Calcium-based lubricating grease and preparation method thereof

Abstract

The invention provides calcium-based lubricating grease and a preparation method thereof. Based on the total weight of the lubricating grease, the calcium-based lubricating grease comprises the following components in percentage by weight: 0.1 to 3 percent of tetraphenyl ethylene derivative, 10 to 40 percent of high-base-number calcium sulfonate, 0.1 to 12 percent of calcium compound of a transforming agent, 3 to 30 percent of a calcium-based thickening agent and 50 to 80 percent of lubricating base oil. The calcium-based lubricating grease provided by the invention has excellent antioxidant performance, can predict the consumption of the antioxidant through fluorescence intensity, and also has good mechanical stability, wear resistance, corrosion resistance, water resistance and adhesion.

Description

Technical Field

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

[0002] Calcium sulfonate is used as a detergent and rust inhibitor for lubricating oil and has been widely used in lubricating oil for internal combustion engines. Later, people found that the dropping point of calcium sulfonate-based grease made with calcium sulfonate as a thickener is much higher than that of grease made with fatty acid calcium soap, so they started to study calcium sulfonate-based grease.

[0003] As early as the 1950s, US2,535,101 used petroleum calcium sulfonate and relatively low molecular weight calcium ethyl sulfonate as thickeners in a certain ratio to thicken mineral oil to obtain calcium sulfonate-based grease, with a dropping point of about 205°C, which is much higher than that of general calcium-based grease, but the thickening ability is relatively weak. In the 1960s and 1970s, US 3,242,079, US 3,376,222, US 3,816,310, US 4,261,840, etc. reported methods for converting Newtonian calcium sulfonate into non-Newtonian with thixotropic properties, and introduced the high-basification technology of calcium sulfonate to produce high-basic calcium sulfonate-based grease. However, these early calcium sulfonate-based greases were relatively viscous, and their poor low-temperature pumpability hindered their application. In the mid-1980s, US 4,560,489 disclosed a high-alkalinity composite calcium sulfonate-based grease improved with boric acid. Its composition and performance are very different from those of previous composite calcium sulfonate-based greases. It not only overcomes the shortcomings of poor low-temperature pumpability and aging hardening, but also has better high and low temperature performance, mechanical stability, colloid stability, oxidation stability, water resistance, corrosion resistance, and rust and wear resistance.

[0004] The service life of grease is closely related to its antioxidant performance. The remaining life of grease can be effectively determined by examining the exhaustion of antioxidants. However, the inspection of antioxidant exhaustion often requires the use of instruments such as mid-infrared spectroscopy and gas chromatography, which is expensive and time-consuming. Introducing fluorescent groups with aggregation-induced emission (AIE) behavior into antioxidant molecules is conducive to the rapid, convenient and low-cost inspection of antioxidant exhaustion, and then predicting the remaining life of grease. At present, there are few literature reports on hindered phenolic antioxidants with fluorescent effects.

[0005] The development of calcium-based greases that can predict their own service life remains a research and development direction for those skilled in the art. Summary of the invention

[0006] The invention provides a calcium-based lubricating grease and a preparation method thereof.

[0007] The calcium-based lubricating grease of the present invention comprises, based on the total weight of the lubricating grease, 0.1% to 3% of a tetraphenylethylene derivative, 10% to 40% of a high-base calcium sulfonate, 0.1% to 12% of a calcified product of a converting agent, 3% to 30% of a calcium-based thickener and 50% to 80% of a lubricating base oil, wherein the preparation method of the tetraphenylethylene derivative comprises the following steps:

[0008] (1) reacting a compound represented by formula (α) with a peroxide;

[0009]

[0010] 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;

[0011] (2) subjecting the reaction product of step (1) to a hydrolysis reaction;

[0012] (3) reacting the hydrolysis product of step (2) with a compound represented by formula (β), and collecting the product;

[0013]

[0014] The X group is selected from F, Cl, Br, I, and OH.

[0015] 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 C 1-10 A straight or branched alkylene group, R3 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.

[0016] 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.

[0017] 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.

[0018] 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.

[0019] 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).

[0020] 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.

[0021] 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.

[0022] 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.

[0023] 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.

[0024] 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.

[0025] 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.

[0026] 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.

[0027] 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.

[0028] 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.

[0029] 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.

[0030] 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.

[0031] 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.

[0032] The preparation method of the tetraphenylethylene derivative of the invention has simple steps and high conversion rate in the reaction process.

[0033] 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.

[0034] According to the present invention, the base value of the overbased calcium sulfonate may be 300 to 450 mgKOH / g, preferably 320 to 420 mgKOH / g.

[0035] According to the present invention, the conversion agent in the calcified conversion agent can be selected from C 8 ~C 20 Alkyl substituted benzenesulfonic acid, C 6 ~C 20 Cyclohexane acid, C 1 ~C 5 One or more carboxylic acids or aqueous solutions of these substances, specifically dodecylbenzenesulfonic acid, C 8 ~C 16One or more of cyclohexane acid, acetic acid or their aqueous solutions, for example, a mixed acid of acetic acid and dodecylbenzenesulfonic acid or their aqueous solutions, or a mixture of acetic acid and C 8 ~C 16 The mixed acid of cyclohexane acid or its aqueous solution. The conversion agent can be added in an amount of 1% to 30% (preferably 1% to 25%) of the weight of the high-based calcium sulfonate. The conversion agent can convert the non-Newtonian high-based calcium sulfonate into a Newtonian high-based calcium sulfonate.

[0036] According to the present invention, the calcified product of the conversion agent is a calcified product generated by the reaction of the conversion agent with a portion of calcium carbonate contained in the overbased calcium sulfonate.

[0037] According to the present invention, the calcium-based thickener is a reaction product of an acid and calcium hydroxide. The acid may be a single acid or a composite acid. The single acid may 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, preferably 12-hydroxystearic acid, and the auxiliary acid may be one or more of terephthalic acid, isophthalic acid, phthalic acid, boric acid, adipic acid, azelaic acid, sebacic acid and phosphoric acid, preferably one or more of terephthalic acid, isophthalic acid, phthalic acid and boric acid or aqueous solutions of these substances, for example, the composite acid may be a mixed acid of 12-hydroxystearic acid and terephthalic acid, or a mixed acid of 12-hydroxystearic acid and boric acid. The molar ratio between the fatty acid and the auxiliary acid may be 0.1 to 10:1. The amount of acid to calcium hydroxide in the calcium-based thickener may comply with the prior art and is not particularly limited, for example, the equivalent ratio of acid to calcium hydroxide may be 1:0.9 to 1.2.

[0038] 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°C2 / s lubricating base oil.

[0039] Different types of additives may be added to the calcium-based grease of the present invention, and the amount of additives used may comply with the prior art and is not particularly limited. According to the present invention, the preparation method of the calcium-based grease comprises:

[0040] (1) Add part of the lubricating base oil and high base calcium sulfonate into a fat making kettle, stir evenly, heat to 40-50° C., add a conversion agent, heat to 55-65° C., and keep the temperature constant for 30-120 minutes;

[0041] (2) adding calcium hydroxide or its aqueous solution, then adding acid or its aqueous solution, stirring, heating to 105-115° C., maintaining for 30-90 minutes for dehydration, maintaining a constant temperature of 120-140° C. for 10-30 minutes, and heating to 190-220° C. for high-temperature refining for 2-10 minutes;

[0042] (3) Cooling to 130-170° C., adding the remaining lubricating base oil, cooling to 100-120° C., adding tetraphenylethylene derivative, stirring evenly, homogenizing, and degassing to obtain the finished product.

[0043] The calcium-based grease of the invention has excellent antioxidant properties, and the consumption of the antioxidant can be predicted by the fluorescence intensity. It also has good mechanical stability, wear resistance, corrosion resistance, water resistance and adhesion. DETAILED DESCRIPTION

[0044] The present invention is further described below by way of examples, but they are not intended to limit the present invention.

[0045] The main raw materials used are from the following sources:

[0046] Cardanol, Shanghai Wujing Chemical Technology Co., Ltd., Industrial Products

[0047] Zinc chloride, Sinopharm Chemical Reagent Co., Ltd., analytical grade

[0048] Concentrated sulfuric acid, Sinopharm Chemical Reagent Co., Ltd., analytical grade

[0049] Hydrogen peroxide (30%), Sinopharm Chemical Reagent Co., Ltd., analytical grade

[0050] Formic acid, Sinopharm Chemical Reagent Co., Ltd., analytical grade

[0051] 4-(1,2,2-Triphenylvinyl)benzoic acid, Sinopharm Chemical Reagent Co., Ltd., chemically pure

[0052] Tert-butyl chloride, Sinopharm Chemical Reagent Co., Ltd., analytical grade

[0053] Toluene, Sinopharm Chemical Reagent Co., Ltd., analytical grade

[0054] Dimethylformamide, analytical grade, Sinopharm Chemical Reagent Co., Ltd.

[0055] Overbased calcium sulfonate, 320mgKOH / g, Jinzhou Huifa Tianhe Chemical Co., Ltd., Industrial products

[0056] Overbased calcium sulfonate, 400mgKOH / g, Jinzhou Huifa Tianhe Chemical Co., Ltd., Industrial products

[0057] HVI 150BS, Taioxing (Tianjin) Co., Ltd.

[0058] HVI 500SN, Taioxing (Tianjin) Co., Ltd.

[0059] Dodecylbenzenesulfonic acid, Shanghai Aladdin Biochemical Technology Co., Ltd.

[0060] C 10 Cyclohexane acid, Shanghai Aladdin Biochemical Technology Co., Ltd.

[0061] 12-Hydroxystearic acid, Sinopharm Chemical Reagent Co., Ltd., analytical grade

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

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

[0064] Comparison of antioxidant T501, Petrochemical Research Institute Xingpu Company, Industrial Products

[0065] Example 1 Preparation of tert-butylated cardanol

[0066] 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.

[0067] 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.

[0068] Example 2

[0069] 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%.

[0070] Example 3

[0071] 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%.

[0072] Example 4

[0073] 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%.

[0074] Example 5 Preparation of grease

[0075] Raw material components: high base calcium sulfonate (320mgKOH / g, 30kg); HVI 150BS (20kg); HVI 500SN (28kg); dodecylbenzenesulfonic acid (2.8kg); acetic acid (0.56kg); Ca(OH) 2 (1.8kg); 12-hydroxystearic acid (2kg); boric acid (2.32kg); W-01 (0.2kg).

[0076] 30 kg of high-base calcium sulfonate with a total base number of 320 mg KOH / g and 20 kg of a 100°C kinematic viscosity of 31 mm were added to a normal pressure reactor equipped with a heating, stirring and cooling device. 2 / s HVI 150BS lubricating base oil, stir, heat to 50℃, add 2.8kg dodecylbenzene sulfonic acid, add 0.56kg acetic acid and a mixed solution of water 4 times the weight of acetic acid, stir, heat to 60℃, keep constant temperature for 90 minutes, add 1.8kg Ca(OH) 2 and Ca(OH) 2 The mixture was stirred with 4 times the weight of water, 2 kg 12-hydroxystearic acid and 2.32 kg boric acid were added, stirred, heated to 110 ° C, kept for 60 minutes, dehydrated, kept at 120 ° C for 20 minutes, heated to 200 ° C and kept at this temperature for 5 minutes, then cooled to 160 ° C, and 28 kg of 100 ° C kinematic viscosity of 11 mm was added. 2 / s of HVI 500SN lubricating base oil; when the temperature is cooled to 110°C, 0.2kg W-01 is added, stirred for 10 minutes, homogenized and degassed to obtain the finished grease.

[0077] Example 6 Preparation of Grease

[0078] Raw material components: high base calcium sulfonate (320mgKOH / g, 30kg); HVI 150BS (15kg); HVI 500SN (32kg); C 10 Cycloalkane acid (2.8 kg); Acetic acid (0.56 kg); Ca(OH) 2 (1.8kg); 12-hydroxystearic acid (2kg); terephthalic acid (3.5kg); W-02 (0.2kg).

[0079] 30 kg of high-base calcium sulfonate with a total base value of 320 mg KOH / g and 15 kg of a 100°C kinematic viscosity of 31 mm were added to a normal pressure reactor equipped with a heating, stirring and cooling device. 2 / s HVI 150BS lubricating base oil, stir, heat to 50℃, add 2.8kg C 10To cyclohexane acid, add 0.56 kg of acetic acid and a mixed solution of water 4 times the weight of acetic acid, stir, heat to 60°C, keep constant temperature for 90 minutes, add 1.8 kg of Ca(OH) 2 and Ca(OH) 2 The mixture of water 4 times its weight was stirred, 2kg 12-hydroxystearic acid and 3.5kg terephthalic acid were added, stirred, heated to 110°C, kept for 60 minutes, dehydrated, kept at 120°C for 20 minutes, heated to 200°C and kept at this temperature for 5 minutes, then cooled to 160°C, and 32kg of 100°C kinematic viscosity of 11mm was added. 2 / s of HVI 500SN lubricating base oil; when the temperature is cooled to 110°C, 0.2kg W-02 is added, stirred for 10 minutes, homogenized and degassed to obtain the finished grease.

[0080] Example 7 Preparation of Lubricating Grease

[0081] Raw material components: overbased calcium sulfonate (400 mgKOH / g, 30 kg); HVI 150BS (30 kg); HVI 500SN (17 kg); dodecylbenzenesulfonic acid (2.8 kg); acetic acid (0.56 kg); Ca(OH) 2 (1.8kg); 12-hydroxystearic acid (2kg); terephthalic acid (3.5kg); W-03 (0.2kg).

[0082] 30 kg of high-base calcium sulfonate with a total base value of 400 mg KOH / g and 30 kg of 100°C kinematic viscosity of 31 mm were added to a normal pressure reactor equipped with a heating, stirring and cooling device. 2 / s HVI 150BS lubricating base oil, stir, heat to 50℃, add 2.8kg dodecylbenzene sulfonic acid, add 0.56kg acetic acid and a mixed solution of water 4 times the weight of acetic acid, stir, heat to 60℃, keep constant temperature for 90 minutes, add 1.8kg Ca(OH) 2 and Ca(OH) 2 The mixture of 4 times the weight of water was stirred, 2 kg of 12-hydroxystearic acid and 3.5 kg of terephthalic acid were added, stirred, heated to 110 ° C, kept for 60 minutes, dehydrated, kept at 120 ° C for 20 minutes, heated to 200 ° C and kept at a constant temperature for 5 minutes, then cooled to 160 ° C, and 17 kg of 100 ° C kinematic viscosity of 11 mm was added. 2 / s of HVI 500SN lubricating base oil; when the temperature is cooled to 110°C, 0.2kg W-03 is added, stirred for 10 minutes, homogenized and degassed to obtain the finished grease.

[0083] Comparative Example 1 Preparation of comparative grease

[0084] Raw material components: high base calcium sulfonate (320mgKOH / g, 30kg); HVI 150BS (20kg); HVI 500SN (28kg); dodecylbenzenesulfonic acid (2.8kg); acetic acid (0.56kg); Ca(OH) 2 (1.8kg); 12-hydroxystearic acid (2kg); boric acid (2.32kg); T501 (0.2kg).

[0085] 30 kg of high-base calcium sulfonate with a total base number of 320 mg KOH / g and 20 kg of a 100°C kinematic viscosity of 31 mm were added to a normal pressure reactor equipped with a heating, stirring and cooling device. 2 / s HVI 150BS lubricating base oil, stir, heat to 50℃, add 2.8kg dodecylbenzene sulfonic acid, add 0.56kg acetic acid and a mixed solution of water 4 times the weight of acetic acid, stir, heat to 60℃, keep constant temperature for 90 minutes, add 1.8kg Ca(OH) 2 and Ca(OH) 2 The mixture was stirred with 4 times the weight of water, 2 kg 12-hydroxystearic acid and 2.32 kg boric acid were added, stirred, heated to 110 ° C, kept for 60 minutes, dehydrated, kept at 120 ° C for 20 minutes, heated to 200 ° C and kept at this temperature for 5 minutes, then cooled to 160 ° C, and 28 kg of 100 ° C kinematic viscosity of 11 mm was added. 2 / s of HVI 500SN lubricating base oil; when the temperature is cooled to 110°C, 0.2kg T501 is added, stirred for 10 minutes, homogenized and degassed to obtain the finished grease.

[0086] Comparative Example 2 Preparation of Comparative Grease

[0087] Raw material components: overbased calcium sulfonate (400 mgKOH / g, 30 kg); HVI 150BS (30 kg); HVI 500SN (17 kg); dodecylbenzenesulfonic acid (2.8 kg); acetic acid (0.56 kg); Ca(OH) 2 (1.8kg); 12-hydroxystearic acid (2kg); terephthalic acid (3.5kg).

[0088] Add 30 kg of high-base calcium sulfonate with a total base value of 400 mgKOH / g and 30 kg of 100°C kinematic viscosity of 31 mm into a normal pressure reactor equipped with a heating, stirring and cooling device. 2 / s HVI 150BS lubricating base oil, stir, heat to 50℃, add 2.8kg dodecylbenzene sulfonic acid, add 0.56kg acetic acid and a mixed solution of water 4 times the weight of acetic acid, stir, heat to 60℃, keep constant temperature for 90 minutes, add 1.8kg Ca(OH)2 and Ca(OH) 2 The mixture of 4 times the weight of water was stirred, 2 kg of 12-hydroxystearic acid and 3.5 kg of terephthalic acid were added, stirred, heated to 110 ° C, kept for 60 minutes, dehydrated, kept at 120 ° C for 20 minutes, heated to 200 ° C and kept at a constant temperature for 5 minutes, then cooled to 160 ° C, and 17 kg of 100 ° C kinematic viscosity of 11 mm was added. 2 / s of HVI 500SN lubricating base oil; after cooling to 110°C, stirring for 10 minutes, homogenizing and degassing to obtain the finished grease.

[0089] The performance of the greases of the embodiments and comparative examples was evaluated, and the evaluation methods and results are shown in Table 1. 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.

[0090] It can be seen from Table 1 that the calcium-based grease of the present invention has excellent antioxidant properties and can predict its oxidation status through fluorescence intensity. It also has good mechanical stability, wear resistance, corrosion resistance, water resistance and adhesion.

[0091] Table 1 Performance evaluation of each grease sample

[0092]

Claims

1. A calcium-based grease, comprising, based on the total weight of the grease, 0.1% to 3% of a tetraphenylethylene derivative, 10% to 40% of a high-base calcium sulfonate, 0.1% to 12% of a calcified product of a conversion agent, 3% to 30% of a calcium-based thickener, and 50% to 80% of a lubricating base oil, 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.

2. The calcium-based grease according to claim 1, 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.

3. The calcium-based grease according to claim 1, 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.

4. The calcium-based grease according to claim 1, 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.

5. The calcium-based grease according to claim 1, 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.

6. The calcium-based lubricating grease according to claim 1, 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).

7. The calcium-based lubricating grease according to claim 1, characterized in that: The alkalinity of the overbased calcium sulfonate is 300 to 450 mgKOH / g.

8. The calcium-based lubricating grease according to claim 1, characterized in that: The conversion agent in the calcified conversion agent is selected from C8~C 20 Alkyl substituted benzenesulfonic acid, C6~C 20 One or more of cycloalkane acid, C1-C5 carboxylic acid or their aqueous solutions.

9. The calcium-based lubricating grease according to claim 1, characterized in that: The calcium-based thickener is a reaction product of acid and calcium hydroxide; the lubricating base oil is selected from one or more of mineral oil, synthetic oil and vegetable oil.

10. The method for preparing the calcium-based grease according to any one of claims 1 to 9, comprising: (1) Add part of the lubricating base oil and high base calcium sulfonate into a fat making kettle, stir evenly, heat to 40-50° C., add a conversion agent, heat to 55-65° C., and keep the temperature constant for 30-120 minutes; (2) adding calcium hydroxide or its aqueous solution, then adding acid or its aqueous solution, stirring, heating to 105-115° C., maintaining for 30-90 minutes for dehydration, maintaining a constant temperature of 120-140° C. for 10-30 minutes, and heating to 190-220° C. for high-temperature refining for 2-10 minutes; (3) Cooling to 130-170° C., adding the remaining lubricating base oil, cooling to 100-120° C., adding tetraphenylethylene derivative, stirring evenly, homogenizing, and degassing to obtain the finished product.

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