Anti-corrosion lubricating grease for ships and warships in seawater environment and preparation method of anti-corrosion lubricating grease

Abstract

The invention discloses anti-corrosion lubricating grease for ships and warships in a seawater environment and a preparation method of the anti-corrosion lubricating grease, and belongs to the technical field of lubricating grease. The lubricating grease comprises the following components in parts by mass: 70-80 parts of composite base oil, 1-5 parts of an environment-friendly biological inhibitor, 1-10 parts of a hydrophobic blocking agent, 1-5 parts of an antirust agent, 1-3 parts of an antioxidant, 1-2 parts of an anti-wear reagent at extreme pressure and 10-20 parts of a thickening agent. The lubricating grease prepared by the invention can be applied to seawater ships, has strong corrosion resistance to seawater, reduces the moisture content of the lubricating grease through the separation effect on seawater, effectively deals with seawater microorganisms and secretions thereof, reduces the corrosion to the lubricating grease, has environmental protection performance, and has small influence on marine organisms (fishes, plants and the like).

Description

Technical Field

[0001] The present invention belongs to the technical field of greases, and particularly relates to an anti-corrosion grease for ships in a seawater environment and a preparation method thereof. Background Art

[0002] Lubricating grease for ships in seawater is a lubricant specially designed for marine environments, mainly used for underwater components of ships, such as bearings, gears, etc. This lubricating grease needs to have good seawater resistance, anti-marine biofouling, extreme pressure and anti-wear, and anti-corrosion properties to ensure the normal operation of ship equipment in harsh marine environments.

[0003] The marine environment is completely different from the land environment. Firstly, the lubricating grease is easily eroded by seawater salt and causes loss; moreover, it is easily affected by marine organisms. For example, barnacles, algae, and microorganisms will accelerate the loss of the lubricating grease's function. However, the currently used biocides are toxic to marine organisms and will cause pollution to the ocean in the long term; not only that, during the use of the lubricating grease, it is easier to wrap seawater and cause the device to rust.

[0004] Therefore, there is a need for a marine ship lubricating grease that is green, has strong rust resistance, and has a hydrophobic effect on seawater. Summary of the Invention

[0005] In view of this, the purpose of the present invention is to provide an anti-corrosion grease for ships in a seawater environment and a preparation method thereof. The lubricating grease prepared by the present invention can be applied to seawater ships, has strong corrosion resistance to seawater, reduces the moisture content of the lubricating grease through the hydrophobic effect on seawater, effectively deals with seawater microorganisms and their secretions to reduce the corrosion of the lubricating grease, and at the same time has environmental protection performance and little impact on marine organisms (such as fish, plants, etc.).

[0006] To achieve the above purpose, the present invention provides the following technical solutions:

[0007] The present invention provides an anti-corrosion grease for ships in a seawater environment, comprising the following components in parts by mass:

[0008] 70 - 80 parts of composite base oil, 1 - 5 parts of environmentally friendly biocide, 1 - 10 parts of hydrophobic barrier agent, 1 - 5 parts of rust inhibitor, 1 - 3 parts of antioxidant, 1 - 2 parts of extreme pressure and anti-wear agent, and 10 - 20 parts of thickener.

[0009] Preferably, the composite base oil is a mixture of PAO synthetic oil and modified castor oil ester in a mass ratio of 50:(10 - 30).

[0010] Preferably, the preparation method of the environmentally friendly biocide is as follows:

[0011] A. Mix the graphene oxide dispersion, sodium hydroxide, and chloroacetic acid and react to obtain carboxylated graphene;

[0012] B. Mix the carboxylated graphene with a copper sulfate solution, stir, and then add ascorbic acid to react to obtain nano-copper-carboxylated graphene;

[0013] C. Mix nano-copper-carboxylated graphene, tannic acid, and an ethanol solution, react, and then centrifuge to obtain an environmentally friendly biocide.

[0014] Preferably, in step A, the volume-mass ratio of the graphene oxide dispersion, sodium hydroxide, and chloroacetic acid is 100 mL : (0.1 - 3) g : (0.5 - 1) g; the concentration of the graphene oxide dispersion is 10 mg / mL.

[0015] Preferably, in step B, the mass-volume ratio of carboxylated graphene, copper sulfate solution, and ascorbic acid is 100 mg : (5 - 15) mL : 5 mL; the concentration of the copper sulfate solution is 0.1 - 0.3 mol / L, and the concentration of the ascorbic acid is 0.2 - 0.5 mol / L.

[0016] Preferably, the stirring time in step B is 2 - 4 h, the reaction temperature is 70 °C, and the time is 2 - 4 h.

[0017] Preferably, in step C, the mass ratio of nano-copper-carboxylated graphene, tannic acid, and ethanol solution is (1 - 5) : (1 - 5) : 100.

[0018] Preferably, the reaction temperature in step C is 40 - 50 °C, and the reaction time is 3 - 6 h.

[0019] By adopting the above technical solution, graphene acts as a carrier to prevent the oxidation of nano-copper. At the same time, its high specific surface area increases the adsorption amount of the rust inhibitor, forming a double protection of "physical barrier + chemical corrosion inhibition". Nano-copper inhibits the metabolism of microorganisms to produce acid and prevents microbially induced corrosion by releasing copper ions to damage the microbial cell membrane. The catechol groups in tannic acid molecules form five-membered ring chelates with copper ions, covering the active sites on the metal surface and inhibiting the electrochemical corrosion reaction; at the same time, tannic acid replaces toxic zinc salts by destroying the integrity of the microbial cell membrane and inhibiting enzyme activity.

[0020] Preferably, the preparation method of the hydrophobic barrier agent is as follows:

[0021] Disperse nano-silica in absolute ethanol, add 1,1,2,2,3,3,4,4,5,5,6,6,7,7,7 - heptadecafluorodecyltriethoxysilane and react at 60 °C for 2 hours, and then add polydimethylsiloxane and azobisisobutyronitrile to react to obtain fluorinated polysiloxane grafted nano-silica, that is, the hydrophobic barrier agent.

[0022] By adopting the above technical solution, fluorinated polysiloxane contains a large number of fluorocarbon chains and its surface energy is extremely low, making the surface of the material difficult to be wetted by water. This low surface energy significantly increases the contact angle, forming a super hydrophobic state. Nano-silica particles (particle size 30-200nm) are grafted on the surface of fluorinated polysiloxane to form a micro-nano composite structure. This roughness further amplifies the hydrophobicity, making it difficult for water droplets to penetrate the surface, but instead rolls off in a spherical shape. When seawater (Na + , Cl + When fluorinated polysiloxane (such as fluorinated polysiloxane) contacts a super-hydrophobic surface, salt is difficult to deposit due to surface repulsion. At the same time, the chemical stability of fluorinated polysiloxane can resist salt corrosion and prevent the destruction of the grease structure due to salt crystallization. Traditional greases tend to form water-in-oil (W / O) emulsions when exposed to seawater, resulting in a sudden increase in viscosity. Fluorinated polysiloxane grafted nano-silica destroys the stability of the emulsion and prevents encapsulation by reducing the interfacial tension gradient (>5mN / m·cm).

[0023] Preferably, the rust inhibitor is one or more of calcium petroleum sulfonate, barium petroleum sulfonate, alkyl diphenylamine, and benzotriazole.

[0024] Preferably, the antioxidant is alkyl diphenylamine or 2,6-di-tert-butyl-p-cresol.

[0025] Preferably, the extreme pressure anti-wear agent is one of thiophosphate acrylate, di-n-butyl phosphite, and dibutyl dithiocarbamate molybdenum.

[0026] Preferably, the thickener is a lithium soap-based thickener or a complex calcium sulfonate-based thickener.

[0027] The present invention also provides a method for preparing the above-mentioned anti-corrosion grease for ships in seawater environment: the composite base oil and thickener are mixed at 80°C and then environmentally friendly bio-inhibitors, hydrophobic barriers, rust inhibitors, antioxidants and extreme pressure anti-wear agents are added in sequence and mixed evenly.

[0028] Contains at least the following beneficial technical effects:

[0029] The grease prepared by the present invention can be used in seawater ships, has strong resistance to seawater corrosion, reduces the water content of the grease by distancing the seawater, and effectively responds to seawater microorganisms and their secretions to reduce corrosion to the grease. It also has environmentally friendly properties and has little impact on marine life (fish, plants, etc.). DETAILED DESCRIPTION

[0030] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0031] It should be understood that the terms used in the present invention are only for describing specific embodiments and are not intended to limit the present invention. Additionally, for the numerical ranges in the present invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Each intermediate value within any stated value or stated range, as well as each smaller range between any other stated value or intermediate value within the stated range, is also included in the present invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0032] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the present invention pertains. Although the present invention only describes preferred methods and materials, any methods and materials similar or equivalent to those described herein can also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials related to the documents. In case of conflict with any incorporated document, the content of this specification shall prevail.

[0033] Without departing from the scope or spirit of the present invention, various improvements and changes can be made to the specific embodiments of the present invention specification, which are obvious to those skilled in the art. Other embodiments obtained from the specification of the present invention are obvious to those skilled in the art. The specification and examples of this application are merely exemplary.

[0034] Regarding "comprising", "including", "having", "containing", etc. used herein, they are all open-ended terms, meaning including but not limited to.

[0035] As used in the present invention, "room temperature" and "normal temperature" are both calculated as 25 ± 2°C unless otherwise specified.

[0036] Unless otherwise specified, the raw materials or instruments used in the following examples of the present invention are all obtained commercially.

[0037] Example 1

[0038] This example provides an anti-corrosion lubricating grease for ships in a seawater environment, and the steps are as follows:

[0039] 1. Prepare an environmentally friendly biocide:

[0040] A. Mix a 10 mg / mL graphene oxide dispersion, sodium hydroxide, and chloroacetic acid in a volume-to-mass ratio of 100 mL: 2 g: 0.8 g and react to obtain carboxylated graphene;

[0041] B. Mix the carboxylated graphene with copper sulfate solution and stir for 3 h, then add ascorbic acid and react at 70 °C for 3 h to obtain nano-copper-carboxylated graphene; the mass-volume ratio of carboxylated graphene, copper sulfate solution, and ascorbic acid is 100 mg: 10 mL: 5 mL;

[0042] C. Mix nano-copper-carboxylated graphene, tannic acid, and ethanol solution according to the mass ratio of 3:3:100, react at 45 °C for 4 h, and then centrifuge to obtain an environment-friendly biological inhibitor.

[0043] 2. Prepare a hydrophobic barrier agent:

[0044] Disperse nano-silica with a particle size of 100 nm in anhydrous ethanol, add 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10 - heptadecafluorodecyltriethoxysilane and react at 60 °C for 2 h, then add polydimethylsiloxane and azobisisobutyronitrile to react to obtain fluorinated polysiloxane grafted nano-silica, which is the hydrophobic barrier agent; the mass ratio of nano-silica, 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10 - heptadecafluorodecyltriethoxysilane, polydimethylsiloxane, and azobisisobutyronitrile is 8:2:1:0.1.

[0045] 3. Mix 75 parts of the composite base oil and 15 parts of the thickening agent at 80 °C, then sequentially add 3 parts of the environment-friendly biological inhibitor, 5 parts of the hydrophobic barrier agent, 2 parts of the rust inhibitor (calcium petroleum sulfonate), 2 parts of the antioxidant (alkyl diphenylamine), and 1.5 parts of the extreme pressure and anti-wear agent (thiolated phosphoric acid acrylate) and mix evenly to obtain the anti-corrosion lubricating grease for ships in a seawater environment; the composite base oil is composed of PAO synthetic oil and modified castor oil ester mixed according to the mass ratio of 50:20.

[0046] Example 2

[0047] This example provides an anti-corrosion lubricating grease for ships in a seawater environment, and the steps are as follows:

[0048] 1. Prepare an environment-friendly biological inhibitor:

[0049] A. Mix a 10 mg / mL graphene oxide dispersion, sodium hydroxide, and chloroacetic acid according to the volume-mass ratio of 100 mL: 3 g: 1 g and react to obtain carboxylated graphene;

[0050] B. Mix the carboxylated graphene with copper sulfate solution and stir for 4 h, then add ascorbic acid and react at 70 °C for 4 h to obtain nano-copper-carboxylated graphene; the mass-volume ratio of carboxylated graphene, copper sulfate solution, and ascorbic acid is 100 mg: 15 mL: 5 mL;

[0051] C. Mix nano-copper-carboxylated graphene, tannic acid, and ethanol solution according to the mass ratio of 5:5:100, react at 50 °C for 6 h, and then centrifuge to obtain an environment-friendly biological inhibitor.

[0052] 2. Preparation of hydrophobic barrier agent:

[0053] Disperse nanosilica with a particle size of 200 nm in absolute ethanol, add heptadecafluorodecyltriethoxysilane and react at 60 °C for 2 hours, then add polydimethylsiloxane and azobisisobutyronitrile for reaction to obtain fluorinated polysiloxane grafted nanosilica, namely the hydrophobic barrier agent, where the mass ratio of nanosilica, heptadecafluorodecyltriethoxysilane, polydimethylsiloxane, and azobisisobutyronitrile is 10:2:2:0.1.

[0054] 3. Mix 75 parts of the composite base oil and 15 parts of the thickening agent at 80 °C, and then sequentially add 3 parts of the environmentally friendly biocide, 5 parts of the hydrophobic barrier agent, 5 parts of the rust inhibitor (alkyl diphenylamine), 3 parts of the antioxidant (2,6 - di - tert - butyl - p - cresol), and 2 parts of the extreme pressure and anti - wear agent (di - n - butyl phosphite) and mix evenly to obtain the anti - corrosion lubricating grease for ships in a seawater environment; the composite base oil is composed of PAO synthetic oil and modified castor oil ester mixed in a mass ratio of 50:10.

[0055] Example 3

[0056] This example provides an anti - corrosion lubricating grease for ships in a seawater environment, and the steps are as follows:

[0057] 1. Preparation of environmentally friendly biocide:

[0058] A. Mix a 10 mg / mL graphene oxide dispersion, sodium hydroxide, and chloroacetic acid in a volume - mass ratio of 100 mL:0.1 g:0.5 g and react to obtain carboxylated graphene.

[0059] B. Mix the carboxylated graphene with a copper sulfate solution and stir for 2 h, then add ascorbic acid and react at 70 °C for 2 h to obtain nano - copper - carboxylated graphene; the mass - volume ratio of carboxylated graphene, copper sulfate solution, and ascorbic acid is 100 mg:5 mL:5 mL.

[0060] C. Mix nano - copper - carboxylated graphene, tannic acid, and an ethanol solution in a mass ratio of 1:1:100, react at 40 °C for 3 h, and then centrifuge to obtain the environmentally friendly biocide.

[0061] 2. Preparation of hydrophobic barrier agent:

[0062] Disperse nanosilica with a particle size of 30 nm in absolute ethanol, add heptadecafluorodecyltriethoxysilane and react at 60 °C for 2 hours, then add polydimethylsiloxane and azobisisobutyronitrile for reaction to obtain fluorinated polysiloxane grafted nanosilica, namely the hydrophobic barrier agent; the mass ratio of nanosilica, heptadecafluorodecyltriethoxysilane, polydimethylsiloxane, and azobisisobutyronitrile is 1:1:1:0.1.

[0063] 3. Mix 70 parts of the composite base oil and 10 parts of the thickening agent at 80 °C, and then sequentially add 1 part of the environment-friendly biological inhibitor, 1 part of the hydrophobic barrier agent, 1 part of the rust inhibitor (calcium petroleum sulfonate, barium petroleum sulfonate, alkyl diphenylamine, benzotriazole), 1 part of the antioxidant (alkyl diphenylamine or 2,6-di-tert-butyl-p-cresol), and 1 part of the extreme pressure and anti-wear agent (thiolated phosphoric acid acrylate, di-n-butyl phosphite, molybdenum dibutyldithiocarbamate) and mix evenly to obtain the anti-corrosion lubricating grease for ships in a seawater environment; the composite base oil is composed of PAO synthetic oil and modified castor oil ester mixed in a mass ratio of 50:10.

[0064] Comparative Example 1

[0065] The preparation method of this comparative example is the same as that of Example 1, except that the environment-friendly biological inhibitor is not added.

[0066] Comparative Example 2

[0067] The preparation method of this comparative example is the same as that of Example 1, except that the hydrophobic barrier agent is not added.

[0068] Experimental Example 1

[0069] Perform performance detection on the prepared lubricating grease, and the inspection results are shown in Table 1.

[0070] Table 1

[0071]

[0072]

[0073] Experimental Example 2

[0074] Anti-seawater microorganism detection

[0075] 1. Experimental bacteria (organisms):

[0076] Sulfate-reducing bacteria, iron-oxidizing bacteria, seawater diatoms, source of the bacterial strains: purchased standard strains.

[0077] 2. Metal substrate:

[0078] Low-carbon steel bearing (Q235).

[0079] 3. Experimental steps

[0080] (1) Microorganism culture and inoculation

[0081] Activation of bacterial strains:

[0082] Inoculate sulfate-reducing bacteria, iron-oxidizing bacteria, and seawater diatoms into the liquid medium respectively, and culture until both sulfate-reducing bacteria and iron-oxidizing bacteria reach 10 6CFU / mL, marine diatoms (10 5 cells / mL), and after mixing, a simulated seawater microbial community was formed.

[0083] (2) Sample treatment and exposure experiment

[0084] Pretreatment of metal substrate:

[0085] Ultrasonic cleaning with acetone, and after drying, 20 g of the greases of Examples 1-3 and Comparative Examples 1-2 were respectively coated.

[0086] Exposure experiment design:

[0087] Experimental group: The greased samples were immersed in seawater containing mixed microorganisms (3.5% NaCl, pH 8.1), and then the bearings were run at a rotational speed of 300 r / min.

[0088] Period: 7 days, 14 days, 28 days.

[0089] (3) Performance detection methods

[0090] Detection of microbial activity

[0091] The survival rate was calculated by viable count (CFU / mL);

[0092] The survival rate was calculated by cell count (hemocytometer).

[0093] Detection of water content in the grease. After removing the bearings, 5 g of the grease was taken to calculate the water content.

[0094] Analysis of corrosion behavior

[0095] After the experiment, the grease was removed, and pickling (500 mL HCl + 3.5 g hexamethylenetetramine) was used to remove the corrosion products, and the corrosion degree was calculated.

[0096] (4) Detection results, see Table 2

[0097] Table 2

[0098]

[0099] The above are only the preferred embodiments of the present invention. It should be pointed out that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can be made, and these improvements and refinements should also be regarded as the protection scope of the present invention.

Claims

1. An anti-corrosion lubricating grease for ships in a seawater environment, characterized in that, It comprises the following components in parts by mass: 70 - 80 parts of compound base oil, 1 - 5 parts of environment-friendly biocide, 1 - 10 parts of hydrophobic barrier agent, 1 - 5 parts of rust inhibitor, 1 - 3 parts of antioxidant, 1 - 2 parts of extreme pressure and anti-wear agent, 10 - 20 parts of thickener.

2. The anti-corrosion lubricating grease for ships in seawater environment according to claim 1, characterized in that, The compound base oil is a mixture of PAO synthetic oil and modified castor oil ester in a mass ratio of 50:(10 - 30).

3. The anti-corrosion lubricating grease for ships in a seawater environment according to claim 1, wherein, The preparation method of the environment-friendly biocide is as follows: A. React graphene oxide dispersion, sodium hydroxide, and chloroacetic acid to obtain carboxylated graphene; B. Mix the carboxylated graphene with copper sulfate solution, stir, and then add ascorbic acid to react to obtain nano-copper-carboxylated graphene; C. Mix nano-copper-carboxylated graphene, tannic acid, and ethanol solution, react, and then centrifuge to obtain the environment-friendly biocide.

4. The anti-corrosion lubricating grease for ships in a seawater environment according to claim 3, wherein In step A, the volume-mass ratio of graphene oxide dispersion, sodium hydroxide, and chloroacetic acid is 100 mL:(0.1 - 3) g:(0.5 - 1) g; the concentration of the graphene oxide dispersion is 10 mg / mL.

5. The anti-corrosion lubricating grease for ships in seawater environment according to claim 3, characterized in that, In step B, the mass-volume ratio of carboxylated graphene, copper sulfate solution, and ascorbic acid is 100 mg:(5 - 15) mL:5 mL; the concentration of the copper sulfate solution is 0.1 - 0.3 mol / L, and the concentration of the ascorbic acid is 0.2 - 0.5 mol / L.

6. The anti-corrosion lubricating grease for ships in a seawater environment according to claim 3, wherein, In step C, the mass ratio of nano-copper-carboxylated graphene, tannic acid, and ethanol solution is (1 - 5):(1 - 5):

100.

7. The anti-corrosion lubricating grease for ships in a seawater environment according to claim 1, characterized in that, The preparation method of the hydrophobic barrier agent is as follows: Disperse nano-silica in absolute ethanol, add 1H,1H,2H,2H-perfluorodecyltriethoxysilane, react at 60 °C for 2 hours, and then add polydimethylsiloxane and azobisisobutyronitrile to react to obtain fluorinated polysiloxane grafted nano-silica, i.e., the hydrophobic barrier agent.

8. The anti-corrosion lubricating grease for ships in seawater environment according to claim 1, wherein The extreme pressure and anti-wear agent is one of thiophosphoric acid acrylate, dibutyl phosphite, and molybdenum dibutyldithiocarbamate.

9. The anti-corrosion lubricating grease for ships in seawater environment according to claim 1, wherein, The thickener is a lithium soap-based thickener or a composite calcium sulfonate-based thickener.

10. Preparation method of the anti-corrosion lubricating grease for ships in seawater environment according to any one of claims 1 - 9: Mix the compound base oil and the thickener at 80 °C, and then sequentially add the environment-friendly biocide, hydrophobic barrier agent, rust inhibitor, antioxidant, and extreme pressure and anti-wear agent, and mix evenly.

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