A d1 specification diesel engine oil composition, its preparation method and application

Abstract

The application provides a D1 specification diesel engine oil composition and a preparation method and application thereof. The dispersible viscosity index improver is prepared by copolymerization of an aromatic amine monomer and an alkyl-substituted alkyl acrylate. The D1 specification diesel engine oil composition comprises diesel engine oil composite agent 12.0-18.0%, alkyl phosphate anti-wear agent 0.2-1.0%, phosphoric acid phenol ester anti-wear agent 0.1-1.0%, metal deactivator 0.1-0.5%, dispersible viscosity index improver 2.0-10.0%, pour point depressant 0.2-0.8% and type II base oil 68.7-85.4%. The D1 specification diesel engine oil composition has good oxidation resistance, wear resistance and high-temperature detergency, and passes the D1 specification simulation performance test and bench test.

Description

Technical Field

[0001] This invention belongs to the field of lubricating oil technology, specifically relating to a D1 specification diesel engine oil composition, its preparation method, and its application. Background Technology

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

[0003] With the development of the automotive industry, automotive technology has made great strides. The performance requirements for diesel engine oils are also becoming increasingly stringent. D1 specification diesel engine oil is developed specifically for China VI emission standard diesel engines, featuring low sulfur, low phosphorus, and low ash content, meeting the lubrication requirements of China VI and below emission standard diesel engines.

[0004] The D1 specification performance test is based on the test method established by engines such as FAW CA6DM3, Weichai WP13, Dongfeng DCI11, and JAC 2.0CTI. The method evaluates the comprehensive performance of the oil, including its detergency, oxidation resistance, anti-wear properties, and dispersibility, under full power or low-speed, high-torque operating conditions.

[0005] Patent CN116004308A discloses a method for composing a low-carbon, emission-reducing CJ-4 diesel engine oil composition. This diesel engine oil is composed of different single agents and meets the CJ-4 specification. Patent CN115505446A discloses a diesel engine oil composition that meets the requirements of the CI-4 quality grade. Currently, there are no reports of D1 specification diesel engine oil products. Summary of the Invention

[0006] To address the aforementioned problems, the present invention aims to provide a D1 specification diesel engine oil composition, its preparation method, and its application. This D1 specification diesel engine oil composition has the characteristics of good antioxidant properties, good anti-wear properties, and good high-temperature detergency, and has passed the D1 specification bench test.

[0007] To achieve the above objectives, the present invention provides a dispersion viscosity index improver, which is obtained by copolymerization of an aromatic amine monomer and an alkyl-substituted alkyl acrylate, wherein the aromatic amine monomer has the structure shown in Formula I:

[0008]

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

[0010]

[0011] In Formula II, R1 is selected from C1-C4 alkyl groups, and R2 is selected from C1-C4 alkyl groups. 18 Alkyl groups.

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

[0013] This invention also provides a method for preparing the above-mentioned dispersible viscosity index improver, which includes the following steps:

[0014] (1) Maleic anhydride and 4-aminodiphenylamine were dissolved in N,N-dimethylformamide and refluxed at 136℃-144℃ for 5-10 hours to obtain a monomer containing aromatic amine.

[0015] (2) The aromatic amine monomer obtained in step (1) and the alkyl-substituted alkyl acrylate are reacted at 100℃-150℃ for 6-10 hours under the action of an initiator to obtain the dispersion viscosity index improver.

[0016] According to a specific embodiment of the present invention, preferably, the molar ratio of the aromatic amine 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 includes the following steps:

[0020] (1) Maleic anhydride and 4-aminodiphenylamine in a molar ratio of 1:1 were dissolved in N,N-dimethylformamide and refluxed at 136℃-144℃ for 5-10 hours. The solvent was removed by vacuum evaporation and the product was recrystallized from ethanol to obtain a monomer containing aromatic amine.

[0021] (2) The aromatic amine monomer obtained in step (1) and the alkyl-substituted alkyl acrylate are reacted at 100℃-150℃ for 6-10 hours with xylene as solvent and tert-butyl peroxide-2-ethylhexanoate as initiator. The solvent is then removed by vacuum distillation to obtain the dispersion viscosity index improver.

[0022] The present invention also provides a D1 specification diesel engine oil composition, which, calculated by weight of 100%, comprises: diesel engine oil compound: 12.0-18.0%; alkyl phosphate anti-wear agent: 0.2-1.0%; phenolic phosphate anti-wear agent: 0.1-1.0%; metal passivator: 0.1-0.5%; the above-mentioned dispersible viscosity index improver: 2.0-10.0%; pour point depressant: 0.2-0.8%; and Group 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 an alkalinity ≥ 60.0 mg KOH / g and a nitrogen content ≥ 1.0%.

[0025] According to a specific embodiment of the present invention, preferably, the diesel engine oil compound includes RHY3160, which was developed by the Lanzhou Lubricating Oil R&D Center of China National Petroleum Corporation. This compound has excellent antioxidant, soot dispersion, wear resistance and high-temperature detergency properties.

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

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

[0028]

[0029] In Equation III, the two R3s may be the same or different, and each is independently selected from C1-C2. 10 Alkyl group, R4 is C 12 -C 20 Alkyl groups.

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

[0031] According to a specific embodiment of the present invention, preferably, the phosphate phenol ester anti-wear agent has the 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 passivating agent is 0.1-0.4%.

[0035] According to a specific embodiment of the present invention, preferably, the metal passivating agent includes a benzotriazole derivative metal passivating agent.

[0036] According to a specific embodiment of the present invention, preferably, the mass fraction of the dispersible 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 polyalphaolefin 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 has passed the physicochemical tests such as elemental content and sulfate ash content of D1 specification diesel engine oil, as well as the 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 has passed the test of engine benches such as the D1 specification CA6DM3.

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

[0043] The present invention also provides the application of the above-mentioned D1 specification diesel engine oil composition in diesel engines with emission standards of China VI and below.

[0044] The D1 specification diesel engine oil composition of the present invention has the characteristics of good anti-oxidation performance, good anti-wear performance, and good high-temperature cleaning performance. It has passed the physicochemical test, simulated 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 diesel engines of China VI and below. Attached Figure Description

[0045] Figure 1 This is the proton NMR spectrum of an aromatic amine monomer;

[0046] Figure 2 Carbon spectra of aromatic amine monomers;

[0047] Figure 3 The gel chromatogram is for the dispersible viscosity index improver obtained in Example 1. Detailed Implementation

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

[0049] The following methods for preparing diesel engine oil compositions are as follows: mix all raw materials and stir thoroughly for at least 2 hours until homogeneous.

[0050] Preparation Example 1

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

[0052] (1) Maleic anhydride and 4-aminodiphenylamine were reacted in a molar ratio of 1:1 with N,N-dimethylformamide as solvent under reflux at 140°C for 7 hours. The solvent was removed under reduced pressure and the product was recrystallized from ethanol to obtain a monomer containing aromatic amine.

[0053] (2) 2.1 g of the prepared aromatic amine monomer and 46 g of dodecyl methacrylate were reacted in 50 g of xylene solvent with 0.2 g of tert-butyl peroxide-2-ethylhexanoate initiator. The temperature was increased from 100 °C to 150 °C over 6 hours. After the reaction was completed, the solvent was evaporated under reduced pressure to obtain a dispersion-type viscosity index improver. The proton NMR spectrum of the prepared aromatic amine monomer is shown below. Figure 1 Carbon spectrum, such as Figure 2 The gel chromatography of the obtained dispersible viscosity index improver is as follows: Figure 3 .

[0054] The following examples use the dispersible 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, calculated by mass fraction, are shown in Table 1:

[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, calculated by mass fraction, are shown in Table 2.

[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, calculated by mass fraction, are shown in Table 3.

[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, calculated by mass fraction, are shown in Table 4.

[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, calculated by mass fraction, are shown in Table 5:

[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, calculated by mass fraction, are shown in Table 6.

[0078] Table 6

[0079]

[0080] Test Example 1

[0081] This test case is a major physicochemical analysis test of the oil, and the test method is carried out in accordance with the D1 specification diesel engine oil standard.

[0082] Table 7 shows the physicochemical analysis results of the oils obtained in Examples 1, 2, and 3.

[0083] Table 7

[0084]

[0085]

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

[0087] Test Example 2

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

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

[0090] Table 8

[0091]

[0092] As can be seen from the test results in Table 8, the simulated performance test results of the oil products of the present invention meet the index requirements.

[0093] Test Example 3

[0094] This test case is an engine bench test of the oil obtained in Example 2. The oil obtained in Example 2 was subjected to engine bench testing. 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 for Example 2 and the comparative sample.

[0096] Table 9

[0097]

[0098] As can be seen from the test results in Table 9, the oil of Example 2 of the present invention passed all engine bench tests. Among them, the CA6DM3 test mainly examines the oil's antioxidant performance. Comparative Sample 1 and Comparative Sample 2 failed the test by this method, further demonstrating that the product of the present invention has excellent antioxidant performance. The WP13 test mainly examines the oil's anti-wear performance. Comparative Sample 1 and Comparative Sample 2 also failed the test by this method, demonstrating that the product of the present invention has excellent anti-wear performance. The 2.0CTI test mainly examines the oil's high-temperature detergency performance. Comparative Sample 1 failed the test by this method, demonstrating that the product of the present invention has excellent high-temperature detergency performance.

Claims

1. A D1 specification diesel engine oil composition, wherein the composition is as follows, calculated based on 100% by weight of the D1 specification diesel engine oil composition: Diesel engine oil additives: 12.0-18.0%; Alkyl phosphate anti-wear agent: 0.2-1.0%; Phenolic phosphate anti-wear agent: 0.1-1.0%; Metal passivator: 0.1-0.5%; Dispersible viscosity index improver: 2.0-10.0%; Pour point depressant: 0.2-0.8%; Group II base oil: 68.7-85.4%; The dispersion viscosity index improver is obtained by copolymerization of an aromatic amine monomer and an alkyl-substituted alkyl acrylate, wherein the aromatic amine monomer has the structure shown in Formula I: Formula I; The alkyl-substituted alkyl acrylate has the structure shown in Formula II: Formula II, In Formula II, R1 is selected from C1-C4 alkyl groups, and R2 is selected from C1-C4 alkyl groups. 18 Alkyl groups; The diesel engine oil compound has an alkalinity ≥ 60.0 mg KOH / g and a nitrogen content ≥ 1.0%. The alkyl phosphate anti-wear agent has the structure shown in Formula III: Formula III, In Equation III, the two R3s may be the same or different, and each is independently selected from C1-C2. 10 Alkyl group, R4 is C 12 -C 20 Alkyl groups; The phosphate phenol ester anti-wear agent has the structure shown in Formula IV: Formula IV, In Formula IV, R5 is a C1-C4 alkyl group.

2. The D1 specification diesel engine oil composition according to claim 1, wherein, In Formula II, R1 is selected from C1-C4 n-alkyl groups, and R2 is selected from C1-C4 n-alkyl groups. 18 n-alkyl groups.

3. The D1 specification diesel engine oil composition according to claim 1, wherein, The preparation method of the dispersible viscosity index improver includes the following steps: (1) Maleic anhydride and 4-aminodiphenylamine are dissolved in N,N-dimethylformamide and refluxed at 136℃-144℃ for 5-10 hours to obtain a monomer containing aromatic amine; (2) The aromatic amine monomer obtained in step (1) and the alkyl-substituted alkyl acrylate are reacted at 100℃-150℃ for 6-10 hours under the action of an initiator to obtain the dispersion viscosity index improver.

4. The D1 specification diesel engine oil composition according to claim 3, wherein, The molar ratio of the aromatic amine monomer to the alkyl-substituted alkyl acrylate is 1:20-100.

5. The D1 specification diesel engine oil composition according to claim 3, wherein, The mass ratio of the initiator to the alkyl-substituted alkyl acrylate is 1:100-500.

6. The D1 specification diesel engine oil composition according to claim 3, wherein, In step (2), the mass ratio of the solvent and the alkyl-substituted alkyl acrylate used in the reaction is 1-4:

1.

7. The D1 specification diesel engine oil composition according to claim 3, wherein, The preparation method includes the following steps: (1) Maleic anhydride and 4-aminodiphenylamine in a molar ratio of 1:1 were dissolved in N,N-dimethylformamide and refluxed at 136℃-144℃ for 5-10 hours. The solvent was removed by vacuum evaporation and the product was recrystallized from ethanol to obtain a monomer containing aromatic amine. (2) The aromatic amine monomer obtained in step (1) and the alkyl-substituted alkyl acrylate are reacted at 100℃-150℃ for 6-10 hours with xylene as solvent and tert-butyl peroxide-2-ethylhexanoate as initiator. The solvent is then removed by vacuum distillation to obtain the dispersion viscosity index improver.

8. The D1 specification diesel engine oil composition according to claim 1, wherein, The mass fraction of the diesel engine oil compound is 12.0-17.0%.

9. The D1 specification diesel engine oil composition according to claim 1, wherein, The diesel engine oil compound includes RHY3160.

10. The D1 specification diesel engine oil composition according to claim 1, wherein, The mass fraction of the alkyl phosphate anti-wear agent is 0.2-0.8%.

11. The D1 specification diesel engine oil composition according to claim 1, wherein, The mass fraction of the phosphate phenol ester anti-wear agent is 0.1-0.6%.

12. The D1 specification diesel engine oil composition according to claim 1, wherein, The mass fraction of the metal passivating agent is 0.1-0.4%.

13. The D1 specification diesel engine oil composition according to claim 1, wherein, The metal passivating agent includes benzotriazole derivative metal passivating agents.

14. The D1 specification diesel engine oil composition according to claim 1, wherein, The mass fraction of the dispersible viscosity index improver is 2.0-8.0%.

15. The D1 specification diesel engine oil composition according to claim 1, wherein, The pour point depressant has a mass fraction of 0.2-0.6%.

16. The D1 specification diesel engine oil composition according to claim 1, wherein, The pour point depressant includes polyalphaolefin and / or polymethyl methacrylate.

17. The D1 specification diesel engine oil composition according to claim 1, wherein, The mass fraction of the Group II base oil is 72.4-85.4%.

18. The D1 specification diesel engine oil composition according to claim 1, wherein, Group II base oils include HVIH4 and / or HVIH6.

19. The D1 specification diesel engine oil composition according to claim 1, wherein, The D1 specification diesel engine oil composition passed the physicochemical tests and simulated performance tests of D1 specification diesel engine oil.

20. The D1 specification diesel engine oil composition according to claim 1, wherein, The D1 specification diesel engine oil composition passed the D1 specification engine bench test.

21. A method for preparing the D1 specification diesel engine oil composition according to any one of claims 1-20, comprising the following steps: The diesel engine oil compound, alkyl phosphate anti-wear agent, phenolic phosphate anti-wear agent, metal passivator, dispersible viscosity index improver, pour point depressant, and Group II base oil are mixed and stirred for more than 2 hours to obtain the D1 specification diesel engine oil composition.

22. The application of the D1 specification diesel engine oil composition according to any one of claims 1-20 in diesel engines with emission standards of China VI and below.

Images