CN105586134B - Excellent calcium base grease composition of a kind of Wear vesistance and preparation method thereof - Google Patents

Abstract

The invention discloses a calcium-based lubricating grease composition with excellent wear-reducing performance. Based on the weight of the lubricating grease composition, the lubricating grease composition includes the following components: 65-95% by weight of lubricating base oil, 5 -35% by weight of calcium-based thickener and 0.1-15% by weight of additives, the additives contain compounds of the structure shown in formula (I). The invention also provides a preparation method of the calcium-based lubricating grease composition with excellent wear-reducing performance. The calcium-based lubricating grease composition of the present invention greatly improves the anti-friction ability and anti-oxidation ability of the lubricating grease due to containing multi-effect additives, and at the same time has little effect on other properties of the calcium-based lubricating grease, and still has excellent resistance High temperature performance, colloidal stability and bearing capacity make the grease composition suitable for harsh working conditions such as high temperature, high speed, high load and excess water.

Description

Calcium-based lubricating grease composition with excellent wear-reducing performance and preparation method thereof

technical field

The invention relates to the field of lubricating grease, in particular to a calcium-based lubricating grease composition containing a specific additive with excellent wear-reducing performance and a preparation method thereof.

Background technique

my country began to produce calcium-based lubricating grease in the 1940s. Because of its simple production process and equipment, easy access to raw materials, and low product cost, it is very popular among producers and users. Calcium-based grease has good water resistance, is not easy to emulsify, has good adhesion to metal surfaces, and has good colloidal stability. It does not separate oil during storage, but because it contains a certain amount of structural water, when used When the temperature exceeds 100°C, the water is easy to evaporate and lose, causing the structure of the calcium-based grease to be destroyed and the lubricating effect to be lost. Therefore, the calcium-based grease is generally only used on friction parts where the working temperature does not exceed 60°C.

Complex calcium-based grease is the earliest complex soap-based grease developed. It is a lubricating grease made of complex calcium soap thickened with medium-viscosity mineral lubricating oil or synthetic lubricating oil made of fatty acid calcium soap and low molecular acid calcium salt. Grease products have high temperature resistance, and the consistency changes little at high temperatures; at the same time, they have good water resistance, mechanical stability, colloidal stability and good extreme pressure properties, and they have a wide range of operating temperatures. High quality grease for a wide range of uses. However, due to the hardening problem of calcium complex grease during storage and use, its popularization and application are greatly limited.

In recent years, in order to improve the performance of complex calcium-based grease, there are improvements in formula and manufacturing process, such as CN1888036 and CN101935573A; some have adjusted the selection and proportion of small molecule acids and long-chain organic acids, and selected Some small molecular acids (boric acid) and other auxiliary substances (titanium dioxide) improve the hardening problem of complex calcium-based grease, but the production time is too long and the degree of hardening improvement is limited; there are also polyurea greases to improve its performance , such as CN1493673, US5084193 and US4902435, the complex calcium-based grease is mixed with polyurea-based grease, but the production raw materials and process are more complicated.

Anhydrous calcium-based grease does not contain water, the dropping point is higher than 140°C, the maximum operating temperature is 50°C higher than ordinary calcium-based grease, and can reach 120°C in a short period of time; water resistance and mechanical stability are better than mixed calcium-based grease ;Compared with complex calcium-based grease, anhydrous calcium-based grease has no storage hardening and heat hardening problems, and the production process is relatively simple, and the manufacturing cost is lower than complex calcium-based grease. Anhydrous calcium-based grease has excellent performance, good oxidation stability, water resistance, colloidal stability, wear resistance, low temperature fluidity, rust resistance and mechanical stability.

In recent years, with the development of modern industry, industrial departments such as bearings, automobiles, printing and dyeing, mining, metallurgy, and aerospace have put forward more and more stringent requirements for the quality of lubricating grease. Many lubricating parts are filled with grease once. It is no longer supplemented or replaced in the grease, so the requirements for the anti-wear performance of the grease are relatively high.

Contents of the invention

The object of the present invention is to provide a calcium-based lubricating grease composition with excellent anti-friction performance and a preparation method thereof in order to meet the high requirement on the anti-wear performance of the grease.

The inventor of the present invention finds in research, the additive in the grease composition contains the multi-effect additive of structure shown in formula (I):

The lubricating grease composition can have excellent properties such as anti-friction and anti-oxidation.

Therefore, in order to achieve the above object, on the one hand, the present invention provides a calcium-based grease composition with excellent anti-friction properties, based on the weight of the grease composition, the grease composition includes the following components: 65 -95% by weight of lubricating base oil, 5-35% by weight of calcium-based thickener and 0.1-15% by weight of additives, the additives contain compounds of the structure shown in formula (I):

Preferably, based on the weight of the grease composition, the grease composition includes the following components: 70-90% by weight of lubricating base oil, 8-30% by weight of calcium-based thickener and 0.5-10% by weight % additives.

Preferably, based on the weight of the grease composition, the content of the compound represented by formula (I) is 0.1-10% by weight, more preferably 1-5% by weight.

In another aspect, the present invention provides a method for preparing a calcium-based grease composition with excellent anti-friction performance, the method comprising:

(1) Mix and heat part of lubricating base oil, higher fatty acid, optional middle molecular acid and small molecular acid, calcium hydroxide, and carry out saponification reaction;

(2) heat up and refine;

(3) Add the remaining lubricating base oil, cool to 100-130°C, and then add additives;

(4) Grinding 2-4 times by a three-roll machine;

Wherein, based on the weight of the grease composition, the amount of lubricating base oil is 65-95% by weight; Consumption is 5-35% by weight, and the consumption of additive is 0.1-15% by weight, and described additive contains the compound of structure shown in formula (I):

Preferably, based on the weight of the grease composition, the amount of lubricating base oil is 70-90% by weight, and the calcium-based thickener prepared from higher fatty acids, optional medium-molecular acid and small-molecular acid, and calcium hydroxide The dosage of the additive is 8-30% by weight, and the dosage of the additive is 0.5-10% by weight.

Preferably, based on the weight of the grease composition, the amount of the compound represented by formula (I) is 0.1-10% by weight, more preferably 1-5% by weight.

The calcium-based lubricating grease composition of the present invention greatly improves the anti-friction ability and anti-oxidation ability of the lubricating grease due to containing multi-effect additives, and at the same time has little effect on other properties of the calcium-based lubricating grease, and still has excellent resistance High temperature performance, colloidal stability and bearing capacity make the grease composition suitable for harsh working conditions such as high temperature, high speed, high load and excess water.

Other features and advantages of the present invention will be described in detail in the detailed description that follows.

Description of drawings

Fig. 1 is the reaction equation of the step (a) of preparing multi-effect additive.

Fig. 2 is the reaction equation of the step (b) of preparing multi-effect additive.

Fig. 3 is the hydrogen spectrogram of the multi-effect additive prepared by the preparation example.

Fig. 4 is the carbon spectrogram of the multi-effect additive prepared by the preparation example.

Fig. 5 is the mass spectrogram of the multi-effect additive prepared in the preparation example.

Detailed ways

Specific embodiments of the present invention will be described in detail below. It should be understood that the specific embodiments described here are only used to illustrate and explain the present invention, and are not intended to limit the present invention.

The invention provides a calcium-based lubricating grease composition with excellent anti-friction performance. Based on the weight of the lubricating grease composition, the lubricating grease composition includes the following components: 65-95% by weight of lubricating base oil, 5-35% The calcium-based thickener of weight % and the additive of 0.1-15 weight %, additive contains the compound of structure shown in formula (I):

In the present invention, the multi-effect additive refers to the compound with the structure shown in formula (I).

In the present invention, preferably, based on the weight of the grease composition, the grease composition includes the following components: 70-90% by weight of lubricating base oil, 8-30% by weight of calcium-based thickener and 0.5-10% by weight of additives.

In the present invention, based on the weight of the grease composition, the content of the compound represented by formula (I) is preferably 0.1-10% by weight, more preferably 1-5% by weight.

The purpose of the present invention is to realize the purpose of the invention through the additive in the calcium-based grease composition containing the compound represented by formula (I), even if the calcium-based grease composition has excellent properties such as anti-wear and anti-oxidation. Therefore, there are no specific restrictions on the selection of each conventional component in the calcium-based grease.

In the present invention, the lubricating base oil may be a lubricating base oil conventionally used in the art, such as at least one of mineral oil, vegetable oil and synthetic oil. The 100°C kinematic viscosity of the lubricating base oil is preferably 4-60 mm ² /s, more preferably 5-32 mm ² /s. There is no special limitation on the specific types of mineral oil, vegetable oil and synthetic oil. Mineral oil, vegetable oil and synthetic oil commonly used in this field can be used. For example, mineral oil can be selected from paraffin base and naphthenic series, and vegetable oil can be castor oil , rapeseed oil, peanut oil, soybean oil, etc., and the synthetic oil can be at least one of polyalphaolefin oil (PAO), ester oil, fluorine oil, and silicone oil.

In the present invention, the calcium-based thickener can be a calcium-based thickener commonly used in the art, for example, it can be formed by the reaction of an acid and calcium hydroxide, and the acid includes higher fatty acids, optional middle-molecular acid and small-molecular acid.

In the present invention, "optionally" means that there may or may not be present. "Optional middle molecular acid and small molecular acid" means that both the middle molecular acid and the small molecular acid are optional components, which may include these two components, or may not include these two components, that is, The calcium-based thickener of the present invention can be produced by the reaction of higher fatty acid and calcium hydroxide, and can also be produced by the reaction of higher fatty acid, middle molecular acid and small molecular acid and calcium hydroxide.

Wherein, the higher fatty acid can be a C12-C25 fatty acid, preferably at least one of lauric acid, palmitic acid, stearic acid and 12-hydroxystearic acid, more preferably stearic acid and/or 12-hydroxystearic acid acid.

Among them, the middle molecular acid is preferably a C6-C10 carboxylic acid, more preferably at least one of octanoic acid, benzoic acid, terephthalic acid, azelaic acid and sebacic acid.

Among them, the small molecular acid is preferably acetic acid.

The calcium-based thickener mentioned above can be obtained by various methods conceivable by those skilled in the art.

In the present invention, since the multi-effect additive with the structure shown in formula (I) has better compatibility with other additives, therefore, according to the use requirements of lubricating grease, the additive of the present invention can also contain other antioxidants, extreme pressure at least one of an antiwear agent and an antirust agent.

In the present invention, there are no special requirements on the types and contents of other antioxidants, extreme pressure antiwear agents, and rust inhibitors, and conventional types and contents in the field can be used. For example, the antioxidant can be an aromatic amine antioxidant, preferably at least one of diphenylamine, phenyl-α-naphthylamine and diisooctyldiphenylamine, more preferably diisooctyldiphenylamine, anti-oxidant The content of the oxygen agent can account for 0.01-5% by weight of the total weight of the grease composition, preferably 0.1-2.5% by weight; the extreme pressure antiwear agent can be zinc dithiodialkylphosphate, dithiodialkyl carbamic acid Molybdenum, lead dithiodialkylcarbamate, molybdenum disulfide, polytetrafluoroethylene, antimony dibutyldithiocarbamate, tungsten disulfide, selenium disulfide, graphite fluoride, calcium carbonate, and zinc oxide At least one, the content of the extreme pressure antiwear agent can account for 0.5-12% by weight of the total weight of the grease composition, preferably 0.5-5% by weight; the antirust agent can be barium petroleum sulfonate, calcium petroleum sulfonate, benzene At least one of thiazole, benzotriazole, zinc naphthenate and alkenyl succinic acid, the content of the rust inhibitor can account for 0.01-4.5% by weight of the total weight of the grease composition, preferably 0.1-2 weight%.

Among the present invention, the preparation method of the compound of structure shown in formula (I) preferably comprises:

(a) react aniline, sulfur chloride and 4-chloroaniline to generate intermediate M shown in formula (II),

(b) carrying out nucleophilic substitution reaction between the intermediate M obtained in step (a) and dimercapto-1,3,4-thiadiazole under alkaline conditions to generate the multi-effect additive shown in formula (I),

In step (a) of the present invention, the specific mode of reacting aniline, sulfur chloride and 4-chloroaniline preferably includes:

(i) fully reacting aniline and sulfur chloride at -20-0°C in the first solvent under an inert atmosphere;

(ii) Add 4-chloroaniline into the reaction system of step (i), and react at 15-30° C. for 1-3 h.

In the present invention, the inert atmosphere can be a conventional inert atmosphere in the field, for example, it can be provided by nitrogen, argon and other gases.

In step (i) of the present invention, the first solvent is preferably at least one selected from dichloromethane, tetrahydrofuran, toluene, xylene and dioxane, more preferably dichloromethane and/or tetrahydrofuran, even more preferably dichloromethane.

In the step (i) of the present invention, fully carrying out the reaction means that the reaction is complete, that is, the reaction raw materials are completely reacted. The reaction can be monitored by methods commonly used in the art to confirm the completion of the reaction, for example, thin layer chromatography (TLC) or gas chromatography can be used for monitoring.

In step (ii) of the present invention, react at 15-30°C for 1-3h, preferably after step (i) is fully reacted, gradually raise the temperature of the reaction system to 15-30°C, and then add 4-chloroaniline for reaction 1-3h. In this preferred case, the reaction yield can be further improved.

In step (ii) of the present invention, 4-chloroaniline is preferably added in portions, for example, it may be added in 3-4 portions. In this preferred case, the reaction yield can be further improved. When adding in batches, the amount added each time can be the same or different. For the convenience of operation, the amount added each time is preferably the same.

In step (ii) of the present invention, react 1-3h, the mode of stopping reaction can be the various modes that those skilled in the art can think of, for example, can add quenching agent to quench, and quenching agent can be common in this field The quenching agent, for example, can be saturated saline.

In the present invention, the consumption of aniline, sulfur chloride and 4-chloroaniline is basically an equimolar amount, but aniline and sulfur chloride can be properly excessive. The molar ratio of aniline, sulfur chloride and 4-chloroaniline is preferably 0.9-1.5:0.9-1.5:0.8-1.2.

It should be understood by those skilled in the art that in step (a) of the present invention, in order to obtain a relatively pure intermediate M, it is also necessary to post-treat the system after the reaction. The post-processing method may include washing, drying, and removing For the solvent, for example, wash the quenched reaction system with distilled water and saturated brine, and then add a desiccant such as anhydrous calcium chloride or anhydrous calcium sulfate at 15-30° C. for 10-60 minutes. After removing the desiccant by filtration, the solvent was removed at 0.01-0.05 MPa, 40-60° C. to obtain intermediate M.

In step (a) of the present invention, the reaction equation that aniline, sulfur chloride and 4-chloroaniline react is as shown in Figure 1, and in Figure 1, what the first solvent adopts is methylene chloride, only for the purpose of illustration, It is not intended to limit the scope of the invention.

In the step (b) of the present invention, the conditions of the nucleophilic substitution reaction preferably include: under an inert atmosphere, in a second solvent, dimercapto-1,3,4-thiadiazole, an alkaline reagent and a catalyst in 15- Mix at 30°C for 10-30min, then add intermediate M, and fully react. That is, alkaline conditions are provided by alkaline reagents.

"Inert atmosphere" and "sufficient reaction" are as mentioned above, and will not be repeated here.

In the present invention, the intermediate M is preferably added slowly, for example, it can be added in portions, generally it can be added in 3-4 portions. In this preferred case, the reaction yield can be further improved. When adding in batches, the amount added each time can be the same or different. For the convenience of operation, the amount added each time is preferably the same.

In the present invention, the second solvent is preferably at least one selected from dichloromethane, tetrahydrofuran, toluene, xylene, N,N-dimethylformamide, more preferably dichloromethane and/or N,N-dimethylformamide Methylformamide is more preferably N,N-dimethylformamide.

In the present invention, the alkaline reagent is preferably at least one selected from inorganic bases such as potassium carbonate, calcium carbonate, and calcium methoxide.

In the present invention, the catalyst is preferably potassium sulfate.

In step (b) of the present invention, the amount of dimercapto-1,3,4-thiadiazole, basic reagent and intermediate M is basically an equimolar amount, but dimercapto-1,3,4-thiadiazole And alkaline reagents can be properly excess. The molar ratio of dimercapto-1,3,4-thiadiazole, basic reagent and intermediate M is preferably 0.9-3.0:0.9-5.0:0.8-1.5.

In the step (b) of the present invention, the amount of the catalyst can be a catalytic amount, based on the moles of dimercapto-1,3,4-thiadiazole, the amount of the catalyst is preferably 5-100 mole%, more preferably 10 -50 mol%.

In step (b) of the present invention, the reaction equation of dimercapto-1,3,4-thiadiazole and intermediate M is as shown in Figure 2. In Figure 2, the alkaline reagent used is potassium carbonate, which is only The purpose of illustration is not to limit the scope of the present invention.

Those skilled in the art should understand that, in order to obtain a relatively pure final product, that is, the multi-effect additive of the present invention, the method for preparing the multi-effect additive of the present invention preferably also includes post-processing the system after the reaction, and the mode of post-treatment can be Including washing, drying, and removing the solvent under reduced pressure, for example, the fully reacted system is poured into 1-10 times the volume of ethyl acetate (or methylene chloride), washed with distilled water and saturated brine, and then washed in 15- Add desiccant such as anhydrous calcium chloride or anhydrous calcium sulfate at 30°C and keep for 10-60min. After removing the desiccant by filtration, the solvent is removed at 0.01-0.05 MPa, 40-60° C. to obtain the final product.

Each step of the method for preparing the compound represented by formula (I) in the present invention is preferably carried out under stirring, there is no special requirement for the stirring speed, it can be a conventional stirring speed in the art, for example, the stirring speed can be 100-800rpm.

In the present invention, there is no special requirement on the amount of the first solvent and the second solvent, which can be conventional solvent amounts in the art, which are well known to those skilled in the art, and will not be repeated here.

As mentioned above, the purpose of the present invention is to realize the purpose of the invention by the additive in the calcium-based grease composition containing the compound of formula (I), even if the grease composition has excellent properties such as anti-friction and anti-oxidation. Therefore, there is no special requirement for the preparation method of calcium-based grease, and methods commonly used in the art can be used, for example, in the second aspect, the present invention also provides a preparation method of a calcium-based grease composition with excellent anti-friction properties , the method includes:

(1) Mix and heat part of lubricating base oil, higher fatty acid, optional middle molecular acid and small molecular acid, calcium hydroxide, and carry out saponification reaction;

(2) heat up and refine;

(3) Add the remaining lubricating base oil, cool to 100-130°C, and then add additives;

(4) Grinding 2-4 times by a three-roll machine;

Wherein, based on the weight of the grease composition, the amount of lubricating base oil is 65-95% by weight; Consumption is 5-35% by weight, and the consumption of additive is 0.1-15% by weight, and additive contains the compound of structure shown in formula (I):

In the method of the present invention, preferably, based on the weight of the grease composition, the amount of lubricating base oil is 70-90% by weight, prepared from higher fatty acids, optional middle molecular acid and small molecular acid, calcium hydroxide The dosage of the calcium-based thickener is 8-30% by weight, and the dosage of the additive is 0.5-10% by weight.

In the method of the present invention, the molar ratio of the total amount of higher fatty acid and optional middle molecular acid and small molecular acid to calcium hydroxide is preferably a stoichiometric ratio, and calcium hydroxide can also be in excess of 1-10% by weight. The molar ratio of optional middle molecular acid to higher fatty acid is preferably 1:0.37-3.4, and the molar ratio of the total amount of higher fatty acid and optional middle molecular acid to optional small molecular acid is preferably 1:0.9-4. It should be understood by those skilled in the art that, according to the amount of calcium-based thickener prepared by higher fatty acid, optional middle molecular acid and small molecular acid and calcium hydroxide, the higher fatty acid, middle molecular acid and small molecular acid can be deduced in reverse. The consumption of acid and calcium hydroxide is known to those skilled in the art, and will not be repeated here.

In the present invention, as mentioned above, "optional" means that there may or may not be present. "Optional middle molecular acid and small molecular acid" means that both the middle molecular acid and the small molecular acid are optional components, and these two components may or may not be included. "The molar ratio of the total amount of higher fatty acid and optional middle molecular acid and small molecular acid to calcium hydroxide is the stoichiometric ratio" means that when the middle molecular acid and small molecular acid are not contained, the ratio of higher fatty acid to calcium hydroxide The molar ratio is stoichiometric ratio, when containing middle molecular acid and small molecular acid, the molar ratio of higher fatty acid and middle molecular acid and small molecular acid total amount to calcium hydroxide is stoichiometric ratio. "The molar ratio of the optional middle molecular acid to the higher fatty acid is 1:0.37-3.4, and the molar ratio of the total amount of the higher fatty acid and the optional middle molecular acid to the optional small molecular acid is 1:0.9-4" that is It means that when middle molecular acid and small molecular acid are contained, the molar ratio of middle molecular acid to higher fatty acid is 1:0.37-3.4, and the molar ratio of the total amount of higher fatty acid and middle molecular acid to small molecular acid is 1:0.9- 4. In a word, those skilled in the art should understand that the calcium-based thickener of the present invention can be produced by the reaction of higher fatty acids and calcium hydroxide, and can also be produced by the reaction of higher fatty acids, middle molecular acids and small molecular acids and calcium hydroxide.

In the method of the present invention, based on the weight of the grease composition, the amount of the compound represented by formula (I) is preferably 0.1-10% by weight, more preferably 1-5% by weight.

Those skilled in the art should understand that, in the method of the present invention, the amount of the lubricating base oil is the sum of the amount of the part of the lubricating base oil and the amount of the remaining lubricating base oil. The weight ratio of part lubricating base oil to remaining lubricating base oil is preferably 50-75:25-50.

In step (1) of the method of the present invention, when there is no middle molecular acid and small molecular acid, step (1) preferably includes: mixing and heating part of the lubricating base oil and higher fatty acid, and raising the temperature to 80-105°C, more preferably 80- At 95°C, add calcium hydroxide to carry out saponification reaction, the saponification reaction time is 0.2-1.5h, more preferably 0.5-1h; when containing medium molecular acid and small molecular acid, step (1) preferably includes: partially lubricating base oil Mix with calcium hydroxide, at 15-50°C, add small molecular acid for the first saponification reaction, then raise the temperature to 80-100°C, add higher fatty acid for the second saponification reaction, then add middle molecular acid for the third saponification reaction , the time of the first saponification reaction, the second saponification reaction and the third saponification reaction is 10-60min, more preferably 20-40min.

In the step (2) of the method of the present invention, when the middle molecular acid and the small molecular acid are not contained, in the step (2), the temperature is preferably raised to 140-160°C for refining, and the refining time is preferably 5-15min; For medium molecular acid and small molecular acid, in step (2), the temperature is preferably raised to 180-220°C, more preferably 190-210°C for refining, and the refining time is preferably 5-15min.

Each step of the method of the present invention is preferably carried out under stirring, and there is no special requirement for the stirring speed, which can be a conventional stirring speed in the art, for example, the stirring speed can be 20-400rpm.

The lubricating base oil, higher fatty acid, medium molecular acid, small molecular acid, calcium hydroxide, and additives are as mentioned above, and will not be repeated here.

Example

The following examples will further illustrate the present invention, but do not limit the present invention thereby.

In the following examples and comparative examples:

The method for monitoring the complete reaction: thin-layer chromatography (TLC) fluorescence color method.

Total yield = molar amount of final product/molar amount of aniline × 100%

The physical and chemical analysis method of the product: the element content was determined by inductively coupled plasma ion emission spectrometry.

Structural characterization methods: nuclear magnetic resonance ( ¹ H hydrogen spectrum, ¹³ C carbon spectrum), high-resolution mass spectrometry.

Preparation example

Fill a 500ml flask with an electromagnetic stirrer (stirring speed is 300rpm) with nitrogen protection, add 150ml of dichloromethane, then add 0.2mol of sulfur chloride, fully cool in an ice-water bath, add 0.2mol of aniline . Remove the ice-water bath after monitoring until the reaction is complete, and place it at room temperature of 25°C. After the reaction system gradually rises to 25°C, add 4-chloroaniline in 3 times for reaction. The amount added each time is the same, and 4-chloroaniline is added in total 0.15mol. After continuing the reaction for 2 hours, 30ml of saturated brine was added to quench the reaction, and then the reaction system was transferred to a separatory funnel, washed with 50ml of distilled water and 50ml of saturated brine, and dried by adding 10g of anhydrous calcium sulfate at 25°C for 20min. The filtered filtrate was evaporated to remove the solvent at 40° C. and 0.05 MPa to obtain intermediate M1.

Fill a 500ml flask with an electromagnetic stirrer (stirring speed at 400rpm) with nitrogen protection, add 150ml of DMF (N,N-dimethylformamide), and then add 0.2mol dimercapto-1,3,4- Thiadiazole, 0.2 mol of potassium carbonate and 0.05 mol of potassium sulfate were stirred at 25°C for 20 minutes, and the above-mentioned intermediate M1 was added in 3 times with the same amount each time, and a total of 10.12 mol of intermediate M was added. Monitor until the reaction is complete, then add 250ml of ethyl acetate to the reaction system, and transfer to a separatory funnel, wash with 100ml of distilled water (twice) and 50ml of saturated brine, and add 15g of anhydrous calcium sulfate to dry at 25°C 20min. The filtered filtrate was evaporated to remove the solvent at 40° C. and 0.03 MPa to obtain the final product S1. The overall yield was calculated to be 76%.

The physical and chemical analysis data of the product are as follows: sulfur content, 41.3%; nitrogen content, 13.9%.

The structure of S1 was characterized, and the hydrogen spectrum, carbon spectrum and high-resolution mass spectrum were obtained respectively, as shown in Figure 3, Figure 4 and Figure 5, respectively.

It can be seen from the physical and chemical analysis data of the above preparation examples, Fig. 3, Fig. 4 and Fig. 5 that S1 has the structure shown in formula (I).

Example 1

This example is used to illustrate the calcium-based grease composition of the present invention and its preparation method.

(1) Add 54kg of 150BS base oil (viscosity of 30mm ² /s at 100°C, the same below) and 6kg of 12-hydroxystearic acid into the fat-making kettle, stir and heat at 180rpm, raise the temperature to 85°C, and add 0.76kg of hydrogen A mixture of calcium oxide and 4kg of water was subjected to saponification for 0.5h;

(2) heating up to 140°C, refining for 15 minutes;

(3) Add 18kg of 150BS base oil, stir and cool down to 120°C, add 1.6kg of S1, and stir evenly at 180rpm;

(4) Grinding through a three-roll machine twice to form fat. The product performance is shown in Table 1.

In the lubricating grease obtained in this embodiment, based on the weight of the lubricating grease, the composition is: 8% by weight of calcium 12-hydroxystearate; 90% by weight of lubricating base oil; and 12% by weight of S.

Example 2

This example is used to illustrate the calcium-based grease composition of the present invention and its preparation method.

(1) Add 25kg of 500SN base oil (viscosity of 10mm ² /s at 100°C, the same below) and 13.6kg of stearic acid into the fat-making kettle, stir and heat at 200rpm, raise the temperature to 80°C, and add 1.83kg of calcium hydroxide Mixture with 2kg of water, carry out saponification reaction for 1h;

(2) heating up to 145°C, refining for 8 minutes;

(3) Add 10kg of 500SN base oil, stir and cool down to 105°C, add 0.5kg of S1, and stir evenly at 200rpm;

(4) Grind 3 times by a three-roll machine to form fat. The product performance is shown in Table 1.

In the lubricating grease obtained in this embodiment, based on the weight of the lubricating grease, the composition is: calcium stearate 29% by weight; lubricating base oil 70% by weight; S11% by weight.

Example 3

This example is used to illustrate the calcium-based grease composition of the present invention and its preparation method.

(1) Add 22kg of PAO6 synthetic hydrocarbon oil (viscosity at 100°C to 5.8mm ² /s, the same below) and 10.9kg of stearic acid into the fat-making kettle, stir and heat at 300rpm, raise the temperature to 95°C, and add 1.5kg of hydrogen The mixture of calcium oxide and 4kg water is subjected to saponification reaction for 0.8h;

(2) Heating up to 160°C, refining for 5 minutes;

(3) Add 21.5kg PAO6 synthetic hydrocarbon oil, stir and cool down to 130°C, add 2.9kg S1, and stir evenly at 300rpm;

(4) Grinding through a three-roll machine 4 times to form fat. The product performance is shown in Table 1.

In the lubricating grease obtained in this embodiment, based on the weight of the lubricating grease, the composition is: 20% by weight of calcium stearate; 75% by weight of lubricating base oil; 15% by weight of S.

Example 4

This example is used to illustrate the calcium-based grease composition of the present invention and its preparation method.

(1) Add 40kg of 500SN and 150BS mixed oil (viscosity of 16mm ² /s at 100°C, the same below) and 11.3kg of 12-hydroxystearic acid into the fat-making kettle, stir and heat at 230rpm, and raise the temperature to 90°C. Add a mixture of 1.45kg calcium hydroxide and 2.8kg water to carry out saponification reaction for 0.6h;

(2) Heating up to 150°C and refining for 10 minutes;

(3) Add 25.6kg of mixed oil of 500SN and 150BS, stir and cool down to 100°C, add 2.4kg of S1, and stir evenly at 230rpm;

(4) Grinding through a three-roll machine twice to form fat. The product performance is shown in Table 1.

In the lubricating grease obtained in this embodiment, based on the weight of the lubricating grease, the composition is: 15% by weight of calcium 12-hydroxystearate; 82% by weight of lubricating base oil; and 13% by weight of S.

Comparative example 1

Calcium-based grease was prepared according to the method of Example 4, except that S1 was not added. The product performance is shown in Table 1.

In the lubricating grease obtained in this comparative example, based on the weight of the lubricating grease, the composition is: 15.5% by weight of calcium 12-hydroxystearate, and 84.5% by weight of lubricating base oil.

Example 5

This example is used to illustrate the calcium-based grease composition of the present invention and its preparation method.

(1) Add 64.1kg of 500SN base oil (viscosity of 10mm ² /s at 100°C, the same below) and a suspension containing 2kg of calcium hydroxide (the content of calcium hydroxide is 8% by weight) into the fat-making kettle, at 180rpm Stir and mix, add 1.6kg of acetic acid at 25°C, react for 20min, then raise the temperature to 80°C, add 2.3kg of 12-hydroxystearic acid, react for 30min, then add 2.7kg of octanoic acid, react for 40min;

(2) heating up to 190°C, refining for 15 minutes;

(3) Add 21.4kg of 500SN base oil, stir and cool down to 120°C, add 1.9kg of S1, and stir evenly at 180rpm;

(4) Grinding through a three-roll machine twice to form fat. The product performance is shown in Table 2.

In the lubricating grease obtained in the present embodiment, taking the lubricating grease weight as a benchmark, it consists of: 2.55% by weight of calcium 12-hydroxystearate; 3.25% by weight of calcium octanoate; 2.2% by weight of calcium acetate, and 90% by weight of lubricating base oil; S12 weight%.

Example 6

This example is used to illustrate the calcium-based grease composition of the present invention and its preparation method.

(1) Add 13kg of 150BS base oil (100°C viscosity of 30mm ² /s, the same below) and 3.9kg of calcium hydroxide-containing suspension (calcium hydroxide content is 10% by weight) into the fat-making kettle, at 200rpm Stir and mix, add 4.5kg of acetic acid at 15°C, react for 40min, then raise the temperature to 100°C, add 2.8kg of 12-hydroxystearic acid, react for 20min, then add 1.5kg of terephthalic acid, react for 30min;

(2) heating up to 210°C, refining for 5 minutes;

(3) Add 130kg of 150BS base oil, stir and cool down to 100°C, add 0.4kg of S1, and stir evenly at 200rpm;

(4) Grind 3 times by a three-roll machine to form fat. The product performance is shown in Table 2.

In the lubricating grease obtained in the present embodiment, taking the lubricating grease weight as a benchmark, it consists of: 7.95% by weight of calcium 12-hydroxystearate; 5.33% by weight of calcium terephthalate; 15.72% by weight of calcium acetate; 70% by weight of lubricating base oil %; S11 wt%.

Example 7

This example is used to illustrate the calcium-based grease composition of the present invention and its preparation method.

(1) 10kg PAO6 synthetic hydrocarbon oil (100 DEG C viscosity is 5.8mm ^/ s, the same below) and the suspension containing 1.1kg calcium hydroxide (calcium hydroxide content is 12% by weight) are added in the fat making kettle, Stir and mix at 300rpm, add 0.73kg of acetic acid at 35°C, react for 25min, then raise the temperature to 90°C, add 2.9kg of stearic acid, react for 40min, then add 0.6kg of sebacic acid, react for 20min;

(2) Heating up to 195°C and refining for 10 minutes;

(3) Add 8kg PAO6 synthetic hydrocarbon oil, stir and cool down to 110°C, add 1.2kg S1, and stir evenly at 300rpm;

(4) Grinding through a three-roll machine 4 times to form fat. The product performance is shown in Table 2.

In the lubricating grease obtained in the present embodiment, based on the weight of the lubricating grease, the composition is: 12.99% by weight of calcium stearate; 3.03% by weight of calcium sebacate; 3.98% by weight of calcium acetate; 75% by weight of lubricating base oil; %.

Example 8

This example is used to illustrate the calcium-based grease composition of the present invention and its preparation method.

(1) Add 37.8kg of 500SN and 150BS mixed oil (viscosity of 13mm ² /s at 100°C, the same below) and a suspension containing 2.9kg of calcium hydroxide (calcium hydroxide content is 16% by weight) into the fat-making kettle , stirred and mixed at 230rpm, added 3kg of acetic acid at 50°C, reacted for 30min, then raised the temperature to 95°C, added 4.75kg of stearic acid, reacted for 25min, then added 1.2kg of octanoic acid, reacted for 35min;

(2) heating up to 205°C, refining for 8 minutes;

(3) Add 19kg of 500SN and 150BS mixed oil, stir and cool down to 130°C, add 2.1kg of S1, and stir evenly at 230rpm;

(4) Grinding through a three-roll machine twice to form fat. The product performance is shown in Table 2.

In the lubricating grease that present embodiment obtains, take the lubricating grease weight as a benchmark, consist of: 7.32% by weight of calcium stearate; 1.97% by weight of calcium caprylate; 5.71% by weight of calcium acetate; 82% by weight of lubricating base oil; S13% by weight.

Comparative example 2

Calcium-based grease was prepared according to the method of Example 8, except that S1 was not added. The product performance is shown in Table 2.

In the lubricating grease obtained in this comparative example, based on the weight of the lubricating grease, the composition is: 7.55% by weight of calcium stearate; 2.03% by weight of calcium octanoate; 5.89% by weight of calcium acetate; and 84.53% by weight of lubricating base oil.

Table 1

Test methods for each index: dropping point: GB/T 3498; working penetration: GB/T 269; oxidation initiation temperature: ASTMD5483; steel mesh oil separation: SH/T 0324; copper sheet corrosion: GB/T 7326; Corrosion: GB/T 5018; Friction coefficient: SH/T0847.

Table 2

Test methods for various indicators: dropping point: GB/T 3498; working penetration: GB/T 269; surface hardening value: GB/T269; oxidation initiation temperature: ASTM D5483; steel mesh oil separation: SH/T 0324; four balls Machine test PB, PD: SH/T 0202; friction coefficient: SH/T 0847; copper sheet corrosion: GB/T 7326; corrosion resistance: GB/T 5018.

Those skilled in the art should understand that the higher the dropping point, the better the high temperature resistance of the grease; the smaller the working penetration, the better the thickening performance of the grease thickener; the smaller the surface hardening value, the better the grease The better the anti-hardening performance; the higher the oxidation initiation temperature, the better the anti-oxidation ability of the grease; the smaller the oil separation value of the steel mesh, the better the colloidal stability of the grease; The better the bearing capacity; the smaller the coefficient of friction, the better the antifriction performance of the grease.

Embodiment 4 is compared with comparative example 1, and embodiment 8 is compared with comparative example 2. It can be seen that the grease of the present invention has better high temperature resistance, oxidation resistance, colloidal stability, bearing capacity and Anti-friction properties.

The calcium-based lubricating grease composition of the present invention greatly improves the anti-friction ability and anti-oxidation ability of the lubricating grease due to containing multi-effect additives, and at the same time has little effect on other properties of the calcium-based lubricating grease, and still has excellent resistance High temperature performance, colloidal stability and bearing capacity make the grease composition suitable for harsh working conditions such as high temperature, high speed, high load and excess water.

The preferred embodiment of the present invention has been described in detail above in conjunction with the accompanying drawings, but the present invention is not limited to the specific details of the above embodiment, within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, These simple modifications all belong to the protection scope of the present invention.

In addition, it should be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable way if there is no contradiction. The combination method will not be described separately.

In addition, various combinations of different embodiments of the present invention can also be combined arbitrarily, as long as they do not violate the idea of the present invention, they should also be regarded as the disclosed content of the present invention.

Claims (25)

1. A calcium-based lubricating grease composition with excellent antifriction performance, based on the weight of the lubricating grease composition, the lubricating grease composition comprises the following components: 65-95% by weight of lubricating base oil, 5-35% % by weight calcium-based thickener and 0.1-15% by weight of additives, characterized in that the additives contain compounds of the formula (I): 2. The grease composition according to claim 1, wherein, based on the weight of the grease composition, the grease composition comprises the following components: 70-90% by weight of lubricating base oil, 8-30 Calcium-based thickener in weight percent and additives in 0.5-10 weight percent. 3. The grease composition according to claim 1 or 2, wherein, based on the weight of the grease composition, the content of the compound represented by formula (I) is 0.1-10% by weight. 4. The grease composition according to claim 3, wherein, based on the weight of the grease composition, the content of the compound represented by formula (I) is 1-5% by weight. 5. The grease composition according to claim 1 or 2, wherein the lubricating base oil is at least one of mineral oil, vegetable oil and synthetic oil. 6. The grease composition according to claim 1 or 2, wherein the calcium-based thickener is generated by the reaction of an acid with calcium hydroxide, and the acid comprises a higher fatty acid, optional middle molecular acid and small molecule acid. 7. The lubricating grease composition according to claim 6, wherein the higher fatty acid is a C12-C25 fatty acid; the middle molecular acid is a C6-C10 carboxylic acid; and the small molecular acid is acetic acid. 8. The grease composition according to claim 7, wherein the higher fatty acid is at least one of lauric acid, palmitic acid, stearic acid and 12-hydroxystearic acid, and the middle molecular acid is octanoic acid , at least one of benzoic acid, terephthalic acid, azelaic acid and sebacic acid. 9. The grease composition according to claim 1 or 2, wherein the additive further contains at least one of other antioxidants, extreme pressure antiwear agents and rust inhibitors. 10. The grease composition according to claim 9, wherein the antioxidant is an aromatic amine antioxidant. 11. The grease composition according to claim 10, wherein the antioxidant is at least one of diphenylamine, phenyl-α-naphthylamine and diisooctyldiphenylamine. 12. The grease composition according to claim 9, wherein the extreme pressure antiwear agent is zinc dithiodialkylphosphate, molybdenum dithiodialkylcarbamate, dithiodialkylamino At least one of lead formate, molybdenum disulfide, polytetrafluoroethylene, antimony dibutyldithiocarbamate, tungsten disulfide, selenium disulfide, graphite fluoride, calcium carbonate and zinc oxide. 13. The lubricating grease composition according to claim 9, wherein the rust inhibitor is barium petroleum sulfonate, sodium petroleum sulfonate, benzothiazole, benzotriazole, zinc naphthenate and alkenyl butyl at least one of the diacids. 14. The preparation method of the grease composition according to claim 1, said method comprising: (1) Mix and heat part of lubricating base oil, higher fatty acid, optional middle molecular acid and small molecular acid, calcium hydroxide, and carry out saponification reaction; (2) heat up and refine; (3) Add the remaining lubricating base oil, cool to 100-130°C, and then add additives; (4) Grinding 2-4 times by a three-roll machine. 15. The method according to claim 14, wherein, taking the weight of the grease composition as a basis, the consumption of lubricating base oil is 70-90% by weight, consisting of higher fatty acid, optional middle molecular acid and small molecular acid, The dosage of the calcium-based thickener prepared by calcium hydroxide is 8-30% by weight, and the dosage of the additive is 0.5-10% by weight. 16. The method according to claim 14 or 15, wherein, based on the weight of the grease composition, the amount of the compound represented by formula (I) is 0.1-10% by weight. 17. The method according to claim 16, wherein, based on the weight of the grease composition, the amount of the compound represented by formula (I) is 1-5% by weight. 18. The method according to claim 14 or 15, wherein the weight ratio of the part lubricating base oil to the remaining lubricating base oil is 50-75:25-50. 19. according to the method described in claim 14 or 15, wherein, the mol ratio of optional middle molecular acid and higher fatty acid is 1:0.37-3.4, the total amount of higher fatty acid and optional middle molecular acid and optional The molar ratio of the small molecule acid is 1:0.9-4. 20. The method of claim 14 or 15, wherein, When there is no middle molecular acid and small molecular acid, step (1) includes: mixing and heating part of the lubricating base oil and higher fatty acid, raising the temperature to 80-105°C, adding calcium hydroxide for saponification reaction, and the saponification reaction time is 0.2- 1.5h; When containing medium molecular acid and small molecular acid, step (1) includes: mixing part of the lubricating base oil and calcium hydroxide, at 15-50°C, adding small molecular acid to carry out the first saponification reaction, and then heating up to 80- 100°C, add higher fatty acid to carry out the second saponification reaction, then add middle molecular acid to carry out the third saponification reaction, the time of the first saponification reaction, the second saponification reaction and the third saponification reaction are all 10-60min. 21. The method according to claim 20, wherein, when no middle molecular acid and small molecular acid are contained, the step (1) comprises: mixing and heating part of the lubricating base oil and higher fatty acid, and raising the temperature to 80-95°C. 22. The method according to claim 20, wherein, when no middle molecular acid and small molecular acid are contained, step (1) comprises: adding calcium hydroxide to carry out saponification reaction, and the saponification reaction time is 0.5-1h. 23. The method according to claim 20, wherein, when containing middle molecular acid and small molecular acid, step (1) comprises: the time of the first saponification reaction, the second saponification reaction, the third saponification reaction is 20- 40min. 24. The method of claim 14 or 15, wherein, When no middle molecular acid and small molecular acid are contained, in step (2), the temperature is raised to 140-160°C for refining, and the refining time is 5-15min; When containing middle molecular acid and small molecular acid, in step (2), the temperature is raised to 180-220° C. for refining, and the refining time is 5-15 minutes. 25. The method of claim 24, wherein, When middle molecular acid and small molecular acid are contained, in step (2), the temperature is raised to 190-210° C. for refining, and the refining time is 5-15 minutes.