High-performance clean anti-wear hydraulic oil complexing agent and preparation method thereof

Abstract

The invention discloses a high-performance clean type anti-wear hydraulic oil complexing agent which is prepared from the following substances in parts by mass: 30 to 60 parts of an antioxidant, 20 to 40 parts of an anti-wear agent, 2 to 5 parts of boronized polyisobutylene bis-succinimide, 2 to 7 parts of thiocarbamate, 4 to 10 parts of dodecenylsuccinic acid and 0.2 to 2 parts of graphene nanosheets. The lubricating oil is prepared from the following components in parts by weight: 0.5-1.5 parts of a metal deactivator, 0-2 parts of DISUPER S24 and 30-50 parts of base oil. The preparation method comprises the following steps: S21, heating the base oil, adding the boronized polyisobutylene bis-succinimide and the thiocarbamate, and stirring; s22, sequentially adding an antioxidant, an anti-wear agent, dodecenylsuccinic acid, DISUPER S24 and a metal deactivator into the solution obtained in the step S11, heating to 80 DEG C, and reacting for 2 hours; and S23, adding graphene nanosheets into the solution obtained in the step S22, and carrying out ultrasonic dispersion for 1 hour to obtain the product.

Description

Technical Field

[0001] The present invention belongs to the technical field of hydraulic oils, and particularly relates to a high-performance clean anti-wear hydraulic oil compound and a preparation method thereof. Background Art

[0002] Hydraulic oil is the working medium used to transfer energy in a hydraulic system and is an important component of the hydraulic system. Hydraulic oil needs to perform multiple functions in the hydraulic system, such as transferring energy and signals, lubricating hydraulic components, dissipating heat, preventing rust, and providing diagnostic information for component and system failures. Hydraulic oil can be said to be the "blood" of the hydraulic system and has a very important impact on the working life, performance, and reliability of hydraulic equipment.

[0003] At present, hydraulic systems equipped with electro-hydraulic servo valves need to use clean hydraulic oil, and have high requirements for the quality of hydraulic oil, especially the solid particles in the oil should not exceed a certain range. The harm of solid particles to the hydraulic system is serious. It causes premature wear of precision components such as hydraulic pumps and hydraulic valves on a large scale and loses their working ability, and the hydraulic system cannot operate normally. The reasons for the generation of solid particles are various. Those inherent in the refined oil, secondary pollution caused by improper transportation and storage management of the oil products, and incomplete cleaning during equipment installation and maintenance will all bring new pollution to the hydraulic oil. The solid particle pollution caused by these factors can be improved by means of repeated precision filtration. On the other hand, the thermal stability and oxidation stability of the hydraulic oil itself are the most important factors affecting the long-term stable operation of the hydraulic system. Usually, when hydraulic oil acts in an environment of high temperature and the presence of oxygen for a certain period of time, due to the decomposition of additives, oxidation reactions, etc., substances such as sludge, gum, and coke are gradually generated, and these substances are highly harmful to the equipment. This problem should be fully emphasized during the development of oil products. The key to solving this problem is to develop clean hydraulic oil with good thermal stability, excellent oxidation stability, and long life. Adding a compound to the hydraulic oil is an effective method.

[0004] CN 109628199 A discloses a novel anti-wear hydraulic oil compound, which relates to the technical field of hydraulic oil and comprises the following components (by mass percentage): high molecular weight phenolic antioxidant: 15-19%, silicon hydroxide: 2-4%, sodium silicate: 2.5-3.5%, boric acid: 5-7%, dodecenyl succinic acid: 14-18%, viscosity index improver: 8-10%, demulsifier: 2.3-2.5%, defoamer: 4.5-4.7%, metal deactivator: 0.5-1.5%, and the balance is base oil. The present invention also discloses a preparation method of the novel anti-wear hydraulic oil compound, which comprises four steps. By adjusting each raw material and formula, the compound prepared by the present invention can reduce the wear scar diameter of the blended hydraulic oil, has the effect of improving the anti-wear performance of the blended hydraulic oil, and at the same time, the hydraulic oil blended with the compound also has good antioxidant, lubricating, anti-wear and anti-corrosion performances. The present invention can adjust the viscosity of the compound according to different contents of the viscosity index improver to adapt to different equipment. However, the use effect is still not very ideal. Summary of the Invention

[0005] To solve the above technical problems, in view of the deficiencies of the prior art, the present invention provides a high-performance clean anti-wear hydraulic oil compound and a preparation method thereof. The high-performance clean anti-wear hydraulic oil compound is composed of the following substances in parts by mass: Antioxidant 30-60 parts Anti-wear agent 20-40 parts Borated polyisobutylene bisimide 2-5 parts Thiocarbamate 2-7 parts Dodecenyl succinic acid 4-10 parts Graphene nanosheets 0.2-2 parts Metal passivator 0.5-1.5 parts DISUPER S24 (Core Chemistry) 0-2 parts Base oil 30-50 parts.

[0006] The formula of the present invention forms a three-dimensional adsorption film through the synergistic effect of borated polyisobutylene bisimide and graphene. Boron atoms form B-O-Fe chemical bonds with the metal surface and cooperate with the sp² hybrid carbon of graphene, reducing the friction coefficient by more than 40%. Graphene nanosheets are oriented on the friction pair surface, reducing the boundary friction coefficient. DISUPER S24 inhibits the aggregation of deposits through steric hindrance effects, and the terminal carboxyl group reacts in situ with the hydroxyl groups generated by wear to achieve surface self-repair.

[0007] Furthermore, the antioxidant is a mixture of p-phenylenediamine and 2,6-di-tert-butyl-4-methylphenol, and the mass ratio of p-phenylenediamine to 2,6-di-tert-butyl-4-methylphenol is 1: 1. The hindered phenol and aromatic amine composite system still maintains more than 90% of the free radical capture ability at 180°C, the hindered phenol captures alkyl free radicals, and the aromatic amine decomposes peroxides, and has a strong antioxidant ability.

[0008] Furthermore, the metal passivator is a mixture of methylbenzotriazole and 2,5-di(tert-dodecyl disulfide)-1,3,4-thiadiazole, and the mass ratio of methylbenzotriazole and 2,5-di(tert-dodecyl disulfide)-1,3,4-thiadiazole is 1:2. Toluene triazole is directionally adsorbed on the surface of copper alloy, inhibiting catalytic oxidation and reducing metal corrosion weight loss. 2,5-di(tert-dodecyl disulfide)-1,3,4-thiadiazole can capture active sulfur in oil products and inhibit metal corrosion. Because it contains polysulfide bonds, it can form a sulfide film with the metal surface, thereby effectively inhibiting the catalytic effect of metal ions on oil products, and synergistically improving the performance of oil products with methylbenzotriazole.

[0009] Furthermore, the anti-wear agent is a mixture of triphenyl thiophosphate and pentaerythritol stearate, and the mass ratio of triphenyl thiophosphate to pentaerythritol stearate is 1: 2. Due to the presence of phosphoric acid groups, it decomposes under extreme pressure conditions to form an iron phosphate film, which forms a gradient protective layer with boron.

[0010] Furthermore, the base oil is a mixture of bio-based trimethylolpropane oleate and trioctyl phosphate, and the mass ratio of bio-based trimethylolpropane oleate to trioctyl phosphate is 4: 1. By introducing bio-based esters and synthetic esters to form a eutectic structure, the polar groups of bio-esters enhance the adsorption capacity of additives, and the tribological properties are improved.

[0011] Furthermore, the surface of the graphene nanosheet is loaded with MOF-74. The MOF pore structure realizes the on-demand release of boron atoms, and releases boron elements under the triggering of friction heat (>80°C), so that the wear spot diameter is dynamically reduced.

[0012] The method for loading MOF-74 on the surface of the graphene nanosheets is as follows: S11. Pre-treating the graphene nanosheets by ultrasonic cleaning to increase their surface activity; S12. Add MOF-74 to anhydrous ethanol with a mass 5 times that of the MOF-74 to obtain an ethanol mixture, wherein the mass of the MOF-74 is 8-13% of the graphene nanosheets in step S11.

[0013] S13. The graphene nanosheets pretreated by ultrasonic cleaning obtained in step S11 and the ethanol mixture obtained in step S12 are uniformly mixed, and the energy input of ultrasonic cleaning is controlled to depolymerize the graphene sheets to avoid agglomeration; S14. React the mixture obtained in step S13 at 120 - 140 °C for 18 h, then cool down, wash and dry to obtain graphene nanosheets loaded with MOF-74.

[0014] The preparation method of the high-performance clean anti-wear hydraulic oil compound agent described above includes the following steps: S21. Heat the base oil to 60 - 70 °C, add borated polyisobutylene bis-succinimide and thiocarbamate and stir for 30 minutes; S22. Continuously add antioxidant, anti-wear agent, dodecenyl succinic acid, DISUPER S24 and metal deactivator to the solution obtained in step S11 in sequence, heat up to 80 °C and react for 2 h; S23. Add graphene nanosheets to the solution obtained in step S22, ultrasonically disperse for 1 h to obtain a high-performance clean anti-wear hydraulic oil compound agent.

[0015] The present invention also provides a hydraulic oil prepared by using the above-mentioned high-performance clean anti-wear hydraulic oil compound agent, a hydraulic oil prepared by adding 0.6 wt% of the high-performance clean anti-wear hydraulic oil compound agent to No. 46 hydraulic oil.

[0016] The hydraulic oil prepared by the high-performance clean anti-wear hydraulic oil compound agent prepared by the present invention has good performance, and the test data of hydrolysis stability, thermal stability and anti-wear performance in the double-pump (T6H20C) test are all good, and it can be applied to harsh application conditions and has high popularization and application value. Specific embodiments

[0017] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention clearer, the present invention will be further described in detail below in conjunction with embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0018] Example 1

[0019] A high-performance clean anti-wear hydraulic oil compound agent is composed of the following substances in parts by mass: Antioxidant 60 g Anti-wear agent 36 g Borated polyisobutylene bis-succinimide 5 g Thiocarbamate 7 g Dodecenyl succinic acid 10 g Graphene nanosheets loaded with MOF-74 2 g Metal deactivator 1.5 g DISUPER S24 2 g Base oil 50 g.

[0020] The antioxidant is 30 g of p-phenylenediamine and 30 g of 2,6-di-tert-butyl-4-methylphenol.

[0021] The metal deactivator is 0.5 g of methylbenzotriazole and 1 g of 2,5-bis(tert-dodecyl dithiocarbonyl)-1,3,4-thiadiazole.

[0022] The antiwear agent is 12 g of triphenyl thiophosphate and 24 g of pentaerythritol stearate.

[0023] The base oil is 40 g of biobased trimethylolpropane oleate and 10 g of trioctyl phosphate.

[0024] The preparation method of the high-performance clean antiwear hydraulic oil compound includes the following steps: S21. Heat the base oil to 60-70 °C, add boronated polyisobutylene bisimide and thiocarbamate and stir for 30 minutes; S22. Continue to add the antioxidant, antiwear agent, dodecene succinic acid, DISUPER S24 and metal deactivator to the solution obtained in step S11 in sequence, and heat up to 80 °C and react for 2 hours; S23. Add graphene nanosheets to the solution obtained in step S22, and ultrasonically disperse for 1 hour to obtain the high-performance clean antiwear hydraulic oil compound.

[0025] The method for loading MOF-74 on the surface of the graphene nanosheets is as follows: S11. Ultrasonically clean and pretreat the graphene nanosheets to increase their surface activity; S12. Add MOF-74 to anhydrous ethanol with a mass 5 times that of MOF-74 to obtain an ethanol mixture, and the mass of MOF-74 is 10% of the graphene nanosheets in step S11.

[0026] S13. Mix the ultrasonically cleaned and pretreated graphene nanosheets obtained in step S11 and the ethanol mixture obtained in step S12 evenly; S14. React the mixture obtained in step S13 at 120-140 °C for 18 h, then cool down, wash and dry to obtain graphene nanosheets loaded with MOF-74.

[0027] The hydraulic oil prepared by using the above high-performance clean antiwear hydraulic oil compound is the hydraulic oil prepared by adding 0.6 wt% of the high-performance clean antiwear hydraulic oil compound to No. 46 hydraulic oil.

[0028] Example 2

[0029] A high-performance clean antiwear hydraulic oil compound is composed of the following substances in parts by mass: Antioxidant 36 g Antiwear agent 24 g Borated polyisobutylene bis-succinimide 2 g Thiocarbamate 2 g Dodecenylsuccinic acid 5 g Supported MOF-74 graphene nanosheets 2 g Metal deactivator 0.6 g DISUPER S24 1 g Base oil 35 g.

[0030] The antioxidant is 18 g of p-phenylenediamine and 18 g of 2,6-di-tert-butyl-4-methylphenol.

[0031] The metal deactivator is 0.2 g of methylbenzotriazole and 0.4 g of 2,5-bis(tert-dodecyl dithio)-1,3,4-thiadiazole.

[0032] The antiwear agent is 8 g of triphenyl thiophosphate and 16 g of pentaerythritol stearate.

[0033] The base oil is 28 g of biobased trimethylolpropane oleate and 7 g of trioctyl phosphate.

[0034] The preparation method of the high-performance cleaning antiwear hydraulic oil compound includes the following steps: S21. Heat the base oil to 60 - 70 °C, add borated polyisobutylene bis-succinimide and thiocarbamate and stir for 30 minutes; S22. Continuously add antioxidant, antiwear agent, dodecenylsuccinic acid, DISUPER S24 and metal deactivator to the solution obtained in step S11, heat to 80 °C and react for 2 hours; S23. Add graphene nanosheets to the solution obtained in step S22, ultrasonically disperse for 1 hour to obtain the high-performance cleaning antiwear hydraulic oil compound.

[0035] The method for loading MOF-74 on the surface of the graphene nanosheets is as follows: S11. Ultrasonically clean and pre-treat the graphene nanosheets to increase their surface activity; S12. Add MOF-74 to anhydrous ethanol with a mass 5 times that of it to obtain an ethanol mixture, and the mass of MOF-74 is 10% of the graphene nanosheets in step S11.

[0036] S13. Mix the ultrasonically cleaned and pre-treated graphene nanosheets obtained in step S11 and the ethanol mixture obtained in step S12 evenly; S14. React the mixture obtained in step S13 at 120 - 140 °C for 18 h, then cool down, wash, and dry to obtain graphene nanosheets loaded with MOF-74.

[0037] The hydraulic oil prepared with the above high-performance clean anti-wear hydraulic oil compounding agent is prepared by adding 0.6 wt% of the high-performance clean anti-wear hydraulic oil compounding agent to No. 46 hydraulic oil.

[0038] Example 3

[0039] A high-performance clean anti-wear hydraulic oil compounding agent is composed of the following substances in parts by mass: Antioxidant 60 g Anti-wear agent 36 g Borated polyisobutylene bis(succinimide) 5 g Thiocarbamate 7 g Dodecenylsuccinic acid 10 g Graphene nanosheets loaded with MOF-74 2 g Metal deactivator 1.5 g Base oil 50 g.

[0040] The antioxidant is 30 g of p-phenylenediamine and 30 g of 2,6-di-tert-butyl-4-methylphenol.

[0041] The metal deactivator is 0.5 g of methylbenzotriazole and 1 g of 2,5-bis(tert-dodecyl dithio)-1,3,4-thiadiazole.

[0042] The anti-wear agent is 12 g of triphenyl thiophosphate and 24 g of pentaerythritol stearate.

[0043] The base oil is 40 g of biobased trimethylolpropane oleate and 10 g of trioctyl phosphate.

[0044] The preparation method of the high-performance clean anti-wear hydraulic oil compounding agent includes the following steps: S21. Heat the base oil to 60 - 70 °C, add borated polyisobutylene bis(succinimide) and thiocarbamate, and stir for 30 minutes; S22. Continuously add the antioxidant, anti-wear agent, dodecenylsuccinic acid, and metal deactivator to the solution obtained in step S11 in sequence, heat to 80 °C, and react for 2 hours; S23. Add graphene nanosheets to the solution obtained in step S22, and ultrasonically disperse for 1 hour to obtain the high-performance clean anti-wear hydraulic oil compounding agent.

[0045] The method for loading MOF-74 on the surface of the graphene nanosheets is as follows: S11. Ultrasonically clean and pre-treat the graphene nanosheets to increase their surface activity; S12. Add MOF-74 to anhydrous ethanol with a mass 5 times that of MOF-74 to obtain an ethanol mixture. The mass of MOF-74 is 10% of the graphene nanosheets in step S11.

[0046] S13. Mix the ultrasonically cleaned and pre-treated graphene nanosheets obtained in step S11 and the ethanol mixture obtained in step S12 evenly; S14. React the mixture obtained in step S13 at 120 - 140 °C for 18 h, then cool down, wash, and dry to obtain graphene nanosheets loaded with MOF-74.

[0047] The hydraulic oil prepared using the above high-performance clean anti-wear hydraulic oil compound is a hydraulic oil prepared by adding 0.6 wt% of the high-performance clean anti-wear hydraulic oil compound to No. 46 hydraulic oil.

[0048] Example 4

[0049] Replace the graphene nanosheets loaded with MOF-74 in Example 3 with graphene nanosheets, and the rest is the same as in Example 3, which will not be elaborated here.

[0050] Comparative Example 1 Remove the graphene nanosheet component in Example 4, and the rest is the same as in Example 3, which will not be elaborated here, which will not be elaborated here.

[0051] Comparative Example 2 Remove the 2,6-di-tert-butyl-4-methylphenol component in Example 4, and the rest is the same as in Example 3, which will not be elaborated here, which will not be elaborated here.

[0052] Comparative Example 3 Remove the 2,5-bis(tert-dodecyl dithiocarbonyl)-1,3,4-thiadiazole component in Example 4, and the rest is the same as in Example 3, which will not be elaborated here, which will not be elaborated here.

[0053] Comparative Example 4 Remove the boronated polyisobutylene bis(succinimide) component in Example 4, and the rest is the same as in Example 3, which will not be elaborated here, which will not be elaborated here.

[0054] Perform performance tests on the hydraulic oils prepared in the above examples and comparative examples. The results are shown in Table 1 and Table 2. The cleanliness of the hydraulic oils prepared in the above examples is not lower than Grade 4.

[0055] Table 1 Test Items and Test Standards

[0056] Table 2 Test Data of the Hydraulic Oils Prepared in the Comparative Examples and Examples (the test items in Table 2 are the same as those in Table 1)

[0057] As can be seen from the data in the above table, the data of Examples 1 to 4 show that the hydraulic oil prepared from the high-performance clean anti-wear hydraulic oil compound prepared by the present invention has good performance, and the test data of hydrolysis stability, thermal stability, and anti-wear performance double pump (T6H20C) are all good, and it can be applied to harsh application conditions. The data of Example 4 show that the load MOF-74 graphene nanocomposite has better technical effects. The data of Comparative Examples 1 to 4 show that graphene nanosheets, 2,6-di-tert-butyl-4-methylphenol, 2,5-bis(tert-dodecyl dithiocarbonyl)-1,3,4-thiadiazole, and borated polyisobutylene bisimide can all improve the product performance. Among them, borated polyisobutylene bisimide has the greatest improvement in product performance, and 2,5-bis(tert-dodecyl dithiocarbonyl)-1,3,4-thiadiazole has the least improvement in product performance.

Claims

1. A high-performance clean anti-wear hydraulic oil compound, characterized in that, The high-performance clean anti-wear hydraulic oil compound is composed of the following substances in parts by mass as follows: Antioxidant: 30 - 60 parts Anti-wear agent: 20 - 40 parts Borated polyisobutylene bis-succinimide: 2 - 5 parts Thiocarbamate: 2 - 7 parts Dodecene-based succinic acid: 4 - 10 parts Graphene nanosheets: 0.2 - 2 parts Metal deactivator: 0.5 - 1.5 parts DISUPER S24: 0 - 2 parts Base oil: 30 - 50 parts.

2. The high-performance clean anti-wear hydraulic oil compound according to claim 1, wherein The antioxidant is a mixture of p-phenylenediamine and 2,6-di-tert-butyl-4-methylphenol, and the mass ratio of p-phenylenediamine to 2,6-di-tert-butyl-4-methylphenol is 1:

1.

3. The high-performance clean anti-wear hydraulic oil compound according to claim 1, characterized in that The metal deactivator is a mixture of methylbenzotriazole and 2,5-bis(tert-dodecyldithio)-1,3,4-thiadiazole, and the mass ratio of methylbenzotriazole to 2,5-bis(tert-dodecyldithio)-1,3,4-thiadiazole is 1:

2.

4. The high-performance clean anti-wear hydraulic oil compound according to claim 1, characterized in that, The anti-wear agent is a mixture of triphenyl thiophosphate and pentaerythritol stearate, and the mass ratio of triphenyl thiophosphate to pentaerythritol stearate is 1:

2.

5. The high-performance clean anti-wear hydraulic oil compound according to claim 1, characterized in that, The base oil is a mixture of biobased trimethylolpropane oleate and trioctyl phosphate, and the mass ratio of biobased trimethylolpropane oleate to trioctyl phosphate is 4:

1.

6. The high-performance clean anti-wear hydraulic oil compound according to claim 1, wherein The graphene nanosheets are surface-loaded with MOF-74.

7. The high-performance clean anti-wear hydraulic oil compound according to claim 6, characterized in that, The method for surface-loading MOF-74 on the graphene nanosheets is as follows: S11. Ultrasonically clean and pre-treat the graphene nanosheets to increase their surface activity; S12. Add MOF-74 to anhydrous ethanol at 5 times its mass to obtain an ethanol mixture. The mass of MOF-74 is 8 - 13% of the graphene nanosheets in step S11. S13. Mix the ultrasonically cleaned and pre-treated graphene nanosheets obtained in step S11 and the ethanol mixture obtained in step S12 evenly; S14. React the mixture obtained in step S13 at 120 - 140 °C for 18 h, then cool down, wash, and dry to obtain graphene nanosheets loaded with MOF-74.

8. A method for preparing the high-performance clean anti-wear hydraulic oil compound according to any one of claims 1 to 6, characterized in that, It includes the following steps: S21. Heat the base oil to 60 - 70 °C, add borated polyisobutylene bis-succinimide and thiocarbamate, and stir for 30 minutes; S22. Continuously add the antioxidant, anti-wear agent, dodecene-based succinic acid, DISUPERS24, and metal deactivator to the solution obtained in step S11 in sequence, and heat to 80 °C and react for 2 hours; S23. Add the graphene nanosheets to the solution obtained in step S22, and ultrasonically disperse for 1 hour to obtain a high-performance clean anti-wear hydraulic oil compound.

9. A hydraulic oil prepared by using the high-performance clean anti-wear hydraulic oil compound as described in any one of claims 1 to 6, characterized in that, Hydraulic oil prepared by adding 0.6 wt% of the high-performance clean anti-wear hydraulic oil compound to No. 46 hydraulic oil.

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