CN115960656B - Composite lithium-based lubricating grease and preparation method thereof - Google Patents
Composite lithium-based lubricating grease and preparation method thereof Download PDFInfo
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Abstract
The invention provides composite lithium-based lubricating grease, which comprises a composite lithium-based thickening agent, an additive and a main amount of lubricating base oil, wherein the additive comprises a mixture of an organoboron compound, an oiliness agent and an antirust agent, and the structure of the organoboron compound is shown as a formula (I):
Description
Technical Field
The invention relates to lubricating grease, in particular to composite lithium-based lubricating grease and a preparation method thereof.
Background
Grease is a necessary working medium in the normal operation of mechanical equipment and in the material manufacturing process. The composite lithium-based lubricating grease is high-temperature multi-effect lubricating grease developed in the 60 th century, has a higher dropping point than the lithium-based lubricating grease, is more suitable for being used at high temperature, has good multi-effect properties such as good colloid stability, shear stability, water resistance and long service life, has strong thickening capacity on various types of mineral oil and synthetic oil, and can be applied to bearing, automobile, printing and dyeing, mine, metallurgy, aerospace and other industrial departments with strict requirements on oxidation resistance, high-low temperature performance, extreme pressure wear resistance, water resistance, mechanical stability and the like of the lubricating grease.
In recent years, with the progress of industrial technology, the working condition of the application part of the lubricating grease is more severe, which puts higher requirements on the lubricating grease additive, and with the restriction of environmental protection, new demands of low ash content and low phosphorus content are also put forward. The boron-containing lubricating material has the characteristics of extreme pressure wear resistance, high temperature oxidation resistance, corrosion resistance, rust resistance, good sealing and environmental adaptability, no toxicity, no odor and the like, and the nitrogen-containing lubricating material has the characteristics of no ash, high electronegativity, small atomic radius, easiness in forming hydrogen bonds among molecules adsorbed on the metal surface to improve the oil film strength and the like; and both types of lubricating materials have the advantages of multifunction, designable molecular structure, combinable active elements and the like. Therefore, research on nitrogen-containing organoboron lubricating materials has attracted considerable attention in the field of modern friction and lubrication. The development of grease products associated therewith is also a direction of development by those skilled in the art.
Disclosure of Invention
The invention provides a composite lithium-based lubricating grease and a preparation method thereof.
The composite lithium-based lubricating grease comprises a composite lithium-based thickening agent, an additive and a main amount of lubricating base oil, wherein the additive comprises a mixture of an organoboron compound, an oiliness agent and an antirust agent, and the structure of the organoboron compound is shown as a formula (I):
In formula (I), a repeating units L and b boron-containing groups are present, a being an integer between 1 and 10 (preferably an integer between 1 and 5), b being an integer between 1 and 5 (preferably an integer between 1 and 3), a being identical or different from each other and each independently selected from groups of formula (II);
In formula (II), HO is bonded to the benzene ring (HO is preferably located in the meta position of the chain on the benzene ring where R 1 is located); y R groups are bonded to the benzene ring; y is selected from integers between 0 and 4 (preferably integers between 1 and 3); the R groups are each independently selected from H and C 1-20 straight or branched alkyl (preferably each independently selected from H and C 1-4 straight or branched alkyl, more preferably t-butyl); n is an integer between 1 and 10 (preferably an integer between 1 and 3); r 1 is each independently selected from a single bond and a C 1-20 linear or branched alkylene (preferably selected from a single bond and a C 1-4 linear or branched alkylene); r 2 in the n repeating units, equal to or different from each other, are each independently selected from a single bond and a C 1-20 linear or branched alkylene group (preferably each independently selected from a single bond and a C 1-4 linear or branched alkylene group); r 3 is selected from H and C 1-20 linear or branched alkyl (preferably from H and C 1-4 linear or branched alkyl); the A groups in the n repeating units are identical or different from each other and are each independently selected from single bonds, A group represented by the formula (III) and a group represented by the formula (IV),
The R 4 groups are each independently selected from H and C 1-20 linear or branched alkyl (preferably from H and C 1-4 linear or branched alkyl);
m is an integer between 0 and 10 (preferably an integer between 1 and 5);
The R 5 groups are each independently selected from C 1-20 linear or branched alkyl groups of valency 3 (preferably each independently selected from C 1-4 linear or branched alkyl groups of valency 3);
Each G 2 group is independently selected from the group consisting of a binding end bonded to a G 4 group present in other L groups than the L group in which it is located, C 1-10 straight or branched alkyl, -R 6G3, H; each G 3 group is independently selected from-OG 1、C1-10 linear or branched alkyl, H (preferably each is independently selected from-OG 1、C1-4 linear or branched alkyl, OH, H);
The R 6 groups are selected from C 1-20 linear or branched alkylene groups (preferably each independently selected from C 1-4 linear or branched alkylene groups);
The G 1 group is selected from the group consisting of a binding end bonded to the boron-containing group, H;
The G 4 group is selected from the binding end, H, bonded to the G 2 group present in the other L groups than the L group in which it is located;
Of the a groups, at least one A group is selected from the group represented by formula (III), and at least one G 1 group is selected from the binding end bonded to the boron element in the boron-containing group;
each a ' group of b said boron-containing groups is independently selected from the group consisting of a binding end bonded to a G 1 group present in the L group, a group of formula (V), OH, -OR ', said R ' groups being C 2-20 linear OR branched alkyl groups (preferably C 1-4 linear OR branched alkyl groups);
In formula (V), m is an integer between 0 and 10 (preferably an integer between 1 and 5);
The R 0 groups are each independently selected from C 1-10 linear or branched alkyl, -R 6G5, H (preferably each independently selected from C 1-4 linear or branched alkyl, -R 6G5, H);
The R 5 groups are each independently selected from C 1-20 linear or branched alkyl groups of valency 3 (preferably each independently selected from C 1-4 linear or branched alkyl groups of valency 3);
The group G 6 is selected from the group consisting of-R 6G5、C1-4 straight or branched alkyl, H;
The R 6 groups are selected from C 1-20 linear or branched alkylene groups (preferably each independently selected from C 1-4 linear or branched alkylene groups);
Each G 5 group is independently selected from-OG 1、C1-4 linear or branched alkyl, OH, H, wherein the G 1 group is selected from the group consisting of a binding end bonded to the boron element in the boron-containing group, C 1-4 linear or branched alkyl, H;
In the group represented by the formula (V), at least one G 1 group is selected from the binding end bonded to the boron element in the boron-containing group;
Of the b boron-containing groups, at least one a' group is present selected from the binding end to which the G 1 group present in the L group is bonded;
each group in the organoboron compound conforms to the bond formation rules.
According to the invention, the binding end of the two of formula (III) or (IV) bound to formula (II) may be bound to the group of formula (II) in any way, for example in one direction or in the opposite direction.
Examples of the organoboron compound which may be cited according to the present invention include one or more of the following structural compounds:
wherein the R group is a linear or branched alkyl group of C 2-C20.
According to the present invention, the method for preparing an organoboron compound comprises the steps of:
(1) Reacting a compound represented by formula (X) with a peroxide;
In formula (X), HO is bonded to the benzene ring (HO is preferably located in the meta position of the chain on the benzene ring where R 1 is located); y R groups are bonded to the benzene ring; y is selected from integers between 0 and 4 (preferably integers between 1 and 3); the R groups are each independently selected from H and C 1-20 linear or branched alkyl (preferably each independently selected from H and C 1-4 linear or branched alkyl, more preferably selected from t-butyl); n is an integer between 1 and 10 (preferably an integer between 1 and 3); r 1 is each independently selected from a single bond and a C 1-20 linear or branched alkylene (preferably selected from a single bond and a C 1-4 linear or branched alkylene); r 2 in the n repeating units, equal to or different from each other, are each independently selected from a single bond and a C 1-20 linear or branched alkylene group (preferably each independently selected from a single bond and a C 1-4 linear or branched alkylene group); r 3 is selected from H and C 1-20 linear or branched alkyl (preferably from H and C 1-4 linear or branched alkyl); a' in n repeating units, which are identical or different from each other, are each independently selected from the group consisting of single bonds, Wherein each of said R 4 groups is independently selected from H and C 1-20 straight or branched alkyl (preferably from H and C 1-4 straight or branched alkyl); in the formula (X), at least one A' is
(2) Reacting the reaction product of step (1) with a compound represented by formula (Y);
In formula (Y), m is an integer between 0 and 10 (preferably an integer between 1 and 5); the R 0' groups are each independently selected from C 1-10 straight or branched alkyl, -R 6 OH, H (preferably each independently selected from C 1-4 straight or branched alkyl, -R 6 OH, H); the R 5 groups are each independently selected from C 1-20 linear or branched alkyl groups of valency 3 (preferably each independently selected from C 1-4 linear or branched alkyl groups of valency 3); each G 5' group is independently selected from C 1-4 straight or branched alkyl, OH, H; the G 6' group is selected from C 1-10 straight-chain or branched-chain alkyl, -R 6 OH and H; the R 6 groups are each independently selected from C 1-20 linear or branched alkylene (preferably each independently selected from C 1-4 linear or branched alkylene);
In formula (Y), at least one G 5 ' group is selected from OH or at least one G 6 ' group or R 0 ' group is selected from-R 6 OH, and at least one R 0 ' group or G 6 ' group is H;
(3) Reacting the reaction product of step (2) with an inorganic boron compound, and collecting the product.
According to the present invention, in step (1), the compound represented by formula (X) may be selected from cardanol, alkylated cardanol, which may be obtained by reacting cardanol with an alkylating agent, for example, tert-butylated cardanol may be obtained by reacting cardanol with tert-butylchloride.
According to the present invention, in the step (1), the peroxide is preferably one or more of hydrogen peroxide, peroxyformic acid, peroxyacetic acid, peroxysulfonic acid, m-chloroperoxybenzoic acid, t-butyl hydroperoxide, t-butyl peroxyacetate, methyl ethyl ketone peroxide, dibenzoyl peroxide and cyclohexanone peroxide, more preferably one or more of hydrogen peroxide, peroxyformic acid, peroxyacetic acid and peroxysulfonic acid.
According to the present invention, in the step (2), the compound represented by the formula (Y) may be selected from one or more of aliphatic amine, polyene polyamine, one or more hydroxyl-substituted aliphatic amine, one or more hydroxyl-substituted polyene polyamine, and for example, one or more of ethanolamine, diethanolamine, hydroxyethyl ethylenediamine (i.e., N- (2-hydroxyethyl) ethylenediamine), diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine may be selected.
According to the invention, in step (3), the inorganic boron compound is preferably selected from one or more of boric acid, boric oxide and boric acid half-ester, wherein the boric acid half-ester can be selected from monoalkyl borate and dialkyl borate, and the alkyl is C 2-C20 straight-chain or branched-chain alkyl.
According to the present invention, the equivalent ratio between the compound represented by the formula (X) and the peroxide, the compound represented by the formula (Y), the inorganic boron compound is preferably 1:0.5 to 10:0.5 to 10:0.5 to 5, more preferably 1: 2-3: 2-3: 1 to 2.
According to the present invention, the reaction temperature in step (1) is preferably 0 to 100 ℃, more preferably 20 to 80 ℃; the reaction temperature in the step (2) is preferably 50 to 150 ℃, more preferably 60 to 100 ℃; the reaction temperature in the step (3) is preferably 80 to 200℃and more preferably 110 to 150 ℃.
According to the present invention, the longer the reaction time of step (1), step (2) and step (3), the better, the reaction time of step (1) is preferably 1 to 10 hours, more preferably 3 to 5 hours; the reaction time in the step (2) is preferably 1 to 10 hours, more preferably 2 to 4 hours; the reaction time in the step (3) is preferably 1 to 10 hours, more preferably 3 to 5 hours.
According to the invention, the reaction steps (1), (2) or (3) may be carried out in the presence of a diluent and/or solvent, or may be carried out without a diluent and/or solvent.
According to the present invention, in the reaction of step (3), a compound represented by formula (Y) may be further added, the equivalent ratio between the compound represented by formula (Y) and the inorganic boron compound preferably being 1:0.5 to 5, more preferably 1:0.8 to 3.
According to the invention, the diluent can be one or more of API I, II, III, IV and V base oils, and common commercial products or marks comprise 150SN、200SN、350SN、500SN、650SN、150BS、HVI-100、HVI-150、HVI-200、HVI-350、HVI-400、HVI-500、HVI-150BS、PAO4、PAO6、PAO8、PAO10、 alkylbenzene, alkyl naphthalene and the like.
According to the present invention, the solvent may be selected from C 6-20 aromatic hydrocarbons (such as benzene, toluene, xylene and cumene), C 6-10 alkanes (such as n-hexane, cyclohexane and petroleum ether), solvent gasoline, and the like. These solvents may be used alone or in combination of two or more. The solvent may be distilled off after the reaction is completed, using a means well known to those skilled in the art, for example, under normal pressure or reduced pressure.
According to a particular embodiment of the present invention, the diluent and/or solvent may be added at any stage of the reaction step in an amount conventional in the art, without particular limitation.
According to the invention, it is evident that the reaction step is generally carried out under protection of an inert gas atmosphere. Examples of the inert gas include nitrogen and argon, but are not particularly limited.
According to the present invention, in step (3), an accelerator for promoting completion of the reaction may be added, and common accelerators include water, ethanol, propanol, butanol, ammonia water, etc. If accelerators are added, they can be distilled off after the end of the reaction, using means known to the person skilled in the art, for example under atmospheric or reduced pressure.
According to the present invention, by the aforementioned method for producing an organoboron compound, a single organoboron compound, a mixture of plural organoboron compounds, or a mixture of one or more of the organoboron compounds and the aforementioned diluent (if used) can be produced as a reaction product. These reaction products are all contemplated by the present invention and the differences in their form of presence do not affect the achievement of the effects of the present invention. Accordingly, these reaction products are collectively referred to herein without distinction as organoboron compounds. In view of this, according to the present invention, there is no absolute necessity of further purifying the reaction product, or further separating an organoboron compound of a specific structure from the reaction product. Of course, this purification or isolation is preferred for further enhancement of the intended effect of the invention, but is not required for the invention. The purification or separation method may be, for example, a method of purifying or separating the reaction product by column chromatography or preparative chromatography.
The organic boron compound has excellent oxidation resistance, wear resistance and antifriction performance.
According to the invention, the oiliness agent is preferably one or more of fatty amine derivatives, vulcanized animal and vegetable oils and organic molybdenum compounds, more preferably one or more of benzotriazole fatty amine salt derivatives, vulcanized vegetable oils and molybdenum thiocarbamate, for example, one or more of benzotriazole octadecylamine salt, vulcanized olefin cottonseed oil and dibutyl molybdenum dithiocarbamate can be selected, and common commercial products comprise T406, T405, T351 and the like.
According to the invention, the rust inhibitor is preferably one or more of sulfonate, naphthenate, imidazoline compound, carboxylate and carboxylic acid, more preferably one or more of petroleum sulfonate, naphthenate and alkenyl imidazoline alkenyl succinate, for example, one or more of barium petroleum sulfonate, calcium petroleum sulfonate, zinc naphthenate and heptadecenyl imidazoline alkenyl succinate can be selected, and common commercial products include T701, T702, T704, T703 and the like.
According to the invention, the additive preferably comprises a mixture of an organoboron compound, an oily agent and an anti-rust agent, wherein the mass ratio between the three is 1:0.01 to 1:0.1 to 10, more preferably 1:0.05 to 0.5:0.3 to 2.
According to the invention, the composite lithium-based thickener is preferably obtained by saponification of an acid with lithium hydroxide. The temperature of the saponification reaction is preferably 60 to 180 ℃, more preferably 70 to 160 ℃. The saponification reaction time is preferably 30 to 300 minutes, more preferably 50 to 240 minutes. The acid is preferably a mixed acid of fatty acid and auxiliary acid, the fatty acid is preferably selected from fatty acid of C 12～C20 and/or hydroxy fatty acid of C 12～C20, for example, one or more of lauric acid, myristic acid, palmitic acid, oleic acid, stearic acid and 12-hydroxy stearic acid, more preferably 12-hydroxy stearic acid and/or stearic acid; the auxiliary acid is preferably one or more selected from acetic acid, propionic acid, butyric acid, valeric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, terephthalic acid, phosphoric acid and boric acid, more preferably sebacic acid and/or azelaic acid. The molar ratio of the fatty acid to the auxiliary acid is preferably 2 to 0.1:2, more preferably 1.5 to 0.5:2. water is preferably added during the saponification reaction. The water can directly participate in the saponification reaction, or can participate in the saponification reaction after being mixed with the lithium hydroxide into a solution. Part of the lubricating base oil may be added during the saponification reaction. The composite lithium-based thickener may be a composite lithium-based thickener comprising a portion of a lubricating base oil.
According to the present invention, the lubricating base oil is preferably one or more of mineral oil, vegetable oil and synthetic oil. The mineral oil may be one or more of a paraffinic base oil, an intermediate base oil, and a naphthenic base oil; the vegetable oil can be one or more of castor oil, rapeseed oil, peanut oil and soybean oil; the synthetic oil may be one or more of poly alpha-olefin oil, ester oil, fluorine oil and silicone oil. The lubricating base oil is preferably a lubricating base oil having a kinematic viscosity of 5 to 60mm 2/s at 100 ℃, and most preferably a lubricating base oil having a kinematic viscosity of 10 to 30mm 2/s at 100 ℃.
According to the present invention, preferably, the additive accounts for 1% -10% of the complex lithium-based grease; the composite lithium-based thickener accounts for 4% -30% of the composite lithium-based lubricating grease; the lubricating base oil accounts for 65% -95% of the composite lithium-based lubricating grease; more preferably, the additive accounts for 2% -8% of the complex lithium-based grease; the composite lithium-based thickener accounts for 8% -20% of the composite lithium-based lubricating grease; the lubricating base oil accounts for 75% -90% of the composite lithium-based lubricating grease.
The preparation method of the lubricating grease provided by the invention comprises the following steps: the composite lithium-based thickener and part of lubricating base oil are subjected to high-temperature refining at 190-220 ℃, cooled, added with the additive and the rest of lubricating base oil, and ground into grease. The refining time is preferably 1 to 25 minutes.
The composite lithium-based lubricating grease provided by the invention has excellent oxidation resistance and wear resistance, good colloid stability and excellent mechanical stability, can be used for severe working conditions such as high temperature, high speed, high load, much water and the like, and can be used for a long time at a high temperature of 150 ℃.
Detailed Description
In this specification, the term "single bond" is sometimes used in the definition of a group. By "single bond" is meant that the group is absent. For example, assume the structural formula-CH 2-A-CH3, wherein the group a is defined as selected from single bonds and methyl. In view of this, if A is a single bond, this means that the group A is absent, in which case the formula is correspondingly reduced to-CH 2-CH3.
In the context of the present specification, the expression "number +valence +group" or the like means a group obtained by removing the number of hydrogen atoms represented by the number from a basic structure (such as a chain, a ring, or a combination thereof, etc.) to which the group corresponds, preferably a group obtained by removing the number of hydrogen atoms represented by the number from carbon atoms (preferably saturated carbon atoms and/or non-identical carbon atoms) contained in the structure. For example, "3-valent linear or branched alkyl group" refers to a group obtained by removing 3 hydrogen atoms from a linear or branched alkane (i.e., the basic chain to which the linear or branched alkyl group corresponds).
The invention is further illustrated by the following examples, which are not to be construed as limiting the invention.
The main raw materials used are as follows:
Cardanol, shanghai Material competition technology Co., ltd, industrial products
Zinc chloride, national medicine group chemical reagent Co., ltd., analytical grade
Concentrated sulfuric acid, national pharmaceutical group chemical reagent Co., ltd., analytical grade
Hydrogen peroxide (30%), national medicine group chemical reagent Co., ltd., analytical grade
Formic acid, national medicine group chemical reagent Co., ltd., analytical grade
Boric acid, national pharmaceutical group chemical reagent Co., ltd., chemical purity
Diethanolamine, national medicine group chemical reagent Co., ltd., chemical purity
Diethylenetriamine, national medicine group chemical reagent Co., ltd., chemical purity
Ethanolamine, a chemical reagent of national medicine group Co., ltd., chemical purity
N- (2-hydroxyethyl) ethylenediamine, national medicine group chemical reagent Co., ltd., chemical purity
Tert-butyl chloride, national medicine group chemical reagent Co., ltd., analytically pure
T406, octadecylamine benzotriazole salt, hui Huadan oil additive Co., ltd., industrial products
T704, zinc naphthenate, suzhou special oil product factory, industrial product
EXAMPLE 1 preparation of tert-butylated epoxy Cardanol
100 G of cardanol, 8 g of formic acid, 0.3 g of sulfuric acid and 200 g of hydrogen peroxide are taken and added into a three-neck flask with a mechanical stirring and reflux condenser and temperature control, and stirring and heating are started. The reaction temperature was maintained at 70℃and the reaction was carried out for 3 hours. And cooling after the reaction is finished to obtain brownish red transparent liquid. Filtering the reaction product, performing alkali washing with 5% KOH solution, washing with distilled water to neutrality, and distilling the organic phase under reduced pressure at 100Pa and 150 ℃ for 1h to remove water and unreacted raw materials to obtain the orange-red transparent liquid epoxidized cardanol.
35 G of epoxidized cardanol is dissolved in 100ml of acetone, the dissolved cardanol is put into a 250ml three-neck reaction flask, 0.9g of zinc chloride catalyst is added, and stirring and heating are started. The reaction temperature was maintained at 60℃and 9.5 g of t-butyl chloride was slowly added dropwise to the reaction flask, followed by further reaction for 3 hours after completion of the dropwise addition. And cooling after the reaction is finished to obtain brownish red transparent liquid. Filtering the reaction product, performing alkali washing with 5% KOH solution, washing with distilled water to neutrality, and performing reduced pressure distillation at 1000Pa and 120 ℃ for 1h to remove solvent, water and unreacted raw materials to obtain brownish red viscous liquid tert-butyl epoxy cardanol.
An example reaction scheme of the above reaction is shown below.
Example 2
22G of the tert-butylated hydroxycardanol prepared in example 1, 5g of N- (2-hydroxyethyl) ethylenediamine and 90g of toluene were charged into a 250mL three-necked flask, and the mixture was heated with stirring to react at 90℃for 3 hours. After the reaction, the solvent and unreacted raw materials are removed by reduced pressure distillation for 1h to obtain dark brown red viscous liquid tert-butyl amino cardanol, then 3 g of boric acid, 10 g of N- (2-hydroxyethyl) ethylenediamine and 90g of cyclohexane are added into a reaction vessel, stirring, heating, dehydrating, reacting for 3h at 120 ℃, and finally filtering, evaporating the solvent and unreacted N- (2-hydroxyethyl) ethylenediamine to obtain an organoboron compound W-01.
An exemplary reaction scheme is shown below, wherein R is H.
The product prepared in example 2 was subjected to infrared spectroscopic analysis, and the analysis results are shown in table 1.
TABLE 1 Infrared analysis results of the products
The characteristic peaks such as C-OH stretching vibration peak, C-NH stretching vibration peak, benzene ring skeleton stretching vibration peak, N-C stretching vibration peak, O-C stretching vibration peak and B-O stretching vibration peak are shown in Table 1, and the synthesized product can be indicated as the target compound.
Example 3
36 G of the tert-butylated hydroxycardanol prepared in example 1, 10 g of diethanolamine and 90 g of toluene were charged into a 250mL three-necked flask, heated with stirring and reacted at 100℃for 4 hours. After the reaction is finished, the solvent and unreacted raw materials are removed through reduced pressure distillation for 1h, dark brown red viscous liquid tertiary butyl amino cardanol is obtained, then 6 g boric acid, 20g diethanolamine and 90 g cyclohexane are added into a reaction vessel, stirring and heating are carried out, water is removed, the reaction is carried out for 4h at 150 ℃, and finally the solvent and unreacted diethanolamine are filtered and distilled off, thus obtaining the organoboron compound W-02.
Example 4
21.5G of the tert-butylated hydroxycardanol prepared in example 1, 6g of diethylenetriamine and 90g of toluene were charged into a 250mL three-necked flask and heated with stirring to react at 95℃for 2 hours. After the reaction, distilling under reduced pressure for 1h, removing the solvent and unreacted raw materials to obtain dark brown red viscous liquid tert-butyl amino cardanol, adding 6g boric acid, 8g cetyl alcohol, 10.5g diethylenetriamine and 90g cyclohexane into a reaction vessel, stirring, heating, removing water, reacting at 145 ℃ for 5h, and finally filtering, evaporating to remove the solvent and unreacted diethylenetriamine to prepare the organoboron compound W-03.
Example I-1
The raw material components are as follows: PAO4 1037 g (viscosity at 100 ℃ C. 3.9mm 2/s); 23.96 grams of lithium hydroxide monohydrate; 88.65 g of 12-hydroxystearic acid; azelaic acid 28.04 g; 6.15 g of zinc naphthenate; 1.37 g of benzotriazole octadecylamine salt and 5.92 g of W-01 organoboron compound.
Adding 411 g of PAO4 base oil, 88.65 g of 12-hydroxystearic acid and 28.04 g of azelaic acid into a lipid preparation kettle, uniformly stirring, heating to 80 ℃, adding lithium hydroxide aqueous solution (containing 24.67 g of lithium hydroxide monohydrate and 200 g of water) for saponification reaction for 120min, continuously heating to 120 ℃ for dehydration reaction, adding 227 g of PAO4 base oil after dehydration, and heating to 200 ℃ for high-temperature refining for 5min; 399 g of PAO4 base oil was added, the temperature was lowered to 100℃and 6.15 g of zinc naphthenate, 1.37 g of octadecylamine benzotriazole salt and 5.92 g of W-01 organoboron compound were added, and the mixture was stirred uniformly and ground into a grease by a three-roll mill.
Example I-2
The raw material components are as follows: 500SN 938 g (viscosity at 100 ℃ C. 11mm 2/s); 36.11 g of lithium hydroxide monohydrate; 134.21 g of 12-hydroxystearic acid; 40.05 g of sebacic acid; 5.91 g of zinc naphthenate; 1.17 g of benzotriazole octadecylamine salt and 11.17 g of W-02 organoboron compound.
Firstly, 472 g of 500SN base oil, 134.21 g of 12-hydroxystearic acid and 40.05 g of sebacic acid are added into a fat preparation kettle, uniformly stirred, heated to 80 ℃, added with lithium hydroxide aqueous solution (containing 36.11 g of lithium hydroxide monohydrate and 204 g of water) for saponification reaction for 120min, continuously heated to 150 ℃ for dehydration reaction, added with 174 g of 500SN base oil after dehydration, heated to 210 ℃ for high-temperature refining for 5min; 292 g of 500SN base oil is added, the temperature is reduced to 110 ℃, 5.91 g of zinc naphthenate, 1.17 g of benzotriazole octadecylamine salt and 11.17 g of organoboron compound W-02 are added, the mixture is stirred uniformly, and the mixture is ground into grease by a three-roll machine.
Example I-3
The raw material components are as follows: PAO10 g (viscosity 10mm 2/s at 100 ℃); 14.77 grams of lithium hydroxide monohydrate; 56 grams of 12-hydroxystearic acid; 17.4 g of azelaic acid; 4.22 g of zinc naphthenate; 0.98 g of benzotriazole octadecylamine salt; 4.22 g of W-03 organoboron compound.
Adding 352 g of PAO10 base oil, 56 g of 12-hydroxystearic acid and 17.4 g of azelaic acid into a lipid preparation kettle, uniformly stirring, heating to 80 ℃, adding lithium hydroxide aqueous solution (containing 14.77 g of lithium hydroxide monohydrate and 126 g of water) for saponification reaction for 150min, continuously heating to 150 ℃ for dehydration reaction, adding 204 g of PAO10 base oil after dehydration, and heating to 190 ℃ for high-temperature refining for 5min; 159 g of PAO10 base oil is added, the temperature is reduced to 120 ℃, 4.22 g of zinc naphthenate, 0.98 g of benzotriazole octadecylamine salt and 4.22 g of organic boron compound W-03 are added, the mixture is stirred uniformly, and the mixture is ground into grease by a three-roller machine.
Example I-4
The raw material components are as follows: 500SN 794 grams (viscosity 11mm 2/s at 100 ℃); 21.25 grams of lithium hydroxide monohydrate; 78.39 g of 12-hydroxystearic acid; 24.99 g of sebacic acid; 4.64 grams of zinc naphthenate; 0.93 g of benzotriazole octadecylamine salt; 9.76 g of W-03 organoboron compound.
Firstly, adding 340 g of 500SN base oil, 78.39 g of 12-hydroxystearic acid and 24.99 g of sebacic acid into a fat preparation kettle, uniformly stirring, heating to 80 ℃, adding lithium hydroxide aqueous solution (containing 21.25 g of lithium hydroxide monohydrate and 165 g of water) for saponification reaction for 120min, continuously heating to 120 ℃ for dehydration reaction, adding 198 g of 500SN base oil after dehydration, heating to 200 ℃ for high-temperature refining for 5min; 256 g of 500SN base oil is added, the temperature is reduced to 100 ℃, 4.64 g of zinc naphthenate, 0.93 g of benzotriazole octadecylamine salt and 9.76 g of organoboron compound W-03 are added, the mixture is stirred uniformly, and the mixture is ground into grease by a three-roller machine.
Example I-5
The raw material components are as follows: PAO6 811 g (viscosity at 100 ℃ C. Of 5.8mm 2/s); 14.92 g of lithium hydroxide monohydrate; 57 grams of dodecahydroxystearic acid; 19 grams of azelaic acid; 4.55 g of zinc naphthenate; 0.90 g of benzotriazole octadecylamine salt; 4.48 g of W-03 organoboron compound.
Firstly adding 414 g of PAO6 base oil, 57 g of 12-hydroxystearic acid and 19 g of azelaic acid into a fat preparation kettle, uniformly stirring, heating to 80 ℃, adding lithium hydroxide aqueous solution (containing 14.92 g of lithium hydroxide monohydrate and 120 g of water) for saponification reaction for 120min, continuously heating to 150 ℃ for dehydration reaction, adding 163 g of PAO6 base oil after dehydration, and heating to 200 ℃ for high-temperature refining for 5min; 234 g of PAO6 base oil is added, the temperature is reduced to 100 ℃, 4.55 g of zinc naphthenate, 0.90 g of benzotriazole octadecylamine salt and 4.48 g of organoboron compound W-03 are added, the mixture is stirred uniformly, and the mixture is ground into grease by a three-roll machine.
Comparative example D-1
The raw material components are as follows: 500SN 791 g (viscosity at 100 ℃ C. 11mm 2/s); 21.34 grams of lithium hydroxide monohydrate; 78.51 g of 12-hydroxystearic acid; 25.10 g of sebacic acid; 4.58 grams of zinc naphthenate; 0.91 g of benzotriazole octadecylamine salt.
Adding 342 g of 500SN base oil, 78.51 g of 12-hydroxystearic acid and 25.10 g of sebacic acid into a fat preparation kettle, uniformly stirring, heating to 80 ℃, adding lithium hydroxide aqueous solution (containing 21.34 g of lithium hydroxide monohydrate and 170 g of water) for saponification reaction for 120min, continuously heating to 120 ℃ for dehydration reaction, adding 190 g of 500SN base oil after dehydration, and heating to 200 ℃ for high-temperature refining for 5min; 259 g of 500SN base oil is added, the temperature is reduced to 100 ℃, 4.58 g of zinc naphthenate and 0.91 g of benzotriazole octadecylamine salt are added, the mixture is stirred uniformly, and the mixture is ground into grease by a three-roller machine.
The properties of the grease obtained were evaluated, and the evaluation items, evaluation methods and evaluation results are shown in Table 2.
Table 2 grease performance assessment
Claims (11)
1. A complex lithium-based grease comprising a complex lithium-based thickener, an additive, and a major amount of a lubricating base oil, wherein the additive comprises a mixture of an organoboron compound, an oleaginous agent, and a rust inhibitor, the organoboron compound comprising one or more of the following structural compounds:
wherein the R group is a linear or branched alkyl group of C 2-C20.
2. Grease according to claim 1, characterized in that the preparation process of the organoboron compound comprises the following steps:
(1) Enabling cardanol to have an epoxidation reaction with peroxide and then have an alkylation reaction with tertiary butyl chloride;
(2) Reacting the reaction product of step (1) with a compound represented by formula (Y); the compound shown in the formula (Y) is selected from N- (2-hydroxyethyl) ethylenediamine, diethanolamine and diethylenetriamine;
(3) Reacting the reaction product of step (2) with an inorganic boron compound, and collecting the product.
3. A grease according to claim 2, wherein,
In step (1), the peroxide is selected from one or more of hydrogen peroxide, peroxyformic acid, peroxyacetic acid, peroxysulfonic acid, m-chloroperoxybenzoic acid, tert-butyl hydroperoxide, tert-butyl peroxyacetate, methyl ethyl ketone peroxide, dibenzoyl peroxide and cyclohexanone peroxide;
And/or, in the step (3), the inorganic boron compound is selected from one or more of boric acid and boron oxide.
4. Grease according to claim 2, wherein the equivalent ratio between cardanol and peroxide, compound of formula (Y), inorganic boron compound is 1:0.5 to 10:0.5 to 10:0.5 to 5.
5. Grease according to claim 2, wherein the equivalent ratio between cardanol and peroxide, compound of formula (Y), inorganic boron compound is 1: 2-3: 2-3: 1 to 2.
6. The grease of claim 2, wherein the reaction temperature of step (2) is 50 to 150 ℃; the reaction temperature of the step (3) is 80-200 ℃.
7. The grease of claim 2, wherein the reaction temperature of step (2) is 60 to 100 ℃; the reaction temperature of the step (3) is 110-150 ℃.
8. Grease according to any one of claims 1 to 7, wherein the oily agent comprises one or more of fatty amine derivatives, sulphurised animal and vegetable oils and organo-molybdenum compounds; the antirust agent comprises one or more of sulfonate, naphthenate, imidazoline compounds, carboxylate and carboxylic acid; the composite lithium-based thickener is obtained by saponification reaction of acid and lithium hydroxide, wherein the acid is selected from mixed acid of fatty acid and auxiliary acid, the fatty acid is selected from fatty acid of C 12～C20 and/or hydroxy fatty acid of C 12～C20, and the auxiliary acid is selected from one or more of acetic acid, propionic acid, butyric acid, valeric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, terephthalic acid, phosphoric acid and boric acid; the lubricating base oil is selected from one or more of mineral oil, vegetable oil and synthetic oil.
9. Grease according to any of claims 1 to 7, wherein the additive comprises a mixture of an organoboron compound, an oily agent and a rust inhibitor, wherein the mass ratio between the three is 1:0.01 to 1:0.1 to 10.
10. Grease according to any one of claims 1 to 7, wherein the additive comprises 1% to 10% of the complex lithium-based grease; the composite lithium-based thickener accounts for 4% -30% of the composite lithium-based lubricating grease; the lubricating base oil accounts for 65% -95% of the composite lithium-based lubricating grease.
11. A method of preparing the grease of any one of claims 1 to 10, comprising: and (3) refining the composite lithium-based thickener and part of lubricating base oil at a high temperature of 190-220 ℃, cooling, adding the additive and the rest of lubricating base oil, and grinding into grease.
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