A heavy-load gas engine oil composition

Abstract

The present invention provides a heavy-duty gas engine lubricating oil composition comprising an organophosphorus compound, a polyisobutylene succinimide ashless dispersant, an amine antioxidant, a detergent, a zinc dialkyl dithiophosphate, a viscosity index improver, a pour point depressant, 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 gas engine lubricating oil composition of the present invention exhibits excellent high-temperature antioxidant, high-temperature detergency, anti-wear, and dispersancy properties, meeting the requirements of high-performance gas engine lubricants.

Description

Technical Field

[0001] The present invention relates to a lubricating oil composition, in particular to a lubricating oil composition for a heavy-load gas engine. Background Art

[0002] Gas engines offer excellent clean combustion characteristics, economy, and safety, and are widely used in areas such as taxis and city buses. Compared to gasoline and diesel engines, gas engines have higher combustion chamber temperatures and higher exhaust temperatures. This high temperature, on the one hand, causes rapid oxidation and deterioration of the oil, necessitating improvements in the oil's antioxidant capacity; on the other hand, it hinders the formation of the lubricating oil film, necessitating improvements in the oil's anti-wear capabilities. The intensity of vehicle deployment and traffic congestion in large and medium-sized cities across China have resulted in buses and other vehicles being severely overloaded and experiencing prolonged periods of stop-and-go traffic. This makes these gas engine oils more susceptible to contamination, aging, and deterioration. In response to customer demands for improved gas engine performance and extended oil change intervals, there is an urgent need to develop high-performance lubricants specifically for gas engines.

[0003] CN 107653044 uses phenolic antioxidants to improve the viscosity retention and antioxidant capacity of oil products, but this is only for oil products that meet lower quality grades and is difficult to adapt to the increasingly high performance requirements. CN 112111317 can achieve synergistic effects between antioxidants and metal deactivators by screening the types and ratios of the antioxidants and metal deactivators, thereby improving the antioxidant properties of gas engine oils, but there is still room for further improvement in antioxidant properties. CN 112391222 provides an antioxidant and anti-wear lubricant additive composition comprising a phosphate anti-wear agent and a composite antioxidant of hydroquinone and 2-butylformyl-3-butylphenol, which can improve the anti-wear properties of lubricants and enhance their thermal stability and antioxidant properties. The antioxidant, cleansing, dispersibility, and anti-wear properties of gas engine oils in the prior art still need to be further improved and enhanced.

[0004] Therefore, the prior art still requires a heavy-duty gas engine lubricating oil composition that can not only meet the increasingly stringent requirements of gas engines for anti-oxidation performance and customers' requirements for extended oil change cycles, but also has excellent detergency, dispersancy and anti-wear properties. Summary of the Invention

[0005] The present invention provides a heavy-load gas engine lubricating oil composition.

[0006] The heavy-duty gas engine lubricating oil composition of the present invention comprises an organophosphorus compound, a polyisobutylene succinimide ashless dispersant, an amine antioxidant, a detergent, a zinc dialkyl dithiophosphate, a viscosity index improver, a pour point depressant, and a major amount of a lubricating base oil; wherein the structure of the organophosphorus compound is as shown in formula (I):

[0007]

[0008] 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);

[0009]

[0010] The R4 groups are each independently selected from H and C 1-20 Straight-chain or branched alkyl group;

[0011] 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;

[0012] * in formula (II), formula (III) and formula (IV) represents the end connected to formula (I);

[0013] 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;

[0014]

[0015] In formula (I'), HO, R, y, R1, R2, R3, and n are as defined in formula (I);

[0016] 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'),

[0017]

[0018] 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;

[0019] 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.

[0020] 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.

[0021] 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 1-10 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.

[0022] 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.

[0023] According to the present invention, each group in the organic phosphorus compound complies with the bonding rules.

[0024] According to the present invention, examples of the organophosphorus compound include one or more of the following structural compounds:

[0025]

[0026]

[0027]

[0028] According to the present invention, the method for preparing the organophosphorus compound comprises the following steps:

[0029] (1) reacting a compound represented by formula (α) with a peroxide;

[0030]

[0031] 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;

[0032] (2) reacting the reaction product of step (1) with a compound represented by formula (β), and collecting the product;

[0033]

[0034] 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.

[0035] 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.

[0036] 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.

[0037] 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 1-4A 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.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] 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.

[0051] The organic phosphorus compound of the present invention also has excellent anti-oxidation, anti-wear and friction-reducing properties.

[0052] The preparation method of the organophosphorus compound of the present invention has simple steps and high conversion rate in the reaction process.

[0053] According to the present invention, the number average molecular weight of the polyisobutylene portion of the polyisobutylene succinimide ashless dispersant is preferably 800 to 4000, more preferably 1500 to 3000; the polyisobutylene succinimide ashless dispersant is further preferably a mixture of high molecular weight polyisobutylene succinimide and mono-heptyl polyisobutylene succinimide, and the mass ratio between the two is preferably 1:1 to 5. The polyisobutylene succinimide ashless dispersant can be selected from T161, T161A, T161B produced by the Additive Factory of Jinzhou Petrochemical Branch, T161 produced by Shanghai Hairun Co., Ltd., LZL157 produced by Lubrizol Lanlian Additive Co., Ltd., LZ6418 and LZ6420 produced by Lubrizol, Hitec646 produced by Afton Chemical, T151 produced by Wuxi Nanfang Petroleum Additive Co., Ltd., T151 produced by Shanghai Hairun Co., Ltd., LZL151A produced by Lanlian Additive Co., Ltd., etc.

[0054] 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 Corporation of the United States, and p-, p-diisooctyldiphenylamine RC7001 produced by Rhein Chemie of Germany.

[0055] According to the present invention, the detergent is preferably one or more of sulfonates, sulfurized alkylphenates, salicylates, and alkylphenates, and more preferably a mixture of high-based sulfonates, medium-based sulfonates, and sulfurized alkylphenates. The mass ratio of the high-based sulfonates to the medium-based sulfonates is preferably 1:1-5, and the mass ratio of the high-based sulfonates to the sulfurized alkylphenates is preferably 1:1-3. The base number of the high-based sulfonates is preferably (200-450) mgKOH / g, the base number of the medium-based sulfonates is preferably (100-200) mgKOH / g, and the base number of the sulfurized alkylphenates is preferably (150-350) mgKOH / g. The sulfonates and sulfurized alkylphenols can be selected from T107 and S206 produced by Wuxi Southern Petroleum Additives Co., Ltd., T122, T106B, and T105 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, and C9340 produced by Infineum.

[0056] According to the present invention, the alkyl group in the zinc dialkyl dithiophosphate is preferably selected from one or more primary and secondary alkyl groups of C2 to C8, and can be selected from T202 and T203 produced by Wuxi Nanfang 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 Runyinlian, Hitec7169 and Hitec1656 produced by Afton Chemical, etc.

[0057] According to the present invention, the viscosity index improver is preferably selected from OCP type viscosity index improvers, and can be 8065E produced by Chevron Oronite Company or 7067 produced by Lubrizol Corporation.

[0058] According to the present invention, the pour point depressant is preferably selected from one or more of poly-α-olefins, alkyl naphthalenes and polymethacrylates, and can be selected from T801 and T803B of Wuxi Nanfang Petroleum Additives Company, T866 of Xingpu Company, etc.

[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, the organic phosphorus compound accounts for 0.1% to 10% (preferably 0.2% to 5%) of the total mass of the gas engine lubricating oil composition; the polyisobutylene succinimide ashless dispersant accounts for 0.5% to 15% (preferably 1% to 10%) of the total mass of the gas engine lubricating oil composition; the amine antioxidant accounts for 0.1% to 10% (preferably 0.2% to 5%) of the total mass of the gas engine lubricating oil composition; the detergent accounts for 0.2% of the total mass of the gas engine lubricating oil composition. ~15% (preferably 0.5%~8%); the zinc dialkyl dithiophosphate accounts for 0.5%~10% (preferably 1%~5%) of the total mass of the gas engine lubricating oil composition; the viscosity index improver accounts for 3%~20% (preferably 5%~15%) of the total mass of the gas engine lubricating oil composition; the pour point depressant accounts for 0.01%~5% (preferably 0.1%~3%) of the total mass of the gas engine lubricating oil composition; and the lubricating base oil constitutes the main component of the gas engine lubricating oil composition.

[0061] The gas engine lubricating oil composition of the present invention has excellent high-temperature oxidation resistance, high-temperature detergency, anti-wear performance and dispersibility, and can meet the requirements of high-performance gas 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 1-3 of Gas Engine Lubricating Oil Compositions

[0094] According to the formulation in Table 3, Examples 5-7 and Comparative Examples 1-3 of the gas engine lubricating oil compositions were prepared, wherein the main raw materials used were from the following sources:

[0095] T161, polymer succinimide ashless dispersant, Shanghai Hairun Additive Co., Ltd.

[0096] T151, single-hang succinimide ashless dispersant, Shanghai Hairun Additive Co., Ltd.

[0097] T534, Alkyl diphenylamine, Xinxiang Ruifeng New Materials Co., Ltd.

[0098] T106B, overbased sulfonate, Wuxi Southern Petroleum Additives Co., Ltd.

[0099] T105, medium base sulfonate, Xinxiang Ruifeng New Materials Co., Ltd.

[0100] T122, calcium alkyl phenate sulfide, Xinxiang Ruifeng New Materials Co., Ltd.

[0101] T203, zinc dialkyl dithiophosphate, Xinxiang Ruifeng New Materials Co., Ltd.

[0102] 8065E, OCP viscosity index improver, Chevron Oronite Company

[0103] T803B, polyalphaolefin pour point depressant, Wuxi Nanfang Petroleum Additives Co., Ltd.

[0104] HVI II 8, hydrogenated base oil, Sinopec Gaoqiao Petrochemical Company

[0105] PAO4, polyalphaolefin synthetic base oil, Sinopec Maoming Petrochemical Company

[0106] Comparative additive T512, phenolic ester antioxidant, Xinxiang Ruifeng New Materials Co., Ltd.

[0107] Comparative additive T307, ammonium salt of phosphorothioate complex ester, Huihua Petroleum Additive Co., Ltd.

[0108] Table 3

[0109]

[0110] The high-temperature oxidation resistance, high-temperature detergency, anti-wear performance, and dispersancy performance of the gas engine lubricating 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.

[0111] Method for evaluating the performance of gas engine lubricating oil compositions

[0112] (1) Antioxidant performance evaluation

[0113] Gas engine lubricating oil compositions prepared in the Examples or Comparative Examples were used as test samples to evaluate their high-temperature antioxidant properties 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.

[0114] (2) Cleaning performance evaluation

[0115] Gas engine lubricating oil compositions prepared in the Examples or Comparative Examples were used as test samples for high-temperature detergency evaluation using a coke plate test. Test conditions were: oil temperature of 120°C, plate temperature of 320°C, and a test duration of 6 hours. The lower the amount of coke on the coke plate surface at the end of the test, the better the oil's detergency.

[0116] (3) Anti-wear performance evaluation

[0117] Gas engine lubricating oil compositions prepared in the Examples or Comparative Examples were used as test samples for high-temperature anti-wear testing using a four-ball testing machine. The testing method was conducted in accordance with SH / T 0189, Condition B. The test conditions were: load 392 N, speed 1200 r / min, temperature 75°C, and test time 60 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.

[0118] (4) Spot dispersion test

[0119] A spot dispersion test was used to compare the dispersion performance of gas engine lubricating oil compositions prepared in the Examples or Comparative Examples. The test oil was mixed evenly with the same waste engine oil in a 1:1 ratio, then dripped onto filter paper. The mixture was then placed in an 80°C oven. After 2 hours, the sludge spot dispersion value of the sample was calculated based on the sludge and oil stain circle diameters that appeared on the filter paper after diffusion. A higher sludge spot dispersion value indicates better dispersion performance.

[0120] Table 4

[0121]

[0122] As can be seen from Table 4, the gas engine lubricating oil composition suitable for heavy-load vehicles of the present invention has excellent high-temperature antioxidant performance, high-temperature detergency, anti-wear performance and dispersancy performance.

Claims

1. A heavy-duty gas engine lubricating oil composition comprising an organophosphorus compound, a polyisobutylene succinimide ashless dispersant, an amine antioxidant, a detergent, a zinc dialkyl dithiophosphate, a viscosity index improver, a pour point depressant, 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 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 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 portion of the polyisobutylene succinimide ashless dispersant is 800-4000; 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 zinc dialkyldithiophosphate is selected from one or more of primary and secondary alkyl groups of C2 to C8; the viscosity index improver is selected from OCP-type viscosity index improvers; the pour point depressant is selected from one or more of polyα-olefins, alkylnaphthalenes and polymethacrylates; and 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 10% of the total mass of the gas engine lubricating oil composition; the polyisobutylene succinimide ashless dispersant accounts for 0.5% to 15% of the total mass of the gas engine lubricating oil composition; the amine antioxidant accounts for 0.1% to 10% of the total mass of the gas engine lubricating oil composition; the detergent accounts for 0.2% to 15% of the total mass of the gas engine lubricating oil composition; the zinc dialkyl dithiophosphate accounts for 0.5% to 10% of the total mass of the gas engine lubricating oil composition; the viscosity index improver accounts for 3% to 20% of the total mass of the gas engine lubricating oil composition; the pour point depressant accounts for 0.01% to 5% of the total mass of the gas engine lubricating oil composition; and the lubricating base oil constitutes the main component of the gas engine lubricating oil composition.

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