Lubricating grease composition containing organic bismuth and organic copper and application of lubricating grease composition in constant velocity universal joint

Abstract

The invention relates to the technical field of lubricating grease, in particular to a lubricating grease composition containing organic bismuth and organic copper and application of the lubricating grease composition in a constant velocity universal joint. The lubricating grease composition includes at least one base oil, at least one organobismuth, at least one organocopper, at least one organomolybdenum, and at least one thickener. Experimental research finds that organic bismuth and organic copper generate a synergistic effect in the lubricating grease, in the synergistic effect, the organic bismuth can improve the extreme pressure resistance of the universal joint lubricating grease, and the organic copper can provide a repair effect on a metal surface, so that the NVH (Noise Vibration and Harshness) performance of a universal joint is improved, the transmission efficiency is improved, and the service life of the universal joint is prolonged.

Description

Technical Field

[0001] The invention relates to the technical field of lubricating grease, in particular to a lubricating grease composition containing organic bismuth and organic copper and application thereof in a constant velocity universal joint. Background Art

[0002] Front-wheel drive cars have CV joints on both ends of the drive shaft. The inner CV joint connects the drive shaft to the transmission. The outer CV joint connects the drive shaft to the wheels. Many rear-wheel drive and four-wheel drive cars and trucks have CV joints. There are two most common types of CV joints: ball and tripod. In front-wheel drive cars, ball CV joints are used on the outside of the drive shaft, while tripod CV joints are mostly used on the inside. The movement of the components within a CV joint is complex, combining rolling and sliding. When the joint is subjected to torque, the components are loaded together, which can cause not only wear on the component contact surfaces, but also rolling contact fatigue and significant friction between the surfaces. Constant velocity joints also have a sealing boot of elastomeric material, usually in the shape of a bellows, which is connected to the outside of the CV joint at one end and to the interconnecting shaft or output shaft of the CV joint at the other end. The sealing boot retains grease in the joint and keeps out dust and moisture. Not only must the grease reduce wear and friction and prevent premature rolling contact fatigue in the CV joint, it must also be compatible with the elastomeric material that the boots are made of. Otherwise, the boot material can degrade, leading to premature boot failure, which in turn can cause the grease to escape and ultimately lead to CV joint failure. One of the most common problems with CV joints occurs when the protective boots become cracked or damaged. Once this happens, in addition to the grease escaping, moisture and dirt can enter, causing the CV joint to wear faster and eventually fail from lack of lubrication and corrosion. Typically, the outer CV joint boots break first because they have to withstand more movement than the inner boots. If the CV joint itself is worn, it cannot be repaired and must be replaced with a new or refurbished part.

[0003] At present, the global oil reserves are getting less and less, and major economic powers are also facing the troubles brought by the continuous reduction of available energy. In addition, ensuring air quality has become a common need of people. The exhaust gas of traditional cars contains a large number of major pollutants that affect air quality. Therefore, for automobile companies, it is urgent to research and create new energy car washes. New energy vehicles require CVJ products, better transmission efficiency and higher transmission torque. Reducing the friction coefficient can improve transmission efficiency and improve ACFG performance. Excellent ACFG performance means excellent transmission efficiency. In addition, improving extreme pressure performance can improve transmission torque.

[0004] As an environmentally friendly catalyst, organic bismuth compounds are being used in organic synthesis, biomedicine, coatings and other fields. For example, in the production of polyurethane coatings, polyurethane leather, polyurethane adhesives, polyurethane rubber, PU resin slurry, etc. In recent years, some people have introduced it into lubricating products to improve extreme pressure performance. For example, CN102703168A discloses an extreme pressure anti-wear additive composition containing organic bismuth. Experiments have shown that the extreme pressure anti-wear additive composition can be added to lubricating grease to improve the extreme pressure and anti-wear properties of the grease, and effectively inhibit the metal corrosion of the grease and improve the anti-oxidation performance of the grease.

[0005] As the workload of modern machinery becomes higher and higher and the operating environment becomes more and more harsh, the wear and life of mechanical parts are affected. Therefore, improving the lubricating properties of lubricants, such as improving extreme pressure properties, anti-wear properties and compatibility of sheath materials, is crucial to improving the wear and life of mechanical equipment.

[0006] The present application develops for the first time a lubricating grease composition having organic bismuth and organic copper and its application in a constant velocity joint. The lubricating grease composition exhibits good synergistic performance in terms of wear resistance and extreme pressure performance. Summary of the invention

[0007] In view of the deficiencies of the prior art described above, the object of the present invention is to provide a lubricating grease composition having organic bismuth and organic copper and application thereof in a constant velocity universal joint (CV universal joint). The present invention finds through experimental studies that organic bismuth and organic copper produce a synergistic effect in the lubricating grease. In the synergistic effect, organic bismuth can improve the extreme pressure resistance of the universal joint lubricating grease, and organic copper can provide a repairing effect on the metal surface, thereby improving the NVH (Noise, Vibration, Harshness) performance of the universal joint and increasing the life of the universal joint.

[0008] To achieve the above-mentioned and other related purposes, one aspect of the present invention provides a lubricating grease composition, which comprises the following components: a) at least one base oil; b) at least one organic bismuth; c) at least one organic copper; d) at least one organic molybdenum; and e) at least one thickener.

[0009] In some embodiments of the present invention, relative to the total amount of the lubricating grease composition, the total content of the organic bismuth, the organic copper and the organic molybdenum is 0.50-11.0% by weight.

[0010] In some embodiments of the present invention, the grease composition comprises the following components by weight percentage:

[0011] a1) at least one base oil 60-95%; b1) at least one organic bismuth 0.1-3%; c1) at least one organic copper 0.1-3%;

[0012] d1) at least one organic molybdenum 0.1-5%; e1) at least one thickener 2-30%.

[0013] In some embodiments of the present invention, at least one of the following technical features is also included:

[0014] a11) the base oil is selected from at least one of poly-α-olefins, metallocene poly-α-olefins, naphthenic oils, paraffinic oils, polyether polyols, or synthetic organic esters;

[0015] b11) the organic bismuth is selected from at least one of bismuth neodecanoate, bismuth cyclohexaneate, bismuth oleate, bismuth octoate, bismuth dithiocarbamate, or bismuth dithiophosphate;

[0016] c11) the organic copper is selected from at least one of copper naphthenate, copper oleate, copper octoate, copper neodecanoate, copper dithiocarbamate, or copper dithiophosphate;

[0017] d11) the organic molybdenum is selected from at least one of dithiophosphate molybdenum, dithiocarbamate molybdenum, or phosphorus-free and sulfur-free organic molybdenum;

[0018] e11) The thickener is selected from at least one of urea thickener, lithium soap, lithium complex soap, sodium-based soap, complex sodium-based soap, calcium soap, or complex calcium-based soap.

[0019] In some embodiments of the present invention, the base oil comprises 30-85% paraffin-based oil by weight relative to the total amount of the base oil.

[0020] In some embodiments of the present invention, the base oil comprises 15 to 80% of cyclohexane oil by weight relative to the total amount of the base oil.

[0021] In some embodiments of the present invention, the base oil comprises 30-80% paraffinic oil and 15-70% naphthenic oil, based on weight percentage, relative to the total amount of the base oil.

[0022] In some embodiments of the present invention, the essential additives include at least one of the following technical features:

[0023] e) at least one thickener; f) the grease composition further comprises at least one organic zinc; g) the grease composition further comprises at least one antioxidant.

[0024] In some embodiments of the present invention, the grease composition further comprises at least one of the following technical features by weight percentage: f1) 0.1-3.0% of at least one organic zinc; g1) 0.1-2.0% of at least one antioxidant.

[0025] In some embodiments of the present invention, at least one of the following technical features is also included:

[0026] f11) the organic zinc is selected from at least one of primary zinc dithiophosphate, secondary zinc dithiophosphate, or tertiary zinc dithiophosphate;

[0027] g11) The antioxidant is selected from phenolic antioxidants and / or amine-containing phenolic antioxidants.

[0028] A second aspect of the present invention is use of the lubricating grease composition in a constant velocity joint.

[0029] Preferably, the constant velocity universal joint is a constant velocity universal joint specially used for new energy vehicles and motor vehicles; or, the constant velocity universal joint is a tripod universal joint or a ball universal joint.

[0030] According to a third aspect of the present invention, there is provided a constant velocity universal joint comprising the lubricating grease composition as described above.

[0031] Compared with the prior art, the beneficial effects achieved by the present invention are: organic bismuth and organic copper produce a synergistic effect in the lubricating grease. Specifically, organic bismuth can improve the extreme pressure resistance of the universal joint lubricating grease, and organic copper can provide a repairing effect on the metal surface, thereby improving the NVH (Noise, Vibration, Harshness) performance of the universal joint and increasing the life of the universal joint. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 Shown is a graph of LTFS test data in an embodiment of the present application, with the horizontal axis being time (s).

[0033] Figure 2 Shown is a data graph of the friction coefficient of lubricating grease in the examples of the present application.

[0034] Figure 3 Shown is the ACFG test data graph of B1 and B2 in the examples of the present application.

[0035] Figure 4 Shown is the ACFG test data graph of A1, A2 and B1 in the embodiments of the present application.

[0036] Figure 5 This is a data graph showing the extreme pressure load of lubricating grease in the examples of this application. DETAILED DESCRIPTION

[0038] The following detailed description specifically discloses an implementation method of the application of a lubricating grease composition of the present application.

[0039] "Scope" disclosed in the present application is defined in the form of lower limit and upper limit, and a given range is defined by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of a particular range. The scope defined in this way can include or exclude end values, and can be combined arbitrarily, that is, any lower limit can be combined with any upper limit to form a scope. For example, if a scope of 60-70 and 80-90 is listed for a particular parameter, it is understood that a scope of 70-80 is also expected. In the present application, unless otherwise specified, the numerical range "ab" represents an abbreviation of any real number combination between a and b, wherein a and b are real numbers.

[0040] The inventor of the present invention has provided a lubricating grease composition after a large number of exploratory experiments, and found that organic bismuth and organic copper produce a synergistic effect in the lubricating grease. In the synergistic effect, organic bismuth can improve the extreme pressure resistance of the universal joint lubricating grease, and organic copper can provide a repairing effect on the metal surface. And experiments have proved that the formula of the present invention has excellent ACFG performance and excellent sheath compatibility. On this basis, the present invention is completed.

[0041] Related explanation

[0042] "Constant velocity universal joint", the function of the constant velocity universal joint is to connect two rotating shafts with an angle or a change in relative position between the shafts, and make the two shafts transmit power at the same angular velocity. It can overcome the problem of non-constant velocity in ordinary cross-axis universal joints and is particularly suitable for the use of steering drive axles. Constant velocity universal joints are generally used as speed transmission shafts for new energy cars and motor vehicles. Generally, they include tripod universal joints, ball-type fixed joints or ball-type moving joints. NVH has three dimensions, namely noise (Noise), vibration (Vibration) and acoustic roughness (Harshness). The performance of NVH directly affects consumers' experience of the car. At the same time, the improvement of NVH performance also means the improvement of transmission efficiency. "Sealing performance", the compatibility of lubricating grease and sealing materials (sheath compatibility) will directly affect the sealing performance. Regarding LTFS testing, ACFG testing, extreme pressure testing and evaluation, tripod high torque life testing and evaluation, and the testing and evaluation of the compatibility of sheath materials and lubricating grease can refer to relevant standards or as recorded in this application. DETAILED DESCRIPTION OF THE INVENTION

[0044] The first aspect of the present invention provides a lubricating grease composition, comprising the following components: a) at least one base oil; b) at least one organic bismuth; c) at least one organic copper; d) at least one organic molybdenum; and e) at least one thickener.

[0045] a) Specifically, base oil is an indispensable liquid phase component in lubricating grease. Lubricating grease is a two-phase dispersion system with a structural skeleton. Base oil is the dispersion medium of this dispersion system. The viscosity of base oil not only affects the consistency of lubricating grease, but also affects the stability of lubricating grease. As at least one base oil according to the present invention, the base oil is selected from at least one of poly-α-olefins, metal poly-α-olefins, cycloalkane oils (high viscosity), paraffin-based oils (medium viscosity), polyether polyols, or synthetic organic esters. Among them, synthetic organic esters can be synthesized with different viscosities. The kinematic viscosity of the base oil at 40°C should preferably be between 32 and 250 mm 2 / sec, and the kinematic viscosity at 100°C is 5 to 40 mm 2 / sec. The organic synthetic ester is preferably a dicarboxylic acid derivative having a subunit based on a fatty alcohol. Preferably, the fatty alcohol has a primary carbon chain, a straight carbon chain or a branched carbon chain of 2 to 20 carbon atoms. Preferably, the organic synthetic ester is selected from bis(2-ethylhexyl) sebacic acid ("dioctyl sebacate" (DOS)), bis(2-ethylhexyl) adipate ("dioctyl adipate" (DOA)), dioctyl phthalate (DOP) and / or bis(2-ethylhexyl) azelaic acid ("dioctyl azelaic acid (DOZ)). If the poly-α-olefin is present in the base oil, the poly-α-olefin is preferably a 1-dodecene oligomer, a 1-decene oligomer, a 1-octene or a mixture thereof. The poly-α-olefins are preferably selected from poly-α-olefins having a kinematic viscosity at 40° C. in the range of 2 to 60 centistokes. The naphthenic oil selected for at least one base oil preferably has a kinematic viscosity at 40° C. in the range of about 3 to 370 mmHg. 2 / second, more preferably in the range of 20 to 150 mm 2 / sec. Density (measured according to ASTM D1250) at 15.6°C is about 0.9 to about 1.0 g / cm 3 The paraffinic base oil present in at least one base oil is preferably selected from the group consisting of chain saturated alkanes, branched saturated alkanes and cyclic saturated alkanes of polyolefins, hydroisomerized Fischer-Tropsch waxes and Fischer-Tropsch oligoolefins, preferably isoparaffins, cycloalkanes containing a monocyclic and / or polycyclic structure. Preferably, the paraffinic base oil has a carbonyl content of 9 mm at 40°C. 2 / sec~170mm 2 The kinematic viscosity is in the range of 50 mm / s at 40°C. 2 / second to about 150mm 2 Kinematic viscosity / sec.

[0046] In some specific embodiments of the present invention, the at least one base oil in the grease composition accounts for 60-95% by weight, and the proportion can be 60-65%, 65-70%, 70-75%, 75-80%, 80-85%, 85-90% or 90-95%.

[0047] Preferably, in some specific embodiments, relative to the total amount of the base oil, by weight percentage: the base oil contains 30-85% paraffin-based oil, which may be 30-35%, 35-45%, 45-55%, 55-65%, 65-75%, 75-85%.

[0048] Preferably, in some specific embodiments, relative to the total amount of the base oil, by weight percentage: the base oil contains 15-80% of cycloparaffinic oil, which may be 15-20%, 20-30%, 30-40%, 40-50%, 50-60%, 70-80%.

[0049] b) Specifically, bismuth belongs to the heavy metal element of the 5th main group of the sixth period in the periodic table, is located at the junction of metal and non-metal, and has special physical and chemical properties. It has been reported in the prior art that it is applied to lubricating grease to improve the extreme pressure and anti-wear properties of lubricating grease. The organic bismuth used in this application can be selected from at least one of neodecanoic acid bismuth, cyclohexane acid bismuth, oleic acid bismuth, octanoic acid bismuth, dithiocarbamate bismuth, or dithiophosphate bismuth. The organic bismuth can be various oil-soluble organic bismuth compounds common in the art. Specifically, as the organic acid constituting the organic acid bismuth, aromatic organic acid, aliphatic organic acid or alicyclic organic acid can be used. Specific examples of organic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, 2-ethylhexanoic acid, capric acid, azelaic acid, capric acid, undecanoic acid, lauric acid and tridecanoic acid. Monovalent saturated fatty acids, such as myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, azelaic acid, arachidic acid, monovalent unsaturated fatty acids, such as acrylic acid, crotonic acid, undecenoic acid, oleic acid, gardenic acid, etc.; malonic acid, methylmalonic acid, succinic acid, methylsuccinic acid, dimethylmalonic acid, ethylmalonic acid, glutaric acid, adipic acid, dimethylsuccinic acid, phenylmalonic acid, tetramethylsuccinic acid, suberic acid, azelaic acid, sebacic acid, brassic acid; divalent saturated fatty acids, such as fumaric acid, maleic acid, oleic acid, etc.; fatty acid derivatives, such as tartaric acid, citric acid, etc.; aromatic organic substances, such as benzoic acid, phthalic acid, trimellitic acid, pyromellitic acid, etc.; alicyclic organic acids, etc.

[0050] In some specific embodiments of the present invention, the at least one organic bismuth in the grease composition accounts for 0.1-3% by weight, and the proportion can be 0.1-0.5%, 0.5-1.0%, 1.0-1.5%, 1.5-2.0%, 2.0-2.5%, or 2.5-3.0%.

[0051] c) Specifically, organic copper is widely used. For example, copper cyclohexaneate is an environmentally friendly wood preservative and an additive in antifouling paint for ships and submarine cables. The present application applies it to lubricating grease. Specifically, the organic copper is selected from at least one of copper cyclohexaneate, copper oleate, copper octanoate, copper neodecanoate, copper dithiocarbamate, or copper dithiophosphate. Copper dithiocarbamate, for example, is shown in formula (I), R1 and R2 may be the same or different, and each represents a straight-chain or branched alkyl group with 1 to 10 carbon atoms, preferably a straight-chain alkyl group with 1 to 4 carbon atoms.

[0052]

[0053] In some specific embodiments of the present invention, the at least one organic copper in the grease composition accounts for 0.1-3% by weight, and the proportion can be 0.1-0.5%, 0.5-1.0%, 1.0-1.5%, 1.5-2.0%, 2.0-2.5%, or 2.5-3.0%.

[0054] d) Specifically, molybdenum has the advantages of high strength, high melting point, corrosion resistance, wear resistance, etc., and is often added to lubricating greases. The organic molybdenum used in this application is selected from at least one of dithiophosphate molybdenum, dithiocarbamate molybdenum, or phosphorus-free and sulfur-free organic molybdenum. The organic molybdenum can be various oil-soluble organic molybdenum compounds commonly found in the art, for example, dialkyl dithiophosphate molybdenum, dialkyl dithiocarbamate molybdenum, dialkyl dithiocarbamate sulfide molybdenum, molybdenum amine complex, cyclopentane acid molybdenum and alkyl salicylic acid molybdenum. Preferably, the organic molybdenum is dialkyl dithiocarbamate molybdenum and / or dialkyl dithiocarbamate sulfide molybdenum. The carbon number of the alkyl or cycloalkyl in the above-mentioned organic molybdenum can be 1-6. For example, the alkyl in the organic molybdenum can be methyl, ethyl, propyl, n-butyl, etc., and the cyclopentane acid molybdenum can be cyclohexanecarboxylic acid molybdenum, etc.

[0055] e) The thickener is selected from at least one of a urea thickener, a lithium soap thickener, a lithium complex soap thickener, a sodium-based soap thickener, a complex sodium-based soap thickener, a calcium soap thickener, or a complex calcium-based soap thickener. The at least one thickener is preferably a lithium soap thickener (or a urea thickener, wherein lithium soap thickeners are most preferably used. Lithium soap thickeners are the reaction product of at least one fatty acid with lithium hydroxide. Preferably, the thickener may be a simple lithium soap formed from stearic acid, 12-hydroxystearic acid, hydrogenated castor oil or from other similar fatty acids or mixtures thereof or methyl esters of these acids. Alternatively, a lithium complex soap may be formed, for example, from a mixture of a long chain fatty acid with a complexing agent such as a borate of one or more dicarboxylic acids. The use of a lithium complex soap allows the grease composition according to the invention to be operated at temperatures up to about 180°C, whereas with a simple lithium soap the grease composition would only be operable at temperatures up to about 120°C. The urea thickener may be selected from diurea compounds and polyurea compounds. For example, the diurea compound is selected from the group consisting of a monoamine and a diisocyanate compound such as phenylene diisocyanate, diphenyl diisocyanate, phenylene diisocyanate, diphenylmethane diisocyanate, octadecane diisocyanate, ... The polyurea compound is selected from the group obtained by reacting diamines with diisocyanate compounds such as the above diisocyanates, and the diamines include ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, octanediamine, phenylenediamine, toluenediamine and xylenediamine; or the urea thickener is selected from the group obtained by reacting aromatic amines such as p-toluidine or aniline, cyclohexylamine or others. The grease composition is preferably a grease composition comprising a mixture of the urea and diurea compounds. The urea and diurea compounds are preferably obtained by reacting a mixture of the urea and diurea compounds with a diisocyanate. The aromatic group of the diurea compound, if present, preferably consists of 6 or 7 carbon atoms. However, mixtures of all the above thickeners, such as lithium soap thickeners and urea thickeners, may also be used. The grease composition may contain 2 to 30% by weight of the at least one thickener, which may be 2 to 3%, 3 to 5%, 5 to 10%, 10 to 15%, 15 to 20%, 20 to 25%, or 25 to 30%.

[0056] In some specific embodiments of the present invention, the at least one organic molybdenum content of the grease composition is 0.1-5% by weight, and the proportion can be 0.1-0.5%, 0.5-1.0%, 1.0-1.5%, 1.5-2.0%, 2.0-2.5%, 2.5-3.0%, 3.0-3.5%, 3.5-4.0%, 4.0-4.5%, 4.5-5.0%.

[0057] It is worth noting that in some preferred embodiments of the present invention, the total content of the organic bismuth, the organic copper and the organic molybdenum is 0.50-11.0%, which can be 0.50-1.0%, 1.0-2.0%, 2.0-3.0%, 3.0-4.0%, 4.0-5.0%, 5.0-6.0%, 6.0-7.0%, 7.0-8.0%, 8.0-9.0%, 9.0-10.0%, 10.0-11.0%.

[0058] In addition, the lubricating grease also includes some necessary additives, and the necessary additives include at least one of the following technical features: f) the lubricating grease composition also includes at least one organic zinc; g) the lubricating grease composition also includes at least one antioxidant.

[0059] In some specific embodiments, the grease composition has an essential additive content of 0.2-5% by weight, which may be 0.2-0.5%, 0.5-1%, 1-1.5%, 1.5-2%, or 2.5-3%.

[0060] In some specific embodiments, the organic zinc is selected from at least one of primary zinc dithiophosphate, secondary zinc dithiophosphate, or tertiary zinc dithiophosphate. The zinc dithiophosphate is, for example, as shown in formula (II), R3 is a primary, secondary, or tertiary aliphatic hydrocarbon group or an aromatic hydrocarbon group, and the number of carbon atoms of R3 can be 1-10.

[0061]

[0062] In the grease composition, the at least one organic zinc accounts for 0.1-3.0% by weight, and can be 0.1-0.5%, 0.5-1.0%, 1.0-1.5%, 1.5-2.0%, 2.0-2.5%, or 2.5-3.0%.

[0063] In some specific embodiments, the antioxidant is selected from phenolic antioxidants and / or phenolic antioxidants containing amines, preferably aromatic amines, more preferably aniline, N-phenyl compounds reacted with 2,4,4-trimethylpentene or selected from octyl / butyl diphenylamine, more preferably dioctyl diphenylamine, octyl diphenylamine, octyl / styryl diphenylamine, diheptyl diphenylamine, dinonyl diphenylamine or mixtures thereof. Preferably, the at least one antioxidant selected has a 250 mm 2 / second to about 370mm 2 / sec kinematic viscosity (according to ASTM D445) and has a viscosity of about 0.9 g / cm at 20°C 3 To about 1.0g / cm 3The density of the grease composition is (according to ASTM D1298). The at least one antioxidant is used to prevent oxidation-related degradation of the grease composition. The grease composition, by weight percentage, comprises 0.1 to 2.0% of the at least one antioxidant, which may be 0.1 to 0.2%, 0.2 to 0.5%, 0.5 to 1.0%, 1.0 to 1.5%, or 1.5 to 2.0%.

[0064] In some specific embodiments of the present invention, the grease composition comprises the following components, measured by weight percentage relative to the total amount of the lubricating grease composition: at least one base oil accounts for 80-90%, and the at least one base oil is selected from naphthenic oil (high viscosity), and the kinematic viscosity of the naphthenic oil at 40° C. is preferably 50-150 mm 2 / sec. At least one organic bismuth 0.5-1.5%, the at least one organic bismuth is selected from one or more of diamyl dithiocarbamate, dioctyl dithiocarbamate, diamyl dithiocarbamate, diisononyl dithiocarbamate, 2-ethylhexyl dithiophosphate bismuth. At least one organic copper 0.5-1.5%, the at least one organic copper is selected from one or more of dimethyl dithiocarbamate, diethyl dithiocarbamate, dipropyl dithiocarbamate or dibutyl dithiocarbamate; d) at least one organic molybdenum 2.0-3.0%, the at least one organic molybdenum is selected from one or more of N,N'-di-n-butyl dithiocarbamate molybdenum, N,N'-di-n-octyl dithiocarbamate molybdenum or N,N'-diisooctyl dithiocarbamate molybdenum.

[0065] In some specific embodiments of the present invention, the grease composition comprises the following components, measured by weight percentage relative to the total amount of the lubricating grease composition: at least one base oil accounts for 80-90%, and the at least one base oil is selected from naphthenic oil (high viscosity), and the kinematic viscosity of the naphthenic oil at 40° C. is preferably 50-150 mm 2 / sec. At least one organic bismuth 0.5-1.5%, the at least one organic bismuth is selected from one or more of diamyl dithiocarbamate, dioctyl dithiocarbamate, diamyl dithiocarbamate, diisononyl dithiocarbamate, 2-ethylhexyl dithiophosphate bismuth. At least one organic copper 0.5-1.5%, the at least one organic copper is selected from one or more of dimethyl dithiocarbamate, diethyl dithiocarbamate, dipropyl dithiocarbamate or dibutyl dithiocarbamate; d) at least one organic molybdenum 2.0-3.0%, the at least one organic molybdenum is selected from one or more of N,N'-di-n-butyl dithiocarbamate molybdenum, N,N'-di-n-octyl dithiocarbamate molybdenum or N,N'-diisooctyl dithiocarbamate molybdenum. At least one thickener 5-20%, preferably a lithium soap thickener, using a mixture of long-chain fatty acids and complexing agents (such as one or more dicarboxylic acid borates) to form a lithium complex soap. At least one organic zinc 0.5-1.5%, the at least one organic zinc is selected from one or more of diisooctyl zinc dithiophosphate, dioctyl zinc dithiophosphate, dimethyl zinc dithiophosphate, diethyl zinc dithiophosphate or dipropyl zinc dithiophosphate. At least one antioxidant 0.5-1.5%, one or more of dioctyl diphenylamine, octyl diphenylamine, octyl / styryl diphenylamine, diheptyl diphenylamine or dinonyl diphenylamine.

[0066] In some specific embodiments of the present invention, the composition includes, by weight percentage, at least one base oil accounting for 80-90% of the total amount of the lubricating grease composition, wherein the at least one base oil is selected from a mixture of cyclohexane oil (high viscosity) and paraffin oil (medium viscosity), wherein the cyclohexane oil preferably has a kinematic viscosity at 40° C. of 100-150 mm 2 / sec; paraffin-based oil has 50mm at 40°C 2 / sec~100mm 2 / second range of kinematic viscosity; wherein, relative to the total amount of the base oil, by weight percentage: the base oil contains 30-80% paraffinic oil and 15-70% cyclohexane oil. Relative to the total weight of the composition, it also includes at least one organic bismuth 0.5-1.5%, the at least one organic bismuth is selected from the group consisting of diamyl dithiocarbamate bismuth, dioctyl dithiocarbamate bismuth, diamyl dithiocarbamate bismuth, diisononyl dithiocarbamate bismuth, 2-ethylhexyl dithiophosphate bismuth or a mixture of one or more. 0.5-1.5% of at least one organic copper, the at least one organic copper is selected from one or more of dimethyl copper dithiocarbamate, diethyl copper dithiocarbamate, dipropyl copper dithiocarbamate or dibutyl copper dithiocarbamate; d) 2.0-3.0% of at least one organic molybdenum, the at least one organic molybdenum is selected from one or more of N,N'-di-n-butyl molybdenum dithiocarbamate, N,N'-di-n-octyl molybdenum dithiocarbamate or N,N'-di-isooctyl molybdenum dithiocarbamate. 5-20% of at least one thickener, preferably a lithium soap thickener, using a mixture of long-chain fatty acids and complexing agents (such as borates of one or more dicarboxylic acids) to form a lithium complex soap. 0.5-1.5% of at least one organic zinc, the at least one organic zinc is selected from one or more of zinc diisooctyl dithiophosphate, zinc dioctyl dithiophosphate, zinc dimethyl dithiophosphate, zinc diethyl dithiophosphate or zinc dipropyl dithiophosphate. At least one antioxidant 0.5-1.5%, one or more of dioctyl diphenylamine, octyl diphenylamine, octyl / styryl diphenylamine, diheptyl diphenylamine or dinonyl diphenylamine. Of course, some necessary extreme pressure additives may also be included.

[0067] The second aspect of the present application also provides the use of the lubricating grease composition described above in a constant velocity joint. Preferably, the constant velocity joint is a constant velocity joint dedicated to new energy vehicles and motor vehicles; or, the constant velocity joint is a three-pin universal joint or a ball universal joint. The CV universal joint particularly includes a sealing sleeve, which is at least partially filled with the lubricating grease composition according to the present invention, and the sealing sleeve has a first attachment area assigned to the universal joint and a second attachment area assigned to the shaft. The sealing sleeve can be fixed to the universal joint and / or the shaft with a conventional clamping device.

[0068] The third aspect of the present invention provides a constant velocity universal joint, comprising the lubricating grease composition as described above. The beneficial effects of the present invention are further described below in conjunction with embodiments.

[0069] In order to make the invention purpose, technical scheme and beneficial technical effect of the present invention clearer, the present invention is further described in detail below in conjunction with examples. However, it should be understood that the examples of the present invention are only for explaining the present invention, not for limiting the present invention, and the examples of the present invention are not limited to the examples given in the specification. The specific experimental conditions or operating conditions not specified in the examples are made under conventional conditions, or are made under the conditions recommended by the material supplier.

[0070] In the following examples, the reagents, materials and instruments used are all commercially available unless otherwise specified.

[0071] Example

[0072] Related tests and test methods are shown in Table 1

[0073] Table 1

[0074]

[0075]

[0076] Table 2 shows the composition and test results of lubricating grease products A1-A3, B1-B5. The base oil is a mixture of paraffin oil and cyclohexane oil; the organic bismuth uses bismuth neonarate (Minghuan (Shanghai) Biotechnology Co., Ltd.); the organic copper uses copper cyclohexane (Minghuan (Shanghai) Biotechnology Co., Ltd.); the organic molybdenum uses molybdenum dialkyl dithiophosphate (Pacific Union (Beijing) Petrochemical Co., Ltd.), or molybdenum dialkyl dithiocarbamate (Pacific Union (Beijing) Petrochemical Co., Ltd.), or molybdenum amine ester compound (Super Lubricity Technology (Foshan) Co., Ltd.); the organic zinc uses zinc dialkyl dithiophosphate (Xinxiang Ruifeng New Materials Co., Ltd.); the extreme pressure additive uses sulfided isobutylene (LUBRIZOL); the antioxidant uses octylated and butylated diphenylamine (RT Vanderbilt Company, Inc.).

[0077] Table 2

[0078] Components / Products A1 A2 A3 B1 B2 B3 B4 B5 Polyurea 8 8 8 8 Calcium-based soap 15 Lithium soap 7 6 7 Base oil 85.5 78.5 87.5 87 89 88.5 86.5 86.5 Organic bismuth 1.0 1.0 1.0 1.0 Organic copper 1.0 1.0 1.0 1.0 Organic molybdenum 3 3 3 4.0 3.0 3 3 3 Organic zinc 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Extreme pressure additives 0.5 0.5 Antioxidants 1.0 1.0 1.0 0.5 0.5 1.0 1.0 1.0 LFTS test + + + O - + + - Three-pin section ACFG ++ ++ ++ + - ND ND ND 4-ball extreme pressure performance + O + + - -- --- - Tripod high torque life + ND ND O O ND ND ND Sheath material compatibility + ND ND - O ND ND ND

[0079] (1) Perform the LTFS test on products A1, B1, and B2 using the above method: For details, see Figure 1 From the test graph, we can see that at 55 minutes, the friction coefficients of products A1, B1, and B2 are at the same level. The test conclusions: 1) Product A1 does not need to be run-in to reach a low friction coefficient. 2) Product B1 needs a certain amount of time to be run-in before the friction coefficient is reduced, and the ACFG test meets the requirements. 3) It takes a relatively long time to be run-in, and the friction coefficient is reduced, but the ACFG data does not meet the requirements.

[0080] (2) Perform the LTFS test on products A1, A2, A3, B1, B2, B3, B4, and B5 using the above method: For details, refer to Figure 2 In product B5, only organic bismuth was added to increase the friction coefficient, which had a negative effect. However, after organic copper was added to A1, A2 and A3, organic copper and organic bismuth produced a synergistic effect, reducing the friction coefficient.

[0081] (3) Products A1, A2, B1, B2 are tested with ACFG as above: Figure 3 As shown, B1 meets the ACFG requirements; B2 does not meet the ACFG requirements. Figure 4 As shown, products A1 and A2 meet the requirements, and the ACFG performance is greatly improved.

[0082] (4) Perform extreme pressure test on products A1, A2, A3, B1, B2, B3, B4, B5 using the above method: Figure 5 As shown: 1) Product B4 with organic copper confirmed that organic copper had no effect on extreme pressure performance; 2) Product B5 with organic bismuth had improved extreme pressure performance; 3) Products A1 and A2 with organic bismuth and organic copper had a synergistic effect in extreme pressure performance. The pressure in the universal joint is very high, and improving extreme pressure performance helps to increase the life of the universal joint.

[0083] (5) HT life test results of A1 and B1 Table 3

[0084] Table 3

[0085]

[0086] Compared with the existing product B1, the life of A1 has been improved.

[0087] (6) The test results of the compatibility of sheath material and lubricant are shown in Table 4

[0088] Table 4

[0089]

[0090] As mentioned above, in terms of sheath compatibility, various performances have been improved compared with the existing products B1 and B2.

[0091] The above is only a preferred embodiment of the present invention, and is not any formal or substantial limitation of the present invention. It should be pointed out that ordinary technicians in this technical field can make several improvements and supplements without departing from the method of the present invention, and these improvements and supplements should also be regarded as the protection scope of the present invention. Any technician familiar with this profession, without departing from the spirit and scope of the present invention, can make some changes, modifications and evolutions of the technical content disclosed above, which are equivalent embodiments of the present invention; at the same time, any changes, modifications and evolutions of any equivalent changes made to the above embodiments based on the essential technology of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. A lubricating grease composition, characterized in that: The grease composition comprises the following components: a) at least one base oil; b) at least one organic bismuth; c) at least one organic copper; d) at least one organic molybdenum; e) at least one thickener.

2. The lubricating grease composition according to claim 1, characterized in that: Relative to the total amount of the lubricating grease composition, by weight percentage: the total content of the organic bismuth, the organic copper and the organic molybdenum is 0.50-11.0%.

3. The lubricating grease composition according to claim 1 or 2, characterized in that: The grease composition comprises the following components by weight percentage: a1) 60-95% of at least one base oil; b1) 0.1-3.0% of at least one organic bismuth; c1) 0.1-3.0% of at least one organic copper; d1) 0.1-5.0% of at least one organic molybdenum; e1) at least one thickener, 2-30%. Necessary additives: 0.2-5%.

4. The lubricating grease composition according to claim 1, characterized in that: Also includes at least one of the following technical features: a11) the base oil is selected from at least one of poly-α-olefins, metallocene poly-α-olefins, naphthenic oils, paraffinic oils, polyether polyols, or synthetic organic esters; b11) the organic bismuth is selected from at least one of bismuth neodecanoate, bismuth cyclohexaneate, bismuth oleate, bismuth octoate, bismuth dithiocarbamate, or bismuth dithiophosphate; c11) the organic copper is selected from at least one of copper naphthenate, copper oleate, copper octoate, copper neodecanoate, copper dithiocarbamate, or copper dithiophosphate; d11) the organic molybdenum is selected from at least one of dithiophosphate molybdenum, dithiocarbamate molybdenum, or phosphorus-free and sulfur-free organic molybdenum; e11) The thickener is selected from at least one of urea thickener, lithium soap, lithium complex soap, sodium-based soap, complex sodium-based soap, calcium soap, or complex calcium-based soap.

5. The lubricating grease composition according to claim 1, 2 or 4, characterized in that: Relative to the total amount of the base oil, by weight percentage: the base oil comprises 30 to 85% of paraffin-based oil; And / or, relative to the total amount of the base oil, by weight percentage: the base oil contains 15-80% of cyclohexane oil.

6. The lubricating grease composition according to claim 3, characterized in that: The necessary additives include at least one of the following technical features: f) the grease composition further comprises at least one organic zinc; g) The grease composition further comprises at least one antioxidant.

7. The lubricating grease composition according to claim 6, characterized in that: The grease composition further comprises at least one of the following technical features by weight percentage: f1) 0.1-3.0% of at least one organic zinc; g1) at least one antioxidant 0.1-2.0%.

8. The lubricating grease composition according to claim 6 or 7, characterized in that: Also includes at least one of the following technical features: f11) the organic zinc is selected from at least one of primary zinc dithiophosphate, secondary zinc dithiophosphate, or tertiary zinc dithiophosphate; g11) The antioxidant is selected from phenolic antioxidants and / or amine-containing phenolic antioxidants.

9. Use of the lubricating grease composition according to any one of claims 1 to 8 in a constant velocity joint.

10. The use according to claim 9, characterized in that The constant velocity universal joint is a constant velocity universal joint specially used for new energy vehicles and motor vehicles; Alternatively, the constant velocity universal joint is a tripod universal joint or a ball universal joint.

11. A constant velocity universal joint, characterized in that: The lubricating grease composition comprises the lubricating grease composition according to any one of claims 1 to 8.

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