Anti-marine organism lubricating grease as well as preparation method and application thereof

Abstract

The invention relates to the technical field of lubricating grease, and provides anti-marine organism lubricating grease as well as a preparation method and application thereof. The anti-marine organism lubricating grease provided by the invention comprises the following components in percentage by mass: 47-88% of base oil, 5-10% of a composite aluminum-based thickening agent, 0.5-2% of an adhesive, 0.5-3% of an antioxidant, 5.0-30% of an anti-wear reagent at extreme pressure, 0.5-3% of an anti-rust agent and 0.5-5% of a marine organism inhibitor, wherein the marine organism inhibitor is one or more of cuprous oxide, copper pyrithione and copper pyrrolidinyl dithioformate. The anti-marine organism performance of the lubricating grease is improved under the condition that the physical and chemical properties of the lubricating grease are not changed, and the obtained lubricating grease has the characteristics of marine organism resistance, seawater resistance, extreme pressure wear resistance and the like, can meet the lubricating protection requirements of water surface and underwater ship related parts in a marine environment, and has a wide application prospect.

Description

Technical Field

[0001] The present invention relates to the technical field of lubricating grease, and in particular to an anti-marine organism lubricating grease and a preparation method and application thereof. Background Art

[0002] The occurrence of marine biofouling problems will have a serious impact on the normal operation and service performance of ship equipment. Various moving parts of ships working in seawater environments are also threatened by marine biofouling. Marine organisms attach and grow in the gaps between 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] Grease is often used to lubricate moving parts such as bearings and gears under water on ships, but conventional grease does not have the function of resisting the attachment of marine organisms. In the marine environment, marine organisms such as barnacles and mussels will attach to the surface of underwater parts of ships, including parts with grease. The attachment of these marine organisms will increase the surface roughness of moving parts and destroy the grease layer, thus causing lubrication failure. So far, there is no grease for ships with the function of resisting marine organisms. Summary of the invention

[0004] In view of this, the present invention provides an anti-marine organism lubricating grease and its preparation method and application. The anti-marine organism lubricating grease provided by the present invention has the characteristics of anti-marine organism, seawater resistance, extreme pressure and anti-wear, and can meet the lubrication and protection needs of moving parts of surface and underwater ships.

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0006] An anti-marine organism grease comprises the following components in percentage by mass: 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 raw materials for preparing the composite aluminum-based thickener include aluminum isopropoxide, benzoic acid, straight-chain saturated fatty acid and water; the marine organism inhibitor is one or more of cuprous oxide, copper pyrithione and copper pyrrolidino 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 to 100 mm 2 / s.

[0008] Preferably, the number of carbon atoms of 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); the ratio of the molar amount 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, and the mass ratio of the 2,6-di-tert-butyl-p-cresol to the 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, dodecenylsuccinic acid and heptadecenyl imidazoline succinate.

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

[0014] Mixing part of the base oil with aluminum propoxide, stearic acid and benzoic acid for saponification reaction, mixing the obtained saponification reaction liquid with water for hydration reaction, refining the obtained hydration reaction liquid and mixing it with the remaining base oil to obtain a base grease;

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

[0016] Preferably, the temperature of the saponification reaction is 90 to 130° C., and the reaction time is 1 to 3 hours;

[0017] The temperature of the hydration reaction is 80-100° C., and the reaction time is 0.5-3 hours.

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

[0019] The invention provides an anti-marine organism grease, comprising the following components in percentage by mass: 47-88% of base oil, 5-10% of a composite aluminum-based thickener, 0.5-2% of an adhesive, 0.5-3% of an antioxidant, 5-30% of an extreme pressure anti-wear agent, 0.5-3% of a rust inhibitor, and 0.5%-5% of a marine organism inhibitor; the raw materials for preparing the composite aluminum-based thickener include aluminum isopropoxide, benzoic acid, a straight-chain saturated fatty acid and water; the marine organism inhibitor is one or more of cuprous oxide, copper pyrithione and copper pyrrolidino dithiocarbamate. The present invention adopts one or more of cuprous oxide, copper pyrithione and copper pyrrolidino dithiocarbamate as marine life inhibitors and adds them to the grease, which can effectively prevent marine life from approaching the target structure or preventing it from attaching and settling on it, thereby improving the anti-marine life performance of the grease; and the marine life inhibitor is embedded in the grease, and after contacting with seawater or being washed by seawater, the marine life inhibitor will be gradually exposed to play a corresponding role, thereby achieving a slow release effect; the present invention adopts a composite aluminum-based thickener to thicken the base oil, and the formed composite aluminum-based grease has good sensitivity to various additives, can still maintain the structure of the grease after mixing with water, has a small amount of oil separation during storage, and is more suitable for marine environment application; by adding an adhesive, the loss of grease in the marine environment can be reduced, thereby ensuring effective lubrication and protection; by adding an antioxidant, the grease is prevented from premature oxidation and decay, thereby extending the storage and service life of the grease; by adding an extreme pressure anti-wear agent, while improving the extreme pressure anti-wear performance of the grease, excellent friction reduction performance is provided. In summary, the present invention improves the anti-marine organism performance of the grease without changing the physical and chemical properties of the grease itself. The obtained grease has the characteristics of resistance to marine organisms, resistance to seawater, extreme pressure and anti-wear, and can meet the lubrication and protection needs of relevant parts of surface and underwater ships in the marine environment. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 The actual pictures of the grease obtained in Example 1 (a), Example 2 (b), Example 3 (c), Example 4 (d), Example 5 (e) and Example 6 (f);

[0021] Figure 2 Fluorescence microscope photographs of the adhesion performance of Porphyridium on the surface of grease obtained from a blank glass slide (a), Example 1 (b), Example 2 (c), Example 3 (d), Example 4 (e), Example 5 (f) and Example 6 (g). DETAILED DESCRIPTION

[0022] The invention provides an anti-marine organism grease, comprising the following components in percentage by mass: 47-88% of base oil, 5-10% of a composite aluminum-based thickener, 0.5-2% of an adhesive, 0.5-3% of an antioxidant, 5-30% of an extreme pressure anti-wear agent, 0.5-3% of a rust inhibitor, and 0.5%-5% of a marine organism inhibitor; the raw materials for preparing the composite aluminum-based thickener include aluminum isopropoxide, benzoic acid, and a straight-chain saturated fatty acid; the marine organism inhibitor is one or more of cuprous oxide, copper pyrithione, and copper pyrrolidino dithiocarbamate.

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

[0024] In terms of mass percentage, the anti-marine biological grease provided by the present invention includes 47-88% of base oil, specifically 47%, 50%, 55%, 60%, 65%, 70%, 75%, 80% or 88%; 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 the present invention, the PAO synthetic oil is preferably PAO40; the kinematic viscosity of the base oil at 100°C is preferably 10-100mm 2 / s, more preferably 30 to 60 mm 2 In the present invention, the PAO synthetic oil has good hydrolysis stability, a high viscosity index, stable friction performance, and good compatibility with other additives.

[0025] In terms of mass percentage, the anti-marine organism grease provided by the present invention 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 acids and water; the number of carbon atoms of the straight-chain saturated fatty acids 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 ratio of the molar amount of aluminum isopropoxide to the total molar amount 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] In terms of mass percentage, the anti-marine biological grease provided by the present invention includes 0.5-2%, preferably 1-2%, and specifically 1%, 1.3%, 1.5%, 1.8% or 2% of an adhesive; 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 the present 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 the present invention, the main function of the adhesive is to increase the adhesion of the grease on the surface of the mechanical parts, reduce the loss of the grease in the marine environment, and ensure effective lubrication and protection. In a specific embodiment of the present invention, the hydrogenated styrene pentadiene star copolymer can play the above role without significantly changing the consistency of the grease.

[0027] In terms of mass percentage, the anti-marine organism grease provided by the present invention includes 0.5-3% of an 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, the alkyl diphenylamine is one of dioctyl diphenylamine, butyl octyl diphenylamine or dinonyl diphenylamine, preferably butyl octyl diphenylamine; the mass ratio of the 2,6-di-tert-butyl-p-cresol to the 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. The present invention adopts 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 in a wider temperature range, avoid premature oxidation and decay of the grease, and extend the storage and service life of the grease.

[0028] In terms of mass percentage, the anti-marine biological grease provided by the present invention includes 5-30% extreme pressure anti-wear agent, preferably 20-30%, specifically 20%, 22%, 25% or 30%; the extreme pressure anti-wear agent is preferably nano-activated calcium carbonate, and the particle size of the nano-activated calcium carbonate is preferably 50-500nm; 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 up even if it leaks underwater, and can effectively reduce the vibration noise of moving parts and increase the concealment performance of underwater ships.

[0029] In terms of mass percentage, the anti-marine biological grease provided by the present invention includes 0.5-3%, preferably 1-2%, and specifically 1%, 1.3%, 1.5%, 1.8% or 2% of a rust inhibitor; the rust inhibitor is preferably one or more of sulfonate, dodecenyl succinic acid and heptadecenyl imidazoline alkenyl succinate; the sulfonate preferably includes one or more of sulfonate magnesium salt, sulfonate barium salt and sulfonate calcium salt; in a specific embodiment of the present invention, the rust inhibitor is preferably heptadecenyl imidazoline alkenyl succinate. The rust inhibitor used in the present invention has good compatibility with additives such as antioxidants and adhesives, and can provide good rust prevention performance for the anti-marine biological grease.

[0030] The anti-marine biological grease provided by the present invention comprises 0.5% to 5% of marine biological inhibitor, preferably 1% to 3%, and specifically 1%, 1.2%, 1.5%, 2%, 2.5%, 2.8% or 3% by weight; the marine biological inhibitor is one or more of cuprous oxide, copper pyrithione and copper pyrrolidino dithiocarbamate. The present invention does not specifically limit the source of the copper pyrrolidino dithiocarbamate, and it can be prepared by a method 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 spectroscopy study of N'-ethyl-N-piperazinyl dithiocarbamate copper (II) complex Cu(S2CNC4H8NC2H5)2 [J]. Journal of Inorganic Chemistry, 2008, (05): 691-695."

[0031] In the present invention, the density of the anti-marine biomass grease is greater than 1 g / cm 3 In the specific embodiment of the present invention, when the types and proportions of the base oil and various additives are different, the density of the obtained anti-marine biological grease is also different, but can reach more than 1g / cm 3 , so that even if it leaks underwater, it will not float up, which can effectively reduce the vibration noise of moving parts and increase the concealment performance of underwater ships.

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

[0033] Mixing part of the base oil with aluminum propoxide, stearic acid and benzoic acid for saponification reaction, mixing the obtained saponification reaction liquid with water for hydration reaction, refining the obtained hydration reaction liquid and mixing it with the remaining base oil to obtain a base grease;

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

[0035] The present invention mixes part of the base oil with aluminum propoxide, stearic acid and benzoic acid for saponification reaction, mixes the obtained saponification reaction liquid with water for hydration reaction, and mixes the obtained hydration reaction liquid with the remaining base oil after refining to obtain a base grease. In the present invention, the temperature of the saponification reaction is preferably 90-130°C, more preferably 95-120°C, specifically 95°C, 100°C, 110°C or 120°C; the time of the saponification reaction is preferably 1-3h, more preferably 1.5-2h, specifically 1.5h, 1.8h or 2h. In a specific embodiment of the present invention, the mixing of part of the base oil and the raw materials for preparing the aluminum-based thickener for saponification reaction includes: firstly mixing aluminum isopropoxide and part of the base oil and heating to the temperature of the saponification reaction, adding straight-chain saturated fatty acids after the aluminum isopropoxide melts and stirring for 0.5-1h, and then adding benzoic acid and reacting for 1-2h under heat preservation conditions.

[0036] In the present 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 the present 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 the refining is completed, the present invention mixes the refined liquid with the remaining base oil, and the remaining base oil acts as cooling oil.

[0038] After obtaining the base grease, the present invention mixes the base grease with an adhesive, an antioxidant, an extreme pressure anti-wear agent, a rust inhibitor and a marine life inhibitor and grinds the mixture to obtain an anti-marine life grease. In the present invention, the temperature at which the base grease is mixed with the adhesive, the antioxidant, the extreme pressure anti-wear agent, the rust inhibitor and the marine life inhibitor is preferably 60 to 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] The present invention also provides the application of the anti-marine organism lubricating grease described in the above scheme and the anti-marine organism lubricating grease prepared by the preparation method described in the above scheme in ships. The anti-marine organism lubricating grease provided by the present invention has the characteristics of anti-marine organism, seawater resistance, extreme pressure and anti-wear, etc., can meet the lubrication and protection requirements of surface and underwater ship moving parts, and has broad application prospects.

[0040] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions of the present invention. Obviously, the described embodiments are only 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.

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

[0042] The base oil PAO40 was purchased from Mobil, and the 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 Materials Co., Ltd., with an aluminum content of 12.5% ​​to 14.9%;

[0044] Stearic acid was purchased from Beijing Xinao 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 content of 99.8%;

[0046] Distilled water was prepared in the laboratory;

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

[0048] Hydrogenated styrene isoprene star copolymer was purchased from Shell Company with the brand name SV620;

[0049] Butyl octyl diphenylamine was purchased from BASF, brand L57;

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

[0051] Heptadecenyl imidazoline succinate was purchased from Shanghai Midgard Chemical Co., Ltd., brand number T703;

[0052] Cuprous oxide was purchased from Taixing Smelter Co., Ltd., with a content of 97%;

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

[0054] Copper pyrrolidinodithiocarbamate (Cu(S2CNC4H8)2) was prepared in the laboratory according to the method described in "Wang Ying, Lu Yong, Luo Chengyan, et al. Crystal structure and spectroscopic study of N′-ethyl-N-piperazinyldithiocarbamate copper (II) complex Cu(S2CNC4H8NC2H5)2 [J]. Journal of Inorganic Chemistry, 2008, (05): 691-695.)". The specific preparation steps are as follows: (1) Pyrrolidine (14.24 g, 0.20 mol) was added to 400 mL of acetone. The reaction temperature was controlled below 4°C. The stirrer was started and carbon disulfide (15.20 g, 0. 05mol) and sodium hydroxide (50% aqueous solution, 0.20mol), after the addition is complete, continue stirring for 3-4h. After the reaction is completed, filter and recrystallize the filter cake in acetonitrile to obtain white sodium pyrrolidino dithiocarboxylate (C4H8NCS2Na); (2) Take (22.35g, 0.15mol) of C4H8NCS2Na and dissolve it in water. Add (9.38g, 0.05mol) of saturated aqueous solution of copper nitrate and stir until a brown precipitate appears. Filter to obtain a crude product of dipyrrolidino dithiocarboxylate copper. The crude product is recrystallized from acetone and dried over P2O5 to obtain a black pure product of dipyrrolidino dithiocarboxylate copper.

[0055] Example 1

[0056] Mix 13.42g of aluminum isopropoxide and 203.43g of PAO40 and heat to 120°C. After the aluminum isopropoxide melts, slowly add 16.4g of stearic acid, stir and react for 30 minutes, then add 7.03g of benzoic acid, react at 120°C for 1h, cool to 96°C, slowly add 1.5g of distilled water, react for 1h, heat to 210°C, keep for 10min, add 102.4g of PAO40 as cooling oil, cool naturally to 60°C, and grind to homogenize to obtain grease.

[0057] The blank base grease prepared in this example has a mass percentage of 8% of the composite aluminum-based thickener, a molar ratio of stearic acid to benzoic acid of 1:1, and a molar ratio of the total molar amount of stearic acid and benzoic acid to aluminum isopropoxide of 1.75:1.

[0058] Example 2

[0059] Mix 13.42g of aluminum isopropoxide and 203.43g of PAO40 and heat to 120°C. After the aluminum isopropoxide melts, slowly add 16.4g of stearic acid, stir and react for 30 minutes, then add 7.03g of benzoic acid, react at 120°C for 1h, cool to 96°C, slowly add 1.50g of distilled water, react for 1h, heat to 210°C, keep for 10min, add 102.4g of PAO40 as cooling oil, cool to 80°C, then add 3.36g of cuprous oxide, stir for 30min, cool to 60°C, and grind to obtain grease.

[0060] The mass percentage of cuprous oxide in the above grease is 1.0%.

[0061] Example 3

[0062] Mix 13.42g of aluminum isopropoxide and 203.43g of PAO40 and heat to 120°C. After the aluminum isopropoxide melts, slowly add 16.4g of stearic acid, stir and react for 30 minutes, then add 7.03g of benzoic acid, react at 120°C for 1h, cool to 96°C, slowly add 1.5g of distilled water, react for 1h, heat to 210°C, keep for 10min, add 102.40g of PAO40 as cooling oil, cool to 80°C, then add 6.78g of cuprous oxide, stir for 30min, cool to 60°C, and grind to homogenize to obtain grease.

[0063] The mass percentage of cuprous oxide in the above grease is 2%.

[0064] Example 4

[0065] Mix 13.42g of aluminum isopropoxide and 203.43g of PAO40 and heat to 120°C. After the aluminum isopropoxide melts, slowly add 16.40g of stearic acid, stir and react for 30 minutes, then add 7.03g of benzoic acid, react at 120°C for 1h, cool to 96°C, slowly add 1.50g of distilled water, react for 1h, heat to 210°C, keep for 10min, add 102.40g of PAO40 as cooling oil, cool to 80°C, then add 10.27g of cuprous oxide, stir for 30min, cool to 60°C, and grind to obtain grease.

[0066] The mass percentage of cuprous oxide in the above grease is 3%.

[0067] Example 5

[0068] Mix 13.42g of aluminum isopropoxide and 203.43g of PAO40 and heat to 120°C. After the aluminum isopropoxide melts, slowly add 16.40g of stearic acid, stir and react for 30 minutes, then add 7.03g of benzoic acid, react at 120°C for 1h, cool to 96°C, slowly add 1.50g of distilled water, react for 1h, heat to 210°C, keep for 10min, add 102.40g of PAO40 as cooling oil, cool to 80°C, then add 10.27g of copper pyrithione, stir for 30min, cool to 60°C, and grind to obtain grease.

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

[0070] Example 6

[0071] Mix 13.42g of aluminum isopropoxide and 203.43g of PAO 40 and heat to 120°C. After the aluminum isopropoxide melts, slowly add 16.40g of stearic acid, stir and react for 30min, then add 7.03g of benzoic acid, react at 120°C for 1h, cool to 96°C, slowly add 1.50g of distilled water, react for 1h, heat to 210°C, keep for 10min, add 102.4g of PAO40 as cooling oil, cool to 80°C, then add 10.27g of copper pyrrolidino dithiocarbamate, stir for 30min, cool to 60°C, and grind to obtain grease.

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

[0073] Example 7

[0074] 13.42g of aluminum isopropoxide and 203.43g of PAO40 were mixed and heated to 120°C. After the aluminum isopropoxide melted, 16.40g of stearic acid was slowly added, stirred and reacted for 30min, 7.03g of benzoic acid was added, reacted at 120°C for 1h, cooled to 96°C, 1.50g of distilled water was slowly added, reacted for 1h, heated to 210°C, maintained for 10min, 102.4g of PAO40 was added as cooling oil, cooled to 80°C, 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, stirred for 30min, cooled to 60°C, and ground and homogenized to obtain anti-marine biological grease.

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

[0076] Example 8

[0077] 13.42g of aluminum isopropoxide and 203.43g of PAO40 were mixed and heated to 120°C. After the aluminum isopropoxide melted, 16.40g of stearic acid was slowly added, stirred and reacted for 30min, 7.03g of benzoic acid was added, reacted at 120°C for 1h, cooled to 96°C, 1.50g of distilled water was slowly added, reacted for 1h, heated to 210°C, maintained for 10min, 102.40g of PAO40 was added as cooling oil, cooled to 80°C, 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 pyrithione were added, stirred for 30min, cooled to 60°C, and ground and homogenized to obtain anti-marine biological grease.

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

[0079] Example 9

[0080] 13.42g of aluminum isopropoxide and 203.43g of PAO40 were mixed and heated to 120°C. After the aluminum isopropoxide melted, 16.40g of stearic acid was slowly added, stirred and reacted for 30min, 7.03g of benzoic acid was added, reacted at 120°C for 1h, cooled to 96°C, 1.50g of distilled water was slowly added, reacted for 1h, heated to 210°C, maintained for 10min, 102.4g of PAO40 was added as cooling oil, cooled to 80°C, 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 dithiocarboxylate were added, stirred for 30min, cooled to 60°C, and ground and homogenized to obtain anti-marine biological grease.

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

[0082] Comparative Example 1

[0083] Mix 13.42g of aluminum isopropoxide and 203.43g of PAO40 and heat to 120°C. After the aluminum isopropoxide melts, slowly add 16.4g of stearic acid, stir and react for 30 minutes, then add 7.03g of benzoic acid, react at 120°C for 1h, cool to 96°C, slowly add 1.50g of distilled water, react for 1h, heat to 210°C, keep for 10min, add 102.40g of PAO40 as cooling oil, cool to 80°C, then add 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, stir for 30min, cool to 60°C, and grind and homogenize to obtain grease.

[0084] The grease obtained in the above comparative example is about 467.93g, without adding marine biological inhibitors, and the mass percentage of each component is approximately: composite aluminum-based thickener 5.7%, base oil 65.3%, calcium carbonate 25.0%, adhesive 1.0%, antioxidant 1.5%, rust inhibitor 1.5%.

[0085] Performance Testing

[0086] (1) Test on adhesion growth performance of Porphyridium cruentum

[0087] The adhesion growth performance of Porphyridium cruentum was tested on Examples 1 to 6, and the test method is as follows:

[0088] Take appropriate amount of lubricating grease samples of Examples 1 to 6 respectively, evenly apply them on 1×1 cm glass slides, take blank glass slides and the basic lubricating grease of Example 1 as comparative samples, place them in a sample box, add the pre-culture solution of Porphyridium cruentum, and culture them in a constant temperature incubator for 24 hours. After the culture is completed, remove the glass sample, rinse it with artificial seawater to remove the suspended algae on the surface, cover it with a glass cover slip and flatten it, observe it with a fluorescence microscope, compare the growth and attachment of the algae, and evaluate the anti-algae and anti-fouling effect of the additive.

[0089] Figure 1 Actual pictures of the greases obtained in Example 1(a), Example 2(b), Example 3(c), Example 4(d), Example 5(e) and Example 6(f).

[0090] Figure 2Fluorescence microscope photos of the adhesion performance of Porphyridium cruentum on the grease surface obtained from a blank glass slide (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 amount of Porphyridium is attached to the blank glass slide and the grease surface prepared in Example 1 after 24 hours of cultivation. Figure 2 Figures c, d, and e show that adding cuprous oxide to the base grease can significantly improve the antifouling performance, and has a positive improvement effect as the amount of addition increases. Figure 2 Figures f and g also show that copper pyrithione and copper pyrrolidino dithiocarbamate are added to the base grease as additives, and the resulting grease has good anti-marine biological performance.

[0091] (2) Physical and chemical properties test

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

[0093] Table 1 Physical and chemical properties test results of grease prepared in Examples 7 to 9 and Comparative Example 1

[0094]

[0095]

[0096] According to Table 1, compared with Comparative Example 1, the various properties of the anti-marine organism greases prepared in Examples 7, 8 and 9 did not show significant attenuation, indicating that the marine organism inhibitors selected in the present invention have good synergistic effects with antioxidants, rust inhibitors, etc. At the same time, the addition of cuprous oxide, copper pyrithione or copper pyrrolidino dithiocarbamate has a significant effect on the anti-wear performance (wear spot diameter) and sintering load (P B ) has a lifting effect.

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

[0098] In summary, the present invention improves the anti-marine organism performance of the grease without changing the physical and chemical properties of the grease itself. The obtained grease has the characteristics of resistance to marine organisms, resistance to seawater, extreme pressure and anti-wear, etc., and can meet the lubrication and protection needs of relevant parts of surface and underwater ships in the marine environment, and has broad application prospects.

[0099] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. An anti-marine biomass grease, characterized in that: The invention comprises the following components in percentage by weight: 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 life inhibitor; the raw materials for preparing the composite aluminum-based thickener include aluminum isopropoxide, benzoic acid, straight-chain saturated fatty acid and water; the marine life inhibitor is one or more of cuprous oxide, copper pyrithione and copper pyrrolidino dithiocarbamate.

2. The anti-marine biomass 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 to 100 mm 2 / s.

3. The anti-marine biomass grease according to claim 1, characterized in that: The number of carbon atoms of 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); the ratio of the molar amount of aluminum isopropoxide to the total molar amount of the straight-chain saturated fatty acid and benzoic acid is (1 to 1.2):

2.

4. The anti-marine biomass grease according to claim 1, characterized in that: The adhesive is one or more of polyisobutylene, ethylene-propylene copolymer, C9 petroleum resin and hydrogenated styrene diene copolymer.

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

6. The anti-marine biomass grease according to claim 1, characterized in that: The extreme pressure anti-wear agent is nano-active calcium carbonate.

7. The anti-marine biomass grease according to claim 1, characterized in that: The rust inhibitor is one or more of sulfonate, dodecenylsuccinic acid and heptadecenyl imidazoline succinate.

8. The method for preparing the anti-marine biological grease according to any one of claims 1 to 7, characterized in that: The following steps are involved: Mixing part of the base oil with aluminum propoxide, stearic acid and benzoic acid for saponification reaction, mixing the obtained saponification reaction liquid with water for hydration reaction, refining the obtained hydration reaction liquid and mixing it with the remaining base oil to obtain a base grease; The base grease is mixed with an adhesive, an antioxidant, an extreme pressure anti-wear agent, a rust inhibitor and a marine life inhibitor, and then homogenized and ground to obtain the marine life-resistant grease.

9. The preparation method according to claim 8, characterized in that: The saponification reaction temperature is 90-130°C and the reaction time is 1-3h; The temperature of the hydration reaction is 80-100° C., and the reaction time is 0.5-3 hours.

10. Use of the anti-marine organism lubricating grease according to any one of claims 1 to 7 or the anti-marine organism lubricating grease prepared by the preparation method according to any one of claims 8 to 9 in ships.

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