D1-specification diesel engine oil composition as well as preparation method and application thereof

Abstract

The invention provides a D1-specification diesel engine oil composition as well as a preparation method and application thereof. The dispersing type viscosity index improver is prepared by copolymerizing an arylamine-containing monomer and alkyl-substituted acrylic acid alkyl ester. The D1-specification diesel engine oil composition comprises the following components in percentage by weight: 12.0-18.0% of a diesel engine oil complexing agent; 0.2%-1.0% of a phosphoric acid alkyl ester anti-wear agent; 0.1 to 1.0 percent of a phosphoric acid phenolic ester anti-wear agent; 0.1%-0.5% of a metal deactivator; 2.0 to 10.0% of a dispersion type viscosity index improver; 0.2 to 0.8 percent of pour point depressant; and 68.7 to 85.4 percent of II type base oil. The D1-specification diesel engine oil composition has good oxidation resistance, wear resistance and high-temperature detergency, and passes a D1-specification simulation performance test and a bench test.

Description

Technical Field

[0001] The invention belongs to the technical field of lubricating oil products, and specifically relates to a D1 specification diesel engine oil composition and a preparation method and application thereof. Background Art

[0002] Lubricating oil, as a high-tech petroleum product, is widely used in various machines and equipment. Its main functions are lubrication, cleaning, cooling, sealing, friction reduction, rust prevention, etc. It is known as the "blood" of industrial machines.

[0003] With the development of the automobile industry, automobile technology has made great progress. Diesel engines have higher and higher requirements for the performance of oil products. D1 diesel engine oil is developed according to the characteristics of National VI diesel engines. It has the characteristics of low sulfur, low phosphorus and low ash, and meets the lubrication requirements of National VI and below emission diesel engines.

[0004] The D1 specification performance test is a test method established for engines such as FAW CA6DM3, Weichai WP13, Dongfeng DCI11, and JAC 2.0CTI. The method uses full power or low-speed high-torque operating conditions to mainly evaluate the comprehensive performance of the oil, including cleanliness, oxidation resistance, wear resistance, and dispersibility.

[0005] Patent CN116004308A reports a method for reducing emission and low carbon CJ-4 diesel engine oil composition, which is composed of different single agents and meets CJ-4 specifications; Patent CN115505446A reports a diesel engine oil composition that meets the requirements of CI-4 quality grade. At present, there is no report on D1 specification diesel engine oil products. Summary of the invention

[0006] In order to solve the above problems, the purpose of the present invention is to provide a D1 specification diesel engine oil composition and its preparation method and application. The D1 specification diesel engine oil composition has the characteristics of good antioxidant performance, good anti-wear performance, good high-temperature detergency, etc., and has passed the D1 specification bench test.

[0007] In order to achieve the above object, the present invention provides a dispersed viscosity index improver, which is prepared by copolymerizing an aromatic amine-containing monomer and an alkyl-substituted alkyl acrylate, wherein the aromatic amine-containing monomer has a structure shown in Formula I:

[0008]

[0009] The alkyl substituted alkyl acrylate has a structure shown in Formula II:

[0010]

[0011] In formula II, R1 is selected from C1-C4 alkyl, R2 is selected from C1-C 18 of alkyl.

[0012] According to a specific embodiment of the present invention, preferably, in formula II, R1 is selected from a C1-C4 normal alkyl group, and R2 is selected from a C1-C 18 of normal alkyl.

[0013] The present invention also provides a method for preparing the above-mentioned dispersed viscosity index improver, which comprises the following steps:

[0014] (1) dissolving maleic anhydride and 4-aminodiphenylamine in N,N-dimethylformamide, and reacting under reflux at 136° C.-144° C. for 5-10 hours to obtain an aromatic amine-containing monomer;

[0015] (2) reacting the aromatic amine-containing monomer obtained in step (1) with an alkyl-substituted alkyl acrylate at 100° C.-150° C. for 6-10 hours in the presence of an initiator to obtain the dispersed viscosity index improver.

[0016] According to a specific embodiment of the present invention, preferably, the molar ratio of the aromatic amine-containing monomer to the alkyl-substituted alkyl acrylate is 1:20-100.

[0017] According to a specific embodiment of the present invention, preferably, the mass ratio of the initiator to the alkyl-substituted alkyl acrylate is 1:100-500.

[0018] According to a specific embodiment of the present invention, preferably, the mass ratio of the reaction solvent to the alkyl-substituted alkyl acrylate is 1-4:1.

[0019] According to a specific embodiment of the present invention, preferably, the above preparation method comprises the following steps:

[0020] (1) dissolving maleic anhydride and 4-aminodiphenylamine in a molar ratio of 1:1 in N,N-dimethylformamide, reacting under reflux at 136° C.-144° C. for 5-10 hours, removing the solvent by evaporation under reduced pressure, and recrystallizing from ethanol to obtain an aromatic amine-containing monomer;

[0021] (2) reacting the aromatic amine monomer obtained in step (1) with an alkyl-substituted alkyl acrylate at 100° C. to 150° C. for 6 to 10 hours in the presence of xylene as a solvent and tert-butyl peroxy-2-ethylhexanoate as an initiator, and removing the solvent under reduced pressure to obtain the dispersed viscosity index improver.

[0022] The present invention also provides a D1 specification diesel engine oil composition, which, based on 100% by weight of the D1 specification diesel engine oil composition, comprises: a diesel engine oil compounding agent: 12.0-18.0%; an alkyl phosphate antiwear agent: 0.2-1.0%; a phosphate phenol antiwear agent: 0.1-1.0%; a metal passivator: 0.1-0.5%; the above-mentioned dispersed viscosity index improver: 2.0-10.0%; a pour point depressant: 0.2-0.8%; and a Class II base oil: 68.7-85.4%.

[0023] According to a specific embodiment of the present invention, preferably, the mass fraction of the diesel engine oil compound is 12.0-17.0%.

[0024] According to a specific embodiment of the present invention, preferably, the diesel engine oil compound has a base value of ≥60.0 mg KOH / g and a nitrogen content of ≥1.0%.

[0025] According to a specific embodiment of the present invention, preferably, the diesel engine oil compound comprises RHY3160, which is developed by the Lanzhou Lubricant Research and Development Center of PetroChina, and the compound has excellent anti-oxidation, soot dispersibility, anti-wear and high-temperature detergency.

[0026] According to a specific embodiment of the present invention, preferably, the mass fraction of the alkyl phosphate antiwear agent is 0.2-0.8%.

[0027] According to a specific embodiment of the present invention, preferably, the alkyl phosphate antiwear agent has a structure shown in Formula III:

[0028]

[0029] In Formula III, two R3 are the same or different and are independently selected from C1-C 10 Alkyl, R4 is C 12 -C 20 of alkyl.

[0030] According to a specific embodiment of the present invention, preferably, the mass fraction of the phosphate phenol antiwear agent is 0.1-0.6%.

[0031] According to a specific embodiment of the present invention, preferably, the phosphate phenol antiwear agent has a structure shown in Formula IV:

[0032]

[0033] In formula IV, R5 is a C1-C4 alkyl group.

[0034] According to a specific embodiment of the present invention, preferably, the mass fraction of the metal passivator is 0.1-0.4%.

[0035] According to a specific embodiment of the present invention, preferably, the metal deactivator comprises a benzotriazole derivative type metal deactivator.

[0036] According to a specific embodiment of the present invention, preferably, the mass fraction of the dispersed viscosity index improver is 2.0-8.0%.

[0037] According to a specific embodiment of the present invention, preferably, the mass fraction of the pour point depressant is 0.2-0.6%.

[0038] According to a specific embodiment of the present invention, preferably, the pour point depressant comprises poly-α-olefin and / or polymethyl methacrylate.

[0039] According to a specific embodiment of the present invention, preferably, the mass fraction of the Group II base oil is 72.4-85.4%. According to a specific embodiment of the present invention, preferably, the Group II base oil includes HVIH4 and / or HVIH6.

[0040] According to a specific embodiment of the present invention, preferably, the D1 specification diesel engine oil composition passes physical and chemical tests such as element content and sulfate ash content of D1 specification diesel engine oil and simulated performance tests such as diesel nozzle shear and high temperature corrosion.

[0041] According to a specific embodiment of the present invention, preferably, the D1 specification diesel engine oil composition passes the test of the D1 specification CA6DM3 or other engine bench.

[0042] The present invention also provides a method for preparing the above-mentioned D1 specification diesel engine oil composition, which comprises the following steps: mixing a diesel engine oil compound, an alkyl phosphate antiwear agent, a phenol phosphate antiwear agent, a metal passivator, a dispersible viscosity index improver, a pour point depressant, and a Class II base oil for more than 2 hours to obtain the D1 specification diesel engine oil composition.

[0043] The present invention also provides the use of the above-mentioned D1 specification diesel engine oil composition in diesel engines with emissions of National VI or below.

[0044] The D1 specification diesel engine oil composition of the present invention has the characteristics of good antioxidant performance, good anti-wear performance, good high-temperature detergency, etc., and has passed the physical and chemical test, simulation performance test and bench test of D1 specification diesel engine oil. The diesel engine oil composition of the present invention is suitable for the lubrication of National VI and below diesel engines. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] Figure 1 This is the hydrogen spectrum of aromatic amine monomer;

[0046] Figure 2 This is the carbon spectrum of aromatic amine monomer;

[0047] Figure 3 This is the gel chromatogram of the dispersed viscosity index improver obtained in Preparation Example 1. DETAILED DESCRIPTION

[0048] In order to have a clearer understanding of the technical features, purposes and beneficial effects of the present invention, the technical solution of the present invention is now described in detail below, but it should not be construed as limiting the applicable scope of the present invention.

[0049] The following methods for preparing the diesel engine oil compositions all include mixing all the raw materials and stirring them thoroughly for at least 2 hours until they are uniform.

[0050] Preparation Example 1

[0051] This preparation example provides a dispersed viscosity index improver, which is prepared by the following steps:

[0052] (1) maleic anhydride and 4-aminodiphenylamine are reacted in a molar ratio of 1:1, with N,N-dimethylformamide as a solvent, at 140° C. for 7 hours, the solvent is evaporated under reduced pressure, and the monomer containing aromatic amine is obtained after recrystallization with ethanol;

[0053] (2) 2.1 g of the prepared aromatic amine monomer and 46 g of dodecyl methacrylate were added to 50 g of xylene solvent, and 0.2 g of tert-butyl peroxy-2-ethylhexanoate initiator was gradually added. The temperature was raised from 100° C. to 150° C. within 6 hours to react. After the reaction was completed, the solvent was evaporated under reduced pressure to obtain a dispersed viscosity index improver. The hydrogen spectrum of the prepared aromatic amine monomer is as follows: Figure 1 , carbon spectrum Figure 2 The gel chromatography of the obtained dispersed viscosity index improver is as follows: Figure 3 .

[0054] The following examples use the dispersed viscosity index improver obtained in this preparation example.

[0055] Example 1

[0056] This embodiment provides a diesel engine oil composition that meets the D1 specification. The raw material composition and content thereof are shown in Table 1, calculated by mass fraction:

[0057] Table 1

[0058]

[0059]

[0060] Example 2

[0061] This embodiment provides a diesel engine oil composition that meets the D1 specification. The raw material composition and content thereof are shown in Table 2, calculated by mass fraction:

[0062] Table 2

[0063]

[0064] Example 3

[0065] This embodiment provides a diesel engine oil composition that meets the D1 specification. The raw material composition and content thereof are shown in Table 3, calculated by mass fraction:

[0066] Table 3

[0067]

[0068]

[0069] Example 4

[0070] This embodiment provides a diesel engine oil composition that meets the D1 specification. The raw material composition and content thereof are shown in Table 4, calculated by mass fraction:

[0071] Table 4

[0072] Example 5

[0073] This embodiment provides a diesel engine oil composition that meets the D1 specification. The raw material composition and content thereof are shown in Table 5, calculated by mass fraction:

[0074] Table 5

[0075]

[0076] Example 6

[0077] This embodiment provides a diesel engine oil composition that meets the D1 specification. The raw material composition and content thereof are shown in Table 6, calculated by mass fraction:

[0078] Table 6

[0079]

[0080] Test Example 1

[0081] This test case is the main physical and chemical analysis test of the oil product, and the test method is carried out in accordance with the D1 specification diesel engine oil standard.

[0082] Table 7 shows the physical and chemical analysis test results of the oil products obtained in Examples 1, 2 and 3.

[0083] Table 7

[0084]

[0085]

[0086] It can be seen from the physical and chemical analysis results in Table 7 that the oil product of the present invention has low sulfur content, phosphorus content and sulfate ash content, and the test indicators all meet the technical requirements.

[0087] Test Example 2

[0088] This test example is a simulated performance test of the oil product, and the test method is carried out in accordance with the D1 specification diesel engine oil standard.

[0089] Table 8 shows the simulation performance test results of the oil products obtained in Examples 1, 2, and 3.

[0090] Table 8

[0091]

[0092] It can be seen from the test results in Table 8 that the simulated performance test results of the oil product of the present invention meet the index requirements.

[0093] Test Example 3

[0094] This test example is an engine bench test investigation of the oil product obtained in Example 2. The oil product obtained in Example 2 is subjected to an engine bench test. Comparative Sample 1 and Comparative Sample 2 are both commercially available CK-4 specification diesel engine oils.

[0095] Table 9 shows the engine performance test results of Example 2 and the comparative sample.

[0096] Table 9

[0097]

[0098] It can be seen from the test results in Table 9 that the oil of Example 2 of the present invention passed all engine bench tests, among which the CA6DM3 test mainly examined the antioxidant performance of the oil, and both the comparative sample 1 and the comparative sample 2 failed the test by this method, further illustrating that the product of the present invention has excellent antioxidant performance; the WP13 test mainly examined the anti-wear performance of the oil, and the comparative sample 1 and the comparative sample 2 also failed the test by this method, illustrating that the product of the present invention has excellent anti-wear performance; the 2.0CTI test mainly examined the high-temperature cleaning performance of the oil, and the comparative sample 1 failed the test by this method, illustrating that the product of the present invention has excellent high-temperature cleaning performance.

Claims

1. A dispersed viscosity index improver, which is prepared by copolymerizing an aromatic amine-containing monomer and an alkyl-substituted alkyl acrylate, wherein: The aromatic amine-containing monomer has a structure shown in Formula I: The alkyl-substituted alkyl acrylate has a structure shown in Formula II: In formula II, R1 is selected from C1-C4 alkyl, R2 is selected from C1-C 18 of alkyl.

2. The dispersed viscosity index improver according to claim 1, wherein In formula II, R1 is selected from a C1-C4 normal alkyl group, and R2 is selected from a C1-C 18 of normal alkyl.

3. The method for preparing the dispersed viscosity index improver according to claim 1 or 2, comprising the following steps: (1) dissolving maleic anhydride and 4-aminodiphenylamine in N,N-dimethylformamide, and reacting under reflux at 136° C.-144° C. for 5-10 hours to obtain an aromatic amine-containing monomer; (2) reacting the aromatic amine-containing monomer obtained in step (1) with an alkyl-substituted alkyl acrylate at 100° C. to 150° C. for 6 to 10 hours in the presence of an initiator to obtain the dispersed viscosity index improver; Preferably, the molar ratio of the aromatic amine-containing monomer to the alkyl-substituted alkyl acrylate is 1:20-100; Preferably, the mass ratio of the initiator to the alkyl-substituted alkyl acrylate is 1:100-500; Preferably, in step (2), the mass ratio of the reaction solvent to the alkyl-substituted alkyl acrylate is 1-4:

1.

4. The preparation method according to claim 3, wherein The preparation method comprises the following steps: (1) dissolving maleic anhydride and 4-aminodiphenylamine in a molar ratio of 1:1 in N,N-dimethylformamide, reacting under reflux at 136° C.-144° C. for 5-10 hours, removing the solvent by evaporation under reduced pressure, and recrystallizing from ethanol to obtain an aromatic amine-containing monomer; (2) reacting the aromatic amine monomer obtained in step (1) with an alkyl-substituted alkyl acrylate at 100° C. to 150° C. for 6 to 10 hours in the presence of xylene as a solvent and tert-butyl peroxy-2-ethylhexanoate as an initiator, and removing the solvent under reduced pressure to obtain the dispersed viscosity index improver.

5. A D1 diesel engine oil composition, which, based on 100% by weight of the D1 diesel engine oil composition, comprises: Diesel engine oil compound: 12.0-18.0%; alkyl phosphate antiwear agent: 0.2-1.0%; phenol phosphate antiwear agent: 0.1-1.0%; metal passivator: 0.1-0.5%; dispersed viscosity index improver: 2.0-10.0%; pour point depressant: 0.2-0.8%; Class II base oil: 68.7-85.4%; in, The dispersed viscosity index improver includes the dispersed viscosity index improver according to claim 1 or 2.

6. The D1 specification diesel engine oil composition according to claim 5, wherein: The diesel engine oil compound has a base value of ≥60.0 mg KOH / g and a nitrogen content of ≥1.0%; Preferably, the mass fraction of the diesel engine oil compound is 12.0-17.0%.

7. The D1 specification diesel engine oil composition according to claim 5, wherein: The diesel engine oil compound comprises RHY3160.

8. The D1 specification diesel engine oil composition according to claim 5, wherein: The mass fraction of the alkyl phosphate antiwear agent is 0.2-0.8%; Preferably, the alkyl phosphate antiwear agent has a structure shown in Formula III: In Formula III, two R3 are the same or different and are independently selected from C1-C 10 Alkyl, R4 is C 12 -C 20 of alkyl.

9. The D1 specification diesel engine oil composition according to claim 5, wherein: The mass fraction of the phenol phosphate antiwear agent is 0.1-0.6%; Preferably, the phosphate phenol antiwear agent has a structure shown in Formula IV: In formula IV, R5 is a C1-C4 alkyl group.

10. The D1 specification diesel engine oil composition according to claim 5, wherein: The mass fraction of the metal passivator is 0.1-0.4%; Preferably, the metal deactivator comprises a benzotriazole derivative type metal deactivator.

11. The D1 specification diesel engine oil composition according to claim 5, wherein: The mass fraction of the dispersed viscosity index improver is 2.0-8.0%.

12. The D1 specification diesel engine oil composition according to claim 5, wherein: The mass fraction of the pour point depressant is 0.2-0.6%; Preferably, the pour point depressant comprises poly-alpha-olefin and / or polymethyl methacrylate.

13. The D1 specification diesel engine oil composition according to claim 5, wherein: The mass fraction of the Class II base oil is 72.4-85.4%; Preferably, the Group II base oil comprises HVIH4 and / or HVIH6.

14. The D1 specification diesel engine oil composition according to claim 5, wherein: The D1 specification diesel engine oil composition has passed the physical and chemical test and the simulated performance test of the D1 specification diesel engine oil.

15. The D1 specification diesel engine oil composition according to claim 5, wherein: The D1 specification diesel engine oil composition passes the D1 specification engine bench test.

16. A method for preparing a D1 specification diesel engine oil composition according to any one of claims 5 to 15, comprising the following steps: The diesel engine oil compound, alkyl phosphate antiwear agent, phenol phosphate antiwear agent, metal passivator, dispersible viscosity index improver, pour point depressant and Class II base oil are mixed and stirred for more than 2 hours to obtain the D1 specification diesel engine oil composition.

17. Use of the D1 specification diesel engine oil composition according to any one of claims 5 to 15 in diesel engines with emission standards of National VI or below.

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