Metal protective additive and hydraulic oil composition containing same

Abstract

The invention relates to the technical field of hydraulic oil, in particular to a metal protective additive and a hydraulic oil composition containing the same. The metal protective additive comprises a sulfonate antirust agent, a carboxylic acid antirust agent and an azole metal deactivator in a weight ratio of (1-2): (0.03-0.3): 1. The metal protection additive with excellent metal protection performance is obtained by compounding the sulfonate antirust agent, the carboxylic acid antirust agent and the metal deactivator, and the metal protection additive is added into the hydraulic oil, so that the hydraulic oil has excellent metal protection performance; meanwhile, the metal protective additive has good compatibility with additives such as an anti-wear reagent at extreme pressure, an antioxidant, a detergent dispersant and the like, and the properties such as copper sheet corrosion, liquid phase corrosion, hydrolytic stability, demulsibility and the like of the hydraulic oil product can be obviously improved.

Description

Technical Field

[0001] The invention relates to the technical field of hydraulic oil, and in particular to a metal protection additive and a hydraulic oil composition containing the metal protection additive. Background Art

[0002] The hydraulic system is prone to rust when in contact with corrosive media such as air, moisture and inorganic salts during long-term operation. Active substances such as extreme pressure anti-wear agents added to hydraulic oil are also very easy to hydrolyze and produce corrosive substances, which further aggravates the tendency of corrosion of metals such as steel and copper. On the one hand, the rust of the hydraulic system causes the accuracy of hydraulic components to decrease, thus hindering the normal operation of the hydraulic system. On the other hand, the corrosive particles generated by rust will aggravate abrasive wear and oil oxidation. Therefore, hydraulic oil is required to have good metal protection performance.

[0003] The liquid phase corrosion test, copper sheet corrosion test and hydrolysis stability test in the hydraulic oil product standard have put forward clear requirements on the corrosion resistance of hydraulic oil under different test conditions. How to provide an additive with excellent metal protection performance to significantly improve the copper sheet corrosion, liquid phase corrosion, hydrolysis stability, anti-emulsification and other properties of hydraulic oil has become a technical problem that needs to be solved urgently in this field. Summary of the invention

[0004] Firstly, the present invention provides a metal protection additive, which can effectively improve the metal protection performance of hydraulic oil.

[0005] The metal protection additive of the invention comprises a sulfonate rust inhibitor, a carboxylic acid rust inhibitor and an azole metal deactivator in a weight ratio of (1-2):(0.03-0.3):1.

[0006] The present invention finds that by compounding the sulfonate rust inhibitor, the carboxylic acid rust inhibitor and the azole metal deactivator according to the above ratio, a good synergistic effect can be obtained, the metal protection performance of the hydraulic oil can be effectively improved, and the requirements of various metal protection related test standards such as copper sheet corrosion, liquid phase corrosion, hydrolysis stability, etc. can be met, and the hydraulic oil has excellent anti-emulsification performance.

[0007] Preferably, the metal protection additive comprises a sulfonate rust inhibitor, a carboxylic acid rust inhibitor and an azole metal deactivator in a weight ratio of (1-1.8):(0.035-0.25):1.

[0008] Preferably, the sulfonate rust inhibitor is at least one of barium dinonylnaphthalenesulfonate, zinc dinonylnaphthalenesulfonate and calcium dinonylnaphthalenesulfonate.

[0009] Preferably, the carboxylic acid rust inhibitor is at least one of alkenyl succinic acid and alkenyl succinate ester type rust inhibitors.

[0010] Preferably, the azole metal deactivator is at least one of a benzotriazole derivative and a thiadiazole derivative;

[0011] Preferably, it is at least one of benzotriazole, methylbenzotriazole, N,N-dialkylaminomethylenebenzotriazole, 2,5-dimercapto-1,3,4-thiadiazole, 2,5-di(alkylthio)-1,3,4-thiadiazole and 2-mercaptobenzothiazole.

[0012] More preferably, the carboxylic acid rust inhibitor is dodecenyl succinate T747, the azole metal deactivator is thiadiazole derivative T561 (provided by Changsha Wangcheng Petrochemical Co., Ltd.), and the sulfonate rust inhibitor is calcium dinonylnaphthalenesulfonate.

[0013] When the above three substances are compounded, the metal protection performance of hydraulic oil is optimal.

[0014] Furthermore, the present invention provides a method for preparing the metal protective additive, comprising mixing a sulfonate rust inhibitor, a carboxylic acid rust inhibitor and an azole metal deactivator, controlling the temperature at 60-70° C., and stirring for 1-2 hours.

[0015] By first preparing the metal protection additive and then adding it to the hydraulic oil composition, the metal protection performance of the hydraulic oil can be improved.

[0016] Furthermore, the present invention provides a hydraulic oil composition, which contains the metal protection additive in any one of the above embodiments.

[0017] Due to the addition of the metal protection additive of the present invention, the prepared hydraulic oil composition meets the requirements of the national standard GB11118.1 for hydraulic oil and has excellent anti-rust performance, anti-emulsification performance and hydrolysis stability performance.

[0018] Preferably, the metal protection additive accounts for 0.02% to 0.15% by weight of the hydraulic oil composition, preferably 0.03% to 0.10%.

[0019] Preferably, the hydraulic oil composition comprises the following components in parts by weight:

[0020]

[0021] The extreme pressure anti-wear agent is a compound containing sulfur and / or phosphorus;

[0022] The antioxidant is at least one of an amine antioxidant and a phenolic antioxidant;

[0023] The detergent dispersant is at least one of sulfonate, alkyl salicylate, alkyl phenol, and succinimide;

[0024] The viscosity index improver is a polymethacrylate viscosity index improver (PMA);

[0025] The pour point depressant is a polymethacrylate pour point depressant;

[0026] The base oil is API Class I base oil or API Class II base oil.

[0027] More preferably, the extreme pressure anti-wear agent is at least one of sulphurized olefins, sulphurized oils and fats, polysulfides, alkyl phosphate amine salts, thiocarbamates and dialkyl dithiophosphates, preferably zinc dialkyl dithiophosphates.

[0028] More preferably, the amine antioxidant is dioctyl diphenylamine, butyl octyl diphenylamine, dinonyl diphenylamine, and the phenolic antioxidant is at least one of 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-p-cresol, 4,4-methylenebis(2,6-di-tert-butylphenol), high molecular weight phenol, and thioether phenol. Preferably, dinonyl diphenylamine or / and 2,6-di-tert-butyl-p-cresol.

[0029] More preferably, the detergent dispersant is sulfurized alkyl phenate calcium.

[0030] More preferably, the viscosity index improver is Viscoplex 8-310 or Viscoplex 8-219.

[0031] More preferably, the pour point depressant is Viscoplex 1-248 or T866.

[0032] More preferably, the API Class I base oil (conventional mineral type) meets the following requirements: viscosity index 80-120, sulfur content>0.03%, saturated hydrocarbon content<90%, such as 150SN, 500SN, etc. The API Class II base oil (using hydrocracking or hydroisomerization cracking process) meets the following requirements: viscosity index 80-120, sulfur content≤0.03%, saturated hydrocarbon content>90%, such as II6 and II10 base oils produced by Shanghai Gaoqiao.

[0033] Preferably, the hydraulic oil composition comprises the following components in parts by weight:

[0034]

[0035] Most preferably, the hydraulic oil composition comprises the following components in parts by weight:

[0036]

[0037]

[0038] Furthermore, the present invention also finds that when the metal protection additive of the present invention is compounded with the combination of the above-mentioned base oils, and the above-mentioned extreme pressure anti-wear agent, antioxidant, detergent dispersant, pour point depressant, and viscosity index improver, the hydraulic oil composition meets the requirements of metal protection related test standards such as copper sheet corrosion, liquid phase rust, and hydrolysis stability, and at the same time, the hydraulic oil composition has good anti-emulsification, antioxidant, wear resistance and thermal stability, and the comprehensive performance of the oil product is better.

[0039] Furthermore, the present invention provides a method for preparing the hydraulic oil composition, comprising mixing the metal protection additive and other components, controlling the temperature at 50-60° C., and stirring for 1-2 hours.

[0040] Compared with the prior art, the present invention has the following beneficial effects:

[0041] The present invention obtains a metal protection additive with excellent metal protection performance by compounding a sulfonate rust inhibitor, a carboxylic acid rust inhibitor and a metal deactivator, and adds the metal protection additive to the hydraulic oil so that the hydraulic oil has excellent metal protection performance. At the same time, the metal protection additive of the present invention has good compatibility with additives such as extreme pressure anti-wear agents, antioxidants, detergents and dispersants, and can significantly improve the copper sheet corrosion, liquid phase rust, hydrolysis stability, anti-emulsification and other properties of the hydraulic oil. DETAILED DESCRIPTION

[0042] In order to make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0043] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0044] Unless otherwise specified, the materials and reagents used in the following examples can be obtained from commercial sources.

[0045] The percentages of the components of the hydraulic oil composition in the following embodiments are weight percentages, and the total weight of all components except the composite antifoaming agent is 100%. The following zinc dialkyl dithiophosphate is dioctyl zinc dithiophosphate T203 purchased from Wuxi Nanfang Petroleum Additives Co., Ltd., the sulfided alkylphenol calcium is T121 purchased from Wuxi Nanfang Petroleum Additives Co., Ltd., the metal deactivator T561 is purchased from Changsha Wangcheng, and the composite antifoaming agent is AF201 produced by Sinopec Lubricant Co., Ltd.

[0046] The preparation method of the hydraulic oil composition of the following embodiment is: weigh the sulfonate rust inhibitor, the carboxylic acid rust inhibitor and the azole metal deactivator, mix them, control the temperature at 65°C, stir for 1 hour to prepare the metal protection additive, weigh the remaining components and mix them, and stir at 60°C for 2 hours to prepare the hydraulic oil composition.

[0047] Example 1

[0048] This embodiment provides a hydraulic oil composition, the components and amounts are as follows:

[0049] II6 53%, II10 45.665%, zinc dialkyl dithiophosphate 0.6%, 2,6-di-tert-butyl-p-cresol 0.15%, dinonyl diphenylamine 0.1%, alkyl phenol calcium sulfide 0.04%, calcium dinonyl naphthalene sulfonate 0.02%, dodecenyl succinic acid half ester T747 0.005%, thiadiazole derivative T561 0.02%, viscosity index improver Viscoplex 8-3100.3%, pour point depressant T866 0.1%, composite antifoaming agent 50ppm.

[0050] Example 2

[0051] This embodiment provides a hydraulic oil composition, the components and amounts are as follows:

[0052] II6 53%, II10 45.6475%, zinc dialkyl dithiophosphate 0.6%, 2,6-di-tert-butyl-p-cresol 0.15%, dinonyl diphenylamine 0.1%, alkyl phenol calcium sulfide 0.04%, calcium dinonyl naphthalene sulfonate 0.03%, dodecenyl succinic acid half ester T747 0.0025%, thiadiazole derivative T561 0.03%, viscosity index improver Viscoplex 8-3100.3%, pour point depressant T866 0.1%, composite antifoaming agent 50ppm.

[0053] Example 3

[0054] This embodiment provides a hydraulic oil composition, the components and amounts are as follows:

[0055] II6 53%, II10 45.6285%, zinc dialkyl dithiophosphate 0.6%, 2,6-di-tert-butyl-p-cresol 0.15%, dinonyl diphenylamine 0.1%, alkyl phenol calcium sulfide 0.04%, calcium dinonyl naphthalene sulfonate 0.04%, dodecenyl succinic acid half ester T747 0.0015%, thiadiazole derivative T561 0.04%, viscosity index improver Viscoplex 8-3100.3%, pour point depressant T866 0.1%, composite antifoaming agent 50ppm.

[0056] Example 4

[0057] This embodiment provides a hydraulic oil composition, the components and amounts are as follows:

[0058] II6 53%, II10 45.625%, zinc dialkyl dithiophosphate 0.6%, 2,6-di-tert-butyl-p-cresol 0.15%, dinonyl diphenylamine 0.1%, alkyl phenol calcium sulfide 0.04%, calcium dinonyl naphthalene sulfonate 0.05%, dodecenyl succinic acid half ester T747 0.005%, thiadiazole derivative T561 0.03%, viscosity index improver Viscoplex 8-3100.3%, pour point depressant T866 0.1%, composite antifoaming agent 50ppm.

[0059] Example 5

[0060] This embodiment provides a hydraulic oil composition, the components and amounts are as follows:

[0061] II6 53%, II10 45.665%, zinc dialkyl dithiophosphate 0.5%, 2,6-di-tert-butyl-p-cresol 0.25%, dinonyl diphenylamine 0.05%, alkyl phenol calcium sulfide 0.05%, calcium dinonyl naphthalene sulfonate 0.05%, dodecenyl succinic acid half ester T747 0.005%, thiadiazole derivative T561 0.03%, viscosity index improver Viscoplex 8-3100.3%, pour point depressant T866 0.1%, composite antifoaming agent 50ppm.

[0062] Comparative Example 1

[0063] This comparative example provides a hydraulic oil composition, the components and amounts of which are as follows:

[0064] II6 53%, II10 45.63%, zinc dialkyl dithiophosphate 0.6%, 2,6-di-tert-butyl-p-cresol 0.15%, dinonyl diphenylamine 0.1%, alkyl phenol calcium sulfide 0.04%, calcium dinonyl naphthalene sulfonate 0.06%, thiadiazole derivative T561 0.02%, viscosity index improver Viscoplex 8-310 0.3%, pour point depressant T866 0.1%, composite antifoaming agent 50ppm.

[0065] Comparative Example 2

[0066] This comparative example provides a hydraulic oil composition, the components and amounts of which are as follows:

[0067] II6 53%, II10 45.635%, zinc dialkyl dithiophosphate 0.6%, 2,6-di-tert-butyl-p-cresol 0.15%, dinonyl diphenylamine 0.1%, alkyl phenol calcium sulfide 0.04%, dodecenyl succinic acid half ester T747 0.055%, thiadiazole derivative T561 0.02%, viscosity index improver Viscoplex 8-310 0.3%, pour point depressant T866 0.1%, composite antifoaming agent 50ppm.

[0068] Comparative Example 3

[0069] This comparative example provides a hydraulic oil composition, the components and amounts of which are as follows:

[0070] II6 53%, II10 45.645%, zinc dialkyl dithiophosphate 0.6%, 2,6-di-tert-butyl-p-cresol 0.15%, dinonyl diphenylamine 0.1%, alkyl phenol calcium sulfide 0.04%, calcium dinonyl naphthalene sulfonate 0.05%, dodecenyl succinic acid half ester T747 0.005%, thiadiazole derivative T561 0.01%, viscosity index improver Viscoplex 8-3100.3%, pour point depressant T866 0.1%, composite antifoaming agent 50ppm.

[0071] Comparative Example 4

[0072] This comparative example provides a hydraulic oil composition, the components and amounts of which are as follows:

[0073] II6 53%, II10 45.61%, zinc dialkyl dithiophosphate 0.6%, 2,6-di-tert-butyl-p-cresol 0.15%, dinonyldiphenylamine 0.1%, alkylphenol calcium sulfide 0.04%, calcium alkylbenzene sulfonate 0.08%, thiadiazole derivative T561 0.02%, viscosity index improver Viscoplex 8-310 0.3%, pour point depressant T866 0.1%, composite antifoaming agent 50ppm.

[0074] Test example

[0075] The 46# anti-wear hydraulic oil composition prepared in the above embodiment and comparative example was compared and evaluated according to the main requirements of GB 11118.1-2011, such as rust prevention performance, hydrolysis stability performance, and anti-emulsification performance. The test results are shown in Table 1.

[0076] Table 1 Performance test

[0077]

[0078]

[0079] According to the test results in Table 1, the liquid phase corrosion, demulsification resistance and hydrolysis stability tests of Examples 1-5 are all qualified, while the liquid phase corrosion test (B method) of Comparative Examples 1 and 4 using sulfonate as the rust inhibitor alone is unqualified, and although the liquid phase corrosion of Comparative Example 2 using organic acid as the rust inhibitor alone is qualified, its demulsification performance is poor, and the copper sheet corrosion in the hydrolysis stability test is unqualified, and although Comparative Example 3 uses the same anti-rust system as the embodiment, due to the improper ratio of the components, the weight loss of the copper sheet in the hydrolysis stability test seriously exceeds the standard.

[0080] It can be seen that the present invention compounds different rust inhibitors and metal deactivators in a specific ratio, and the prepared metal protection additive improves the liquid phase corrosion, copper sheet corrosion, hydrolysis stability, copper sheet weight loss and other properties of the hydraulic oil, and significantly improves the overall metal protection performance of the hydraulic oil.

[0081] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A metal protection additive, characterized in that: The invention comprises a sulfonate rust inhibitor, a carboxylic acid rust inhibitor and an azole metal deactivator in a weight ratio of (1-2):(0.03-0.3):

1.

2. The metal protection additive according to claim 1, characterized in that: The invention comprises a sulfonate rust inhibitor, a carboxylic acid rust inhibitor and an azole metal deactivator in a weight ratio of (1-1.8):(0.035-0.25):

1.

3. The metal protection additive according to claim 1, characterized in that: The sulfonate rust inhibitor is at least one of barium dinonylnaphthalenesulfonate, zinc dinonylnaphthalenesulfonate and calcium dinonylnaphthalenesulfonate.

4. The metal protection additive according to claim 1, characterized in that: The carboxylic acid rust inhibitor is at least one of alkenyl succinic acid and alkenyl succinate ester type rust inhibitors.

5. The metal protection additive according to claim 1, characterized in that: The azole metal deactivator is at least one of a benzotriazole derivative and a thiadiazole derivative; Preferably, it is at least one of benzotriazole, methylbenzotriazole, N,N-dialkylaminomethylenebenzotriazole, 2,5-dimercapto-1,3,4-thiadiazole, 2,5-di(alkylthio)-1,3,4-thiadiazole and 2-mercaptobenzothiazole.

6. A hydraulic oil composition, characterized in that: It contains the metal protection additive according to any one of claims 1 to 5.

7. The hydraulic oil composition according to claim 6, characterized in that: The metal protection additive accounts for 0.02% to 0.15% by weight of the hydraulic oil composition, preferably 0.03% to 0.10%.

8. The hydraulic oil composition according to claim 7, characterized in that: It includes the following components by weight: The extreme pressure anti-wear agent is a compound containing sulfur and / or phosphorus; The antioxidant is at least one of an amine antioxidant and a phenolic antioxidant; The detergent dispersant is at least one of sulfonate, alkyl salicylate, alkyl phenol, and succinimide; The viscosity index improver is a polymethacrylate type viscosity index improver; The pour point depressant is a polymethacrylate pour point depressant; The base oil is APII base oil or APIII base oil.

9. The hydraulic oil composition according to claim 8, characterized in that: It includes the following components by weight:

10. The hydraulic oil composition according to claim 9, characterized in that: It includes the following components by weight:

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