CN110791358B - Lubricating grease and preparation method thereof - Google Patents

Lubricating grease and preparation method thereof Download PDF

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Publication number
CN110791358B
CN110791358B CN201810866663.XA CN201810866663A CN110791358B CN 110791358 B CN110791358 B CN 110791358B CN 201810866663 A CN201810866663 A CN 201810866663A CN 110791358 B CN110791358 B CN 110791358B
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Prior art keywords
lithium hydroxide
hydroxide solution
substituted
grease
oil
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CN110791358A (en
Inventor
刘大军
孙洪伟
段庆华
潘卓
庄敏阳
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
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
    • C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • 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
    • C10M2205/022—Ethene
    • 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
    • C10M2205/024—Propene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
    • 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
    • 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
    • C10M2207/28—Esters
    • C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • 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

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

Abstract

The invention relates to the field of lubricants, and discloses lubricating grease and a preparation method thereof. The preparation method comprises the following steps: (1) in base oil containing ester oil, making hydroxy fatty acid contact with lithium hydroxide solution to carry out saponification reaction; (2) mixing the product obtained by saponification reaction with lithium hydroxide monohydrate to make the mixed system alkaline; (3) refining the product obtained in the step (2), and mixing with optional additives. The invention can obtain the lubricating grease with excellent performance, almost does not contain free acid, does not need to prepare prefabricated soap in advance, can directly contact the hydroxy fatty acid and the lithium hydroxide solution in all base oil for saponification reaction, has simpler and easier preparation method, and is beneficial to improving the production efficiency of the lubricating grease.

Description

Lubricating grease and preparation method thereof
Technical Field
The invention relates to a lubricant, in particular to lubricating grease and a preparation method thereof.
Background
Grease as a lubricant has long been known and consists of three main components, namely base oil, a thickening agent and an additive, which are the same as the preparation process conditions of the grease as important factors for determining and influencing the performance of the grease.
The aviation grease has an important function for ensuring the working reliability and maintainability of the airplane, and is mainly used for lubricating and protecting bearings, gears, chains and control structure nodes of the parts of aviation electromechanics, instruments, engine accessories, airplane wheels and the like. As the use conditions of the aviation grease are harsh, the aviation grease is a type of grease with higher performance requirements, such as high temperature, low temperature, rubber compatibility and the like, and in order to meet the use requirements of the aviation grease, the base oil of the grease is basically PAO and/or ester oil. However, when the base oil is used for preparing the lubricating grease, particularly the lubricating grease containing the ester oil, the alkaline aqueous solution is added in the saponification process, so that the problem of hydrolysis of the base oil, particularly the ester oil exists, the hydrolysis products are remained in the products to influence the quality of the lubricating grease products, and the performances such as corrosion, free acid, mechanical stability, oxidation stability and the like are deteriorated, and the influence of corrosion caused by corrosive acidic substance products remained in the hydrolysis of the ester oil is not solved by adopting PAO and/or the ester oil in the prior art such as CN102250671A, CN104498147A, CN105296052A and the like to prepare the lubricating grease.
In order to avoid hydrolysis in the process of preparing the grease containing ester oil in the prior art, the grease is mostly prepared by firstly preparing preformed soap, then mixing the preformed soap and base oil containing ester oil to prepare the grease, such as CN1184845A, CN104419506A and the like, firstly adding fatty acid and water into a kettle to react with hydroxide alkali solution for 0.5 to 2 hours, then drying for 15 to 40 hours to prepare the preformed soap, and then heating the preformed soap and the ester oil or mixed oil containing the ester oil to prepare the grease.
Disclosure of Invention
The invention aims to provide a method for preparing lubricating grease in order to overcome the problem of low production efficiency in the prior art.
The inventors of the present invention have found that the introduction of lithium hydroxide monohydrate (lithium hydroxide crystals) into the saponification reaction product can avoid the presence of free acid in the resulting grease and improve the performance of the grease, and the preparation process is simpler and easier. Accordingly, in order to achieve the above object, the present invention provides a method of preparing a grease comprising:
(1) In the base oil containing ester oil, the structural formula is shown in
Figure BDA0001751115350000021
In contact with a lithium hydroxide solution to carry out saponification, wherein R1Is hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl; r is2Is a substituted or unsubstituted arylene, substituted or unsubstituted alkylene, or substituted or unsubstituted cycloalkylene;
(2) mixing the product obtained by saponification reaction with lithium hydroxide monohydrate to make the mixed system alkaline;
(3) refining the product obtained in the step (2), and mixing with optional additives.
The invention also provides lubricating grease prepared by the method.
Through the technical scheme, the lubricating grease with excellent performance can be obtained, free acid (small molecular acid) is hardly contained, prefabricated soap does not need to be prepared in advance, the hydroxy fatty acid can be directly contacted with the lithium hydroxide solution in all base oil for saponification, the preparation method is simple and easy to implement, and the production efficiency of the lubricating grease is improved.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
The method for preparing the lubricating grease provided by the invention comprises the following steps:
(1) in the base oil containing ester oil, the structural formula is shown in
Figure BDA0001751115350000031
In contact with a lithium hydroxide solution to carry out saponification, wherein R1Is hydrogen, substituted orUnsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl; r is2Is a substituted or unsubstituted arylene, substituted or unsubstituted alkylene, or substituted or unsubstituted cycloalkylene;
(2) mixing the product obtained by saponification reaction with lithium hydroxide monohydrate to make the mixed system alkaline;
(3) refining the product obtained in the step (2), and mixing with optional additives.
In the present invention, the group used for substitution is at least one of hydroxyl, halogen and carboxyl.
Preferably, R1Is C1-C10(C1、C2、C3、C4、C5、C6、C7、C8、C9Or C10) Alkyl (or straight chain alkyl) groups of (a). More preferably, R1Is C3-C10Linear alkyl group of (1).
Preferably, R2Is C1-C20(C1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19Or C20) Alkylene (or linear alkylene) of (a). More preferably, R2Is C8-C15A linear alkylene group of (a).
In a particularly preferred embodiment of the invention, R1Is C6Linear alkyl radical of (2), R2Is C10I.e., the hydroxy fatty acid is 12-hydroxystearic acid.
In the present invention, the base oil containing the ester oil may be a conventional base oil to which various ester base oils are added, and for example, the ester oil may be at least one of dioctyl sebacate, trimethylolpropane ester, pentaerythritol oleate, and the like. The base oil may be a polyalphaolefin synthetic oil. The weight ratio of the polyalphaolefin synthetic oil to the ester oil in the base oil containing the ester oil may be 1:0.1 to 9, preferably 1:0.4 to 2.5. Preferably, the base oil containing the ester oil contains (or consists of) polyalphaolefin synthetic oil and dioctyl sebacate. The polyalphaolefin synthetic oil and dioctyl sebacate may be compounded in conventional proportions, preferably in a weight ratio of 1:0.1 to 9, more preferably 1:0.4 to 2.5.
In the present invention, the polyalphaolefin synthetic oil may be at least one of PAO2, PAO4, PAO6, PAO8, and PAO 10. Preferably, the polyalphaolefin synthetic oil has a kinematic viscosity at 100 ℃ of 2 to 25mm2S, more preferably 4 to 15mm2And(s) in the presence of a catalyst. In the present invention, the kinematic viscosity is measured with reference to GB/T265-1988.
In a preferred embodiment of the invention, the dioctyl sebacate (also known as bis (2-ethylhexyl) sebacate) has a kinematic viscosity at 100 ℃ of 3-4mm 2/s。
In the present invention, the hydroxystearic acid may be used in an amount of 5 to 20kg per 100 kg of the base oil in step (1).
In the present invention, the concentration of the lithium hydroxide solution is not particularly limited, but it is preferable that the concentration of lithium hydroxide in the lithium hydroxide solution is 2 to 6 mol/L.
In the step (1) of the present invention, the molar ratio between the hydroxy fatty acid and lithium hydroxide in the lithium hydroxide solution is not particularly limited, and the molar amount of lithium hydroxide (in terms of lithium element) may be controlled to be higher (for example, 1 to 10 mol%) than the molar amount of the hydroxy fatty acid.
According to a preferred embodiment of the present invention, in step (1) of the present invention, the hydroxy fatty acid is contacted with the lithium hydroxide solution in a stepwise manner. More preferably, the lithium hydroxide solution is added to a mixture of base oil and hydroxy fatty acid. The addition rate of the lithium hydroxide solution is preferably in the range of 25 to 300mL/min, and more preferably in the range of 50 to 200 mL/min. The performance of the grease obtained can be further improved in a stepwise contact manner as described above.
In the step (1) of the present invention, the saponification reaction conditions are not particularly limited, and for example, the saponification reaction temperature may be 100-120 ℃, preferably 105-115 ℃.
In step (2) of the present invention, the lithium hydroxide monohydrate is generally referred to as lithium hydroxide crystals. The amount of lithium hydroxide monohydrate to be used is not particularly limited as long as it is in excess so that the mixed system is (weakly) basic. The alkalescence can be judged through phenolphthalein test, namely, whether the indicator turns red or not is judged after the indicator is added, the system is judged to be alkalescent if the indicator turns red, and the addition amount of the lithium hydroxide monohydrate is proper; alternatively, the amount of lithium hydroxide monohydrate to be added is judged to be appropriate by examining whether the free base as sodium hydroxide is in the range of 0.01 to 0.1% by weight by the "method for measuring free base and free organic acid of grease". Preferably, the amount of lithium hydroxide monohydrate used in step (2) is preferably 60 to 250g per 100 kg of base oil.
In the step (2) of the present invention, the manner of mixing the product obtained by the saponification reaction with lithium hydroxide monohydrate is not particularly limited, and may be carried out at any temperature of 100 ℃ or higher, and preferably, the conditions of mixing the product obtained by the saponification reaction with lithium hydroxide monohydrate include: the temperature is 130-150 ℃, namely, the lithium hydroxide monohydrate is introduced when the temperature of the system is controlled to be 130-150 ℃.
In the step (3) of the present invention, the refining (constant temperature refining) conditions are not particularly required, and the refining may be performed under conventional conditions. Preferably, the refining conditions include: the temperature is 200-220 ℃, and the time is 5-20 min.
In the present invention, additives are generally used to impart antioxidant, rust preventive, etc. properties to the grease, and the amount of additives used is generally such that the content thereof in the grease to be produced is in the range of 0.005 to 1% by weight, preferably 0.01 to 0.5% by weight.
In the present invention, the additive may include at least one of an antioxidant, a tackifier, and a rust inhibitor. Among them, the antioxidant is preferably an aromatic amine antioxidant, and may be at least one of diphenylamine, phenyl- α -naphthylamine and diisooctyldiphenylamine, and diisooctyldiphenylamine is preferable. The amount of antioxidant is preferably 0.4-1.5kg per 100 kg of base oil.
The tackifier may be selected from at least one of ethylene-propylene copolymer, polymethacrylate, polypropylene, etc., preferably ethylene-propylene copolymer, such as T613. The amount of tackifier used is preferably 1 to 5kg per 100 kg of base oil.
The rust inhibitor can be at least one of petroleum sulfate (such as barium petroleum sulfonate and sodium petroleum sulfonate), benzothiazole, imidazoline rust inhibitor (such as benzotriazole), ester rust inhibitor (such as sorbitol monooleate), zinc naphthenate and alkenyl succinic acid. The amount of the rust inhibitor to be used is preferably 0.2 to 1.5kg per 100 kg of the base oil. In order to make the obtained grease have better rust-proof performance and be used in the aviation field, the rust-proof agent is preferably an imidazoline type rust-proof agent and an ester type rust-proof agent in a weight ratio of 1: 0.4-2.5. More preferably, the antirust agent is benzotriazole and sorbitol monooleate with the weight ratio of 1: 0.4-2.5.
In the present invention, the method may further comprise cooling the refined material, and the additive may be introduced when the temperature is cooled to 120-.
In the method of the present invention, after mixing with optional additives, filtration, homogenization, degassing, etc. may be performed in a conventional manner to obtain a grease finished product.
The invention also provides lubricating grease prepared by the method.
The present invention will be described in detail below by way of examples.
In the following examples, the kinematic viscosity at 100 ℃ of dioctyl sebacate is 3-4mm2(s) from Wenning chemical Industrial, Inc., Tongliao; 12-Hydroxystearic acid was purchased from Tongliotonghua Ricinus chemical Co., Ltd; the T613 tackifier is an ethylene-propylene copolymer and is purchased from Nanjing Oubeke Fine chemical industry, Inc.; lithium hydroxide monohydrate (lithium hydroxide crystals) was purchased from Chengdu-taozi lithium industries, Inc.
The performance test method comprises the following steps:
working cone penetration (0.1 mm): GB/T269-1991;
dropping point: GB/T3498-;
pressure oil separation: GB/T392;
and (3) corrosion: GB/T7326 (copper, steel, aluminum sheets);
oxidation stability: SH/T0325;
acid value after oxidation: SH/T0329;
free base: SH/T0329;
Free acid: SH/T0329.
Example 1
(1)50kg of a PAO4 base oil (kinematic viscosity at 100 ℃ 4 mm)2Per second, from exxon Mobil) and 40kg dioctyl sebacate were added to the reactor, the temperature was raised to 110 ℃ and stirred for 30min, 10kg 12-hydroxystearic acid was weighed and added, 1.4kg lithium hydroxide was weighed and made into a solution with a molar concentration of 3.9mol/L with 95 ℃ hot water; adding the lithium hydroxide solution into a reaction kettle at the speed of 0.05L/min, and adjusting the heating power of the reaction kettle to keep the temperature in the reaction kettle at 110 +/-5 ℃;
(2) after the lithium hydroxide solution is completely added for reaction, heating to 130 ℃, adding 80g of lithium hydroxide monohydrate for neutralization, and sampling to turn red by phenolphthalein test, wherein the free base value is 0.031 (NaOH)%;
(3) heating to the maximum refining temperature of 210 ℃, keeping the temperature for 5min, transferring the mixture into a blending kettle through a material pump, circularly cooling, adding 0.4kg of antioxidant diisooctyl diphenylamine, 0.25kg of antirust benzotriazole, 0.25kg of sorbitol monooleate and 2kg of T613 tackifier at the temperature of 130 ℃, uniformly mixing in the blending kettle, starting a colloid mill, and homogenizing the lubricating grease for 40min through the colloid mill to obtain a lubricating grease finished product, wherein the analysis data of the physical and chemical properties of the lubricating grease is shown in Table 1.
Example 2
(1)32kg of a PAO10 base oil (kinematic viscosity at 100 ℃ of 10 mm)2Per s, from exxon Mobil) and 53kg dioctyl sebacate were added to the reactor, the temperature was raised to 101 ℃, stirred for 30min, 15kg 12-hydroxystearic acid was weighed, 2.1kg lithium hydroxide was weighed, and a solution having a molar concentration of 5.1mol/L was prepared with 95 ℃ hot water; lithium hydroxide solution is pressed at 0.12L +Adding the mixture into a reaction kettle at a speed of min, and adjusting the heating power of the reaction kettle to keep the temperature in the kettle at 110 +/-5 ℃;
(2) after the lithium hydroxide solution is completely added for reaction, heating to 150 ℃, adding 180g of lithium hydroxide monohydrate for neutralization, and sampling to turn red by phenolphthalein test, wherein the free base value is 0.015 (NaOH)%;
(3) heating to the maximum refining temperature of 220 ℃, keeping the temperature for 20min, transferring the mixture into a blending kettle through a material pump, circularly cooling, adding 0.5kg of antioxidant diisooctyl diphenylamine, 0.42kg of antirust benzotriazole, 0.18kg of sorbitol monooleate and 1kg of T613 tackifier at the temperature of 130 ℃, uniformly mixing in the blending kettle, starting a colloid mill, and homogenizing the lubricating grease for 40min through the colloid mill to obtain a lubricating grease finished product, wherein the analysis data of the physical and chemical properties of the lubricating grease is shown in Table 1.
Example 3
(1)46kg of a PAO6 base oil (kinematic viscosity at 100 ℃ C. of 5.9 mm) 2Per s, from exxon Mobil) and 46kg dioctyl sebacate were added to a reaction vessel, the temperature was raised to 115 ℃, stirred for 30min, 8kg 12-hydroxystearic acid was weighed, 1.34kg lithium hydroxide was weighed, and a solution having a molar concentration of 4.0mol/L was prepared with 95 ℃ hot water; adding the lithium hydroxide solution into a reaction kettle at the speed of 0.08L/min, and adjusting the heating power of the reaction kettle to keep the temperature in the kettle at 110 +/-5 ℃;
(2) after the lithium hydroxide solution is completely added for reaction, heating to 140 ℃, adding 60g of lithium hydroxide monohydrate for neutralization, and sampling to turn red by phenolphthalein test, wherein the free base value is 0.056 (NaOH)%;
(3) heating to the maximum refining temperature of 215 ℃, keeping the temperature for 10min, transferring the mixture into a blending kettle through a material pump, circularly cooling, adding 0.8kg of antioxidant diisooctyl diphenylamine, 0.3kg of antirust benzotriazole, 0.7kg of sorbitol monooleate and 3kg of T613 tackifier at the temperature of 130 ℃, uniformly mixing in the blending kettle, starting a colloid mill, and homogenizing the lubricating grease for 40min through the colloid mill to obtain a lubricating grease finished product, wherein the analysis data of the physical and chemical properties of the lubricating grease are shown in Table 1.
Example 4
(1)63kg of a PAO8 base oil (kinematic viscosity at 100 ℃ C. of 8 mm)2S, from AngstromKenmeifu corporation) and 27kg dioctyl sebacate are added into a reaction kettle, the temperature is raised to 110 ℃, the stirring is carried out for 30min, 12kg 12-hydroxystearic acid is weighed and added, 1.5kg lithium hydroxide is weighed, and hot water with the temperature of 95 ℃ is used for preparing solution with the molar concentration of 2.8 mol/L; adding the lithium hydroxide solution into a reaction kettle at the speed of 0.2L/min, and adjusting the heating power of the reaction kettle to keep the temperature in the reaction kettle at 110 +/-5 ℃;
(2) After the lithium hydroxide solution is completely added for reaction, heating to 135 ℃, adding 80g of lithium hydroxide monohydrate for neutralization, and sampling to turn red by phenolphthalein test, wherein the free base value is 0.033 (NaOH)%;
(3) heating to 213 ℃ of the maximum refining temperature, keeping the temperature for 15min, transferring the mixture into a blending kettle through a material pump, cooling the mixture in a circulating manner, adding 1kg of antioxidant diisooctyl diphenylamine, 0.1kg of antirust benzotriazole, 0.1kg of sorbitol monooleate and 3kg of T613 tackifier into the blending kettle at the temperature of 130 ℃, uniformly mixing the mixture in the blending kettle, starting a colloid mill, and homogenizing the lubricating grease through the colloid mill for 40min to obtain the finished lubricating grease, wherein the analysis data of the physical and chemical properties of the finished lubricating grease are shown in Table 1.
Example 5
The procedure of example 1 was followed except that the amounts of benzotriazole and sorbitan monooleate as rust inhibitors were 0.5kg and 0kg, respectively, and the analysis data of the physical and chemical properties of the resulting grease products are shown in Table 2.
Example 6
The procedure of example 1 was followed except that benzotriazole and sorbitan monooleate, which are rust inhibitors, were used in amounts of 0kg and 0.5kg, respectively, and the analysis data of the physical and chemical properties of the resulting grease products are shown in Table 2.
Example 7
The procedure of example 1 was followed except that the amounts of benzotriazole and sorbitan monooleate as rust inhibitors were 0.1kg and 0.4kg, respectively, and the analysis data of the physical and chemical properties of the resulting grease products are shown in Table 2.
Example 8
The procedure of example 1 was followed except that benzotriazole and sorbitan monooleate, which are rust inhibitors, were used in amounts of 0.4kg and 0.1kg, respectively, and the analytical data on the physical and chemical properties of the resulting grease products are shown in Table 2.
Example 9
The procedure was as in example 1, except that the rate of addition of the lithium hydroxide solution in step (1) was 0.025L/min, and the analytical data on the physical and chemical properties of the resulting grease were as shown in Table 2.
Example 10
The procedure was as in example 1, except that the rate of addition of the lithium hydroxide solution in step (1) was 0.3L/min, and the analytical data on the physical and chemical properties of the resulting grease were as shown in Table 2.
Comparative example 1
The procedure of example 1 was followed, except that lithium hydroxide monohydrate was not added in the step (2), and the analysis data of the physical and chemical properties of the resulting grease composition are shown in Table 1.
Comparative example 2
The procedure of example 1 was followed, except that in step (2), 800g of an aqueous 10% by weight lithium hydroxide solution was added in place of 80g of lithium hydroxide monohydrate, and the analysis data of the physical and chemical properties of the resulting grease composition are shown in Table 1.
Comparative example 3
In this comparative example, a preformed soap was prepared and then a grease was prepared according to the prior art, such as CN 1184845A.
Preparing a prefabricated soap: 10.5kg of 12-hydroxystearic acid, 4.5kg of stearic acid and 15L of water are mixed, heated to 85 ℃, added with lithium hydroxide solution with the same molar equivalent weight, reacted for 2.5 hours, and dried at 100 ℃ to obtain the prefabricated soap.
Heating 16kg of dioctyl sebacate and 6kg of prefabricated soap in a reaction kettle, adding T614 (ethylene-propylene copolymer, produced by the Mich petrochemical company) at 100 ℃, adding diisooctyl diphenylamine antioxidant at 180 ℃, heating to 205 ℃, adding 37kg of dioctyl sebacate, circularly cooling to 130 ℃, shearing for 30min, adding 0.3kg of barium dinonylnaphthalene sulfonate, 0.3kg of benzotriazole and 1.8kg of molybdenum oxygen dithiocarbamate at the temperature below 100 ℃, and uniformly stirring. The analysis data of the physical and chemical properties of the finished grease are shown in table 1.
TABLE 1
Figure BDA0001751115350000111
Note: "-" indicates no detection.
TABLE 2
Figure BDA0001751115350000121
Note: "-" indicates no detection.
As can be seen from Table 1, the present invention does not require the soap to be prefabricated, thereby avoiding energy waste. Moreover, the lubricating grease obtained by the invention does not contain detectable free acid (micromolecular acid), has higher dropping point, and has good mechanical stability, oxidation stability and the like.
In addition, the lubricating grease composition disclosed by the invention can not contain elements such as Fe, Al, Cu, Cr, Mo, Zn, Ni, Cd, Si, Ag, Pb, Ti, Sn, Mg, Ba and the like, and meets the monitoring data acquisition requirement of aviation on the lubricating oil element spectrum.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (11)

1. A method of preparing a grease, comprising:
(1) in the base oil containing ester oil, the structural formula is shown in
Figure 581509DEST_PATH_IMAGE001
In contact with a lithium hydroxide solution to carry out a saponification reaction, wherein R1Is hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl; r is2Is a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group; the base oil containing the ester oil contains poly-alpha olefin synthetic oil and dioctyl sebacate, and the weight ratio of the poly-alpha olefin synthetic oil to the dioctyl sebacate is 1: 0.1-9; the concentration of lithium hydroxide in the lithium hydroxide solution is 2-6mol/L, and the contact mode of the hydroxy fatty acid and the lithium hydroxide solution is as follows: adding a lithium hydroxide solution into a mixture of base oil and hydroxy fatty acid, and controlling the adding speed of the lithium hydroxide solution within the range of 25-300 mL/min;
(2) Mixing the product obtained by saponification reaction with lithium hydroxide monohydrate to make the mixed system alkaline;
(3) refining the product obtained in the step (2), and mixing with optional additives;
wherein the amount of hydroxy fatty acid used in step (1) is 5-20kg and the amount of lithium hydroxide monohydrate used in step (2) is 60-250g per 100 kg of base oil.
2. The method according to claim 1, wherein the addition rate of the lithium hydroxide solution is controlled within a range of 50-200 mL/min.
3. The method of claim 1, wherein the group used for substitution is at least one of hydroxyl, halogen, and carboxyl.
4. The method of claim 1 or 3, wherein R1Is C1-C10Alkyl groups of (a);
and/or, R2Is C1-C20An alkylene group of (2).
5. The method of claim 1, wherein the weight ratio of the polyalphaolefin synthetic oil to the dioctyl sebacate is 1: 0.4-2.5.
6. The method of claim 1, wherein the polyalphaolefin synthetic oil has a 100 ℃ movementThe viscosity is 2-25mm2/s；
And/or the kinematic viscosity of the dioctyl sebacate at 100 ℃ is 3-4mm2/s。
7. The method of claim 6, wherein the polyalphaolefin synthetic oil has a kinematic viscosity at 100 ℃ of 4 to 15mm 2/s。
8. The method as claimed in claim 1, wherein the saponification reaction temperature is 100-120 ℃;
and/or, the conditions under which the product obtained from the saponification reaction is mixed with lithium hydroxide monohydrate include: the temperature is 130-150 ℃;
and/or, the refining conditions include: the temperature is 200 ℃ and 220 ℃, and the time is 5-20 min.
9. The method of claim 1, wherein the additive comprises a rust inhibitor, and the rust inhibitor is an imidazoline based rust inhibitor and an ester based rust inhibitor in a weight ratio of 1: 0.4-2.5.
10. The method of claim 9, wherein the rust inhibitor is benzotriazole and sorbitol monooleate in a weight ratio of 1: 0.4-2.5.
11. A grease prepared by the process of any one of claims 1 to 10.
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CN104804842A (en) * 2014-01-27 2015-07-29 中国石油化工股份有限公司 Environmentally friendly lubricating grease composition and preparation method thereof
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CN105925356A (en) * 2016-05-23 2016-09-07 中国石油化工股份有限公司 Low-temperature extreme pressure lubricating grease composition and preparation method thereof
JP2017007996A (en) * 2015-06-25 2017-01-12 住鉱潤滑剤株式会社 Manufacturing method of lithium 12-hydroxystearate, lithium 12-hydroxystearate and grease composition containing the lithium 12-hydroxystearate

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CN102796603A (en) * 2011-05-27 2012-11-28 中国石油化工股份有限公司 Method for preparing lithium lubricating grease
CN104804842A (en) * 2014-01-27 2015-07-29 中国石油化工股份有限公司 Environmentally friendly lubricating grease composition and preparation method thereof
JP2017007996A (en) * 2015-06-25 2017-01-12 住鉱潤滑剤株式会社 Manufacturing method of lithium 12-hydroxystearate, lithium 12-hydroxystearate and grease composition containing the lithium 12-hydroxystearate
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