Diesel engine oil composition

Abstract

The present invention provides a diesel engine oil composition comprising an organophosphorus compound, a boronated polyisobutylene succinimide dispersant, an amine antioxidant, a detergent, a zinc dialkyl dithiophosphate, a viscosity index improver, and a major amount of a lubricating base oil. The organophosphorus compound has a structure as shown in Formula (I): #imgabs0# In Formula (I), 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); #imgabs1# where the definitions of each group are as described in the specification. The diesel engine oil composition of the present invention exhibits excellent high-temperature antioxidant properties, high-temperature detergency, anti-wear properties, and anti-corrosion properties, meeting the requirements of high-performance diesel engine lubricants.

Description

Technical Field

[0001] The present invention relates to a lubricating oil composition, in particular to a diesel engine oil composition. Background Art

[0002] Lubricant performance deteriorates over time due to oxidation, additive depletion, and the influx of foreign contaminants such as water, soot, and dust. When lubricant performance is insufficient to maintain proper equipment operation or even poses a risk of damage, it must be promptly replaced. In recent years, user demand for high-quality lubricants has continued to increase, and leading domestic OEMs have introduced long drain intervals of 40,000 to 80,000 kilometers for diesel engine oils. Consequently, diesel engine oils with extended drain intervals have gained widespread attention.

[0003] The service life of diesel engine oil is closely related to the engine's structure and operating conditions. The use of technologies like delayed injection and EGR in diesel engines has further increased the operating temperature of diesel engine oil, exacerbating oil oxidation, affecting its cleanliness and anti-wear properties, and directly impacting the oil change cycle. Furthermore, with the continuous upgrading of oil specifications, engine tests of corresponding specifications have placed increasingly higher demands on the antioxidant properties of diesel engine oil. The use of higher-performance antioxidant additives can significantly enhance the oil's antioxidant capacity, meeting the antioxidant performance assessment requirements of higher-specification oils and contributing to the long-term use of the oil.

[0004] CN 202011165680 discloses an antioxidant and anti-wear lubricant additive and its application, wherein a phosphate anti-wear agent compounded from diethyl (2-butyloctyl) phosphonate and tricresol phosphate is added, and a methylbenzotriazole passivator and a composite antioxidant are also added, which can improve the anti-wear and friction-reducing properties and antioxidant properties of the lubricant. CN 02825212 discloses an antioxidant system containing sulfided isobutylene and hindered phenol, which is suitable for use in natural gas engines and can improve the antioxidant and anti-nitration properties of engine lubricants. However, when these prior art additives are used in engine oils, their antioxidant properties still need to be further improved and enhanced.

[0005] Therefore, the prior art still requires a diesel engine oil composition that can not only meet the increasingly stringent requirements of today's higher-specification products on anti-oxidation performance, but also has excellent detergency, dispersancy and anti-wear properties. Summary of the Invention

[0006] The present invention provides a diesel engine oil composition.

[0007] The diesel engine oil composition of the present invention comprises an organophosphorus compound, a boronated polyisobutylene succinimide dispersant, an amine antioxidant, a detergent, a zinc dialkyl dithiophosphate, a viscosity index improver, and a major amount of a lubricating base oil; wherein the structure of the organophosphorus compound is as shown in formula (I):

[0008]

[0009] 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);

[0010]

[0011] The R4 groups are each independently selected from H and C 1-20 Straight-chain or branched alkyl group;

[0012] 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;

[0013] * in formula (II), formula (III) and formula (IV) represents the end connected to formula (I);

[0014] 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;

[0015]

[0016] In formula (I'), HO, R, y, R1, R2, R3, and n are as defined in formula (I);

[0017] 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'),

[0018]

[0019] 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;

[0020] 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.

[0021] 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.

[0022] 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 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 1-10 Straight or branched alkyl; the R4 groups are each independently selected from H and C 1-10Straight 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.

[0023] 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.

[0024] According to the present invention, each group in the organic phosphorus compound complies with the bonding rules.

[0025] According to the present invention, examples of the organophosphorus compound include one or more of the following structural compounds:

[0026]

[0027]

[0028]

[0029] According to the present invention, the method for preparing the organophosphorus compound comprises the following steps:

[0030] (1) reacting a compound represented by formula (α) with a peroxide;

[0031]

[0032] 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 C1-20 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;

[0033] (2) reacting the reaction product of step (1) with a compound represented by formula (β), and collecting the product;

[0034]

[0035] 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.

[0036] 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.

[0037] 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 1-10 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.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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 alkylphosphonic acid, for example, one or more of methylphosphonic acid, chloromethylphosphonic acid, phenoxyphosphoric acid, ethoxyphosphoric acid, hydroxymethylphosphonic acid and phenoxymethoxyphosphoric acid.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] The organic phosphorus compound of the present invention also has excellent anti-oxidation, anti-wear and friction-reducing properties.

[0053] The preparation method of the organophosphorus compound of the present invention has simple steps and high conversion rate in the reaction process.

[0054] According to the present invention, the number average molecular weight of the polyisobutylene group in the boronated polyisobutylene succinimide dispersant is preferably 800 to 4000, more preferably 1500 to 3000. T161B and T154B produced by Wuxi Southern Petroleum Additive Co., Ltd. and KT1054B, KT1354B, and KT1962B produced by Jinzhou Kangtai Lubricant Additive Co., Ltd. can be used.

[0055] According to the present invention, the amine antioxidant is preferably alkylated diphenylamine and / or alkylphenyl-α-naphthylamine, and can be selected from IRGANOX L-01 and IRGANOXL-57 produced by BASF of Germany, T534 produced by Beijing Xingpu Company, LZ5150A produced by Lubrizol Lanlian Additives Co., Ltd., Vanlube NA, Vanlube961, dioctyldiphenylamine Vanlube 81, dinonyldiphenylamine Vanlube DND produced by Vanderbilt Company of the United States, and p-, p-diisooctyldiphenylamine RC7001 produced by Rhein Chemie of Germany.

[0056] According to the present invention, the detergent is preferably one or more of sulfonates, sulfurized alkyl phenates, salicylates, and alkyl phenates, more preferably a mixture of sulfonates and sulfurized alkyl phenates, with the mass ratio of the sulfonates and sulfurized alkyl phenates preferably being between 0.3:1 and 5:1. The sulfonates and / or sulfurized alkyl phenates can be selected from T107 and S206 produced by Wuxi Nanfang Petroleum Additives Co., Ltd., RF1107 and T122 produced by Xinxiang Ruifeng New Materials Co., Ltd., LZL115A and LZL115B produced by Lubrizol Lanlian Additives Co., Ltd., LZ6499 and LZ6500 produced by Lubrizol Corporation, Hitec7637 produced by Afton Corporation, OLOA219 produced by Chevron Oronite Company, C9340 produced by Infineum, and the like.

[0057] According to the present invention, the alkyl group in the dialkyl zinc dithiophosphate is preferably selected from C2 to C 12 One or more of the primary and secondary alkyl groups can be selected from T202 and T203 produced by Wuxi Southern Petroleum Additive Co., Ltd., primary and secondary alkyl T204 and secondary alkyl T205 produced by the Additive Factory of Jinzhou Petrochemical Branch, LZ1371 and LZ1375 produced by Lubrizol, C9417, C9425 and C9426 produced by Runyinglian, Hitec7169 and Hitec1656 produced by Afton Chemical, etc.

[0058] According to the present invention, the viscosity index improver is preferably selected from OCP type viscosity index improvers, and can be LZ 7067 produced by Lubrizol Corporation or 8065E produced by Chevron Oronite Company.

[0059] According to the present invention, the lubricating base oil is preferably selected from one or more of API Group I, Group II, Group III, Group IV, and Group V base oils, more preferably one or more of API Group I, Group II, and Group IV base oils.

[0060] According to the present invention, preferably, the organophosphorus compound accounts for 0.1% to 5% of the total mass of the diesel engine oil composition; the boronated polyisobutylene succinimide dispersant accounts for 1% to 15% of the total mass of the diesel engine oil composition; the amine antioxidant accounts for 0.2% to 5% of the total mass of the diesel engine oil composition; the detergent accounts for 0.5% to 10% of the total mass of the diesel engine oil composition; the zinc dialkyl dithiophosphate accounts for 1% to 5% of the total mass of the diesel engine oil composition; the viscosity index improver accounts for 3% to 15% of the total mass of the diesel engine oil composition; and the lubricating base oil constitutes the main component of the diesel engine oil composition.

[0061] The diesel engine oil composition of the present invention has excellent high-temperature antioxidant performance, high-temperature detergency, anti-wear performance and anti-corrosion performance, and can meet the requirements of high-performance diesel engine lubricating oil. DETAILED DESCRIPTION

[0062] The present invention is further described below by way of examples, which however are not intended to limit the present invention.

[0063] The raw materials used are as follows:

[0064] Cardanol, Shanghai Wujing Chemical Technology Co., Ltd., industrial products

[0065] Zinc chloride, analytical grade, Sinopharm Chemical Reagent Co., Ltd.

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

[0067] Hydrogen peroxide (30%), Sinopharm Chemical Reagent Co., Ltd., analytical grade

[0068] Formic acid, Sinopharm Chemical Reagent Co., Ltd., analytical grade

[0069] Methylphosphonic acid, Sinopharm Chemical Reagent Co., Ltd., chemically pure

[0070] Chloromethylphosphonic acid, Sinopharm Chemical Reagent Co., Ltd., chemically pure

[0071] Ethoxyphenoxyphosphoric acid, Sinopharm Chemical Reagent Co., Ltd., chemically pure

[0072] Tert-butyl chloride, Sinopharm Chemical Reagent Co., Ltd., analytical grade

[0073] Example 1 Preparation of tert-butylated cardanol

[0074] 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.

[0075] 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.

[0076] An example reaction formula of the above reaction is shown below.

[0077]

[0078] Example 2

[0079] 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%.

[0080] 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.

[0081]

[0082] 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.

[0083] Table 1 Infrared analysis results of products

[0084]

[0085] 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.

[0086] Table 2 NMR carbon spectrum analysis results of products

[0087]

[0088] The attribution of each C element in Table 2 can indicate that the synthesized product is the target compound.

[0089] Example 3

[0090] 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%.

[0091] Example 4

[0092] 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%.

[0093] Examples 5-7 and Comparative Examples 1-4 of Diesel Engine Oil Compositions

[0094] The components were blended in proportion according to the formulation in Table 3, and stirred at 60° C. for 2 hours to prepare diesel engine oil compositions of Examples 5-7 and Comparative Examples 1-4.

[0095] The main additives used in the diesel engine oil composition of the present invention are as follows:

[0096] T154B, boronated succinimide ashless dispersant, Wuxi Nanfang Petroleum Additives Co., Ltd.

[0097] Vanlube 81, dioctyldiphenylamine, Vanderbilt Corporation

[0098] T512, phenolic ester antioxidant, Xinxiang Ruifeng New Materials Co., Ltd.

[0099] T501, Di-tert-butyl-p-cresol, Xingpu Company, China Academy of Petrochemical Technology

[0100] T306, Tricresyl phosphate, Huihua Petroleum Additives Co., Ltd.

[0101] T107, Overbased magnesium sulfonate, Wuxi Southern Petroleum Additives Co., Ltd.

[0102] T122, calcium alkyl phenate sulfide, Xinxiang Ruifeng New Materials Co., Ltd.

[0103] T203, zinc bis(octyl dithiophosphate), Wuxi Southern Petroleum Additives Co., Ltd.

[0104] LZ 7067, OCP viscosity improver, Lubrizol Corporation

[0105] HVI II 10, hydrogenated base oil, Sinopec Jinan Petrochemical Company

[0106] PAO10, PAO6, polyalphaolefin synthetic base oil, ExxonMobil Corporation

[0107] Table 3

[0108]

[0109] The high-temperature antioxidant performance, high-temperature detergency performance, and anti-wear performance of the diesel engine oil compositions of the above examples and comparative examples were evaluated. The measurement methods are described below, and the measurement results are shown in Table 4.

[0110] Method for evaluating the performance of diesel engine oil compositions

[0111] (1) Antioxidant performance evaluation

[0112] The high-temperature antioxidant properties of the diesel engine oil compositions prepared in the Examples or Comparative Examples were evaluated using pressurized differential scanning calorimetry (PDSC). Test conditions were: temperature 200°C, pressure 0.5 MPa, and an oxygen flow rate of 100 mL / min. The antioxidant properties were measured as the oxidation induction period (in minutes) of the test samples. A longer oxidation induction period indicates better high-temperature antioxidant properties.

[0113] (2) Cleaning performance evaluation

[0114] The high-temperature detergency performance of the diesel engine oil compositions prepared in the Examples or Comparative Examples was evaluated using a coking plate test. The test conditions were: an oil temperature of 140°C, a plate temperature of 320°C, and a test duration of 4 hours. The lower the amount of coke on the coking plate surface at the end of the test, the better the detergency of the oil.

[0115] (3) Anti-wear performance evaluation

[0116] Anti-wear testing was performed on the diesel engine oil compositions prepared in the Examples or Comparative Examples using an Optimol SRV reciprocating friction and wear tester. Test conditions were a load of 200 N, a frequency of 20 Hz, an amplitude of 1 mm, a temperature of 100°C, and a friction time of 30 minutes. After the test, the wear spot diameter of the test piece was measured. The smaller the wear spot diameter, the better the anti-wear performance of the test sample.

[0117] Table 4

[0118]

[0119] As can be seen from Table 4, the diesel engine oil composition of the present invention has excellent high-temperature antioxidant performance, high-temperature detergency and anti-wear performance.

[0120] An oil's ability to control metal corrosion is a key evaluation metric in the specifications for high-end diesel engine oils above CF-4. The compositions of Example 5 and Comparative Example 3 were subjected to high-temperature corrosion testing according to the SH / 0754 method. The oil's ability to control metal corrosion was evaluated by measuring the amount of metal dissolved in the oil. See Table 5. Oils with higher metal corrosion resistance provide superior engine protection and extend oil change intervals.

[0121] Table 5

[0122] Test items Example 5 Comparative Example 3 Cu / (mg / Kg) 19 30 Pb / (mg / Kg) 40 100

[0123] As can be seen from Table 5, the diesel engine oil composition of the present invention also has excellent anti-corrosion performance.

Claims

1. A diesel engine oil composition comprising an organophosphorus compound, a boronated polyisobutylene succinimide dispersant, an amine antioxidant, a detergent, a zinc dialkyl dithiophosphate, a viscosity index improver, and a major amount of a lubricating base oil; wherein the organophosphorus compound is one or more of the following compounds:

2. The composition according to claim 1, characterized in that The preparation method of the organophosphorus compound comprises the following steps: (1) reacting the (α) compound 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 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 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.

5. The composition according to any one of claims 1 to 4, characterized in that The number average molecular weight of the polyisobutylene group in the boronated polyisobutylene succinimide dispersant is 800 to 4000; the amine antioxidant is selected from alkylated diphenylamine and / or alkylphenyl-α-naphthylamine; the detergent is selected from one or more of sulfonates, sulfurized alkylphenols, salicylates and alkylphenols; the alkyl group in the dialkyl dithiophosphate zinc is selected from C2 to C 12 One or more primary and secondary alkyl groups; the viscosity index improver is selected from OCP type viscosity index improver; the lubricating base oil is selected from one or more of API Group I, Group II, Group III, Group IV, and Group V base oils.

6. The composition according to any one of claims 1 to 4, characterized in that The organophosphorus compound accounts for 0.1% to 5% of the total mass of the diesel engine oil composition; the boronated polyisobutylene succinimide dispersant accounts for 1% to 15% of the total mass of the diesel engine oil composition; the amine antioxidant accounts for 0.2% to 5% of the total mass of the diesel engine oil composition; the detergent accounts for 0.5% to 10% of the total mass of the diesel engine oil composition; the zinc dialkyl dithiophosphate accounts for 1% to 5% of the total mass of the diesel engine oil composition; the viscosity index improver accounts for 3% to 15% of the total mass of the diesel engine oil composition; and the lubricating base oil constitutes the main component of the diesel engine oil composition.

Images