Lithium-based lubricating grease and preparation method thereof

Abstract

The invention provides lithium-based lubricating grease and a preparation method thereof. Based on the total weight of the lubricating grease, the lithium-based lubricating grease comprises 0.1-5% of a tetraphenyl ethylene derivative, 0.1-5% of an oxidation and corrosion inhibitor, 0.1-5% of an anti-rust agent, 3-30% of a lithium-based thickening agent and a main amount of lubricating base oil, and the structure of the tetraphenyl ethylene derivative is as shown in a formula (I): # imgabs0. The lithium-based lubricating grease has excellent oxidation resistance, and can be used as a lubricating grease additive. Meanwhile, the consumption of the antioxidant can be predicted through the fluorescence intensity, and the antioxidant also has good extreme pressure anti-wear property, mechanical stability, colloid stability, high dropping point, corrosion resistance and the like.

Description

Technical Field

[0001] The invention relates to a lubricating grease, in particular to a lithium-based lubricating grease with a fluorescent effect and excellent anti-oxidation performance and a preparation method thereof. Background Art

[0002] Since its introduction in 1949, lithium-based grease has been widely used in countries around the world for its excellent performance, and its output ranks first among all types of greases. Lithium-based grease has good water resistance, heat resistance, mechanical stability and oxidation resistance, long service life and wide application range. It is an ideal multi-purpose and long-life grease. Composite lithium-based grease is a high-temperature multi-effect grease developed in the 1960s. It has a higher dropping point than lithium-based grease and is more suitable for use at high temperatures. It has good multi-effect properties, such as good colloidal stability, shear stability, water resistance and long life, and has strong thickening ability for various types of mineral oils and synthetic oils.

[0003] The service life of grease is closely related to its antioxidant performance. The remaining life of the grease can be effectively judged by examining the exhaustion of the antioxidants therein. However, examining the exhaustion of antioxidants often requires the use of instruments such as mid-infrared spectroscopy and gas chromatography, which is expensive and time-consuming. If a fluorescent group with aggregation-induced emission (AIE) behavior is introduced into the molecular structure of the antioxidant, it will help to quickly, conveniently and cost-effectively judge the exhaustion of the antioxidant, and then predict the remaining life of the grease. At present, there are few literature reports on hindered phenol antioxidants with fluorescent effects. Predicting the service life of lithium-based grease by judging the exhaustion of antioxidants is still an important research and development goal for those skilled in the art. Summary of the invention

[0004] The invention provides a lithium-based lubricating grease and a preparation method thereof.

[0005] The lithium-based grease of the present invention comprises, based on the total weight of the grease, 0.1% to 5% of a tetraphenylethylene derivative, 0.1% to 5% of an antioxidant and an anticorrosive agent, 0.1% to 5% of a rust inhibitor, 3% to 30% of a lithium-based thickener and a major amount of a lubricating base oil, wherein the structure of the tetraphenylethylene derivative is as shown in formula (I):

[0006]

[0007] In formula (I), HO is bonded to the benzene ring; y R groups are bonded to the benzene ring; y is selected from an integer between 0 and 4; and each R group is independently selected from H and C 1-10 A straight chain or branched chain alkyl group; n is an integer between 1 and 10; R 1 Each independently selected from C 1-20 A linear or branched alkylene group; R in n repeating units 2The same or different from each other, each independently selected from C 1-20 Straight or branched alkylene; R 3 Selected from H and C 1-20 Straight or branched alkyl; the A groups in the n repeating units are the same or different from each other and are independently selected from The group represented by formula (II), the group represented by formula (III) and the group represented by formula (IV), at least one A group is selected from the group represented by formula (II) and the group represented by formula (III);

[0008]

[0009] The R 4 The groups are each independently selected from H and C 1-20 Straight or branched alkyl; * in formula (II) and formula (III) represents the terminal bonded to formula (I).

[0010] According to the present invention, preferably, in formula (I), HO is located on the benzene ring R 1 The meta position of the chain, y is an integer between 1 and 3, and y R groups are located on the benzene ring R 1 The para or ortho position of the chain, the R group is selected from C 1-4 A straight chain or branched alkyl group, n is an integer between 1 and 5, R 1 Each independently selected from C 1-10 A linear or branched alkylene group, R in n repeating units 2 Each independently selected from C 1-10 A straight or branched alkylene group, R 3 Selected from H and C 1-10 A straight chain or branched chain alkyl group; 4 The groups are each independently selected from H and C 1-10 Straight chain or branched chain alkyl.

[0011] According to the present invention, further preferably, in formula (I), HO is located on the benzene ring R 1 The meta position of the chain, y is 1, and the R group is located on the benzene ring R 1 The para position of the chain, the R group is selected from tert-butyl, n is an integer between 1 and 3, R 1 Each independently selected from C 1-6 A linear or branched alkylene group, R in n repeating units 2 Each independently selected from C 1-6 Chain or branched alkylene, R 3 Selected from H and C 1-6 a chain or branched chain alkyl group; said R 4 The groups are each independently selected from H and C 1-4 Straight chain or branched chain alkyl.

[0012] According to the present invention, examples of the tetraphenylethylene derivatives include one or more of the following structural compounds:

[0013]

[0014] According to the present invention, the preparation method of the tetraphenylethylene derivative comprises the following steps:

[0015] (1) reacting a compound represented by formula (α) with a peroxide;

[0016]

[0017] In formula (α), HO is bonded to the benzene ring; y R groups are bonded to the benzene ring; y is selected from an integer between 0 and 4; and each R group is independently selected from H and C 1-10 A straight chain or branched chain alkyl group; n is an integer between 1 and 10; R 1 Each independently selected from C 1-20 A linear or branched alkylene group; R in n repeating units 2 The same or different from each other, each independently selected from C 1-20 Straight or branched alkylene; R 3 Selected from H and C 1-20 Straight or branched alkyl; the A" groups in the n repeating units are the same or different from each other and are independently selected from The R 4 The groups are each independently selected from H and C 1-20 Straight or branched chain alkyl;

[0018] (2) subjecting the reaction product of step (1) to a hydrolysis reaction;

[0019] (3) reacting the hydrolysis product of step (2) with a compound represented by formula (β), and collecting the product;

[0020]

[0021] The X group is selected from F, Cl, Br, I, and OH.

[0022] According to the present invention, preferably, in formula (α), HO is located on the benzene ring R 1 The meta position of the chain, y is an integer between 1 and 3, and y R groups are located on the benzene ring R 1 The para or ortho position of the chain, the R group is selected from C 1-4 A straight chain or branched alkyl group, n is an integer between 1 and 5, R 1 Each independently selected from C 1-10 A linear or branched alkylene group, R in n repeating units 2 Each independently selected from C1-10 A straight or branched alkylene group, R 3 Selected from H and C 1-10 A straight chain or branched chain alkyl group; 4 The groups are each independently selected from H and C 1-10 Straight chain or branched chain alkyl.

[0023] According to the present invention, further preferably, in formula (α), HO is located on the benzene ring R 1 The meta position of the chain, y is 1, and the R group is located on the benzene ring R 1 The para position of the chain, the R group is selected from tert-butyl, n is an integer between 1 and 3, R 1 Each independently selected from C 1-6 A linear or branched alkylene group, R in n repeating units 2 Each independently selected from C 1-6 Chain or branched alkylene, R 3 Selected from H and C 1-6 a chain or branched chain alkyl group; said R 4 The groups are each independently selected from H and C 1-4 Straight chain or branched chain alkyl.

[0024] According to the present invention, in step (1), the compound represented by formula (α) can be selected from cardanol and alkylated cardanol. The alkylated cardanol can be obtained by reacting cardanol with an alkylating agent, for example, tert-butyl cardanol can be obtained by reacting cardanol with tert-butyl chloride.

[0025] According to the present invention, in step (1), the peroxide is preferably one or more of hydrogen peroxide, performic acid, peracetic acid, persulfonic acid, m-chloroperbenzoic acid, tert-butyl hydroperoxide, tert-butyl peracetate, methyl ethyl ketone peroxide, dibenzoyl peroxide and cyclohexanone peroxide, more preferably one or more of hydrogen peroxide, performic acid, peracetic acid and persulfonic acid.

[0026] According to the present invention, in step (2), the hydrolysis reaction is to allow the reaction product of step (1) to undergo a hydrolysis reaction with water, and the amount of water used can generally be 20% to 200% of the mass of the reaction product of step (1).

[0027] According to the present invention, in step (3), the compound represented by formula (β) can be selected from one or more of 4-(1,2,2-triphenylvinyl)benzoic acid, 4-(1,2,2-triphenylvinyl)benzoyl fluoride, 4-(1,2,2-triphenylvinyl)benzoyl chloride, 4-(1,2,2-triphenylvinyl)benzoyl bromide and 4-(1,2,2-triphenylvinyl)benzoyl iodide, preferably 4-(1,2,2-triphenylvinyl)benzoic acid.

[0028] According to the present invention, the molar ratio of the compound represented by formula (α), the peroxide, and the compound represented by formula (β) is preferably 1:0.5-10:0.5-10, more preferably 1:1-5:1-5.

[0029] According to the present invention, the reaction temperature of step (1) is preferably 50-100°C, more preferably 60-90°C; the reaction temperature of step (2) is preferably 50-150°C, more preferably 70-100°C; the reaction temperature of step (3) is preferably 50-150°C, more preferably 70-120°C.

[0030] According to the present invention, the reaction time of step (1), step (2) and step (3) is usually as long as possible. Generally speaking, the reaction time of step (1) is preferably 1 to 10 hours, more preferably 3 to 5 hours; the reaction time of step (2) is preferably 0.5 to 10 hours, more preferably 1 to 3 hours; the reaction time of step (3) is preferably 1 to 10 hours, more preferably 3 to 6 hours.

[0031] According to the present invention, a catalyst may be added in step (1), and the catalyst is preferably an acidic catalyst, for example, one or more of concentrated sulfuric acid, zinc chloride, aluminum chloride, benzenesulfonic acid and titanate may be selected, and the amount of the catalyst added is preferably 0.01% to 3% of the compound represented by formula (α). After the reaction in step (1) is completed, the catalyst may be removed by alkali washing and / or water washing.

[0032] According to the present invention, a catalyst may be added in step (2), and the catalyst may be an acidic catalyst or a basic catalyst, for example, one of concentrated sulfuric acid, concentrated hydrochloric acid, concentrated nitric acid, sodium hydroxide, and potassium hydroxide, preferably concentrated sulfuric acid, and the amount of the catalyst added is preferably 0.5% to 10% of the sum of the mass of the compound represented by formula (α) in step (1) and the peroxide. After the reaction in step (2) is completed, the catalyst may be removed by alkali washing (using an acidic catalyst), acid washing (using an alkaline catalyst), and water washing.

[0033] According to the present invention, a catalyst may be added in step (3), and the catalyst is preferably an acidic catalyst, for example, one or more of concentrated sulfuric acid, zinc chloride, aluminum chloride, benzenesulfonic acid and titanate, and the amount of the catalyst added is preferably 0.5% to 10% of the compound shown in (α). After the reaction in step (3) is completed, the catalyst may be removed by alkali washing and / or water washing.

[0034] According to the present invention, the reaction steps (1), (2) and (3) may be carried out in the presence of a diluent and / or a solvent, or may be carried out without using a diluent and / or a solvent.

[0035] According to the present invention, the diluent can be selected from one or more of API I, II, III, IV and V base oils. Common products or brands include 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, alkylnaphthalene, etc.

[0036] According to the present invention, the solvent can be selected from water, C 6-20 Aromatics (such as benzene, toluene, xylene and cumene), C 6-10 One or more of alkanes (such as n-hexane, cyclohexane and petroleum ether), solvent gasoline, acetone and dimethylformamide. These solvents can be used alone or in combination of two or more. The solvent can be removed after the reaction is completed using a method known to those skilled in the art, such as under normal pressure or reduced pressure.

[0037] According to a particular embodiment of the present invention, the diluent and / or solvent may be added at any stage of the reaction step according to conventional amounts in the art, without particular limitation.

[0038] According to the present invention, the steps (1), (2) and (3) can be carried out under the protection of an inert gas atmosphere. Examples of the inert gas include nitrogen and argon, and there are no particular limitations.

[0039] According to the present invention, by the aforementioned preparation method, as a reaction product, a single compound can be manufactured, a mixture consisting of multiple compounds can also be manufactured, or a mixture consisting of one or more compounds and the aforementioned diluent (if used). These reaction products are all expected by the present invention, and the difference in their existence forms does not affect the realization of the effect of the present invention. Therefore, in the context of this specification, these reaction products are all collectively referred to as tetraphenylethylene derivatives without distinction. In view of this, according to the present invention, there is no absolute necessity to further purify the reaction product, or to further separate a tetraphenylethylene derivative with a fluorescent effect of a certain specific structure from the reaction product. Of course, the purification or separation is preferred for further improvement of the expected effect of the present invention, but is not necessary for the present invention. Nevertheless, as the purification or separation method, for example, the reaction product can be purified or separated by methods such as column chromatography or preparative chromatography.

[0040] The preparation method of the tetraphenylethylene derivative of the invention has simple steps and high conversion rate in the reaction process.

[0041] The tetraphenylethylene derivative of the present invention has both excellent antioxidant properties and fluorescence effects, and can quickly, conveniently and at low cost determine the exhaustion of the tetraphenylethylene derivative as an antioxidant, thereby predicting the remaining life of the lubricating grease.

[0042] According to the present invention, the antioxidant and anticorrosion agent can be selected from one or more of zinc dialkyl dithiophosphate, molybdenum dialkyl dithiocarbamate, lead dialkyl dithiocarbamate and antimony dialkyl dithiocarbamate, preferably zinc dialkyl dithiophosphate. Common trade names include T202, T203, T205, etc.

[0043] According to the present invention, the rust inhibitor can be selected from one or more of benzothiazole, benzotriazole, barium petroleum sulfonate, sodium petroleum sulfonate, zinc cyclohexaneate and alkenyl succinic acid, preferably benzothiazole.

[0044] According to the present invention, the lithium-based thickener is a saponification product of an acid and lithium hydroxide. The acid can be a single acid or a composite acid. The single acid can be selected from C 8～20 Fatty acids, C 8～20 The hydroxy fatty acid can be selected from one or more of lauric acid, myristic acid, palmitic acid, stearic acid and 12-hydroxystearic acid; the composite acid is a mixed acid of a fatty acid and an auxiliary acid, and the fatty acid can be selected from C 12 ~C 20 Fatty acids, C 12 ~C 20 The hydroxy fatty acid may be, for example, one or more of lauric acid, myristic acid, palmitic acid, stearic acid and 12-hydroxystearic acid, the auxiliary acid may be one or more of acetic acid, propionic acid, butyric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, phosphoric acid, terephthalic acid and boric acid, and the molar ratio between the fatty acid and the auxiliary acid may be 0.1 to 10: 1. The amount of acid and lithium hydroxide in the lithium-based thickener may comply with the prior art and is not particularly limited, for example, the equivalent ratio of acid to lithium hydroxide may be 1: 0.9 to 1.2.

[0045] According to the present invention, the lubricating base oil can be selected from one or more of mineral oil, synthetic oil and vegetable oil. The mineral oil can be one or more of paraffin base oil, intermediate base oil and cycloalkyl base oil; the synthetic oil can be one or more of poly-α-olefin oil, ester oil, fluorine oil and silicone oil; the vegetable oil can be one or more of castor oil, rapeseed oil, peanut oil and soybean oil; the lubricating base oil preferably has a kinematic viscosity of 2 to 60 mm at 100°C. 2 / s lubricating base oil, preferably with a kinematic viscosity of 3 to 40 mm at 100°C 2 / s lubricating base oil.

[0046] Other types of additives may be added to the lithium-based grease of the present invention, and the amount thereof may be in accordance with the prior art and is not particularly limited.

[0047] According to the present invention, the preparation method of the lithium-based grease comprises:

[0048] (1) adding part of the lubricating base oil and the acid into a fat making kettle, stirring evenly, heating to 60 to 95° C., adding a mixed solution of lithium hydroxide and water, and performing a saponification reaction for 30 to 240 minutes;

[0049] (2) heating to 100-180°C for dehydration reaction, and then continuing to heat to 190-220°C for high-temperature refining for 2-10 minutes;

[0050] (3) Cooling to 120-170° C., adding the remaining lubricating base oil, cooling to 100-120° C., adding tetraphenylethylene derivatives, antioxidants, and rust inhibitors, stirring evenly, homogenizing, and degassing to obtain the finished product.

[0051] The grease of the present invention has excellent antioxidant properties, and the consumption of the antioxidant can be predicted by the fluorescence intensity. It also has good extreme pressure anti-wear properties, mechanical stability, colloid stability, high dropping point, corrosion resistance and other properties. DETAILED DESCRIPTION

[0052] The present invention is further described below by way of examples, but they are not intended to limit the present invention.

[0053] The main raw materials used are from the following sources:

[0054] Cardanol, Shanghai Wujing Chemical Technology Co., Ltd., Industrial Products

[0055] Zinc chloride, Sinopharm Chemical Reagent Co., Ltd., analytical grade

[0056] Concentrated sulfuric acid, Sinopharm Chemical Reagent Co., Ltd., analytical grade

[0057] Hydrogen peroxide (30%), Sinopharm Chemical Reagent Co., Ltd., analytical grade

[0058] Formic acid, Sinopharm Chemical Reagent Co., Ltd., analytical grade

[0059] 4-(1,2,2-Triphenylvinyl)benzoic acid, Sinopharm Chemical Reagent Co., Ltd., chemically pure

[0060] Tert-butyl chloride, Sinopharm Chemical Reagent Co., Ltd., analytical grade

[0061] Comparison of antioxidant T501, Petrochemical Research Institute Xingpu Company, Industrial Products

[0062] Toluene, Sinopharm Chemical Reagent Co., Ltd., analytical grade

[0063] Dimethylformamide, analytical grade, Sinopharm Chemical Reagent Co., Ltd.

[0064] Lithium hydroxide, Sinopharm Chemical Reagent Co., Ltd., analytical grade

[0065] 12-Hydroxystearic acid, Sinopharm Chemical Reagent Co., Ltd., analytical grade

[0066] Acetic acid, Sinopharm Chemical Reagent Co., Ltd., analytical grade

[0067] Stearic acid, Sinopharm Chemical Reagent Co., Ltd., analytical grade

[0068] Zinc disulfide dialkyl phosphate T202, Wuxi Nanfang Additive Factory

[0069] Benzothiazole, Sinopharm Chemical Reagent Co., Ltd., analytical grade

[0070] HVI 150BS, Taioxing (Tianjin) Co., Ltd.

[0071] HVI 500SN, Taioxing (Tianjin) Co., Ltd.

[0072] Example 1 Preparation of tert-butylated cardanol

[0073] Take 100g of cardanol, 8g of formic acid, 0.3g of sulfuric acid, and 200g of hydrogen peroxide, add them to a three-necked flask with mechanical stirring, reflux condenser and temperature control, start stirring and heating. Maintain the reaction temperature at 70°C and react for 3 hours. After the reaction is completed, cool down to obtain a brown-red transparent liquid. Filter the reaction product and wash it with 5% KOH solution, then wash it with distilled water until neutral, and distill the organic phase under reduced pressure at 100Pa and 150°C for 1h to remove moisture and unreacted raw materials to obtain an orange-red transparent liquid epoxidized cardanol.

[0074] Dissolve 35g of epoxidized cardanol in 100ml of acetone, put it into a 250ml three-necked reaction flask after dissolving, add 0.9g of zinc chloride catalyst, start stirring and heating. Maintain the reaction temperature at 60°C, slowly drop 9.5g of tert-butyl chloride into the reaction flask, and continue the reaction for 3 hours after the addition is complete. After the reaction is completed, cool down to obtain a brown-red transparent liquid. Filter the reaction product and wash it with 5% KOH solution, then wash it with distilled water until it is neutral, and distill it under reduced pressure at 1000Pa and 120°C for 1h to remove the solvent, moisture and unreacted raw materials to obtain a brown-red viscous liquid tert-butylated epoxidized cardanol.

[0075] An exemplary reaction formula of the above reaction is shown below.

[0076]

[0077] Example 2

[0078] 20g of tert-butylated epoxy cardanol prepared in Example 1, 0.2g of concentrated sulfuric acid, 10g of water, and 10g of toluene were added to a three-necked flask with mechanical stirring and a reflux condenser, stirred, heated, and reacted at 85°C for 1h. After the reaction was completed, 12g of 4-(1,2,2-triphenylvinyl) benzoic acid was dissolved in 80g of dimethylformamide (DMF) and added dropwise to the flask. After the addition was completed, the reflux reaction was continued for 5h, and the reaction was stopped. The product was washed with water 3 times, and the solvent was evaporated to obtain a tetraphenylethylene derivative W-01 with a fluorescent effect, and the conversion rate was 90.8%.

[0079] An exemplary reaction formula of the above reaction is shown below.

[0080]

[0081] The product W-01 prepared in Example 2 was subjected to infrared spectroscopy and nuclear magnetic resonance carbon spectrum tests. The analysis results of the infrared spectrum are shown in Table 1, and the analysis results of the nuclear magnetic resonance carbon spectrum are shown in Table 2.

[0082] Table 1 Infrared analysis results of product W-01

[0083]

[0084] As shown in Table 1, the product W-01 contains characteristic peaks such as OH stretching vibration peak, C-OH stretching vibration peak, C=O stretching vibration peak, benzene ring skeleton stretching vibration peak, aromatic ester COC stretching vibration peak and cis-olefin vibration peak, which indicates that the synthesized product is the target compound.

[0085] Table 2 NMR carbon spectrum analysis results of product W-01

[0086]

[0087] As can be seen from Table 2, the synthetic product can be confirmed to be the target compound based on the attribution of each C element.

[0088] Example 3

[0089] 10g of tert-butylated epoxy cardanol prepared in Example 1, 0.2g of concentrated sulfuric acid, 10g of water, and 10g of toluene were added to a three-necked flask with mechanical stirring and a reflux condenser, stirred, heated, and reacted at 95°C for 1h. After the reaction was completed, 12g of 4-(1,2,2-triphenylvinyl) benzoic acid was dissolved in 80g of dimethylformamide (DMF) and added dropwise to the flask. After the addition was complete, the reflux reaction was continued for 3h, and the reaction was stopped. The product was washed with water 3 times, and the solvent was evaporated to obtain a tetraphenylethylene derivative W-02 with a fluorescent effect, and the conversion rate was 91.1%.

[0090] Example 4

[0091] 20g of tert-butylated epoxy cardanol prepared in Example 1, 0.2g of concentrated sulfuric acid, 10g of water, and 100g of toluene were added to a three-necked flask with mechanical stirring and a reflux condenser, stirred, heated, and reacted at 110°C for 1h. After the reaction was completed, 50g of 4-(1,2,2-triphenylvinyl) benzoic acid was dissolved in 120g of dimethylformamide (DMF) and added dropwise to the flask. After the addition was complete, the reflux reaction was continued for 6h, and the reaction was stopped. The product was washed with water 3 times, and the solvent was evaporated to obtain a tetraphenylethylene derivative W-03 with a fluorescent effect, and the conversion rate was 90.6%.

[0092] Example 5 Preparation of lithium-based grease

[0093] Raw material components: lithium hydroxide (1.6kg); HVI 150BS (20kg); 12-hydroxystearic acid (2.5kg); acetic acid (1kg); HVI 500SN (28kg); W-01 (0.2kg); zinc disulfide dialkyl phosphate T202 (0.5kg); benzothiazole (0.5kg).

[0094] In a normal pressure reactor equipped with a heating, stirring and cooling device, 2.5 kg of 12-hydroxystearic acid, 1 kg of acetic acid and 20 kg of a 100°C kinematic viscosity of 31 mm 2 / s HVI 150BS lubricating base oil, stir evenly, heat to 95℃, add lithium hydroxide aqueous solution (containing 1.6kg lithium hydroxide and 3kg water), and carry out saponification reaction for 1h; heat to 150℃ for dehydration reaction for 2h; then heat to 200℃ for high-temperature refining for 5 minutes, cool to 160℃, add 28kg of 100℃ kinematic viscosity 11mm 2 / s of HVI 500SN lubricating base oil; when the temperature is cooled to 110°C, 0.2kg W-01, 0.5kg zinc disulfide dialkyl phosphate T202, and 0.5kg benzothiazole are added, and the mixture is stirred evenly, homogenized, and degassed to obtain the finished product.

[0095] Example 6 Preparation of lithium-based grease

[0096] Raw material components: lithium hydroxide (1.6 kg); HVI 150BS (20 kg); stearic acid (2 kg); HVI 500SN (28 kg); W-02 (0.2 kg); zinc disulfide dialkyl phosphate T202 (0.5 kg); benzothiazole (0.5 kg).

[0097] Add 2kg of stearic acid and 20kg of 100℃ kinematic viscosity 31mm into a normal pressure reactor equipped with heating, stirring and cooling devices. 2 / s HVI 150BS lubricating base oil, stir evenly, heat to 95℃, add lithium hydroxide aqueous solution (containing 1.6kg lithium hydroxide and 3kg water), and carry out saponification reaction for 1h; heat to 150℃ for dehydration reaction for 2h; then heat to 200℃ for high-temperature refining for 5 minutes, cool to 160℃, add 28kg of 100℃ kinematic viscosity 11mm 2 / s of HVI500SN lubricating base oil; when the temperature is cooled to 110°C, 0.2kg W-02, 0.5kg zinc disulfide dialkyl phosphate T202, and 0.5kg benzothiazole are added, and the mixture is stirred evenly, homogenized, and degassed to obtain the finished product.

[0098] Example 7 Preparation of lithium-based grease

[0099] Raw material components: lithium hydroxide (1.6 kg); HVI 150BS (48 kg); stearic acid (2 kg); W-03 (0.2 kg); zinc disulfide dialkyl phosphate T202 (0.5 kg); benzothiazole (0.5 kg).

[0100] Add 2kg of stearic acid and 20kg of 100℃ kinematic viscosity 31mm into a normal pressure reactor equipped with heating, stirring and cooling devices. 2 / s HVI 150BS lubricating base oil, stir evenly, heat to 95℃, add lithium hydroxide aqueous solution (containing 1.6kg lithium hydroxide and 3kg water), and perform saponification reaction for 1h; heat to 150℃ for dehydration reaction for 2h; then heat to 200℃ for high-temperature refining for 5 minutes, cool to 160℃, add 28kg of 100℃ kinematic viscosity 31mm 2 / s of HVI150BS lubricating base oil; when the temperature is cooled to 110°C, 0.2kg W-01, 0.5kg zinc disulfide dialkyl phosphate T202, and 0.5kg benzothiazole are added, and the mixture is stirred evenly, homogenized, and degassed to obtain the finished product.

[0101] Comparative Example 1 Comparative Preparation of Lithium-Based Grease

[0102] Raw material components: lithium hydroxide (1.6 kg); HVI 150BS (20 kg); 12-hydroxystearic acid (2.5 kg); acetic acid (1 kg); HVI 500SN (28 kg); zinc disulfide dialkyl phosphate T202 (0.5 kg); benzothiazole (0.5 kg).

[0103] In a normal pressure reactor equipped with a heating, stirring and cooling device, 2.5 kg of 12-hydroxystearic acid, 1 kg of acetic acid and 20 kg of a 100°C kinematic viscosity of 31 mm 2 / s HVI 150BS lubricating base oil, stir evenly, heat to 95℃, add lithium hydroxide aqueous solution (containing 1.6kg lithium hydroxide and 3kg water), and carry out saponification reaction for 1h; heat to 150℃ for dehydration reaction for 2h; then heat to 200℃ for high-temperature refining for 5 minutes, cool to 160℃, add 28kg of 100℃ kinematic viscosity 11mm 2 / s of HVI 500SN lubricating base oil; when the temperature is cooled to 110°C, 0.5kg of dialkyl zinc disulfide phosphate T202 and 0.5kg of benzothiazole are added, and the mixture is stirred evenly, homogenized and degassed to obtain the finished product.

[0104] Comparative Example 2 Comparative Preparation of Lithium-Based Grease

[0105] Raw material components: lithium hydroxide (1.6 kg); HVI 150BS (20 kg); stearic acid (2 kg); HVI 500SN (28 kg); zinc disulfide dialkyl phosphate T202 (0.5 kg); benzothiazole (0.5 kg).

[0106] Add 2kg of stearic acid and 20kg of 100℃ kinematic viscosity 31mm into a normal pressure reactor equipped with heating, stirring and cooling devices. 2 / s HVI 150BS lubricating base oil, stir evenly, heat to 95℃, add lithium hydroxide aqueous solution (containing 1.6kg lithium hydroxide and 3kg water), and carry out saponification reaction for 1h; heat to 150℃ for dehydration reaction for 2h; then heat to 200℃ for high-temperature refining for 5 minutes, cool to 160℃, add 28kg of 100℃ kinematic viscosity 11mm 2 / s of HVI500SN lubricating base oil; when the temperature is cooled to 110°C, 0.5kg of dialkyl zinc disulfide phosphate T202 and 0.5kg of benzothiazole are added, and the mixture is stirred evenly, homogenized and degassed to obtain the finished product.

[0107] Comparative Example 3: Preparation of Lithium-Based Grease

[0108] Raw material components: lithium hydroxide (1.6 kg); HVI 150BS (20 kg); stearic acid (2 kg); HVI 500SN (28 kg); T501 (0.2 kg); zinc disulfide dialkyl phosphate T202 (0.5 kg); benzothiazole (0.5 kg).

[0109] Add 2kg of stearic acid and 20kg of 100℃ kinematic viscosity 31mm into a normal pressure reactor equipped with heating, stirring and cooling devices. 2 / s HVI 150BS lubricating base oil, stir evenly, heat to 95℃, add lithium hydroxide aqueous solution (containing 1.6kg lithium hydroxide and 3kg water), and carry out saponification reaction for 1h; heat to 150℃ for dehydration reaction for 2h; then heat to 200℃ for high-temperature refining for 5 minutes, cool to 160℃, add 28kg of 100℃ kinematic viscosity 11mm 2 / s of HVI500SN lubricating base oil; when the temperature is cooled to 110°C, 0.2kg T501, 0.5kg zinc disulfide dialkyl phosphate T202, and 0.5kg benzothiazole are added, and the mixture is stirred evenly, homogenized, and degassed to obtain the finished product.

[0110] The performance of the greases of Examples 5, 6, 7 and Comparative Examples 1, 2, and 3 was evaluated, and the evaluation method and results are shown in Table 3. The oxidation induction period of the samples was tested using the PDSC method, and the testing instrument was a TA5000 DSC instrument of TA Company of the United States. The testing conditions were: 180°C, oxygen pressure 0.6MPa, and heating rate 10°C / min. The samples were tested for fluorescence intensity before and after oxidation, and the testing instrument used was a F-310 fluorescence spectrophotometer of Tianjin Gangdong Technology Co., Ltd.

[0111] Table 3 Grease performance evaluation

[0112]

Claims

1. A lithium-based grease comprising, based on the total weight of the grease, 0.1% to 5% of a tetraphenylethylene derivative, 0.1% to 5% of an antioxidant and an anticorrosive agent, 0.1% to 5% of a rust inhibitor, 3% to 30% of a lithium-based thickener and a major amount of a lubricating base oil, wherein the structure of the tetraphenylethylene derivative is as shown in formula (I): In formula (I), HO is bonded to the benzene ring; y R groups are bonded to the benzene ring; y is selected from an integer between 0 and 4; and each R group is independently selected from H and C 1-10 Straight or branched alkyl; n is an integer between 1 and 10; R1 is independently selected from C 1-20 A linear or branched alkylene group; R2 in n repeating units is the same or different from each other and is independently selected from C 1-20 A straight or branched alkylene group; R3 is selected from H and C 1-20 Straight or branched alkyl; the A groups in the n repeating units are the same or different from each other and are independently selected from The group represented by formula (II), the group represented by formula (III) and the group represented by formula (IV), at least one A group is selected from the group represented by formula (II) and the group represented by formula (III); The R4 groups are each independently selected from H and C 1-20 Straight or branched alkyl; * in formula (II) and formula (III) represents the terminal bonded to formula (I).

2. The lithium-based grease according to claim 1, characterized in that: In formula (I), HO is located at the meta position of the chain where R1 is located on the benzene ring, y is an integer between 1 and 3, y R groups are located at the para or ortho position of the chain where R1 is located on the benzene ring, and the R group is selected from C 1-4 A straight or branched alkyl group, n is an integer between 1 and 5, and R1 is independently selected from C 1-10 A linear or branched alkylene group, wherein R2 in the n repeating units is independently selected from C 1-10 A straight or branched alkylene group, R3 is selected from H and C 1-10 Straight or branched alkyl; the R4 groups are each independently selected from H and C 1-10 Straight chain or branched chain alkyl.

3. The lithium-based grease according to claim 1, characterized in that: In formula (I), HO is located at the meta position of the chain on the benzene ring where R1 is located, y is 1, the R group is located at the para position of the chain on the benzene ring where R1 is located, the R group is selected from tert-butyl, n is an integer between 1 and 3, and R1 is independently selected from C 1-6 A chain or branched alkylene group, wherein R2 in the n repeating units is independently selected from C 1-6 A linear or branched alkylene group, R3 is selected from H and C 1-6 The R4 groups are each independently selected from H and C 1-4 Straight chain or branched chain alkyl.

4. The lithium-based grease according to claim 1, characterized in that: The tetraphenylethylene derivatives include one or more of the following structural compounds:

5. The lithium-based lubricating grease according to claim 1, wherein the preparation method of the tetraphenylethylene derivative comprises the following steps: (1) reacting a compound represented by formula (α) with a peroxide; In formula (α), HO is bonded to the benzene ring; y R groups are bonded to the benzene ring; y is selected from an integer between 0 and 4; and each R group is independently selected from H and C 1-10 Straight or branched alkyl; n is an integer between 1 and 10; R1 is independently selected from C 1-20 A linear or branched alkylene group; R2 in n repeating units is the same or different from each other and is independently selected from C 1-20 A straight or branched alkylene group; R3 is selected from H and C 1-20 Straight or branched alkyl; the A" groups in the n repeating units are the same or different from each other and are independently selected from The R4 groups are each independently selected from H and C 1-20 Straight or branched chain alkyl; (2) subjecting the reaction product of step (1) to a hydrolysis reaction; (3) reacting the hydrolysis product of step (2) with a compound represented by formula (β), and collecting the product; The X group is selected from F, Cl, Br, I, and OH.

6. The lithium-based grease according to claim 5, characterized in that: In formula (α), HO is located at the meta position of the chain where R1 is located on the benzene ring, y is an integer between 1 and 3, y R groups are located at the para or ortho position of the chain where R1 is located on the benzene ring, and the R group is selected from C 1-4 A straight or branched alkyl group, n is an integer between 1 and 5, and R1 is independently selected from C 1-10 A linear or branched alkylene group, wherein R2 in the n repeating units is independently selected from C 1-10 A straight or branched alkylene group, R3 is selected from H and C 1-10 Straight or branched alkyl; the R4 groups are each independently selected from H and C 1-10 Straight chain or branched chain alkyl.

7. The lithium-based grease according to claim 5, characterized in that: In formula (α), HO is located at the meta position of the chain where R1 is located on the benzene ring, y is 1, the R group is located at the para position of the chain where R1 is located on the benzene ring, the R group is selected from tert-butyl, n is an integer between 1 and 3, and R1 is independently selected from C 1-6 A chain or branched alkylene group, wherein R2 in the n repeating units is independently selected from C 1-6 A linear or branched alkylene group, R3 is selected from H and C 1-6 The R4 groups are each independently selected from H and C 1-4 Straight chain or branched chain alkyl.

8. The lithium-based grease according to claim 5, characterized in that: The compound represented by formula (α) is selected from cardanol and alkylated cardanol; the peroxide is selected from one or more of hydrogen peroxide, performic acid, peracetic acid, persulfonic acid, m-chloroperbenzoic acid, tert-butyl hydroperoxide, tert-butyl peracetate, methyl ethyl ketone peroxide, dibenzoyl peroxide and cyclohexanone peroxide; the compound represented by formula (β) is selected from one or more of 4-(1,2,2-triphenylvinyl)benzoic acid, 4-(1,2,2-triphenylvinyl)benzoyl fluoride, 4-(1,2,2-triphenylvinyl)benzoyl chloride, 4-(1,2,2-triphenylvinyl)benzoyl bromide and 4-(1,2,2-triphenylvinyl)benzoyl iodide.

9. The lithium-based grease according to claim 5, characterized in that: The molar ratio of the compound represented by formula (α) to the peroxide and the compound represented by formula (β) is 1:0.5-10:0.5-10; the reaction temperature of step (1) is 50-100°C; the reaction temperature of step (2) is 50-150°C; and the reaction temperature of step (3) is 50-150°C.

10. The lithium-based grease according to claim 5, characterized in that: adding an acidic catalyst in step (1); and / or adding an acidic catalyst or a basic catalyst in step (2); And / or, an acidic catalyst is added in step (3).

11. The lithium-based lubricating grease according to any one of claims 1 to 10, characterized in that: The antioxidant and corrosion inhibitor is selected from one or more of zinc dialkyl dithiophosphate, molybdenum dialkyl dithiocarbamate, lead dialkyl dithiocarbamate and antimony dialkyl dithiocarbamate; the rust inhibitor is selected from one or more of benzothiazole, benzotriazole, barium petroleum sulfonate, sodium petroleum sulfonate, zinc cyclohexane and alkenyl succinic acid; the lithium-based thickener is a saponification product of acid and lithium hydroxide; the lubricating base oil is selected from one or more of mineral oil, synthetic oil and vegetable oil.

12. The method for preparing the lithium-based grease according to claim 11, comprising: (1) adding part of the lubricating base oil and the acid into a fat making kettle, stirring evenly, heating to 60 to 95° C., adding a mixed solution of lithium hydroxide and water, and performing a saponification reaction for 30 to 240 minutes; (2) heating to 100-180°C for dehydration reaction, and then continuing to heat to 190-220°C for high-temperature refining for 2-10 minutes; (3) Cooling to 120-170° C., adding the remaining lubricating base oil, cooling to 100-120° C., adding tetraphenylethylene derivatives, antioxidants, and rust inhibitors, stirring evenly, homogenizing, and degassing to obtain the finished product.

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