An anti-marine organism lubricating grease and its preparation method and application

Abstract

The present application relates to the technical field of lubricating grease, and provides an anti-marine organism lubricating grease, a preparation method and application thereof.The anti-marine organism lubricating grease comprises the following components in mass percentage: base oil 47-88%, composite aluminum base thickening agent 5-10%, adhesion agent 0.5-2%, antioxidant 0.5-3%, extreme pressure anti-wear agent 5.0-30%, antirust agent 0.5-3%, and marine organism inhibitor 0.5%-5%; wherein the marine organism inhibitor is one or more of cuprous oxide, copper pyrithione and copper pyrrolidine dithiocarbamate.The present application improves the anti-marine organism performance of the lubricating grease without changing the physical and chemical properties of the lubricating grease itself, and the obtained lubricating grease has the characteristics of anti-marine organism, seawater resistance, extreme pressure and anti-wear, and can meet the lubrication and protection requirements of the related parts of the water surface and underwater ship in the marine environment, and has a wide application prospect.

Description

Technical Field

[0001] This invention relates to the field of lubricating grease technology, and in particular to an anti-marine organism lubricating grease, its preparation method, and its application. Background Technology

[0002] Marine biofouling can seriously affect the normal operation and service performance of ship equipment. Various moving parts of ships operating in the seawater environment are also threatened by marine biofouling. Marine organisms attach and grow in the gaps of moving parts, which may cause the moving parts to fail or even get stuck, thereby reducing the service life and reliability of the moving parts.

[0003] Bearings, gears, and other moving parts of ships underwater are mostly lubricated with grease. However, conventional greases lack the ability to resist marine organism adhesion. In the marine environment, marine organisms such as barnacles and mussels can attach to the surfaces of underwater ship components, including areas with grease. This adhesion increases the surface roughness of moving parts, damages the grease layer, and leads to lubrication failure. To date, no marine grease with anti-marine organism properties has been found for marine applications. Summary of the Invention

[0004] In view of this, the present invention provides an anti-marine organism grease, its preparation method, and its application. The anti-marine organism grease provided by the present invention possesses properties such as resistance to marine organisms, seawater resistance, and extreme pressure anti-wear, and can meet the lubrication and protection needs of moving parts of surface and underwater vessels.

[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0006] A marine organism-resistant grease comprises the following components in weight percentages: 47-88% base oil, 5-10% composite aluminum-based thickener, 0.5-2% adhesive, 0.5-3% antioxidant, 5-30% extreme pressure anti-wear agent, 0.5-3% rust inhibitor, and 0.5%-5% marine organism inhibitor; the composite aluminum-based thickener is prepared from aluminum isopropoxide, benzoic acid, straight-chain saturated fatty acids, and water; the marine organism inhibitor is one or more of cuprous oxide, copper pyridinium thionate, and copper pyrrolidinyl dithiocarbamate.

[0007] Preferably, the base oil is one or more of mineral oil and polyalphaolefin synthetic oil; the kinematic viscosity of the base oil at 100°C is 10-100 mmHg. 2 / s.

[0008] Preferably, the number of carbon atoms in the straight-chain saturated fatty acid is 16 to 20; the molar ratio of the straight-chain saturated fatty acid to benzoic acid is 1:(0.8 to 1); and the molar ratio of aluminum isopropoxide to the total molar amount of the straight-chain saturated fatty acid and benzoic acid is (1 to 1.2):2.

[0009] Preferably, the adhesive is one or more of polyisobutylene, ethylene-propylene copolymer, C9 petroleum resin and hydrogenated styrene diene copolymer.

[0010] Preferably, the antioxidant is a mixture of 2,6-di-tert-butyl-p-cresol and alkyl diphenylamine, wherein the mass ratio of 2,6-di-tert-butyl-p-cresol to alkyl diphenylamine is (0.2-0.5):(1.0-1.3).

[0011] Preferably, the extreme pressure anti-wear agent is nano-active calcium carbonate.

[0012] Preferably, the rust inhibitor is one or more of sulfonate, dodecenyl succinic acid, and heptadecanyl imidazolinyl succinic acid.

[0013] The present invention also provides a method for preparing the anti-marine biological lubricating grease described in the above-mentioned scheme, comprising the following steps:

[0014] A portion of the base oil is mixed with aluminum propoxide, stearic acid and benzoic acid for saponification. The resulting saponification reaction solution is mixed with water for hydration. The resulting hydration reaction solution is refined and then mixed with the remaining base oil to obtain the base grease.

[0015] The base grease is mixed with an adhesive, antioxidant, extreme pressure anti-wear agent, rust inhibitor and marine organism inhibitor, and then homogenized and ground to obtain the anti-marine organism grease.

[0016] Preferably, the saponification reaction is carried out at a temperature of 90–130°C for 1–3 hours.

[0017] The hydration reaction is carried out at a temperature of 80–100°C for a time of 0.5–3 hours.

[0018] The present invention also provides the application of the anti-marine bio-lubricating grease described in the above-described scheme or the anti-marine bio-lubricating grease prepared by the preparation method described in the above-described scheme in ships.

[0019] This invention provides an anti-marine organism grease comprising the following components by weight percentage: 47-88% base oil, 5-10% composite aluminum-based thickener, 0.5-2% adhesive, 0.5-3% antioxidant, 5-30% extreme pressure anti-wear agent, 0.5-3% rust inhibitor, and 0.5%-5% marine organism inhibitor; the composite aluminum-based thickener is prepared from aluminum isopropoxide, benzoic acid, straight-chain saturated fatty acid, and water; the marine organism inhibitor is one or more of cuprous oxide, copper pyridinium thionate, and copper pyrrolidinyl dithiocarbamate. This invention employs one or more of cuprous oxide, copper pyridinium thionate, and copper pyrrolidinyl dithiocarbamate as marine organism inhibitors added to the grease. This effectively prevents marine organisms from approaching or attaching to and settling on target structures, thus improving the grease's anti-marine organism properties. Furthermore, the marine organism inhibitors are embedded in the grease and gradually exposed upon contact with seawater or after being washed by seawater, achieving a slow release effect. This invention uses a composite aluminum-based thickener to thicken the base oil, resulting in a composite aluminum-based grease that exhibits good sensitivity to various additives. It maintains its structure even after mixing with water, exhibits low oil separation during storage, and is more suitable for marine environments. The addition of an adhesive reduces grease loss in marine environments, ensuring effective lubrication and protection. The addition of antioxidants prevents premature oxidation and degradation of the grease, extending its storage and service life. The addition of extreme pressure anti-wear agents enhances the extreme pressure anti-wear performance of the grease while providing excellent friction-reducing properties. In summary, this invention improves the resistance to marine organisms without altering the physicochemical properties of the grease itself. The resulting grease possesses properties such as resistance to marine organisms, seawater resistance, and extreme pressure anti-wear, which can meet the lubrication and protection needs of relevant parts of surface and underwater vessels in marine environments. Attached Figure Description

[0020] Figure 1 The images show actual photos of the greases obtained in Examples 1(a), 2(b), 3(c), 4(d), 5(e), and 6(f);

[0021] Figure 2 Fluorescence micrographs of the adhesion properties of *Plasmodium purpureum* on the surface of the grease obtained from blank slides (a), Example 1 (b), Example 2 (c), Example 3 (d), Example 4 (e), Example 5 (f), and Example 6 (g). Detailed Implementation

[0022] This invention provides an anti-marine organism grease comprising the following components by weight percentage: 47-88% base oil, 5-10% composite aluminum-based thickener, 0.5-2% adhesive, 0.5-3% antioxidant, 5-30% extreme pressure anti-wear agent, 0.5-3% rust inhibitor, and 0.5%-5% marine organism inhibitor; the composite aluminum-based thickener is prepared from aluminum isopropoxide, benzoic acid, and straight-chain saturated fatty acids; the marine organism inhibitor is one or more of cuprous oxide, copper pyridinium thionate, and copper pyrrolidinyl dithiocarbamate.

[0023] Unless otherwise specified, all raw materials / components used in this invention are commercially available.

[0024] The anti-marine organism grease provided by this invention comprises 47-88% base oil, specifically 47%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, or 88% by weight. The base oil is preferably one or more of mineral oil and polyalphaolefin synthetic oil (PAO synthetic oil), more preferably PAO synthetic oil. In a specific embodiment of this invention, the PAO synthetic oil is preferably PAO40. The kinematic viscosity of the base oil at 100°C is preferably 10-100 mmHg. 2 / s, more preferably 30-60mm 2 / s. In this invention, the PAO synthetic oil has good hydrolytic stability, a high viscosity index, stable frictional properties, and good compatibility with other additives.

[0025] The anti-marine organism lubricating grease provided by the present invention, by mass percentage, comprises 5-10% of a composite aluminum-based thickener, preferably 5%-8%, specifically 5%, 6%, 7%, or 8%. The raw materials for preparing the composite aluminum-based thickener include aluminum isopropoxide, benzoic acid, straight-chain saturated fatty acid, and water. The carbon number of the straight-chain saturated fatty acid is preferably 16-20, specifically 16, 17, 18, 19, or 20. In a specific embodiment of the present invention, the straight-chain saturated fatty acid is preferably stearic acid. The molar ratio of the straight-chain saturated fatty acid to benzoic acid is preferably 1:(0.8-1), specifically 1:0.8, 1:0.9, or 1:1. The molar ratio of aluminum isopropoxide to the total molar ratio of the straight-chain saturated fatty acid and benzoic acid is preferably (1-1.2):2, specifically 1:2, 1.1:2, or 1.2:2. The molar ratio of water to aluminum isopropoxide is preferably (1-3):1.

[0026] The anti-marine organism grease provided by this invention, by weight percentage, comprises an adhesive of 0.5-2%, preferably 1-2%, specifically 1%, 1.3%, 1.5%, 1.8%, or 2%. The adhesive is preferably one or more of polyisobutylene, ethylene-propylene copolymer, C9 petroleum resin, and hydrogenated styrene diene copolymer. The viscosity-average molecular weight of the polyisobutylene is preferably 30,000-60,000. In a specific embodiment of this invention, the adhesive is preferably a hydrogenated styrene diene copolymer, and the hydrogenated styrene diene copolymer is preferably a hydrogenated styrene-pentadiene star copolymer. In this invention, the main function of the adhesive is to increase the adhesion performance of the grease to the surface of mechanical parts, reduce the loss of the grease in a marine environment, and ensure effective lubrication and protection. In a specific embodiment of this invention, the hydrogenated styrene-pentadiene star copolymer can achieve the above-mentioned functions without significantly changing the consistency of the grease.

[0027] The anti-marine organism lubricating grease provided by the present invention, by weight percentage, comprises 0.5-3% antioxidant, preferably 1-1.5%, specifically 1%, 1.2%, 1.3%, or 1.5%; the antioxidant is a mixture of 2,6-di-tert-butyl-p-cresol and alkyl diphenylamine, wherein the alkyl diphenylamine is one of bis(octyl)diphenylamine, but(octyl)diphenylamine, or dinonyldiphenylamine, preferably but(octyl)diphenylamine; the mass ratio of 2,6-di-tert-butyl-p-cresol to alkyl diphenylamine is (0.2-0.5):(1.0-1.3), specifically 0.2:1, 0.2:1.2, 0.4:1.1, 0.5:1, or 0.5:1.3. This invention uses a mixture of 2,6-di-tert-butyl-p-cresol and alkyl diphenylamine as an antioxidant. Compared with a single antioxidant, it can achieve antioxidant performance over a wider temperature range, avoid premature oxidation and degradation of grease, and extend the storage and service life of grease.

[0028] The anti-marine biological grease provided by the present invention comprises 5-30% extreme pressure anti-wear agent, preferably 20-30%, specifically 20%, 22%, 25%, or 30% by mass percentage; the extreme pressure anti-wear agent is preferably nano-activated calcium carbonate, and the particle size of the nano-activated calcium carbonate is preferably 50-500 nm; the present invention uses nano-activated calcium carbonate as an extreme pressure anti-wear agent, which can improve the extreme pressure anti-wear performance and friction reduction performance of the grease, and at the same time improve the density characteristics of the grease, so that it will not float even if it leaks underwater, which can effectively reduce the vibration noise of moving parts and increase the stealth performance of underwater ships.

[0029] The anti-marine organism grease provided by this invention, by weight percentage, comprises 0.5-3% rust inhibitor, preferably 1-2%, specifically 1%, 1.3%, 1.5%, 1.8%, or 2%. The rust inhibitor is preferably one or more of sulfonates, dodecenylsuccinic acid, and heptadecanylimidazolinylsuccinate. The sulfonate preferably includes one or more of magnesium sulfonate, barium sulfonate, and calcium sulfonate. In a specific embodiment of this invention, the rust inhibitor is preferably heptadecanylimidazolinylsuccinate. The rust inhibitor used in this invention has good compatibility with antioxidants, adhesives, and other additives, and simultaneously provides good rust prevention performance for the anti-marine organism grease.

[0030] The anti-marine organism grease provided by the present invention comprises 0.5% to 5% marine organism inhibitors, preferably 1% to 3%, specifically 1%, 1.2%, 1.5%, 2%, 2.5%, 2.8%, or 3% by mass percentage; the marine organism inhibitors are one or more of cuprous oxide, copper pyridinethione and copper pyrrolidinyl dithiocarbamate. The present invention does not have a special limitation on the source of the copper pyrrolidinyl dithiocarbamate, which can be prepared by methods well known to those skilled in the art. In a specific embodiment of the present invention, it can be prepared by referring to the method in "Wang Ying, Lu Yong, Luo Chengyan, et al. Crystal structure and spectroscopic study of N′-ethyl-N-piperazinyl copper dithiocarbamate (II) complex Cu(S2CNC4H8NC2H5)2 [J]. Journal of Inorganic Chemistry, 2008, (05): 691-695."

[0031] In this invention, the density of the anti-marine bio-lubricating grease is greater than 1 g / cm³. 3 In specific embodiments of the present invention, the density of the resulting anti-marine organism lubricating grease varies depending on the type and ratio of the base oil and various additives, but all of them can reach a density greater than 1 g / cm³. 3 This ensures that the ship will not float even if it leaks underwater, effectively reducing vibration and noise from moving parts and increasing the stealth capabilities of underwater vessels.

[0032] The present invention also provides a method for preparing the anti-marine biological lubricating grease described in the above-mentioned scheme, comprising the following steps:

[0033] A portion of the base oil is mixed with aluminum propoxide, stearic acid and benzoic acid for saponification. The resulting saponification reaction solution is mixed with water for hydration. The resulting hydration reaction solution is refined and then mixed with the remaining base oil to obtain the base grease.

[0034] The base grease is mixed with an adhesive, antioxidant, extreme pressure anti-wear agent, rust inhibitor and marine organism inhibitor, and then homogenized and ground to obtain the anti-marine organism grease.

[0035] This invention involves mixing a portion of base oil with aluminum propoxide, stearic acid, and benzoic acid for a saponification reaction. The resulting saponification reaction solution is then mixed with water for a hydration reaction. The resulting hydration reaction solution is refined and mixed with the remaining base oil to obtain a basic lubricating grease. In this invention, the saponification reaction temperature is preferably 90–130°C, more preferably 95–120°C, specifically 95°C, 100°C, 110°C, or 120°C; the saponification reaction time is preferably 1–3 hours, more preferably 1.5–2 hours, specifically 1.5 hours, 1.8 hours, or 2 hours. In a specific embodiment of this invention, the process of mixing a portion of base oil with the raw materials for preparing the aluminum-based thickener for a saponification reaction includes: first, mixing aluminum isopropoxide and a portion of base oil and heating to the saponification reaction temperature; after the aluminum isopropoxide melts, adding straight-chain saturated fatty acids and stirring for 0.5–1 hour; then adding benzoic acid and reacting under heat preservation conditions for 1–2 hours.

[0036] In this invention, the temperature of the hydration reaction is preferably 80-100°C, specifically 80°C, 85°C, 90°C, 96°C or 100°C, and the time of the hydration reaction is preferably 0.5-3h, specifically 0.5h, 1h, 2h, 2.5h or 3h.

[0037] In this invention, the refining temperature is preferably 190–220°C, specifically 190°C, 195°C, 210°C, 215°C, or 220°C, and the refining time is preferably 10–15 minutes. After refining, the refining liquid is mixed with the remaining base oil, which serves as a cooling oil.

[0038] After obtaining the base grease, the present invention mixes the base grease with an adhesive, antioxidant, extreme pressure anti-wear agent, rust inhibitor, and marine organism inhibitor, and then grinds the mixture to obtain an anti-marine organism grease. In the present invention, the mixing temperature of the base grease with the adhesive, antioxidant, extreme pressure anti-wear agent, rust inhibitor, and marine organism inhibitor is preferably 60–110°C, specifically 60°C, 70°C, 80°C, 90°C, 100°C, or 110°C; the grinding is preferably performed using a three-roll mill.

[0039] This invention also provides the application of the anti-marine organism grease described in the above-described scheme and the anti-marine organism grease prepared by the above-described preparation method in ships. The anti-marine organism grease provided by this invention has properties such as resistance to marine organisms, seawater resistance, and extreme pressure anti-wear, which can meet the lubrication and protection needs of moving parts of surface and underwater ships, and has broad application prospects.

[0040] The technical solutions of this invention will be clearly and completely described below with reference to the embodiments thereof. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0041] The composite aluminum-based thickener and grease compositions used in the following examples and comparative examples were all prepared in the laboratory, and the raw materials used included:

[0042] The base oil PAO40 was purchased from Mobil, and its kinematic viscosity at 40°C was 396 mm. 2 / s, kinematic viscosity at 100℃ is 40mm. 2 / s;

[0043] Aluminum isopropoxide was purchased from Yangzhou Zhongtianli New Material Co., Ltd., with an aluminum content of 12.5%–14.9%.

[0044] Stearic acid was purchased from Beijing Xin'ao Xunchi Chemical Co., Ltd., with a saponification value of 210.76.

[0045] Benzoic acid was purchased from Tianjin Dongda Chemical Group Co., Ltd., with a purity of 99.8%.

[0046] The distilled water was prepared in the laboratory.

[0047] Nano-activated calcium carbonate was purchased from Shanxi Xintai Hengxin Nanomaterials Co., Ltd.

[0048] The hydrogenated styrene-isoprene star copolymer was purchased from Shell, brand name SV620;

[0049] Butyldiphenylamine was purchased from BASF, brand name L57;

[0050] 2,6-Di-tert-butyl-p-cresol was purchased from LANSESS, under the brand name Additin RC 7110.

[0051] Heptadecanylimidazolinyl succinate was purchased from Shanghai Midgard Chemical Co., Ltd., grade T703;

[0052] Cuprous oxide was purchased from Taixing Smelting Plant Co., Ltd., with a purity of 97%.

[0053] Copper pyrithione was purchased from Shanghai Yuanye Biotechnology Co., Ltd., with a purity of 97%.

[0054] Pyrrolidinyl copper dithiocarbamate (Cu(S2CNC4H8)2) was a laboratory-prepared product, prepared according to the method described in "Wang Ying, Lu Yong, Luo Chengyan, et al. Crystal structure and spectroscopic study of N′-ethyl-N-piperazinyl copper dithiocarbamate (II) complex Cu(S2CNC4H8NC2H5)2[J]. Journal of Inorganic Chemistry, 2008, (05): 691-695.)". The specific preparation steps are as follows: (1) Add pyrrolidin (14.24 g, 0.20 mol) to 400 mL of acetone, control the reaction temperature below 4 °C, start the stirrer, and add carbon disulfide (15.20 g, 0.20 mol) dropwise. (1) Add 0.5 mol of sodium hydroxide (50% aqueous solution, 0.20 mol) and continue stirring for 3-4 hours after the addition is complete. After the reaction is complete, filter and recrystallize the filter cake in acetonitrile to obtain white sodium pyrrolidinyl dithiocarbamate (C4H8NCS2Na); (2) Dissolve (22.35 g, 0.15 mol) of C4H8NCS2Na in water and add (9.38 g, 0.05 mol) of saturated aqueous solution of copper nitrate. Stir and a brown precipitate appears. Filter to obtain crude copper dipyrrolidinyl dithiocarbamate. The crude product is recrystallized with acetone and dried with P2O5 to obtain black pure copper dipyrrolidinyl dithiocarbamate.

[0055] Example 1

[0056] Mix 13.42g of aluminum isopropoxide with 203.43g of PAO40 and heat to 120℃. After the aluminum isopropoxide melts, slowly add 16.4g of stearic acid and stir for 30 minutes. Then add 7.03g of benzoic acid and react at 120℃ for 1 hour. Cool down to 96℃ and slowly add 1.5g of distilled water and react for 1 hour. Heat up to 210℃ and hold for 10 minutes. Add 102.4g of PAO40 as a cooling oil and allow to cool naturally to 60℃. Grind and homogenize to obtain the grease.

[0057] This embodiment prepares a blank base grease, in which the mass percentage of the composite aluminum-based thickener is 8%. The molar ratio of stearic acid to benzoic acid is 1:1, and the molar ratio of the total molar amount of stearic acid and benzoic acid to aluminum isopropoxide is 1.75:1.

[0058] Example 2

[0059] Mix 13.42g of aluminum isopropoxide and 203.43g of PAO40 and heat to 120℃. After the aluminum isopropoxide melts, slowly add 16.4g of stearic acid and stir for 30 minutes. Then add 7.03g of benzoic acid and react at 120℃ for 1 hour. Cool down to 96℃ and slowly add 1.50g of distilled water. React for 1 hour, then heat to 210℃ and hold for 10 minutes. Add 102.4g of PAO40 as a cooling oil and cool down to 80℃. Then add 3.36g of cuprous oxide and stir for 30 minutes. Cool down to 60℃ and grind to homogenize to obtain the grease.

[0060] The cuprous oxide content in the above-mentioned grease is 1.0% by mass.

[0061] Example 3

[0062] Mix 13.42g of aluminum isopropoxide with 203.43g of PAO40 and heat to 120℃. After the aluminum isopropoxide melts, slowly add 16.4g of stearic acid and stir for 30 minutes. Then add 7.03g of benzoic acid and react at 120℃ for 1 hour. Cool down to 96℃ and slowly add 1.5g of distilled water. React for 1 hour, then heat to 210℃ and hold for 10 minutes. Add 102.40g of PAO40 as a cooling oil and cool down to 80℃. Then add 6.78g of cuprous oxide and stir for 30 minutes. Cool down to 60℃ and grind to homogenize to obtain the grease.

[0063] The cuprous oxide content in the above-mentioned grease is 2% by mass.

[0064] Example 4

[0065] Mix 13.42g of aluminum isopropoxide with 203.43g of PAO40 and heat to 120℃. After the aluminum isopropoxide melts, slowly add 16.40g of stearic acid and stir for 30 minutes. Then add 7.03g of benzoic acid and react at 120℃ for 1 hour. Cool down to 96℃ and slowly add 1.50g of distilled water. React for 1 hour, then heat to 210℃ and hold for 10 minutes. Add 102.40g of PAO40 as a cooling oil and cool down to 80℃. Then add 10.27g of cuprous oxide and stir for 30 minutes. Cool down to 60℃ and grind to homogenize to obtain the grease.

[0066] The cuprous oxide content in the above-mentioned grease is 3% by mass.

[0067] Example 5

[0068] Mix 13.42g of aluminum isopropoxide and 203.43g of PAO40 and heat to 120℃. After the aluminum isopropoxide melts, slowly add 16.40g of stearic acid and stir for 30 minutes. Then add 7.03g of benzoic acid and react at 120℃ for 1 hour. Cool down to 96℃ and slowly add 1.50g of distilled water. React for 1 hour, then heat to 210℃ and hold for 10 minutes. Add 102.40g of PAO40 as a cooling oil and cool down to 80℃. Then add 10.27g of copper pyridinethione and stir for 30 minutes. Cool down to 60℃ and grind to homogenize to obtain the grease.

[0069] The mass percentage of copper pyridinethione in the above-mentioned grease is 3%.

[0070] Example 6

[0071] Mix 13.42g of aluminum isopropoxide and 203.43g of PAO 40 and heat to 120℃. After the aluminum isopropoxide melts, slowly add 16.40g of stearic acid and stir for 30 minutes. Then add 7.03g of benzoic acid and react at 120℃ for 1 hour. Cool down to 96℃ and slowly add 1.50g of distilled water. React for 1 hour, then heat to 210℃ and hold for 10 minutes. Add 102.4g of PAO 40 as a cooling oil and cool down to 80℃. Then add 10.27g of copper pyrrolidinyl dithiocarbamate and stir for 30 minutes. Cool down to 60℃ and grind to homogenize to obtain the grease.

[0072] The mass percentage of copper pyrrolidinyl dithiocarbamate in the above-mentioned grease is 3%.

[0073] Example 7

[0074] 13.42g of aluminum isopropoxide and 203.43g of PAO40 were mixed and heated to 120℃. After the aluminum isopropoxide melted, 16.40g of stearic acid was slowly added. After stirring and reacting for 30 minutes, 7.03g of benzoic acid was added, and the mixture was reacted at 120℃ for 1 hour. The temperature was then lowered to 96℃, and 1.50g of distilled water was slowly added. The mixture was reacted for 1 hour, and the temperature was raised to 210℃ and maintained for 10 minutes. 102.4g of PAO40 was added as a cooling oil. After cooling to 80℃, 122.14g of nano-activated calcium carbonate, 4.89g of SV620, 2.44g of Additin RC 7110, 4.89g of L57, 7.33g of T703, and 14.66g of cuprous oxide were added. The mixture was stirred for 30 minutes, and after cooling to 60℃, it was ground and homogenized to obtain an anti-marine biological lubricant.

[0075] The anti-marine organism grease obtained in the above embodiment weighs approximately 488.58g, and the mass percentage of each component is approximately: 5.4% composite thickener, 62.6% base oil, 25% calcium carbonate, 1% adhesive, 1.5% antioxidant, 1.5% rust inhibitor, and 3% cuprous oxide.

[0076] Example 8

[0077] 13.42g of aluminum isopropoxide and 203.43g of PAO40 were mixed and heated to 120℃. After the aluminum isopropoxide melted, 16.40g of stearic acid was slowly added. After stirring and reacting for 30min, 7.03g of benzoic acid was added, and the mixture was reacted at 120℃ for 1h. The temperature was then lowered to 96℃, and 1.50g of distilled water was slowly added. The mixture was reacted for 1h, and the temperature was raised to 210℃ and held for 10min. 102.40g of PAO40 was added as a cooling oil. After cooling to 80℃, 122.14g of nano-activated calcium carbonate, 4.89g of SV620, 2.44g of Additin RC 7110, 4.89g of L57, 7.33g of T703, and 14.66g of copper pyridinethione were added. The mixture was stirred for 30min, and after cooling to 60℃, it was ground and homogenized to obtain an anti-marine biological lubricant.

[0078] The anti-marine organism grease obtained in the above embodiment weighs approximately 488.58g, and the mass percentage of each component is approximately: 5.4% composite aluminum-based thickener, 62.6% base oil, 25% calcium carbonate, 1% adhesive, 1.5% antioxidant, 1.5% rust inhibitor, and 3% copper pyridinethione.

[0079] Example 9

[0080] 13.42g of aluminum isopropoxide and 203.43g of PAO40 were mixed and heated to 120℃. After the aluminum isopropoxide melted, 16.40g of stearic acid was slowly added. After stirring and reacting for 30min, 7.03g of benzoic acid was added, and the mixture was reacted at 120℃ for 1h. The temperature was then lowered to 96℃, and 1.50g of distilled water was slowly added. The mixture was reacted for 1h, and the temperature was raised to 210℃ and held for 10min. 102.4g of PAO40 was added as a cooling oil. After cooling to 80℃, 122.14g of nano-activated calcium carbonate, 4.89g of SV620, 2.44g of Additin RC 7110, 4.89g of L57, 7.33g of T703, and 14.66g of copper dithiocarbamate were added. The mixture was stirred for 30min, and after cooling to 60℃, it was ground and homogenized to obtain an anti-marine biological lubricant.

[0081] The anti-marine organism grease obtained in the above examples weighs approximately 488.58g, and the mass percentage of each component is approximately: 5.4% composite aluminum-based thickener, 62.6% base oil, 25% calcium carbonate, 1% adhesive, 1.5% antioxidant, 1.5% rust inhibitor, and 3.0% pyrrolidinyl copper dithiocarbamate.

[0082] Comparative Example 1

[0083] 13.42g of aluminum isopropoxide and 203.43g of PAO40 were mixed and heated to 120℃. After the aluminum isopropoxide melted, 16.4g of stearic acid was slowly added. After stirring and reacting for 30 minutes, 7.03g of benzoic acid was added, and the mixture was reacted at 120℃ for 1 hour. The temperature was then lowered to 96℃, and 1.50g of distilled water was slowly added. The mixture was reacted for 1 hour, and the temperature was raised to 210℃ and maintained for 10 minutes. 102.40g of PAO40 was added as a cooling oil. After cooling to 80℃, 116.98g of nano-activated calcium carbonate, 4.68g of SV620, 2.34g of Additin RC 7110, 4.68g of L57, and 7.02g of T703 were added. The mixture was stirred for 30 minutes, and after cooling to 60℃, it was ground and homogenized to obtain the grease.

[0084] The grease obtained in the above comparative example weighed approximately 467.93g, without the addition of marine organism inhibitors. The mass percentages of each component were approximately: 5.7% complex aluminum-based thickener, 65.3% base oil, 25.0% calcium carbonate, 1.0% adhesive, 1.5% antioxidant, and 1.5% rust inhibitor.

[0085] Performance testing

[0086] (1) Test of adhesion and growth performance of *Porphyra yezoensis*

[0087] The adhesion and growth performance of *Porphyra yezoensis* in Examples 1-6 was tested, and the test methods are as follows:

[0088] Appropriate amounts of the lubricating grease samples from Examples 1 to 6 were evenly spread onto 1×1cm glass slides. Blank slides and the basic lubricating grease from Example 1 were used as control samples. These were placed in a sample box, and after adding *Porphyra yezoensis* pre-culture solution, the slides were incubated in a constant temperature incubator for 24 hours. After incubation, the glass slides were removed, rinsed with artificial seawater to remove surface algae, and then covered with a glass coverslip to flatten the surface. The samples were then observed under a fluorescence microscope to compare the growth and attachment of algae, thereby evaluating the algae-inhibiting and anti-fouling efficacy of the additives.

[0089] Figure 1 The images show actual photos of the greases obtained in Examples 1(a), 2(b), 3(c), 4(d), 5(e), and 6(f).

[0090] Figure 2Fluorescence micrographs of the adhesion properties of *Porphyra yezoensis* to the surfaces of greases obtained from blank slides (a), Example 1 (b), Example 2 (c), Example 3 (d), Example 4 (e), Example 5 (f), and Example 6 (g). Figure 2 As can be seen from a and b in the figure, a large number of purple algae adhered to the blank glass slide and the surface of the grease prepared in Example 1 after 24 hours of cultivation. Figure 2 c, d, and e in the figure indicate that adding cuprous oxide to the base grease can significantly improve its anti-fouling performance, and the effect is positively enhanced with the increase of the amount added. Figure 2 The values ​​of f and g in the figure also indicate that when copper pyridinethione and copper pyrrolidinyl dithiocarbamate are added to the base grease as additives, the resulting grease exhibits good resistance to marine organisms.

[0091] (2) Physicochemical performance testing

[0092] The physicochemical properties of the greases prepared in Examples 7-9 and Comparative Example 1 were tested, and the results are shown in Table 1.

[0093] Table 1 shows the physicochemical properties of the greases prepared in Examples 7-9 and Comparative Example 1.

[0094]

[0095]

[0096] As shown in Table 1, compared with Comparative Example 1, the properties of the anti-marine organism greases prepared in Examples 7, 8, and 9 did not show significant attenuation. This indicates that the marine organism inhibitors selected in this invention have a good synergistic effect with antioxidants and rust inhibitors. Furthermore, the addition of cuprous oxide, copper pyridinium thionate, or copper pyrrolidinyl dithiocarbamate improves the anti-wear performance (wear scar diameter) and sintering load (P) of the grease. B It has an enhancing effect.

[0097] In addition, the adhesion and growth performance of the greases prepared in Examples 7 to 9 were tested according to the method in (1). The results showed that the anti-algae and anti-fouling effects of the greases were basically unchanged compared with those in Examples 4 to 6, indicating that they all have excellent anti-fouling performance.

[0098] In summary, this invention improves the resistance to marine organisms in grease without altering its physical and chemical properties. The resulting grease possesses properties such as resistance to marine organisms, seawater resistance, and extreme pressure anti-wear, which can meet the lubrication and protection needs of relevant parts of surface and underwater vessels in marine environments and has broad application prospects.

[0099] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A marine organism-resistant lubricating grease, characterized in that, The product comprises the following components by weight percentage: 47-88% base oil, 5-10% composite aluminum-based thickener, 0.5-2% adhesive, 0.5-3% antioxidant, 5-30% extreme pressure anti-wear agent, 0.5-3% rust inhibitor, and 0.5%-5% marine organism inhibitor; the composite aluminum-based thickener is prepared from aluminum isopropoxide, benzoic acid, straight-chain saturated fatty acids, and water; the marine organism inhibitor is one or more of cuprous oxide, copper pyridinethionate, and copper pyrrolidinyl dithiocarbamate; the adhesive is one or more of polyisobutylene, ethylene-propylene copolymer, C9 petroleum resin, and hydrogenated styrene diene copolymer; and the extreme pressure anti-wear agent is nano-activated calcium carbonate.

2. The anti-marine organism lubricating grease according to claim 1, characterized in that, The base oil is one or more of mineral oil and polyalphaolefin synthetic oil; the kinematic viscosity of the base oil at 100°C is 10~100 mmHg. 2 / s.

3. The anti-marine organism lubricating grease according to claim 1, characterized in that, The linear saturated fatty acid has 16 to 20 carbon atoms; the molar ratio of the linear saturated fatty acid to benzoic acid is 1:(0.8 to 1); and the molar ratio of aluminum isopropoxide to the total molar ratio of the linear saturated fatty acid and benzoic acid is (1 to 1.2):

2.

4. The anti-marine organism lubricating grease according to claim 1, characterized in that, The antioxidant is a mixture of 2,6-di-tert-butyl-p-cresol and alkyl diphenylamine, wherein the mass ratio of 2,6-di-tert-butyl-p-cresol to alkyl diphenylamine is (0.2~0.5):(1.0~1.3).

5. The anti-marine organism lubricating grease according to claim 1, characterized in that, The rust inhibitor is one or more of sulfonate, dodecenyl succinic acid, and heptadecanyl imidazolinyl succinic acid.

6. The method for preparing the anti-marine organism lubricating grease according to any one of claims 1 to 5, characterized in that, Includes the following steps: A portion of the base oil is mixed with aluminum propoxide, stearic acid and benzoic acid for saponification. The resulting saponification reaction solution is mixed with water for hydration. The resulting hydration reaction solution is refined and then mixed with the remaining base oil to obtain the base grease. The base grease is mixed with an adhesive, antioxidant, extreme pressure anti-wear agent, rust inhibitor and marine organism inhibitor, and then homogenized and ground to obtain the anti-marine organism grease.

7. The preparation method according to claim 6, characterized in that, The saponification reaction is carried out at a temperature of 90~130℃ for 1~3 hours. The hydration reaction is carried out at a temperature of 80~100℃ for a time of 0.5~3h.

8. The application of the anti-marine organism grease according to any one of claims 1 to 5 or the anti-marine organism grease prepared by the preparation method according to any one of claims 6 to 7 in ships.

Images