A marine anti-fouling grease composition and a method of making the same

Abstract

The present application relates to the technical field of lubricating grease, and provides a marine antifouling lubricating grease composition and a preparation method thereof.The marine antifouling lubricating grease composition provided by the present application comprises the following components: base oil 42.8-88.98%, thickening agent 4-10%, antioxidant 0.5-2%, extreme pressure anti-wear agent 5-40%, antirust agent 0.5-2%, adhesion agent 0.5-3%, metal passivator 0.02-0.2%, and marine organism inhibitor 0.5-5%.The present application adopts a composite aluminum-based thickening agent with good water resistance as the thickening agent, 4,5-dichloro-2-n-octyl-3-isothiazolinone as the marine organism inhibitor, and nano active calcium carbonate and / or polytetrafluoroethylene as the extreme pressure anti-wear agent, so that the obtained lubricating grease composition can effectively inhibit the adsorption of marine organisms and grow in water, and simultaneously has the functional characteristics of seawater resistance and high wear resistance, and can provide long-term reliable lubrication for mechanical moving parts working in a seawater environment.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of lubricating grease, in particular to a marine anti-fouling lubricating grease composition and a preparation method thereof. BACKGROUND

[0002] The marine environment is a very harsh corrosive and fouling environment, therefore, corrosion and fouling have been the main problems faced by marine engineering, ships and the like. For static surfaces, there are many anti-fouling methods for marine biological contamination, such as mechanical cleaning, ultrasonic cleaning and coating of anti-fouling paint, etc., among which coating of anti-fouling paint is the most economical and effective method with the widest range of applications. However, moving parts working in seawater environment can also be threatened by marine biological fouling, for example, the rudder shaft system of a ship is located below the waterline, and its lubrication conditions are very complex. During long-term port supply and maintenance, marine organisms can easily breed under the conditions of light and rudder shaft staticity. When the marine organisms breed to a certain extent, they can cause the failure of sliding function, and even cause the rudder shaft to be stuck. Marine organism attachment can also cause changes in the friction state of moving parts, and if the lubrication is poor, it can cause the friction between the rudder shaft and the bearing to excite the rudder shaft bearing, support structure and rudder plate to vibrate, and the vibration caused by friction excitation can greatly reduce the service life and reliability of the rudder shaft and bearing.

[0003] At present, lubricating grease is usually used to lubricate moving parts in water equipment such as ships, for example, a lubricating grease composition composed of a composite aluminum base grease and a composite calcium sulfonate base grease is disclosed in the related art, which can meet the lubrication requirements of water equipment such as ships. However, the current lubricating grease does not have anti-fouling properties and cannot inhibit the growth of marine organisms. The attachment of marine organisms on the surface of the lubricating grease can destroy the lubricating grease layer and cause lubrication failure. So far, there has been no related report on lubricating grease with marine anti-fouling properties. SUMMARY

[0004] Therefore, the present application provides a marine anti-fouling lubricating grease composition and a preparation method thereof. The lubricating grease composition provided by the present application can effectively inhibit the growth of marine organisms, and at the same time has the functions of seawater resistance, high wear resistance and the like, and can provide long-term reliable lubrication for mechanical moving parts working in seawater environment.

[0005] In order to achieve the above-mentioned application purposes, the present application provides the following technical solutions:

[0006] A marine anti-fouling lubricating grease composition, comprising the following components in mass percentage: base oil 42.8-88.98%, thickening agent 4-10%, antioxidant 0.5-2%, extreme pressure anti-wear agent 5-40%, anti-rust agent 0.5-2%, adhesion agent 0.5-3%, metal passivator 0.02-0.2%, marine organism inhibitor 0.5-5%;

[0007] The thickening agent is a composite aluminum base thickening agent, and raw materials for preparing the composite aluminum base thickening agent include aluminum isopropoxide, stearic acid, benzoic acid and water.

[0008] The extreme pressure anti-wear agent is one or both of nano active calcium carbonate and polytetrafluoroethylene.

[0009] The marine organism inhibitor is 4, 5-dichloro-2-n-octyl-3-isothiazolinone.

[0010] Preferably, the base oil is one or both of mineral oil and polyalphaolefin synthetic oil, and the base oil has a kinematic viscosity at 100℃ of 10-100mm 2 / s.

[0011] Preferably, the antioxidant is a mixture of 2, 6-di-tert-butyl-p-cresol and alkyl diphenylamine; the mass ratio of 2, 6-di-tert-butyl-p-cresol to alkyl diphenylamine in the mixture is (0.2-0.5) : (1.0-1.3).

[0012] Preferably, the rust inhibitor is one or both of alkyl benzene sulfonate, long-chain organic carboxylic acid and sorbitan oleate.

[0013] Preferably, the adhesion agent is polyisobutylene; the viscosity average molecular weight of the polyisobutylene is 30000-60000.

[0014] Preferably, the metal deactivator is a thiazole octyl mercaptan condensate.

[0015] The application also provides a preparation method of the marine antifouling grease composition, comprising the following steps:

[0016] Part of the base oil is mixed with aluminum propylate, stearic acid and benzoic acid to perform a saponification reaction, the obtained saponification reaction liquid is mixed with water to perform a hydration reaction, and the obtained hydration reaction liquid is mixed with the remaining base oil after refining to obtain a base grease;

[0017] The base grease is mixed with the antioxidant, the extreme pressure anti-wear agent, the rust inhibitor, the adhesion agent, the metal deactivator and the marine organism inhibitor to perform grinding to obtain the marine antifouling grease composition.

[0018] Preferably, the saponification reaction has a temperature of 90-130℃ and a reaction time of 1-3h;

[0019] The hydration reaction has a temperature of 80-100℃ and a reaction time of 0.5-3h.

[0020] Preferably, the refining has a temperature of 190-220℃ and a time of 10-15min.

[0021] Preferably, the temperature for mixing the base grease with the antioxidant, extreme pressure anti-wear agent, anti-rust agent, adhesion agent, metal passivator and marine organism inhibitor is 60-110℃.

[0022] The present application provides a marine anti-fouling grease composition, comprising the following components in mass percentage: base oil 42.8-88.98%, thickening agent 4-10%, antioxidant 0.5-2%, extreme pressure anti-wear agent 5-40%, anti-rust agent 0.5-2%, adhesion agent 0.5-3%, metal passivator 0.02-0.2%, marine organism inhibitor 0.5-5%; the thickening agent is a composite aluminum-based thickening agent, the raw materials for preparing the composite aluminum-based thickening agent include aluminum isopropylate, stearic acid, benzoic acid and water; the extreme pressure anti-wear agent is one or both of nano active calcium carbonate and polytetrafluoroethylene; the marine organism inhibitor is 4,5-dichloro-2-n-octyl-3-isothiazolinone. The present application introduces 4,5-dichloro-2-n-octyl-3-isothiazolinone into the grease composition, relies on the active part on the isothiazolinone heterocycle to form hydrogen bonds with the bases on the DNA molecules in the proteins in the bacteria, and adsorbs on the cells of the bacteria, plays the role of attacking the nucleophile, thereby destroys the structure of the DNA in the cells, makes it lose the ability of replication, and further plays the role of inhibiting the adsorption and growth of marine organisms. Moreover, the present application embeds the marine organism inhibitor in the grease, and after contacting or being washed by seawater, the marine organism inhibitor will gradually be exposed to play the corresponding role, thereby achieving the effect of long-acting and slow release. The present application can expand the function of inhibiting the adsorption and growth of marine organisms without changing the physical and chemical properties of the grease itself, and can gradually release the marine organism inhibitor into seawater during use, forms an effective "poison layer", and further achieves the purpose of preventing marine organisms from adsorbing and growing on the key parts of the rudder shaft and causing fouling.

[0023] The composite aluminum base thickening agent is used to thicken base oil, and the composite aluminum base grease formed has smaller fiber structure, better pumpability than other types of grease, better sensibility to various additives, good water resistance and oxidation stability, can maintain the structure of the grease after mixing with water, has small oil separation amount during storage, has better colloid stability, and is more suitable for centralized lubrication system; the nano active calcium carbonate and / or polytetrafluoroethylene are used as extreme pressure anti-wear agent, which can improve the extreme pressure anti-wear performance of the grease, provide excellent friction reduction performance and improve the density characteristics of the grease composition, so that the grease composition does not float even under water leakage, can effectively reduce the vibration noise of moving parts, and increase the concealment performance of underwater ships. In addition, the antioxidant, rust inhibitor, metal deactivator and adhesion agent are introduced, there is extremely complex interaction between different additives, and finally the obtained grease composition has excellent adhesion performance, oxidation resistance, pumpability, low temperature performance, friction reduction performance and extreme pressure anti-wear performance, and also has good marine biological adsorption inhibition performance. In summary, the grease composition provided by the application has excellent comprehensive performance, can be used for protection and lubrication of ships on water surface and underwater ships in high-humidity environment containing salt, the raw material composition is reasonable, the application range is wide, and the application prospect is broad. BRIEF DESCRIPTION OF DRAWINGS

[0024] Figure 1 Fluorescence microscope photos of purple sulfur bacteria adhesion performance on the surface of the blank glass slide (a) and the grease composition obtained in example 1 (b);

[0025] Figure 2 Fluorescence microscope photos of diatom adhesion performance on the surface of the blank glass slide (a) and the grease composition obtained in example 1 (b);

[0026] Figure 3 Fluorescence microscope photos of diatom adhesion performance on the surface of the blank glass slide (a) and the grease composition obtained in example 1 (b);

[0027] Figure 4 Fluorescence microscope photos of diatom adhesion performance on the surface of the blank glass slide (a) and the grease composition obtained in example 1 (b);

[0028] Figure 5 Fluorescence microscope photos of diatom adhesion performance on the surface of the blank glass slide (a) and the grease composition obtained in example 1 (b);

[0029] Figure 6 Fluorescence microscope photos of diatom adhesion performance on the surface of the blank glass slide (a) and the grease composition obtained in example 1 (b). DETAILED DESCRIPTION

[0030] The application provides a marine antifouling grease composition, which comprises the following components in mass percentage: base oil 42.8-88.98%, thickening agent 4-10%, antioxidant 0.5-2%, extreme pressure anti-wear agent 5-40%, anti-rust agent 0.5-2%, adhesion agent 0.5-3%, metal deactivator 0.02-0.2%, marine organism inhibitor 0.5-5%;

[0031] The thickening agent is a composite aluminum-based thickening agent, and the preparation raw materials of the composite aluminum-based thickening agent comprise aluminum isopropylate, stearic acid, benzoic acid and water.

[0032] The extreme pressure anti-wear agent is one or both of nano active calcium carbonate and polytetrafluoroethylene.

[0033] The marine organism inhibitor is 4,5-dichloro-2-n-octyl-3-isothiazolinone.

[0034] Unless otherwise specified, all the raw materials used are commercially available or prepared by methods well known to those skilled in the art.

[0035] The marine antifouling grease composition provided by the application comprises base oil in mass percentage of 42.8-88.98%, preferably 60-70%, and specifically 60%, 65% or 70%. In the application, the base oil is one or both of mineral oil and polyalphaolefin (PAO) synthetic oil, and preferably PAO synthetic oil. The kinematic viscosity of the PAO synthetic oil at 100°C is preferably 10-100 mm 2 / s, and more preferably 30-60 mm 2 / s. In the application, the PAO synthetic oil has good hydrolysis stability, a high viscosity index, stable friction performance and good compatibility with other additives.

[0036] The marine antifouling grease composition provided by the application comprises thickening agent in mass percentage of 4-10%, preferably 5-8%, and specifically 5%, 6%, 7%, 7.5% or 8%. In the application, the thickening agent is a composite aluminum-based thickening agent, and the preparation raw materials of the composite aluminum-based thickening agent comprise aluminum isopropylate, stearic acid, benzoic acid and water. The water is preferably distilled water. The molar ratio of the stearic acid to the benzoic acid is preferably 1:(0.8-1), and specifically 1:0.8, 1:0.9 or 1:1. The molar ratio of the molar amount of the aluminum isopropylate to the total molar amount of the stearic acid and the benzoic acid is preferably (1-1.2):2, and more preferably (1.05-1.1):2. The molar ratio of the water to the aluminum isopropylate is preferably (1-3):1.

[0037] The marine anti-fouling grease composition provided by the present application comprises 0.5-2% of antioxidant, preferably 1-1.5%, and specifically 1%, 1.2%, 1.4% or 1.5% in terms of mass percentage. In the present application, the antioxidant is preferably a mixture of 2,6-di-tert-butyl-p-cresol and alkyl diphenylamine, and the alkyl diphenylamine is preferably butyl octyl diphenylamine; the mass ratio of 2,6-di-tert-butyl-p-cresol to alkyl diphenylamine in the mixture is preferably (0.2-0.5):(1-1.3), and more preferably (0.3-0.4):(1-1.2).

[0038] The marine anti-fouling grease composition provided by the present application comprises 5-40% of extreme pressure anti-wear agent, preferably 20-30%, and specifically 20%, 22%, 25%, 28 or 30% in terms of mass percentage; the extreme pressure anti-wear agent is one or both of nano active calcium carbonate and polytetrafluoroethylene (PTFE), and more preferably a mixture of nano active calcium carbonate and PTFE, and the mass ratio of nano active calcium carbonate to PTFE in the mixture is preferably (25-29):(1-5), and more preferably (26-28):(2-4), and the average particle size of the PTFE is preferably 4.5±0.5 μm.

[0039] The marine anti-fouling grease composition provided by the present application comprises 0.5-2% of antioxidant, preferably 1-1.5%, and specifically 1%, 1.2%, 1.4% or 1.5% in terms of mass percentage. In the present application, the antioxidant is preferably a mixture of 2,6-di-tert-butyl-p-cresol and alkyl diphenylamine, and the alkyl diphenylamine is preferably butyl octyl diphenylamine; the mass ratio of 2,6-di-tert-butyl-p-cresol to alkyl diphenylamine in the mixture is preferably (0.2-0.5):(1-1.3), and more preferably (0.3-0.4):(1-1.2).

[0040] The marine anti-fouling grease composition provided by the present application comprises 0.5-2% of antioxidant, preferably 1-1.5%, and specifically 1%, 1.2%, 1.4% or 1.5% in terms of mass percentage. In the present application, the antioxidant is preferably a mixture of 2,6-di-tert-butyl-p-cresol and alkyl diphenylamine, and the alkyl diphenylamine is preferably butyl octyl diphenylamine; the mass ratio of 2,6-di-tert-butyl-p-cresol to alkyl diphenylamine in the mixture is preferably (0.2-0.5):(1-1.3), and more preferably (0.3-0.4):(1-1.2).

[0041] The marine anti-fouling lubricating grease composition provided by the present application comprises 0.02-0.2% of metal passivator in terms of mass percentage, preferably 0.05-0.1%, and specifically 0.05%, 0.06%, 0.08%, 0.09% or 0.1%. In the present application, the metal passivator is preferably a thiazole octyl mercaptan condensate. The use of thiazole octyl mercaptan condensate as the metal passivator in the present application can form a protective film on the metal surface, reduce the activity of metal ions, improve the metal corrosion protection performance, and prevent the catalytic oxidation of the lubricating grease by the metal, thus being conducive to improving the protection performance of the lubricating grease composition.

[0042] The marine anti-fouling lubricating grease composition provided by the present application comprises 0.5-5% of marine organism inhibitor in terms of mass percentage, preferably 2-3%, and specifically 2%, 2.5% or 3%. In the present application, the marine organism inhibitor is 4,5-dichloro-2-n-octyl-3-isothiazolinone.

[0043] In the present application, the density of the marine anti-fouling lubricating grease composition is greater than 1 g / cm 3 ; in specific embodiments of the present application, the density of the marine anti-fouling lubricating grease composition varies according to the types and proportions of the base oil and additives, but is all greater than 1 g / cm 3 ; this density characteristic can make the lubricating grease composition of the present application not float even if it leaks underwater, thus increasing the concealment of underwater ships.

[0044] The present application provides a preparation method of the marine anti-fouling lubricating grease composition described in the above technical solutions, comprising the following steps:

[0045] The base oil is mixed with aluminum propylate, stearic acid and benzoic acid to perform a saponification reaction, the obtained saponification reaction liquid is mixed with water to perform a hydration reaction, the obtained hydration reaction liquid is refined and mixed with the remaining base oil to obtain a base lubricating grease;

[0046] The base lubricating grease is mixed with an antioxidant, an extreme pressure anti-wear agent, an anti-rust agent, an adhesion agent, a metal passivator and a marine organism inhibitor to perform grinding, thus obtaining the marine anti-fouling lubricating grease composition.

[0047] The base grease is obtained by mixing base oil with aluminum isopropyl alcohol, stearic acid and benzoic acid to perform a saponification reaction, mixing the obtained saponification reaction liquid with water to perform a hydration reaction, mixing the obtained hydration reaction liquid with remaining base oil after refining, and obtaining the base grease. In the present application, the temperature of the saponification reaction is preferably 90-130°C, and can be specifically 100°C, 110°C or 120°C, and the time of the saponification reaction is preferably 1-3h, and can be specifically 1.5h, 2h, 2.5h or 3h; in a specific embodiment of the present application, the saponification reaction specifically comprises: first mixing aluminum isopropyl alcohol and part of the base oil to heat to the temperature of the saponification reaction, adding stearic acid after the aluminum isopropyl alcohol is melted, stirring for 0.5-1h, and then adding benzoic acid, and reacting for 1-2h under the condition of heat preservation.

[0048] In the present application, the temperature of the hydration reaction is preferably 80-100°C, and can be specifically 80°C, 85°C, 90°C, 95°C or 100°C, and the time of the hydration reaction is preferably 0.5-3h, and can be specifically 0.5h, 1h, 2h, 2.5h or 3h.

[0049] In the present application, the temperature of the refining is preferably 190-220°C, and can be specifically 190°C, 195°C, 210°C, 215°C or 220°C, and the time of the refining is preferably 10-15min. After the refining is completed, the present application mixes the liquid after refining with remaining base oil, and the remaining base oil plays the role of cooling oil.

[0050] After the base grease is obtained, the present application mixes the base grease with an antioxidant, an extreme pressure and wear resistant agent, an antirust agent, an adhesion agent, a metal passivator and a marine organism inhibitor to perform grinding, and obtains a marine antifouling grease composition. In the present application, the temperature of mixing the base grease with the antioxidant, the extreme pressure and wear resistant agent, the antirust agent, the adhesion agent, the metal passivator and the marine organism inhibitor is preferably 60-110°C, and can be specifically 60°C, 70°C, 80°C, 90°C, 100°C or 110°C; and the grinding is preferably performed by a three-roll grinder.

[0051] The technical solutions in the present application will be clearly and completely described below in combination with the embodiments in the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the protection scope of the present application.

[0052] The composite aluminum base thickening agent and the grease composition in the following examples and comparative examples are all prepared in the laboratory, and the sources of the raw materials used include:

[0053] The base oil PAO 40 is purchased from the Mobil Company, and the kinematic viscosity at 40°C is 396mm2 / s, kinematic viscosity at 100°C of 40 mm 2 / s.

[0054] Aluminum isopropoxide was purchased from Yangzhou Zhongtianli New Material Co., Ltd., with aluminum content of 12.5% to 14.9%.

[0055] Stearic acid was purchased from Beijing Xinaoxunchemical Co., Ltd., with saponification value of 210.76.

[0056] Benzoic acid was purchased from Tianjin Dongda Chemical Group Co., Ltd., with content of 99.8%.

[0057] Nano active calcium carbonate was purchased from Xintai Hengxin Nanometer Material Co., Ltd.

[0058] PTFE was purchased from Shanghai Shenyu Industry and Trade Co., Ltd., SYF-9958 type, with average particle size of 4.5±0.5 μm.

[0059] Distilled water was self-made in the laboratory.

[0060] Sorbitan oleate SPAN 80 was purchased from Tianjin Damao Chemical Reagent Factory.

[0061] Butyl octyl diphenylamine was purchased from BASF Company, with trade name of L57.

[0062] 2,6-di-tert-butyl-p-cresol was purchased from LANSESS Company, with trade name of Additin RC 7110.

[0063] Polyisobutylene was purchased from Zhejiang Shunda New Material Co., Ltd., with trade name of SDG-8350, and viscosity average molecular weight of 35000±5000.

[0064] Thiadiazole octyl mercaptan condensate was purchased from Luoyang Pacific Petrochemical Co., Ltd., with trade name of DMTD-8.

[0065] 4,5-dichloro-2-n-octyl-3-isothiazolinone was purchased from Shanghai Jizhisheng Chemical Technology Co., Ltd., with purity of 97%.

[0066] Example 1

[0067] 5.10 g of aluminum isopropoxide was mixed with 81.37 g of PAO40 and heated to 120°C, and after the aluminum isopropoxide was melted, 6.23 g of stearic acid was slowly added, and after stirring for 30 min, 2.68 g of benzoic acid was added, and reacted at 120°C for 1 h, and then cooled to 96°C, and 0.50 g of distilled water was slowly added, and reacted for 1 h, and then heated to 210°C, and maintained for 10 min, and then 40.69 g of PAO40 was added as cooling oil, and after natural cooling to 60°C, the grease composition was obtained by grinding and homogenizing.

[0068] The above example prepared a blank base grease, yielding approximately 132.1 g of base grease. The content of the composite aluminum-based thickener was 7.6%. The molar ratio of stearic acid to benzoic acid was 1:1, and the molar ratio of the total molar amount of stearic acid and benzoic acid to aluminum isopropoxide was 1.76:1.

[0069] Example 2

[0070] 5.10 g of aluminum isopropoxide and 81.37 g of PAO40 were mixed and heated to 120°C. After the aluminum isopropoxide melted, 6.23 g of stearic acid was slowly added and stirred for 30 minutes. Then, 2.68 g of benzoic acid was added and reacted at 120°C for 1 hour. The temperature was lowered to 96°C and 0.50 g of distilled water was slowly added and reacted for 1 hour. The temperature was raised to 210°C and maintained for 10 minutes. 40.69 g of PAO40 was added as cooling oil. After cooling to 80°C, 0.66 g of 4,5-dichloro-2-n-octyl-3-isothiazolinone was added and stirred for 30 minutes. The grease composition was obtained by grinding and homogenizing after cooling to 60°C.

[0071] The mass percentage of 4,5-dichloro-2-n-octyl-3-isothiazolinone in the grease composition is 0.5%.

[0072] Example 3

[0073] 5.10 g of aluminum isopropoxide and 81.37 g of PAO40 were mixed and heated to 120°C. After the aluminum isopropoxide melted, 6.23 g of stearic acid was slowly added and stirred for 30 minutes. Then, 2.68 g of benzoic acid was added and reacted at 120°C for 1 hour. The temperature was lowered to 96°C and 0.50 g of distilled water was slowly added and reacted for 1 hour. The temperature was raised to 210°C and maintained for 10 minutes. 40.69 g of PAO40 was added as cooling oil. After cooling to 80°C, 1.33 g of 4,5-dichloro-2-n-octyl-3-isothiazolinone was added and stirred for 30 minutes. The grease composition was obtained by grinding and homogenizing after cooling to 60°C.

[0074] The mass percentage of 4,5-dichloro-2-n-octyl-3-isothiazolinone in the grease composition is 1.0%.

[0075] Example 4

[0076] Mix 5.10 g aluminum isopropoxide with 81.37 g PAO40 and heat to 120°C. After the aluminum isopropoxide has melted, slowly add 6.23 g stearic acid. After 30 minutes of stirring, add 2.68 g benzoic acid and react at 120°C for 1 hour. Slowly add 0.50 g distilled water at 96°C and react for 1 hour. Heat to 210°C and hold for 10 minutes. Add 40.69 g PAO40 as a cooling oil. After cooling to 80°C, add 2.70 g 4,5-dichloro-2-n-octyl-3-isothiazolinone and stir for 30 minutes. After cooling to 60°C, mill and homogenize to obtain a grease composition.

[0077] The mass percentage of 4,5-dichloro-2-n-octyl-3-isothiazolinone in the above grease composition is 2%.

[0078] Example 5

[0079] Mix 5.10 g aluminum isopropoxide with 81.37 g PAO40 and heat to 120°C. After the aluminum isopropoxide has melted, slowly add 6.23 g stearic acid. After 30 minutes of stirring, add 2.68 g benzoic acid and react at 120°C for 1 hour. Slowly add 0.50 g distilled water at 96°C and react for 1 hour. Heat to 210°C and hold for 10 minutes. Add 40.69 g PAO40 as a cooling oil. After cooling to 80°C, add 4.09 g 4,5-dichloro-2-n-octyl-3-isothiazolinone and stir for 30 minutes. After cooling to 60°C, mill and homogenize to obtain a grease composition.

[0080] The mass percentage of 4,5-dichloro-2-n-octyl-3-isothiazolinone in the above grease composition is 3%.

[0081] Example 6

[0082] Mix 5.10 g aluminum isopropoxide with 81.37 g PAO40 and heat to 120°C. After the aluminum isopropoxide has melted, slowly add 6.23 g stearic acid. After 30 minutes of stirring, add 2.68 g benzoic acid and react at 120°C for 1 hour. Slowly add 0.50 g distilled water at 96°C and react for 1 hour. Heat to 210°C and hold for 10 minutes. Add 40.69 g PAO40 as a cooling oil. After cooling to 80°C, add 38.32 g nano active calcium carbonate, 9.58 g PTFE, 1.91 g SDG-83, 0.96 g Additin RC 71, 1.91 g L57, 2.87 g SPAN80, 0.09 g DMTD-8, and 3.83 g 5-dichloro-2-n-octyl-3-isothiazolinone and stir for 30 minutes. After cooling to 60°C, mill and homogenize to obtain a grease composition.

[0083] The above example can get about 191.59 g of grease composition, the mass percentage of each component is about: 5.2% of composite aluminum base thickening agent, 63.7% of base oil, 20% of nano active calcium carbonate, 5% of PTFE, 1% of adhesive, 1.5% of anti-rust agent, 1.5% of antioxidant, 0.05% of metal passivator, 2% of 4, 5-dichloro-2-n-octyl-3-isothiazolinone.

[0084] Example 7

[0085] 5.1 g of aluminum isopropyl alcohol was mixed with 81.37 g of PAO40 and heated to 120°C, after the aluminum isopropyl alcohol was melted, 6.23 g of stearic acid was slowly added, after stirring for 30 min, 2.68 g of benzoic acid was added, and the reaction was carried out at 120°C for 1 h, then the temperature was lowered to 96°C, 0.50 g of distilled water was slowly added, and the reaction was carried out for 1 h, then the temperature was raised to 210°C, and the reaction was carried out for 10 min, then 40.69 g of PAO40 was added as cooling oil, after cooling to 80°C, 38.88 g of calcium carbonate, 9.72 g of PTFE, 1.94 g of SDG-8350, 0.97 g of Additin RC7110, 1.94 g of L571, 2.91 g of SPAN80, 0.09 g of DMTD-8, and 5.83 g of 5-dichloro-2-n-octyl-3-isothiazolinone were added, and stirring was carried out for 30 min, then the temperature was lowered to 60°C, and the grease composition was obtained by grinding and homogenizing.

[0086] The above example can get about 194.41 g of grease composition, the mass percentage of each component is about: 5.2% of composite aluminum base thickening agent, 62.8% of base oil, 20% of nano active calcium carbonate, 5% of PTFE, 1% of adhesive, 1.5% of anti-rust agent, 1.5% of antioxidant, 0.05% of metal passivator, 3% of 4, 5-dichloro-2-n-octyl-3-isothiazolinone.

[0087] Comparative Example 1

[0088] 5.10 g of aluminum isopropyl alcohol was mixed with 81.37 g of PAO40 and heated to 120°C, after the aluminum isopropyl alcohol was melted, 6.23 g of stearic acid was slowly added, after stirring for 30 min, 2.68 g of benzoic acid was added, and the reaction was carried out at 120°C for 1 h, then the temperature was lowered to 96°C, 0.50 g of distilled water was slowly added, and the reaction was carried out for 1 h, then the temperature was raised to 210°C, and the reaction was carried out for 10 min, then 40.69 g of PAO40 was added as cooling oil, after cooling to 80°C, 38.88 g of calcium carbonate, 9.72 g of PTFE, 1.94 g of SDG-8350, 0.97 g of Additin RC7110, 1.94 g of L571, 2.91 g of SPAN80, 0.09 g of DMTD-8, and 5.83 g of 5-dichloro-2-n-octyl-3-isothiazolinone were added, and stirring was carried out for 30 min, then the temperature was lowered to 60°C, and the grease composition was obtained by grinding and homogenizing.

[0089] The above comparative example can obtain grease composition about 186.18 g, without adding 4,5-dichloro-2-n-octyl-3-isothiazolinone, the mass percentage of each component is about: complex aluminum thickening agent 5.4%, base oil 65.6%, nano active calcium carbonate 20%, PTFE 5.0%, adhesive 1.0%, anti-rust agent 1.5%, antioxidant 1.5%, metal passivator 0.05%.

[0090] Comparative Example 2

[0091] The commercially available No. 1 marine grease was used as Comparative Example 2.

[0092] Performance test

[0093] (1) The purple sulfur bacteria and diatom adhesion growth performance tests were carried out on the greases prepared in Examples 1-5, and the test method was as follows:

[0094] An appropriate amount of samples of Examples 1-5 was uniformly applied to a 1x1 cm glass sheet, and a blank glass slide and the base grease prepared in Example 1 were used as reference samples, which were placed in a sample box, and then the purple sulfur bacteria and diatom pre-culture solution was added and placed in a constant temperature incubator for 24 h. After incubation, the surface suspended algae was washed off with artificial seawater, and then a glass cover glass was placed on it to flatten it, and then observed under a fluorescence microscope to compare the growth and adhesion of the seaweed, so as to evaluate the algae inhibition and antifouling efficiency of the additive.

[0095] The test results are shown in Figures 1-6 , wherein Figure 1 are fluorescence microscope photos of the adhesion performance of purple sulfur bacteria on the surface of the grease compositions obtained in Comparative Example 1 (a) and Example 1 (b); Figure 2 are fluorescence microscope photos of the adhesion performance of purple sulfur bacteria on the surface of the grease compositions obtained in Example 2 (a), Example 3 (b), Example 4 (c) and Example 5 (d); Figure 3 are the adhesion density diagrams of purple sulfur bacteria on the surface of the grease compositions obtained in Comparative Example 1 and Examples 1-5; Figure 4 are fluorescence microscope photos of the adhesion performance of diatoms on the surface of the grease compositions obtained in Comparative Example 1 (a) and Example 1 (b); Figure 5 are fluorescence microscope photos of the adhesion performance of diatoms on the surface of the grease compositions obtained in Example 2 (a), Example 3 (b), Example 4 (c) and Example 5 (d); Figure 6 are the adhesion density diagrams of diatoms on the surface of the grease compositions obtained in Comparative Example 1 and Examples 1-5.

[0096] From Figure 1 and Figure 4It can be seen that the blank slide surface is covered with growing porphyridium and amphora, although the base grease prepared in Example 1 has certain anti-algae performance relative to the blank slide, but there are still a large number of algae adhering and growing on the surface of the blank grease. Figure 2 and Figure 5 It is shown that the addition of 4,5-dichloro-2-n-octyl-3-isothiazolinone into the lubricating base grease can greatly improve the anti-fouling performance, and has a positive effect with the increase of the addition amount.

[0097] Figure 3 The test results in Table 2 show that after adding 0.5% of 4,5-dichloro-2-n-octyl-3-isothiazolinone in the lubricating grease composition, the adhesion density of porphyridium is reduced by 92.7% and 73.6% compared with the blank slide and the blank base grease prepared in Example 1 respectively, and when the addition amount of 4,5-dichloro-2-n-octyl-3-isothiazolinone reaches 3.0%, the adhesion density is reduced by 97.2% and 89.9% respectively. Figure 6 The test results in Table 3 show that when 0.5% of 4,5-dichloro-2-n-octyl-3-isothiazolinone is added in the lubricating grease composition, the adhesion density of amphora is reduced by 98.4% and 91.9% compared with the blank slide and the blank base grease prepared in Example 1 respectively, and if the addition amount reaches 3.0%, the adhesion density is reduced by 99.7% and 98.2% respectively.

[0098] (2) Basic physicochemical performance test

[0099] The performance of the lubricating grease compositions prepared in Example 6 and Example 7 and the comparative example lubricating grease was tested, and the results are shown in Table 1.

[0100] Table 1 Basic physicochemical performance test results of the lubricating grease of Example 6, Example 7 and the comparative example

[0101]

[0102]

[0103] As can be seen from Table 1, the physicochemical performance test results of the marine anti-fouling grease compositions prepared in Examples 6 and 7 are not obviously different from those of Comparative Example 1, indicating that the marine organisms can be effectively inhibited from growing and attaching by using 4, 5-dichloro-2-n-octyl-3-isothiazolinone as the marine organism inhibitor, and the main performance of the grease is not negatively affected. Furthermore, the grease compositions prepared in Examples 6-7 have smaller wear scar diameters than those of Comparative Examples 1-2, indicating that the grease compositions have better positive synergistic effect with other additives in terms of anti-wear performance. Compared with Comparative Example 2, the marine anti-fouling grease composition provided by the present application has outstanding high and low temperature resistance, and is suitable for lubrication and protection in a wider temperature range. The results of copper sheet corrosion, salt spray test, oxidation stability and anti-wear performance show that the marine anti-fouling grease composition provided by the present application has improved overall comprehensive performance to varying degrees compared with Comparative Example 2, and can better provide lubrication and protection for water surface and underwater moving parts in marine environment.

[0104] In addition, the grease prepared in Examples 7-9 was subjected to the Galdieria sulphurica adhesion growth performance test according to the method in (1), and the results show that the anti-fouling performance of the obtained grease composition is basically unchanged compared with Examples 4-5, indicating that the grease composition prepared by the present application has excellent marine anti-fouling performance.

[0105] The above only describes the preferred embodiments of the present application, and it should be noted that those skilled in the art can make several improvements and refinements without departing from the principles of the present application, and these improvements and refinements should also be considered as the protection scope of the present application.

Claims

1. A marine antifouling grease composition, characterized in that The composition includes the following components in percentage by weight: base oil 42.8~88.98%, thickener 4~10%, antioxidant 0.5~2%, extreme pressure and anti-wear agent 5~40%, rust inhibitor 0.5~2%, adhesive 0.5~3%, metal passivator 0.02~0.2%, marine bio-inhibitor 0.5~5%; The thickener is a composite aluminum-based thickener, and the raw materials for preparing the composite aluminum-based thickener include aluminum isopropoxide, stearic acid, benzoic acid and water; The extreme pressure anti-wear agent is one or both of nano-active calcium carbonate and polytetrafluoroethylene; The marine bioinhibitor is 4,5-dichloro-2-n-octyl-3-isothiazolinone; The antioxidant is a mixture of 2,6-di-tert-butyl-p-cresol and alkyl diphenylamine; the mass ratio of 2,6-di-tert-butyl-p-cresol to alkyl diphenylamine in the mixture is (0.2-0.5):(1.0-1.3); The metal passivator is a thiadiazole octyl mercaptan condensate.

2. The marine antifouling grease composition according to claim 1, characterized in that The base oil is one or both of mineral oil and polyalphaolefin synthetic oil, and the kinematic viscosity of the base oil at 100° C. is 10-100 mm 2 / s.

3. The marine antifouling grease composition according to claim 1, characterized in that The rust inhibitor is one or two of alkylbenzene sulfonate, long-chain organic carboxylic acid and sorbitan oleate.

4. The marine antifouling grease composition according to claim 1, characterized in that The adhesive is polyisobutylene; the viscosity average molecular weight of the polyisobutylene is 30,000-60,000.

5. The method for preparing the marine antifouling grease composition according to any one of claims 1 to 4, characterized in that: The marine antifouling grease composition is prepared by the following method: 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 antioxidant, an extreme pressure anti-wear agent, a rust inhibitor, an adhesive, a metal passivator and a marine bio-inhibitor, and then ground to obtain a marine anti-fouling grease composition.

6. The preparation method according to claim 5, characterized in that The saponification reaction temperature is 90-130°C and the reaction time is 1-3 hours; The temperature of the hydration reaction is 80-100° C., and the reaction time is 0.5-3 h.

7. The preparation method according to claim 5, characterized in that The refining temperature is 190-220° C., and the refining time is 10-15 minutes.

8. The preparation method according to claim 5, characterized in that The temperature at which the base grease is mixed with the antioxidant, the extreme pressure anti-wear agent, the rust inhibitor, the adhesive, the metal passivator and the marine life inhibitor is 60-110°C.

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