 1 to 8.
According to the invention, the anhydrous calcium-based thickener is the reaction product of a fatty acid and/or a hydroxy fatty acid with calcium hydroxide. The fatty acid and/or hydroxy fatty acid is preferably C12～C20The fatty acid and/or hydroxy fatty acid of (2) may be, for example, one or more selected from 12-hydroxystearic acid, lauric acid, myristic acid, palmitic acid, stearic acid and oleic acid, and more preferably one or more selected from 12-hydroxystearic acid, stearic acid and oleic acid. The molar ratio between the fatty acid and/or hydroxy fatty acid and calcium hydroxide is preferably 1: 0.2 to 1.2, more preferably 1: 0.4 to 0.8.
According to the invention, the lubricating base oil can be one or more of mineral oil, vegetable oil, ester oil and poly alpha-olefin synthetic oil, and preferably has a kinematic viscosity of 5-60mm at 100 DEG C2A lubricating base oil in a proportion of s, more preferably having a kinematic viscosity at 100 ℃ of from 10 to 30mm2(ii) lubricating base oil per s.
The preparation method of the lubricating grease comprises the following steps: part of lubricating base oil, fatty acid and/or hydroxy fatty acid and calcium hydroxide are subjected to saponification reaction at 90-110 ℃, after the saponification reaction is finished, the temperature is raised to 120-180 ℃ for constant-temperature refining, the rest of base oil is added, the temperature is reduced, the additive is added, the mixture is uniformly stirred and ground into grease.
According to the method for preparing the grease of the present invention, the temperature of the saponification reaction is preferably 95 to 105 ℃. The time for the saponification reaction is preferably 10 to 180min, more preferably 30 to 150 min. The refining operation temperature is preferably 130-160 ℃. The refining operation is preferably carried out for fat formation, and is preferably carried out for 1 to 25 minutes.
The anhydrous calcium-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 anhydrous calcium-based lubricating grease disclosed by the invention can be suitable for harsh working conditions such as 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, 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 acetonitrile, performing ultrasonic treatment for 5 hours at room temperature, and filtering to obtain a white solid;
(2) the 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, 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-a in the example reaction formula.
Figure BDA0002240218220000091
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, 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 BDA0002240218220000101
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 above 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, 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-c in the exemplary reaction formula.
Figure BDA0002240218220000121
Wherein the preparation method of the 3, 5-bis (tert-butyl) -4-hydroxy phenylpropyl 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, 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)δ12.27(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) L-serine methyl ester hydrochloride (represented by formula ii-b) (100mmol, 15.5g) and 40mL of water were sequentially added to a reactor, the temperature was lowered 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 acetonitrile, performing ultrasonic treatment for 5 hours at room temperature, 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, 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-d in the example reaction formula.
Figure BDA0002240218220000131
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, 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)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 anhydrous calcium-based grease
The raw materials used include: 500SN 69 g; 0.77g of calcium hydroxide; 5g of 12-hydroxystearic acid; 1.2g of barium petroleum sulfonate; 2.8g of molybdenum thiophosphate; 0.8g of phosphorus-containing compound I-a.
Adding 30g of 500SN and 5g of 12-hydroxystearic acid into a fat making kettle, stirring and heating, adding a mixture of 0.77g of calcium hydroxide and 1g of water, carrying out saponification reaction at 100 ℃ for 1h, heating to 140 ℃, refining for 15min, adding 39g of 500SN, stirring and cooling to 110 ℃, adding 0.8g of phosphorus-containing compound I-a, 1.2g of barium petroleum sulfonate and 2.8g of molybdenum thiophosphate, uniformly stirring, and grinding by a three-roller machine for 3 times to form fat.
Example 6 preparation of anhydrous calcium-based grease
The used raw materials comprise: PAO 1032 g; 0.8g of calcium hydroxide; 6g of 12-hydroxystearic acid; 0.3g of barium dinonyl naphthalene sulfonate and 0.3g of barium petroleum sulfonate; 1.4g of molybdenum thiophosphate and 0.5g of phosphorus compound I-b.
Adding 20g of PAO10 and 6g of 12-hydroxystearic acid into a fat making kettle, stirring and heating, adding a mixture of 0.8g of calcium hydroxide and 1.5g of water, carrying out saponification reaction at 100 ℃ for 0.5h, heating to 145 ℃, refining for 12min, adding 12g of PAO10, stirring and cooling to 100 ℃, adding 0.5g of phosphorus-containing compound I-b, 0.3g of barium dinonylnaphthalene sulfonate, 0.3g of barium petroleum sulfonate and 1.4g of molybdenum thiophosphate, uniformly stirring, and grinding for 3 times by a three-roller machine to form fat.
Example 7 preparation of anhydrous calcium-based grease
The raw materials used include: 150BS 800 g; 20g of calcium hydroxide; 140g of 12-hydroxystearic acid; 2.6g of barium petroleum sulfonate; 15g of molybdenum thiophosphate; 5g of phosphorus-containing compound I-c.
Adding 400g of 150BS and 140g of 12-hydroxystearic acid into a fat making kettle, stirring and heating, adding a mixture of 20g of calcium hydroxide and 20g of water, carrying out saponification reaction at 100 ℃ for 1.5h, heating to 150 ℃, refining for 20min, adding 400g of 150BS, stirring and cooling to 100 ℃, adding 5g of phosphorus-containing compound I-c, 2.6g of barium petroleum sulfonate and 15g of molybdenum thiophosphate, uniformly stirring, and grinding by a three-roller machine for 3 times to form fat.
Example 8 preparation of anhydrous calcium-based grease
The used raw materials comprise: 500SN65 g; 1.5g of calcium hydroxide; 10g of 12-hydroxystearic acid; 1.9g of barium petroleum sulfonate; 5.6g of molybdenum thiophosphate and 1.1g of phosphorus-containing compound I-d.
Adding 40g of 500SN oil and 10g of 12-hydroxystearic acid into a fat making kettle, stirring and heating, adding a mixture of 1.5g of calcium hydroxide and 2.5g of water, carrying out saponification reaction for 1h at 100 ℃, heating to 150 ℃, refining for 15min, adding 25g of 500SN, stirring and cooling to 100 ℃, adding 1.1g of phosphorus-containing compounds I-d, 1.9g of barium petroleum sulfonate and 5.6g of molybdenum thiophosphate, uniformly stirring, and grinding for 3 times by a three-roller machine to form fat.
Comparative example 1 preparation of anhydrous calcium-based grease comparative example
The used raw materials comprise: PAO 1032 g; 0.8g of calcium hydroxide; 6g of 12-hydroxystearic acid; 0.3g of barium dinonyl naphthalene sulfonate and 0.3g of barium petroleum sulfonate; 1.4g of molybdenum thiophosphate.
Adding 20g of PAO10 and 6g of 12-hydroxystearic acid into a grease making kettle, stirring and heating, adding a mixture of 0.8g of calcium hydroxide and 1.5g of water, carrying out saponification reaction at 100 ℃ for 0.5h, heating to 145 ℃, refining for 12min, adding 12g of PAO10, stirring and cooling to 100 ℃, adding 0.3g of barium dinonylnaphthalene sulfonate, 0.3g of barium petroleum sulfonate and 1.4g of molybdenum thiophosphate, uniformly stirring, and grinding by a three-roller machine for 3 times to form grease.
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 evaluation of grease properties
Figure BDA0002240218220000151

Claims (23)

1. An anhydrous calcium-based lubricating grease comprises the following components:
(a) an additive; (b) an anhydrous calcium-based thickener; (c) a lubricating base oil; wherein the additive is a mixture of a phosphorus-containing compound, a sulfonate rust inhibitor and an organo-molybdenum friction modifier; the structure of the phosphorus-containing compound is as follows:
Figure FDA0003611894390000011
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 FDA0003611894390000012
And at least one of R0Is composed of
Figure FDA0003611894390000013
Wherein x is 2, y is 1, 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 FDA0003611894390000014
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～C6Linear or branched alkyl of (a);
R0the radicals being selected fromH、C1～C10And linear or branched alkyl and
Figure FDA0003611894390000015
R2the radicals being single bonds or C1～C6An alkylene group of (a); r' is selected from C1～C10Straight or branched alkyl and C6～C10Aryl group of (2).
3. A grease according to claim 1, characterised in that in formula (I) the R groups are selected 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～C4Straight or branched alkyl and
Figure FDA0003611894390000016
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 FDA0003611894390000021
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 FDA0003611894390000022
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 FDA0003611894390000023
in formula (II), n is 0; r group is selected from trivalent C1～C30A hydrocarbon group of (1); rbGroup H, C1～C10A hydrocarbon group of (1);
each R is0' the groups, equal to or different from each other, are each independently selected from H, C1～C30A hydrocarbon group of (a);
a ' group is selected from OA ' ″, A ' ″ is selected from F, Cl, Br, I, H; the structure of the inorganic acid salt of the compound shown as the formula (II) is
Figure FDA0003611894390000024
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 is selected from trivalent C1～C30A hydrocarbon group of RbGroup H, C1～C10A hydrocarbon group of (1); each R is0' the groups, equal to or different from each other, are each independently selected from H, C1～C30A hydrocarbon group of (a); the A ' group is selected from OA ' and A ' is selected from F, Cl, Br, I and 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 obtained in the step (1) with a compound shown as a formula (IV), and collecting the product obtained in the step (2);
Figure FDA0003611894390000031
wherein x is 2, y is 1,x number of 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), the Ar group is a benzene ring, R2The radicals being single bonds or C1～C10With 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～C10Straight or branched chain 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; r isbThe 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～C4A linear or branched alkyl group of (b), benzyl or phenyl; r2The radicals being single bonds or C1～C4An alkylene group of (2).
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 according to claim 6, characterized in that the compound of formula (II) and/or its inorganic acid salt 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, 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. A grease lubricant according to claim 6, wherein in step (1), the compound represented by formula (II) and/or the inorganic acid salt thereof is calculated as OA' ", the compound represented by formula (III) is calculated as P-H, and the reaction equivalent ratio between the compound represented by formula (II) and/or the inorganic acid salt thereof and the compound represented by 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 to 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 to 60 ℃.
17. 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 1:2 to 2: 1; the reaction temperature is-20 ℃.
18. Grease according to any of claims 1-17, characterized in that the additive constitutes 1-15% of the anhydrous calcium based grease; the anhydrous calcium-based thickening agent accounts for 3-35% of the anhydrous calcium-based lubricating grease; the lubricating base oil accounts for 60-95% of the anhydrous calcium-based lubricating grease.
19. The grease of any one of claims 1-17 wherein the sulfonate rust inhibitor is a barium sulfonate rust inhibitor; the organic molybdenum friction modifier is molybdenum thiophosphate and/or molybdenum dithio dialkyl carbamate.
20. The grease of claim 19 wherein the sulfonate rust inhibitor is barium petroleum sulfonate and/or alkyl substituted barium naphthalene sulfonate.
21. Grease as claimed in any of claims 1 to 17, characterized in that the weight ratio between the phosphorus-containing compound, the sulphonate rust inhibitor and the organo-molybdenum friction modifier is 1: 0.2-3.5: 0.5 to 10.
22. Grease according to any of claims 1-17, characterized in that the anhydrous calcium-based thickener is a reaction product of a fatty acid and/or a hydroxy fatty acid with calcium hydroxide.
23. A method of making a grease of claim 22 comprising: the method comprises the steps of carrying out saponification reaction on part of lubricating base oil, fatty acid and/or hydroxy fatty acid and calcium hydroxide at 90-105 ℃, heating to 120-160 ℃ after the saponification reaction is finished, carrying out constant-temperature refining, adding the rest of base oil, cooling, adding the additive, uniformly stirring, and grinding into grease.
CN201910997453.9A 2019-10-21 2019-10-21 Anhydrous calcium-based lubricating grease and preparation method thereof Active CN112760161B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910997453.9A CN112760161B (en) 2019-10-21 2019-10-21 Anhydrous calcium-based lubricating grease and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910997453.9A CN112760161B (en) 2019-10-21 2019-10-21 Anhydrous calcium-based lubricating grease and preparation method thereof

Publications (2)

Publication Number Publication Date
CN112760161A CN112760161A (en) 2021-05-07
CN112760161B true CN112760161B (en) 2022-07-15

Family

ID=75691491

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910997453.9A Active CN112760161B (en) 2019-10-21 2019-10-21 Anhydrous calcium-based lubricating grease and preparation method thereof

Country Status (1)

Country Link
CN (1) CN112760161B (en)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2208849A1 (en) * 1971-03-12 1972-09-28 Esso Research and Engineering Co., Linden, N.J. (V .St-A.) Amine salts of phosphorus acids and their use in lubricating oils
US3763287A (en) * 1970-09-28 1973-10-02 Gaf Corp Phosphorus containing derivatives of omega-(3,5-dialkyl-4-hydroxyphenyl)alkanols
CN1228803A (en) * 1996-08-30 1999-09-15 索罗蒂亚公司 Novel water soluble metal working fluids
CN106046047A (en) * 2016-05-26 2016-10-26 清华大学 Method for preparing phosphorylated serine phosphonic acid analogs
CN107109284A (en) * 2014-11-12 2017-08-29 路博润公司 Mixing phosphide for lubricant use
EP3450440A1 (en) * 2016-04-27 2019-03-06 China Petroleum & Chemical Corporation Benzotriazole derivative, manufacturing method therefor and use thereof
CN109694388A (en) * 2017-10-23 2019-04-30 中国石油化工股份有限公司 A kind of phosphorus-containing compound and preparation method thereof, purposes
CN110317660A (en) * 2018-03-28 2019-10-11 中国石油化工股份有限公司 A kind of complex lithium grease and preparation method thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3763287A (en) * 1970-09-28 1973-10-02 Gaf Corp Phosphorus containing derivatives of omega-(3,5-dialkyl-4-hydroxyphenyl)alkanols
DE2208849A1 (en) * 1971-03-12 1972-09-28 Esso Research and Engineering Co., Linden, N.J. (V .St-A.) Amine salts of phosphorus acids and their use in lubricating oils
CN1228803A (en) * 1996-08-30 1999-09-15 索罗蒂亚公司 Novel water soluble metal working fluids
CN107109284A (en) * 2014-11-12 2017-08-29 路博润公司 Mixing phosphide for lubricant use
EP3450440A1 (en) * 2016-04-27 2019-03-06 China Petroleum & Chemical Corporation Benzotriazole derivative, manufacturing method therefor and use thereof
CN106046047A (en) * 2016-05-26 2016-10-26 清华大学 Method for preparing phosphorylated serine phosphonic acid analogs
CN109694388A (en) * 2017-10-23 2019-04-30 中国石油化工股份有限公司 A kind of phosphorus-containing compound and preparation method thereof, purposes
CN110317660A (en) * 2018-03-28 2019-10-11 中国石油化工股份有限公司 A kind of complex lithium grease and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Dual substrate-controlled kinase activity leads to polyphosphorylated lasso peptides;Zhu,SZ et al.;《FEBS LETTERS》;20161031;第590卷(第19期);第3323-3334页 *
可促进润滑油生物降解的新型润滑添加剂研究;黄伟九;《润滑与密封》;20091130;第34卷(第11期);第5-8页 *
可生物降解润滑油的研究进展;韦友亮等;《石油商技》;20141231(第6期);第16-23页 *

Also Published As

Publication number Publication date
CN112760161A (en) 2021-05-07

Similar Documents

Publication Publication Date Title
CN112760156B (en) Calcium-based lubricating grease and preparation method thereof
CN110317669B (en) Lithium-based lubricating grease and preparation method thereof
CN110317660B (en) Composite lithium-based lubricating grease and preparation method thereof
CN112760157B (en) Composite lithium-based lubricating grease and preparation method thereof
CN111320542B (en) Antioxidant containing double hindered phenol structures and preparation method thereof
CN112760161B (en) Anhydrous calcium-based lubricating grease and preparation method thereof
CN112760155B (en) Lubricating oil composition for diesel engine and preparation method thereof
CN110317668B (en) Lubricating grease and preparation method thereof
CN112760152B (en) Lithium-based lubricating grease and preparation method thereof
CA3079982C (en) Secondary alcohol phosphate ester
CN112759610B (en) Phosphorus-containing compound and preparation method and application thereof
CN112760158B (en) Gasoline engine lubricating oil composition and preparation method thereof
CN111057108B (en) Phosphoramidate compound and preparation method and application thereof
KR101827503B1 (en) Dicarboxylic acid derivatives containing dialkyldithiophosphate group and antiwear additives and lubricant compositions comprising the same
KR101278872B1 (en) Norbornene dialkyl ester containing dialkyl dithiocarbamate compounds, antiwear additives and lubricant comprising the same
CN111100156B (en) Silole derivative, preparation method and application thereof, and lubricating grease
KR101785337B1 (en) Free-metal dicarboxylic acid derivatives and antiwear additives and lubricant compositions comprising the same
CN111100157B (en) Silole derivative, preparation method and application thereof, and lubricating grease
CN110204496B (en) Sulfhydryl pyrimidine derivative containing ester group and dithioamino acid group, preparation and application thereof
CN111057103B (en) Thiophosphonate compound and preparation method and application thereof
CN111057101B (en) Phosphoramidate compound and preparation method and application thereof
CN115074168B (en) Lubricating grease and preparation method thereof
CN111057107B (en) Thiophosphonate compound, and preparation method and application thereof
CN111100091B (en) Benzothiazole derivative, preparation method and application thereof, and lubricating grease
CN110317661B (en) Lubricating oil composition for marine medium-speed trunk piston engine and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant