Gasoline engine oil composition and method of making same

Abstract

The present application provides a gasoline engine oil composition, which comprises an aromatic amine dispersant, a naphthylamine antioxidant, a salicylate detergent, an organic molybdenum friction modifier, a metal corrosion inhibitor and a lubricating oil base oil, wherein the aromatic amine dispersant has a structure as shown in formula (I): wherein the definitions of the groups are described in the specification. The gasoline engine oil composition of the present application has very excellent detergent, dispersant, antioxidant and corrosion resistance properties, and can reduce the addition amount of the antioxidant.

Description

TECHNICAL FIELD

[0001] The present application relates to a gasoline engine oil composition, in particular to a gasoline engine oil composition with excellent dispersing, detergency, antioxidant and corrosion resistance and a preparation method thereof. BACKGROUND

[0002] In recent years, gasoline engine oil product specifications have gradually upgraded from SJ / GF-2 to SL / GF-3, SM / GF-4 and SN / GF-5. The dispersing and detergency performance of gasoline engine oil has always been an important indicator in oil product specifications. In the SN / GF-5 specification, more stringent requirements are put forward for the piston detergency of engine lubricating oil in the IIIG engine test, and the piston deposit score is raised from 3.5 to 4. Higher requirements are also put forward for the oil sludge score in the VG engine test, i.e. less oil sludge is generated under more severe operating conditions. These changes also put forward higher requirements for the performance of dispersing and detergency agents.

[0003] However, the gasoline engine oil composition prepared by using the dispersing and detergency agent of the prior art cannot fully meet the requirements of such higher-specification products. The prior art still needs a gasoline engine oil composition with better dispersing and detergency performance. SUMMARY

[0004] The present application provides a gasoline engine oil composition which not only meets the increasingly stringent requirements of higher-specification products for dispersing and detergency performance, but also significantly reduces the addition amount of antioxidants.

[0005] The gasoline engine oil composition of the present application comprises an aromatic amine type dispersant, a naphthylamine type antioxidant, a salicylate detergent, an organic molybdenum friction modifier, a metal corrosion inhibitor and a lubricating oil base oil, wherein the structure of the aromatic amine type dispersant is shown in formula (I):

[0006]

[0007] In formula (I), each R0group is the same or different from each other, and each is independently selected from H, C1-C4 alkyl, C6-C10 aryl; each G group is the same or different from each other, and each is independently selected from H, C1-C4 alkyl, C6-C10 aryl, a group shown in formula (II), and at least one G group is selected from the group shown in formula (II). 10 aryl; each G group is the same or different from each other, and each is independently selected from H, C1-C4 alkyl, C6-C 10 aryl, a group shown in formula (II), and at least one G group is selected from the group shown in formula (II);

[0008]

[0009] In formula (II), the R group is selected from a polyisobutylene group with a number average molecular weight of 1000-5000, and the symbol * represents a binding end with formula (I).

[0010] According to the present invention, optionally, in formula (I), each RO group is independently selected from H, C1-C4 alkyl, phenyl; each G group is independently selected from H, C1-C4 alkyl, phenyl, and the group shown in formula (II); in formula (II), the R group is selected from polyisobutylene groups with a number average molecular weight of 1000-2500.

[0011] According to the present invention, optionally, in formula (I), one, two or three G groups are each independently selected from the groups shown in formula (II).

[0012] According to the present invention, examples of the aromatic amine dispersant include one or more of the following structural compounds:

[0013]

[0014]

[0015] PIB stands for polyisobutylene group.

[0016] According to the present invention, the preparation method of the aromatic amine dispersant includes the following steps:

[0017] (1) React the compound shown in formula (α) with indigo anhydride;

[0018]

[0019] In formula (α), each R0 group may be the same as or different from each other, and each is independently selected from H, C1-C4 alkyl, C6 ... 10 Aryl; each G' group may be the same as or different from the others, and each is independently selected from H, C1-C4 alkyl, C6 ... 10 Aryl group, and at least one G' group is selected from H;

[0020] (2) React the reaction product of step (1) with polyisobutylene maleic anhydride and collect the product.

[0021] According to the present invention, optionally, in formula (α), each RO group is independently selected from H, C1-C4 alkyl, and phenyl; each G' group is independently selected from H, C1-C4 alkyl, and phenyl.

[0022] According to the present invention, optionally, in formula (α), one, two or three G' groups are selected from H.

[0023] According to the present invention, optionally, the compound represented by formula (α) can be tris(4-aminophenyl)amine.

[0024] According to the present invention, the structure of the indocinic anhydride is as follows:

[0025]

[0026] According to the present application, the structure of the polyisobutylene maleic anhydride is as follows:

[0027]

[0028] The PIB group therein is selected from polyisobutylene groups having a number average molecular weight of 1000-5000, preferably from polyisobutylene groups having a number average molecular weight of 1000-2500.

[0029] According to the present application, optionally, in step (1), the molar ratio of the compound of formula (a) to isatoic anhydride is 1:(0.5-3.5), preferably 1:(3-3.2); the reaction temperature is 80-100℃, and the reaction time is 8-12h; preferably, the reaction temperature is 85-95℃, and the reaction time is 9-10h.

[0030] According to the present application, optionally, in step (2), the molar ratio of the reaction product of step (1) to the polyisobutylene maleic anhydride is 1:(0.5-3.5), preferably 1:(3-3.2); the reaction temperature is 140-160℃, and the reaction time is 4-8h; preferably, the reaction temperature is 145-155℃, and the reaction time is 5-7h.

[0031] According to the present application, the steps (1), (2) can be carried out in the presence of a diluent and / or a solvent, or can be carried out without using a diluent and / or a solvent.

[0032] According to the present application, the diluent can be selected from one or more of API I, II, III, IV and V base oils, and common commercial products or brands include 100SN, 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.

[0033] According to the present application, the solvent can be selected from 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 naphtha, etc. These solvents can be used singly, or in combination of two or more. The solvent can be removed after the reaction is completed, using a method known to those skilled in the art, for example, distillation under normal or reduced pressure.

[0034] According to a specific embodiment of the present application, the diluent and / or solvent can be added at any stage of the reaction step according to the conventional amount in the art, and is not particularly limited.

[0035] According to the present application, the reactions of steps (1) and (2) can be carried out under the protection of an inert gas atmosphere. As the inert gas, for example, nitrogen and argon can be mentioned, and is not particularly limited.

[0036] According to the present application, by the aforementioned preparation method, as the reaction product, a single aromatic amine type dispersant can be produced, or a mixture of a plurality of aromatic amine type dispersants, or a mixture of one or more aromatic amine type dispersants and the aforementioned diluent (if used) can be produced. These reaction products are all intended by the present application, and the difference in the form of existence does not affect the realization of the effect of the present application. Therefore, these reaction products are collectively referred to as aromatic amine type dispersants without distinction in the context of the present specification. In view of this, according to the present application, there is no absolute necessity to further purify the reaction product, or to further separate a specific structure of the aromatic amine type dispersant from the reaction product. Of course, the purification or separation is preferred for further improvement of the intended effect of the present application, but is not essential to the present application. Nevertheless, as the purification or separation method, for example, purification or separation of the reaction product by column chromatography or preparative chromatography can be mentioned.

[0037] According to the present application, the polar end of the aromatic amine type dispersant contains a plurality of benzene rings and amide functional groups centered on the N atom, which is more matched with the fused ring aromatic hydrocarbon structure of soot, and has excellent dispersing performance; the aromatic amine type dispersant not only can effectively disperse soot, but also can control the viscosity increase caused by oil during use. The preparation method of the aromatic amine type dispersant of the present application is simple in process and high in synthesis efficiency.

[0038] According to the present application, the naphthylamine type antioxidant can be selected from N-phenyl-α-naphthylamine and / or N-phenyl-β-naphthylamine, and common trade names include T531, Irganox L106, Mobilad C-146, etc.

[0039] According to the present application, the salicylate detergent can be selected from calcium salicylate detergent and / or magnesium salicylate detergent, preferably calcium salicylate detergent, and common trade names include C9375, LZL109A, LZL109B, LZL112, T109A, T109B, T109C, etc.

[0040] According to the present application, the organic molybdenum friction modifier can be selected from one or more of molybdenum dialkyldithiocarbamate, molybdenum dialkyldithiophosphate oxide, molybdenum dialkyldithiophosphate, molybdenum xanthate, molybdenum thioxanthate, trinuclear molybdenum sulfur complex, molybdenum amine complex and molybdate, preferably one or more of the organic molybdenum compounds containing one or more hydrocarbon groups of C 6～60 , more preferably one or more straight chain or branched alkyl groups of C 10～50 , the organic molybdenum friction modifier is preferably selected from molybdenum dialkyldithiocarbamate. Common trade designations include Molyvan 822, Molyvan 855, etc.

[0041] According to the present application, the metal corrosion inhibitor is selected from one or more of thiadiazole derivatives, thiazole derivatives and benzotriazole derivatives, for example can be selected from one or more of 2,5-dimercapto-1,3,4-thiadiazole, 2-dimercapto-5-dithio-1,3,4-thiadiazole, 2-mercapto-5-hydrocarbon-substituted-1,3,4-thiadiazole, 2-mercaptobenzothiazole, 2-mercaptobenzothiazole, benzothiazole, benzotriazole, N,N'-di-n-butylaminomethylenebenzotriazole and N,N'-dihexylaminomethylenebenzotriazole, preferably thiadiazole derivatives. Common trade designations include LZL 561, Cuvan 484, Mobilad C-610, etc.

[0042] According to the present application, the lubricating oil base oil can be selected from one or more of API I, II, III, IV, V class lubricating oil base oils, for example can be selected from mineral base oil and / or synthetic base oil. Common trade designations or designations include 100SN, 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.

[0043] According to the present application, the aromatic amine type dispersant is 0.01% to 20% (preferably 0.02% to 16%) of the total mass of the gasoline engine oil composition; the naphthylamine type antioxidant is 0.02% to 5% (preferably 0.05% to 3%) of the total mass of the gasoline engine oil composition; the salicylate detergent is 0.1% to 10% (preferably 0.2% to 5%) of the total mass of the gasoline engine oil composition; the organic molybdenum friction modifier is 0.01% to 10% (preferably 0.05% to 5%) of the total mass of the gasoline engine oil composition; the metal corrosion inhibitor is 0.01% to 5% (preferably 0.02% to 4%) of the total mass of the gasoline engine oil composition; and the lubricating oil base oil constitutes the main component of the gasoline engine oil composition.

[0044] The method for manufacturing the gasoline engine oil composition of the present application comprises the step of mixing the aromatic amine type dispersant, the naphthylamine type antioxidant, the salicylate detergent, the organic molybdenum friction modifier, the metal corrosion inhibitor and the lubricating oil base oil.

[0045] The gasoline engine oil composition of the present application has very excellent detergency, dispersancy, antioxidation and corrosion resistance, and can reduce the amount of the antioxidant to be added. BRIEF DESCRIPTION OF DRAWINGS

[0046] Figure 1 is the infrared spectrum of the aromatic amine type dispersant prepared in Example 1 of the present application.

[0047] Figure 2 is the infrared spectrum of the intermediate product prepared in Example 1 of the present application. DETAILED DESCRIPTION

[0048] The present application will be further described by way of examples below, but not constitute limitation to the present application.

[0049] The main raw materials used are as follows:

[0050] Indigo anhydride, Fangzhou Pharmaceutical Co., Ltd;

[0051] Tris (4-aminophenyl) amine, Shanghai Adamas Reagent Co., Ltd;

[0052] Polyisobutylene maleic anhydride (PIB number average molecular weight 1000), Yangzi Petrochemical;

[0053] 100SN, 150SN, Maoming Petrochemical;

[0054] Polyisobutylene maleimide (PIB number average molecular weight 1000), Yangzi Petrochemical;

[0055] Naphthylamine type antioxidant, Irganox L106, marked as KY-1, Ciba-Geigy Ltd;

[0056] Salicylate detergent, C9375, Infineum Co., Ltd;

[0057] Organic molybdenum, Vanderbilt Co., USA, marked as Molyvan 822;

[0058] Metal corrosion inhibitor, 2,5-dimercapto-1,3,4-thiadiazole, produced by Liaoning Tianhe Fine Chemical Co., Ltd.

[0059] Example 1

[0060] In a 500ml reaction kettle, 4.89g of isatin anhydride and 2.9g of tris(4- aminophenyl)amine were added, 160ml of toluene was added, nitrogen was introduced, and water reflux was started. The reaction was carried out at 90°C for 10 hours. After the reaction was completed, the toluene was evaporated. Then, 33g of polyisobutylene maleic anhydride (the number average molecular weight of the polyisobutylene was 1000) dissolved in 100ml of 150SN was added, nitrogen was introduced, and water reflux was started. The reaction was carried out at 150°C for 6 hours. After the reaction was completed, the solvent was evaporated to obtain the arylamine dispersant of the present application. -1 . Figure 1 is the infrared spectrum of the arylamine dispersant, Figure 2 is the infrared spectrum of the intermediate product.

[0061] From Figure 1 and Figure 2 it can be seen that the absorption peak of the primary amine connected to the benzene ring in the intermediate product is at 3349cm -1 nearby, and after the reaction with the polyisobutylene maleic anhydride, the absorption peak disappears; the absorption peak of the amide in the intermediate product is at 1600cm -1 nearby, and after the reaction with the polyisobutylene maleic anhydride, the absorption peak becomes weaker; the absorption peak of the newly formed imide in the product is at 1700cm -1 nearby. Figure 1 and Figure 2 can indicate that the target product is obtained.

[0062] The example reaction formula of Example 1 is shown below.

[0063]

[0064] Example 2

[0065] In a 500ml reaction kettle, 4.89g of isatin anhydride and 2.9g of tris(4- aminophenyl)amine were added, 160ml of toluene was added, nitrogen was introduced, and water reflux was started. The reaction was carried out at 80°C for 12 hours. After the reaction was completed, the toluene was evaporated. Then, 33g of polyisobutylene maleic anhydride (the number average molecular weight of the polyisobutylene was 1000) dissolved in 100ml of 150SN was added, nitrogen was introduced, and water reflux was started. The reaction was carried out at 160°C for 5 hours. After the reaction was completed, the solvent was evaporated to obtain the arylamine dispersant of the present application.

[0066] Example 3

[0067] In a 500ml reaction kettle, 4.89g of indigo anhydride and 2.9g of tris(4- aminophenyl)amine were added, 160ml of toluene was added, nitrogen was introduced, and water reflux was started. The reaction was carried out at 100°C for 8 hours. After the reaction was completed, the toluene was removed by evaporation. Then 33g of polyisobutylene maleic anhydride (the number average molecular weight of the polyisobutylene was 1000) dissolved in 100ml of 150SN was added, nitrogen was introduced, and water reflux was started. The reaction was carried out at 140°C for 8 hours. After the reaction was completed, the solvent was removed by evaporation to obtain the arylamine type dispersant of the present application.

[0068] Comparative Example 1

[0069] The method of Example 1 was used, except that indigo anhydride was not added, and tris(4-aminophenyl)amine was reacted with polyisobutylene maleic anhydride at a molar ratio of 1:3. After the reaction was completed, soot ashless dispersant DF1 of the present comparative example was obtained.

[0070] Comparative Example 2

[0071] The method of Example 1 was used, except that tris(4-aminophenyl)amine was replaced by equimolar amount of diamino diphenyl methane to react, soot ashless dispersant DF2 of the present comparative example was obtained.

[0072] Comparative Example 3

[0073] The method of Example 1 was used, except that only polyisobutylene maleimide was used instead of polyisobutylene maleic anhydride to synthesize polyisobutylene maleimide type ashless dispersant, wherein the number average molecular weight of polyisobutylene in polyisobutylene maleimide was 1000. Soot ashless dispersant DF3 of the present comparative example was obtained.

[0074] Comparative Example 4

[0075] Commercially available polyisobutylene succinimide T151 was used as a comparative ashless dispersant.

[0076] Examples 4-6 and Comparative Examples 5-9 of gasoline engine oil composition

[0077] The formulation composition of Examples 4-6 and Comparative Examples 5-9 of gasoline engine oil composition is shown in Table 1. Each component in the table was added to a blending container, heated and stirred at 60°C for 2 hours to obtain the gasoline engine oil composition of the examples and comparative examples.

[0078] The lubricating oil composition prepared in the example or the comparative example is used as a test sample, and the engine crankcase fouling simulation test is used to evaluate the detergency of the test sample. The method is that 300 ml of the test sample is added to the fouling plate simulation instrument, heated to 120°C, and sprayed onto an aluminum plate with a temperature of 300°C in a continuous manner. The amount of coke generated on the aluminum plate after 300 min is weighed to simulate the deposit on the piston. The higher the amount of coke, the worse the piston detergency of the test sample. The deposit results of the fouling plate test are shown in Table 1.

[0079] The lubricating oil composition prepared in the example or the comparative example is used as a test sample, and the pressurized differential scanning calorimetry test (PDSC) is used to evaluate the thermal oxidation stability of the test sample, and the oxidation induction period of the test sample is expressed in min. The temperature of the PDSC test is 205°C, the pressure is 0.5 MPa, and the oxygen flow rate is 100 mL / min. The PDSC test results are shown in Table 1.

[0080] The lubricating oil composition prepared in the example or the comparative example is used as a test sample, and the test oil is uniformly mixed with the oil sludge, then dropped on filter paper, and the diameter of the oil sludge diffusion ring and the diameter of the lubricating oil diffusion ring are measured after 24 h. The ratio of the diameter of the oil sludge diffusion ring to the diameter of the lubricating oil diffusion ring is calculated to obtain the dispersion index, which is used to identify the dispersion performance of the oil product. The larger the ratio, the better the dispersion performance. The oil sludge dispersion simulation test results are shown in Table 1.

[0081] The lubricating oil composition prepared in the example or the comparative example is used as a test sample, and the copper strip corrosion test is carried out on the test sample according to the standard method of ASTM D130. The polished copper strip is immersed in the test sample, heated to a test temperature of 121°C, and kept for 3 h. After the test is completed, the copper strip is taken out, washed, and compared with the corrosion standard color plate to determine the corrosion level. The test results are shown in Table 1.

[0082] As shown in Table 1, the gasoline engine oil composition of the present application has excellent detergency, dispersion performance, oxidation resistance and corrosion resistance.

[0083] Table 1

[0084]

Claims

1. A gasoline engine oil composition comprising an aromatic amine dispersant, a naphthylamine antioxidant, a salicylate detergent, an organomolybdenum friction modifier, a metal corrosion inhibitor, and a lubricating oil base oil, wherein the structure of the aromatic amine dispersant is shown in formula (I): （I）， In formula (I), each R0 group is selected from H; each G group is the same as or different from each other, and is independently selected from H, the group shown in formula (II), and at least one G group is selected from the group shown in formula (II); (II), In formula (II), the R group is selected from polyisobutylene groups with a number average molecular weight of 1000~5000, and the symbol * represents the binding end with formula (I); The naphthylamine antioxidant is selected from N-phenyl-α-naphthylamine and / or N-phenyl-β-naphthylamine; the salicylate detergent is selected from calcium salicylate detergent and / or magnesium salicylate detergent; the organic molybdenum friction modifier is selected from one or more of molybdenum dialkyldithiocarbamate, molybdenum dialkyldithiophosphate oxydiphosphite, molybdenum dialkyldithiophosphate, molybdenum xanthate, molybdenum thioxanthate, trinuclear molybdenum sulfide complex, molybdenum amine complex, and molybdate ester; the metal corrosion inhibitor is selected from one or more of thiadiazole derivatives, thiazolium derivatives, and benzotriazole derivatives; the lubricating oil base oil is selected from one or more of API Group I, II, III, IV, and V lubricating oil base oils.

2. The gasoline engine oil composition according to claim 1, characterized in that, In formula (II), the R group is selected from polyisobutylene groups with a number average molecular weight of 1000 to 2500.

3. The gasoline engine oil composition according to claim 1, characterized in that, The aromatic amine dispersant is one or more of the following structural compounds: , , , PIB stands for polyisobutylene group.

4. The gasoline engine oil composition according to claim 1, characterized in that, The preparation method of the aromatic amine dispersant includes the following steps: (1) React the compound shown in formula (α) with indigo anhydride; （α）， In formula (α), each R0 group is selected from H; each G' group is selected from H; (2) React the reaction product of step (1) with polyisobutylene maleic anhydride and collect the product.

5. The gasoline engine oil composition according to claim 4, characterized in that, The structure of the polyisobutylene maleic anhydride is as follows: ， The PIB group is selected from polyisobutylene groups with a number average molecular weight of 1000-5000.

6. The gasoline engine oil composition according to claim 4, characterized in that, In step (1), the molar ratio of the compound shown in formula (α) to indomethacin anhydride is 1:(0.5~3.5); the reaction temperature is 80-100℃ and the reaction time is 8-12h.

7. The gasoline engine oil composition according to claim 4, characterized in that, In step (2), the molar ratio of the reaction product of step (1) to the polyisobutylene maleic anhydride is 1:(0.5~3.5); the reaction temperature is 140-160℃ and the reaction time is 4-8h.

8. The gasoline engine oil composition according to any one of claims 1 to 7, characterized in that, The aromatic amine dispersant accounts for 0.01% to 20% of the total mass of the gasoline engine oil composition; the naphthylamine antioxidant accounts for 0.02% to 5% of the total mass of the gasoline engine oil composition; the salicylate detergent accounts for 0.1% to 10% of the total mass of the gasoline engine oil composition; the organic molybdenum friction modifier accounts for 0.01% to 10% of the total mass of the gasoline engine oil composition; the metal corrosion inhibitor accounts for 0.01% to 5% of the total mass of the gasoline engine oil composition; and the lubricating oil base oil constitutes the main component of the gasoline engine oil composition.

9. A method for manufacturing the gasoline engine oil composition according to any one of claims 1 to 8, comprising the step of mixing the aromatic amine dispersant, naphthylamine antioxidant, salicylate detergent, organic molybdenum friction modifier, metal corrosion inhibitor and lubricating oil base oil.

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