Gasoline engine lubricating oil composition

Abstract

The present invention provides a gasoline engine lubricating oil composition comprising the following components: (A) an organophosphorus compound, accounting for 0.05% to 10% of the total mass of the composition; (B) an alkyldiphenylamine, accounting for 0.05% to 5% of the total mass of the composition; (C) polyisobutylene succinimide, accounting for 2% to 30% of the total mass of the composition; (D) a sulfonate and / or a sulfurized alkylphenol, accounting for 0.2% to 10% of the total mass of the composition; (E) a zinc dialkyl dithiophosphate, accounting for 0.2% to 10% of the total mass of the composition; (F) an organomolybdenum, accounting for 0.05% to 5% of the total mass of the composition; (G) an ethylene-propylene copolymer, accounting for 2% to 30% of the total mass of the composition; and (H) a major amount of a lubricating oil base oil. The structure of the organophosphorus compound is described in the specification. The gasoline engine lubricating oil composition of the present invention has excellent anti-wear, friction-reducing, antioxidant, and detergency properties, and can inhibit the formation of deposits in turbochargers.

Description

Technical Field

[0001] The present invention relates to a lubricating oil composition, in particular to a gasoline engine lubricating oil composition with excellent anti-wear, friction-reducing, anti-oxidation and detergency properties. Background Art

[0002] To meet increasingly stringent energy-saving and environmental protection requirements, gasoline engines are trending toward smaller and higher-powered engines, resulting in more demanding operating conditions. With the widespread adoption of technologies like turbocharging and direct injection in gasoline engines, temperatures in engine components like the piston have significantly increased, leading to higher operating temperatures for gasoline engine oils. Consequently, the requirements for high-temperature oxidation resistance are also increasing. For example, for SP / GF-6 and SN / GF-5 oils, the percentage increase in kinematic viscosity in the Procedure IIIH test has been reduced from no more than 150 to no more than 100 for SP / GF-6. In addition to smaller and higher-powered engines, gasoline engines also place higher demands on engine oil anti-wear performance, necessitating the use of more advanced anti-wear agents. Furthermore, as gasoline engine oil specifications upgrade, fuel economy requirements are becoming increasingly stringent, further increasing the need for higher friction-reducing properties.

[0003] In the lubricant industry, the development trend of lubricant additives is towards multifunctionality. Developing multifunctional additives can improve the overall performance of additives, reduce the number and dosage of additives in a formulation, improve formulation applicability, and better meet energy conservation and environmental protection requirements. Researchers in this field are also working to develop multifunctional lubricant additives using biomass resources as raw materials that combine good biodegradability with specialized properties.

[0004] The prior art still requires a gasoline engine lubricating oil composition with excellent anti-wear, antioxidant and friction reducing properties to meet the requirements of the continuous advancement of gasoline engine technology. Summary of the Invention

[0005] The present invention provides a gasoline engine lubricating oil composition comprising the following components:

[0006] (A) an organophosphorus compound, accounting for 0.05% to 10% of the total mass of the composition;

[0007] (B) alkyl diphenylamine, accounting for 0.05% to 5% of the total weight of the composition;

[0008] (C) polyisobutylene succinimide, accounting for 2% to 30% of the total mass of the composition;

[0009] (D) sulfonates and / or sulfurized alkylphenols, accounting for 0.2% to 10% of the total mass of the composition;

[0010] (E) zinc dialkyl dithiophosphate, accounting for 0.2% to 10% of the total weight of the composition;

[0011] (F) organic molybdenum, accounting for 0.05% to 5% of the total mass of the composition;

[0012] (G) ethylene-propylene copolymer, accounting for 2% to 30% of the total mass of the composition;

[0013] (H) a major amount of lubricating base oil;

[0014] The structure of the organophosphorus compound is shown in formula (I):

[0015]

[0016] 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; R groups are 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 Straight or branched alkylene; R2 in n repeating units are the same or different from each other and are independently selected from C 1-20 Straight or branched alkylene; 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), the group represented by formula (III) or the group represented by formula (IV);

[0017]

[0018] The R4 groups are each independently selected from H and C 1-20 Straight-chain or branched alkyl group;

[0019] The R0 groups are independently selected from R5, OR5, wherein the R5 groups are selected from H, C 1-20 Straight or branched alkyl and C 6-18 Aryl, said aryl being optionally substituted with one or more C 1-4 The R5 group is optionally substituted with one or more halogens, and the R5 group is optionally substituted with one or more hydroxy groups;

[0020] * in formula (II), formula (III) and formula (IV) represents the end connected to formula (I);

[0021] The G1 groups are independently selected from R6, OR6, and the end bonded to the group of formula (I'), wherein the R6 group is selected from H, C 1-20 Straight or branched alkyl and C 6-18 Aryl, said aryl being optionally substituted with one or more C 1-4 The R6 group is optionally substituted with one or more halogens, and the R6 group is optionally substituted with one or more hydroxy groups;

[0022]

[0023] In formula (I'), HO, R, y, R1, R2, R3, and n are as defined in formula (I);

[0024] The A' group in formula (I') is selected from A group represented by formula (II), a group represented by formula (III), a group represented by formula (IV), a group represented by formula (III'), a group represented by formula (IV'),

[0025]

[0026] The definition of the R0 group in formula (IV') is the same as that of formula (II), formula (III) and formula (IV); * in formula (III') and formula (IV') represents the end bonded to formula (I'); △ in formula (III') and formula (IV') represents the end bonded to formula (I) or the end bonded to a group of formula (I') other than the group of formula (I') in which it is located; △ in formula (III') and formula (IV') are not bonded to each other;

[0027] wherein the G1' groups are independently selected from R6, OR6, and the end of the △ bond present in the group of formula (I') other than the group of formula (I') in which they are located, wherein the R6 group is selected from H, C 1-20 Straight or branched alkyl and C 6-18 Aryl, said aryl being optionally substituted with one or more C 1-4 The R6 group is optionally substituted by one or more halogens, and the R6 group is optionally substituted by one or more hydroxyls.

[0028] According to the present invention, the R5 and R6 groups can be independently selected from methyl, ethyl, hydroxymethyl, chloromethyl, and phenyl. For example, the R5 group is selected from methyl or ethyl, and the R6 group is selected from phenyl.

[0029] According to the present invention, preferably, in formula (I) and 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 position or ortho position of the chain where R1 is located on the benzene ring, and the R group is selected from C1-4 Straight or branched alkyl, n is an integer between 1 and 5, R1 is independently selected from C 1-10 A linear or branched alkylene group, wherein R2 in n repeating units is independently selected from C 1-10 A linear 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 or branched alkyl; the R5 group is selected from H, C 1-10 Straight or branched alkyl and C 6-10 Aryl; the R6 group is selected from H, C 1-10 Straight or branched alkyl and C 6-10 Aryl.

[0030] According to the present invention, further preferably, in formula (I) and formula (I'), 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 1-4 A linear or branched alkylene group, wherein R2 in n repeating units is independently selected from C 1-4 A linear or branched alkylene group, R3 is selected from H and C 1-4 Straight or branched alkyl; the R4 groups are each independently selected from H and C 1-4 Straight or branched alkyl; the R5 group is selected from H, C 1-4 Straight or branched alkyl and phenyl; the R6 group is selected from H, C 1-4 straight-chain or branched alkyl and phenyl groups.

[0031] According to the present invention, each group in the organic phosphorus compound complies with the bonding rules.

[0032] According to the present invention, examples of the organophosphorus compound include one or more of the following structural compounds:

[0033]

[0034]

[0035]

[0036] According to the present invention, the method for preparing the organophosphorus compound comprises the following steps:

[0037] (1) reacting a compound represented by formula (α) with a peroxide;

[0038]

[0039] 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; R groups are 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 Straight or branched alkylene; R2 in n repeating units are the same or different from each other and are independently selected from C 1-20 Straight or branched alkylene; R3 is selected from H and C 1-20 Straight or branched alkyl; A" groups in 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-chain or branched alkyl group;

[0040] (2) reacting the reaction product of step (1) with a compound represented by formula (β), and collecting the product;

[0041]

[0042] In formula (β), the X group is selected from R5, OR5, wherein the R5 group is selected from H, C 1-20 Straight or branched alkyl and C 6-18 Aryl, said aryl being optionally substituted with one or more C 1-4 The R5 group is optionally substituted by one or more halogens, and the R5 group is optionally substituted by one or more hydroxyls; the X' group is selected from R6, OR6, wherein the R6 group is selected from H, C 1-20 Straight or branched alkyl and C 6-18 Aryl, said aryl being optionally substituted with one or more C 1-4 The R6 group is optionally substituted by one or more halogens, and the R6 group is optionally substituted by one or more hydroxyls.

[0043] According to the present invention, the R5 and R6 groups can be independently selected from methyl, ethyl, hydroxymethyl, chloromethyl, and phenyl. For example, the R5 group is selected from methyl or ethyl, and the R6 group is selected from phenyl.

[0044] According to the present invention, preferably, 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 Straight or branched alkyl, n is an integer between 1 and 5, R1 is independently selected from C 1-10 A linear or branched alkylene group, wherein R2 in n repeating units is independently selected from C 1-10 A linear or branched alkylene group, R3 is selected from H and C 1-10Straight or branched alkyl; the R4 groups are each independently selected from H and C 1-10 Straight or branched alkyl; the R5 group is selected from H, C 1-10 Straight or branched alkyl and C 6-10 Aryl; the R6 group is selected from H, C 1-10 Straight or branched alkyl and C 6-10 Aryl.

[0045] According to the present invention, further preferably, 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 1-4 A linear or branched alkylene group, wherein R2 in n repeating units is independently selected from C 1-4 A linear or branched alkylene group, R3 is selected from H and C 1-4 Straight or branched alkyl; the R4 groups are each independently selected from H and C 1-4 Straight or branched alkyl; the R5 group is selected from H, C 1-4 Straight or branched alkyl and phenyl; the R6 group is selected from H, C 1-4 straight-chain or branched alkyl and phenyl groups.

[0046] 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-butylated cardanol can be obtained by reacting cardanol with tert-butyl chloride.

[0047] 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.

[0048] According to the present invention, in step (2), the compound represented by formula (β) can be selected from one or more of alkoxyphosphoric acid, areneoxyphosphoric acid, alkoxyphosphonic acid, halogenated alkylphosphonic acid and hydroxy-substituted alkylphosphoric acid, for example, one or more of methylphosphonic acid, chloromethylphosphonic acid, phenoxyphosphoric acid, ethoxyphosphoric acid, hydroxymethylphosphonic acid, methoxyphenoxyphosphoric acid and ethoxyphenoxyphosphoric acid can be selected.

[0049] According to the present invention, the equivalent 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 1:2-5:2-5.

[0050] According to the present invention, the reaction temperature of step (1) is preferably 0-100°C, more preferably 20-80°C; the reaction temperature of step (2) is preferably 50-150°C, more preferably 70-120°C.

[0051] According to the present invention, a catalyst may be added in step (1). The catalyst is preferably an acidic catalyst, such as one or more of concentrated sulfuric acid, zinc chloride, aluminum chloride, benzenesulfonic acid, and titanate. 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.

[0052] According to the present invention, a catalyst may be added in step (2). The catalyst is preferably an acidic catalyst, such as one or more of concentrated sulfuric acid, zinc chloride, aluminum chloride, benzenesulfonic acid, and titanate. The amount of the catalyst added is preferably 0.5% to 10% of the compound represented by (α). After the reaction in step (2) is completed, the catalyst may be removed by alkali washing and / or water washing.

[0053] According to the present invention, the reaction steps (1) and (2) 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.

[0054] According to the present invention, the diluent can be selected from one or more of API I, II, III, IV and V group 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.

[0055] According to the present invention, the solvent can be selected from water, C 6-20 Aromatic hydrocarbons (such as benzene, toluene, xylene and cumene), C 6-10 Alkanes (such as n-hexane, cyclohexane and petroleum ether), solvent gasoline, etc. These solvents can be used alone or in combination of two or more. The solvent can be removed after the reaction using methods well known to those skilled in the art, such as under normal pressure or reduced pressure.

[0056] According to a particular embodiment of the present invention, the diluent and / or solvent can be added at any stage of the reaction step according to conventional amounts in the art, without particular limitation.

[0057] According to the present invention, the reaction can be carried out under the protection of an inert gas atmosphere. Examples of the inert gas include nitrogen and argon, and are not particularly limited.

[0058] According to the present invention, by the aforementioned preparation method, as a reaction product, a single organophosphorus compound can be produced, or a mixture consisting of multiple organophosphorus compounds can be produced, or a mixture consisting of one or more organophosphorus compounds and the aforementioned diluent (if used). These reaction products are all contemplated by the present invention, and the difference in their existence form does not affect the realization of the effect of the present invention. Therefore, in the context of this specification, these reaction products are collectively referred to as organophosphorus compounds 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 an organophosphorus compound of a specific structure from the reaction product. Of course, this purification or separation is preferred for further improving the expected effect of the present invention, but is not necessary for the present invention. Nevertheless, as the purification or separation method, for example, purification or separation of the reaction product by column chromatography or preparative chromatography can be cited.

[0059] The organic phosphorus compound of the present invention also has excellent anti-oxidation, anti-wear and friction-reducing properties.

[0060] The preparation method of the organophosphorus compound of the present invention has simple steps and high conversion rate in the reaction process.

[0061] According to the present invention, the component (B) is an alkyl diphenylamine, wherein the alkyl group is preferably C 4～10 The alkyl diphenylamine can be selected from IRGANOX L-06 and IRGANOX L-57 produced by BASF, Germany, T534 produced by Xinxiang Ruifeng Chemical Co., Ltd., VANLUBE SS, VANLUBE961 and VANLUBE 81 produced by Vanderbilt Corporation, USA, and 4-diisooctyl diphenylamine RC7001 produced by Rhein Chemie, Germany.

[0062] According to the present invention, the component (C) is polyisobutylene succinimide, wherein the number average molecular weight of the polyisobutylene portion is preferably 1000 to 4000. The polyisobutylene succinimide can be selected from T151 and T161 produced by Wuxi Nanfang Petroleum Additive Co., Ltd., T151 and T161 produced by Sinopec Yangzi Petrochemical Co., Ltd., T151 and T161 produced by Jinzhou Kangtai Lubricant Additive Co., Ltd., and T151 and T161 produced by Xinxiang Ruifeng New Materials Co., Ltd.

[0063] According to the present invention, component (D) is a sulfonate and / or a sulfurized alkyl phenate. The sulfonate preferably has a base number of 20 to 450 mgKOH / g, and can be selected from one or more of low-base sulfonates, medium-base sulfonates, and high-base sulfonates, with high-base sulfonates being preferred. The sulfonate can be selected from RF1104, RF1105, and RF1106 produced by Xinxiang Ruifeng New Materials Co., Ltd., T101, T104, and T106B produced by Wuxi Nanfang Petroleum Additives Co., Ltd., or BD C020, T104, and T106 produced by Jinzhou Kangtai Lubricant Additives Co., Ltd. The sulfurized alkyl phenate preferably has a base number of 100 to 400 mgKOH / g, and can be selected from medium-base sulfonates and / or high-base sulfonates, with high-base sulfonates being more preferred. The sulfided alkylphenol salt can be selected from T121 and T122 produced by Xinxiang Ruifeng New Materials Co., Ltd., T121 and T122 (S206) produced by Wuxi Nanfang Petroleum Additives Co., Ltd., BD P150 and BD P250 produced by Jinzhou Kangtai Lubricant Additives Co., Ltd., etc.

[0064] According to the present invention, the component (E) is a zinc dihydrocarbyl dithiophosphate, wherein the hydrocarbyl group is preferably selected from C 4～10 Straight-chain or branched alkyl, C 6～10 The dialkyl zinc dithiophosphate can be selected from T202, T203, T205 produced by Wuxi Nanfang Petroleum Additive Co., Ltd. and Jinzhou Kangtai Lubricant Additive Co., Ltd., RC3180 produced by Rheinland, Hitec7169, Hitec1656 produced by Afton Chemical, etc.

[0065] According to the present invention, component (F) is an organic molybdenum compound, which can be selected from one or more oil-soluble organic molybdenum friction modifiers such as dialkyl dithiophosphates, dialkyl dithiophosphate oxygen molybdenum, dialkyl dithiocarbamates, molybdenum xanthates, molybdenum thioxanthates, trinuclear molybdenum sulfur complexes, molybdenum amine complexes, and molybdates, preferably dialkyl dithiocarbamates. The organic molybdenum compound has an organic group containing a sufficient number of carbon atoms to make the organic molybdenum compound soluble or dispersible in the base oil, generally having a carbon number between 6 and 60, preferably between 10 and 50. The organic molybdenum compound can be selected from Molyvan 2000, Molyvan L, 822, 855, etc., produced by Vanderbilt Corporation of the United States.

[0066] According to the present invention, the component (G) is an ethylene-propylene copolymer, preferably a dispersed ethylene-propylene copolymer and / or a non-dispersed ethylene-propylene copolymer, which can be produced by Chevron. 8083, 8475, LZ7065, LZ7067, LZ7077, etc. produced by Lubrizol.

[0067] According to the present invention, component (H) is a lubricant base oil, preferably selected from mineral base oils and / or synthetic base oils. Mineral base oils include liquid paraffin oils and hydrorefined mineral lubricating oils, and are generally classified as Groups I, II, and III. Synthetic lubricating oils include polymerized hydrocarbon oils, alkylbenzenes and their derivatives, ester oils, and Fischer-Tropsch synthetic hydrocarbon oils, and are generally classified as Groups IV and V.

[0068] According to the present invention, preferably, the organic phosphorus compound accounts for 0.2% to 5% of the total mass of the composition; the alkyl diphenylamine accounts for 0.1% to 4% of the total mass of the composition; the polyisobutylene succinimide accounts for 3% to 20% of the total mass of the composition; the sulfonate and / or sulfurized alkyl phenol salt accounts for 2% to 8% of the total mass of the composition; the dialkyl dithiophosphate zinc accounts for 0.5% to 5% of the total mass of the composition; the organic molybdenum accounts for 0.1% to 4% of the total mass of the composition; the ethylene propylene copolymer accounts for 3% to 15% of the total mass of the composition; and the lubricating oil base oil constitutes the main component of the composition.

[0069] The gasoline engine lubricating oil composition of the present invention has excellent anti-wear, friction-reducing, anti-oxidation and detergency properties, and can inhibit the generation of deposits in a turbocharger. DETAILED DESCRIPTION

[0070] The present invention is further described below by way of examples, which however are not intended to limit the present invention.

[0071] The main raw materials used are as follows:

[0072] Cardanol, Shanghai Wujing Chemical Technology Co., Ltd., industrial products

[0073] Zinc chloride, analytical grade, Sinopharm Chemical Reagent Co., Ltd.

[0074] Concentrated sulfuric acid, Sinopharm Chemical Reagent Co., Ltd., analytical grade

[0075] Hydrogen peroxide (30%), Sinopharm Chemical Reagent Co., Ltd., analytical grade

[0076] Formic acid, Sinopharm Chemical Reagent Co., Ltd., analytical grade

[0077] Methylphosphonic acid, Sinopharm Chemical Reagent Co., Ltd., chemically pure

[0078] Chloromethylphosphonic acid, Sinopharm Chemical Reagent Co., Ltd., chemically pure

[0079] Ethoxyphenoxyphosphoric acid, Sinopharm Chemical Reagent Co., Ltd., chemically pure

[0080] Tert-butyl chloride, Sinopharm Chemical Reagent Co., Ltd., analytical grade

[0081] 150SN base oil, Sinopec Yanshan Petrochemical Company, industrial products

[0082] T534, Octylbutyldiphenylamine antioxidant, Xinxiang Ruifeng Chemical Co., Ltd., industrial products

[0083] T161, high molecular weight polyisobutylene succinimide dispersant, Sinopec Yangzi Petrochemical Co., Ltd., industrial products

[0084] T106B, Overbased calcium sulfonate detergent, Wuxi Nanfang Petroleum Additives Co., Ltd., Industrial products

[0085] T122, high base value sulfurized calcium alkyl phenol, Wuxi Nanfang Petroleum Additives Co., Ltd., industrial products

[0086] T203, Zinc bis(octyl)dithiophosphate, Wuxi Southern Petroleum Additives Co., Ltd., Industrial products

[0087] Molyvan 2000, Molybdenum dialkyldithiocarbamate, Vanderbilt Corporation, Industrial product

[0088] LZ7065, OCP viscosity index improver, Lubrizol, industrial products

[0089] HVIⅢ-4 base oil, Sinopec Maoming Branch, industrial products

[0090] PAO-4, polyalphaolefin synthetic base oil, Sinopec Maoming Branch, industrial products

[0091] Example 1 Preparation of tert-butylated cardanol

[0092] 100g of cardanol, 8g of formic acid, 0.3g of sulfuric acid, and 200g of hydrogen peroxide were added to a three-necked flask equipped with a mechanical stirrer, a reflux condenser, and temperature control. Stirring and heating were initiated. The reaction temperature was maintained at 70°C for 3 hours. After completion of the reaction, the temperature was lowered to yield a brownish-red transparent liquid. The reaction product was filtered and alkaline-washed with a 5% KOH solution, followed by washing with distilled water until neutral. The organic phase was then distilled under reduced pressure at 100 Pa and 150°C for 1 hour to remove moisture and unreacted raw materials, yielding an orange-red transparent liquid of epoxidized cardanol.

[0093] Dissolve 35g of epoxidized cardanol in 100ml of acetone. Once dissolved, place the mixture in a 250ml three-necked reaction flask. Add 0.9g of zinc chloride catalyst, stir, and heat. Maintain the reaction temperature at 60°C and slowly add 9.5g of tert-butyl chloride dropwise to the reaction flask. Continue the reaction for 3 hours. After the reaction is complete, cool the mixture to yield a brownish-red, transparent liquid. Filter the reaction product, wash it with a 5% KOH solution, then rinse it with distilled water until neutral. Vacuum distillation at 1000 Pa and 120°C for 1 hour removes the solvent, water, and unreacted raw materials, yielding a brownish-red, viscous liquid of tert-butylated epoxidized cardanol.

[0094] An example reaction formula of the above reaction is shown below.

[0095]

[0096] Example 2

[0097] 20 g of tert-butylated epoxy cardanol prepared in Example 1, 0.2 g of concentrated sulfuric acid, 10 g of water, and 100 g of toluene were added to a three-necked flask equipped with a mechanical stirrer and a reflux condenser. The mixture was stirred, heated, and refluxed at 85°C for 1 hour. Then, 50 g of an aqueous solution of methylphosphonic acid (containing 10 g of methylphosphonic acid) was added dropwise. After the addition was complete, the reaction was refluxed for 5 hours before terminating the reaction. The product was washed three times with water, and the solvent was evaporated to obtain organophosphorus compound W-01, which had a phosphorus content of 9.8%.

[0098] Since the reactants are a mixture of mono-epoxy, diepoxy, and tri-epoxy tert-butylated epoxy cardanols, there are many reactions and reaction products. Therefore, the main reaction formula representatively using mono-epoxy tert-butylated epoxy cardanol as the raw material is exemplified below.

[0099]

[0100] The product prepared in Example 2 was subjected to infrared spectroscopy and nuclear magnetic resonance analysis. The infrared spectroscopy analysis results are shown in Table 1, and the nuclear magnetic resonance analysis results are shown in Table 2.

[0101] Table 1 Infrared analysis results of products

[0102]

[0103] Table 1 shows that the product contains characteristic peaks such as C-OH stretching vibration peak, P=O stretching vibration peak, benzene ring skeleton stretching vibration peak, POC stretching vibration peak and PO stretching vibration peak, which indicates that the synthesized product is the target compound.

[0104] Table 2 NMR carbon spectrum analysis results of products

[0105]

[0106] The attribution of each C element in Table 2 can indicate that the synthesized product is the target compound.

[0107] Example 3

[0108] 20 g of tert-butylated epoxy cardanol prepared in Example 1, 0.2 g of concentrated sulfuric acid, 10 g of water, and 100 g of toluene were added to a three-necked flask equipped with a mechanical stirrer and a reflux condenser. The mixture was stirred, heated, and refluxed at 95°C for 1 hour. 50 g of an aqueous solution of chloromethylphosphonic acid (containing 10 g of chloromethylphosphonic acid) was then added dropwise. After the addition was complete, the reaction was refluxed for 3 hours before stopping. The product was washed three times with water, and the solvent was evaporated to obtain organophosphorus compound W-02, whose phosphorus content was 8.1%.

[0109] Example 4

[0110] 20 g of tert-butylated epoxy cardanol prepared in Example 1, 0.2 g of concentrated sulfuric acid, 10 g of water, and 100 g of toluene were added to a three-necked flask equipped with a mechanical stirrer and a reflux condenser. The mixture was stirred, heated, and refluxed at 110°C for 1 hour. 20 g of ethoxyphenoxyphosphoric acid was then added dropwise. After the addition was complete, the reaction was refluxed for 6 hours before terminating. The product was washed three times with water, and the solvent was evaporated to yield organophosphorus compound W-03, which had a phosphorus content of 7.5%.

[0111] A multifunctional organic boron compound produced by Vanderbilt Corporation was selected as a contrast agent, with the brand name VANLUBE 289 and the mark Qa.

[0112] Examples 5 to 9 of the lubricating oil composition and comparative examples Q-1, Q-2 and Q-3

[0113] According to the formulation in Table 3, lubricating oil compositions of Examples 5 to 9 and Comparative Examples Q-1 and Q-2 were prepared. Comparative Example Q-3 is a commercially available gasoline engine oil of API SP specification.

[0114] Table 3 Examples and Comparative Examples of Lubricating Oil Compositions

[0115]

[0116] The lubricating oil compositions of the above examples and comparative examples were used as test samples, and their anti-wear, anti-friction, anti-oxidation and detergency properties were evaluated respectively.

[0117] The performance evaluation tests in the examples and comparative examples were carried out as follows.

[0118] (1) Friction reduction and anti-wear properties

[0119] Lubricating oil compositions from the Examples or Comparative Examples were used as test samples in the High-Frequency Reciprocating Friction Test (HFRR) and the Micro-Traction Test (MTM). The HRRR test conditions were: 1000 g load, 20 Hz frequency, 100°C temperature, and 60 min test time. The friction coefficient and wear spot diameter were recorded. Smaller friction coefficients and wear spot diameters indicate better friction reduction and anti-wear properties. The MTM test conditions were: 37 N load, 1000 rpm speed, 100°C temperature, and 60 min test time. The traction coefficient was recorded.

[0120] (2) Antioxidant properties

[0121] The lubricating oil compositions of the Examples and Comparative Examples were used as test samples. The antioxidant properties of the test samples were evaluated using pressurized differential scanning calorimetry (PDSC) and thin-layer oxygen absorption oxidation stability of gasoline engine oil (TFOUT). The oxidation induction period (in minutes) of the test samples was expressed. The PDSC test conditions were: temperature 200°C, pressure 3.5 MPa, and oxygen flow rate 100 mL / min. The TFOUT test was conducted according to SH / T 0074.

[0122] (3) Cleaning performance

[0123] The lubricating oil compositions of the examples or comparative examples were used as test samples, and the TEOST 33C turbocharger deposit evaluation method was adopted according to ASTM D6335.

[0124] The evaluation results are shown in Table 4.

[0125] Table 4 Performance evaluation results of the embodiments and comparative examples

[0126]

Claims

1. A gasoline engine lubricating oil composition comprising the following components: (A) an organophosphorus compound, accounting for 0.05% to 10% of the total mass of the composition; (B) alkyl diphenylamine, accounting for 0.05% to 5% of the total weight of the composition; (C) polyisobutylene succinimide, accounting for 2% to 30% of the total mass of the composition; (D) sulfonates and / or sulfurized alkylphenols, accounting for 0.2% to 10% of the total mass of the composition; (E) zinc dialkyl dithiophosphate, accounting for 0.2% to 10% of the total weight of the composition; (F) organic molybdenum, accounting for 0.05% to 5% of the total mass of the composition; (G) ethylene-propylene copolymer, accounting for 2% to 30% of the total mass of the composition; (H) a major amount of lubricating base oil; The organophosphorus compound is one or more of the following compounds:

2. The lubricating oil composition according to claim 1, characterized in that The preparation method of the organophosphorus compound comprises the following steps: (1) reacting the compound (α) with a peroxide; The (α) compound is selected from cardanol and alkylated cardanol; (2) reacting the reaction product of step (1) with compound (β) and collecting the product; The (β) compound is selected from one or more of alkoxy phosphoric acid, areneoxy phosphoric acid, alkoxy phosphonic acid, halogenated alkylphosphonic acid and hydroxy-substituted alkyl phosphoric acid.

3. The lubricating oil composition according to claim 2, characterized in that 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.

4. The lubricating oil composition according to claim 2, characterized in that The (β) compound is selected from one or more of methylphosphonic acid, chloromethylphosphonic acid, phenoxyphosphonic acid, ethoxyphosphonic acid, hydroxymethylphosphonic acid, methoxyphenoxyphosphonic acid and ethoxyphenoxyphosphonic acid.

5. The lubricating oil composition according to claim 2, characterized in that The equivalent ratio of the (α) compound to the peroxide and the (β) compound is 1:0.5-10:0.5-10; the reaction temperature of step (1) is 0-100°C; and the reaction temperature of step (2) is 50-150°C.

6. The lubricating oil composition according to any one of claims 1 to 5, characterized in that The alkyl group in the alkyl diphenylamine is C 4～10 The number average molecular weight of the polyisobutylene part in the polyisobutylene succinimide is 1000 to 4000; the sulfonate is selected from sulfonates with a base value of 20 to 450 mgKOH / g, the sulfurized alkylphenol is selected from sulfurized alkylphenols with a base value of 100 to 400 mgKOH / g; the hydrocarbon group in the dialkyl dithiophosphate zinc is selected from C 4～10 Straight-chain or branched alkyl, C 6～10 Aryl; the organic molybdenum is selected from one or more of dialkyl dithiophosphate molybdenum, dialkyl dithiophosphate oxymolybdenum, dialkyl dithiocarbamate molybdenum, xanthate molybdenum, thioxanthate molybdenum, trinuclear molybdenum sulfur complex, molybdenum amine complex, and molybdate; the ethylene-propylene copolymer is selected from dispersed ethylene-propylene copolymer and / or non-dispersed ethylene-propylene copolymer; the lubricating oil base oil is selected from mineral base oil and / or synthetic base oil.

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