An antibacterial composite calcium sulfonate grease composition and its preparation method

Abstract

The present invention relates to the technical field of greases, and particularly to an antibacterial composite calcium sulfonate grease composition and a preparation method thereof. The raw materials for preparing the grease composition include the following components in parts by weight: 15-40 parts of calcium sulfonate, 1-8 parts of conversion promoter, 1-4 parts of surfactant, 0.1-1.5 parts of chitosan, 0.5-4 parts of small molecule acid, 1-4 parts of fatty acid, 1-3 parts of calcium hydroxide, 0.2-1.5 parts of additive, and 44-57 parts of base oil. The surfactant is one or more of cationic surfactants, zwitterionic surfactants and nonionic surfactants; the cationic surfactant is quaternary ammonium salts; the zwitterionic surfactant is betaine-type amphoteric surfactants; the nonionic surfactant is polyoxyethylene-type surfactant and / or fatty acid polyol ester. The grease composition of the present invention not only has antibacterial properties, but also has excellent shear stability and extreme pressure and anti-wear properties.

Description

Technical Field

[0001] The present invention relates to the technical field of greases, and particularly relates to an antibacterial composite calcium sulfonate grease composition and a preparation method thereof. Background Art

[0002] During the long-term operation of transmission mechanisms, sealing rings and gaskets in ship transportation, food processing, and medical devices, bacteria and microorganisms are likely to grow and reproduce after being contaminated by the infiltration of river water, seawater, food debris, and organic substances. This will have an adverse impact on human health and equipment operation. In related technologies, the antibacterial greases prepared generally add antibacterial agents to the grease in the form of additives, which are greatly affected by their components, contents, and processes, and have the disadvantages of single lubrication function and poor long-term antibacterial effect. Chinese Patent CN115305128A discloses an antibacterial grease composition, a preparation method thereof, and an application. This method improves the defect of poor long-term antibacterial effect by introducing inorganic metal oxides such as titanium dioxide and zinc oxide and zinc sulfide as both thickeners and antibacterial components during the preparation process. However, its thickener and solid content are high, and its water resistance, extreme pressure and anti-wear properties, and mechanical stability are poor, resulting in limited application scope.

[0003] Composite calcium sulfonate-based greases have good colloidal stability, mechanical stability, water resistance, extreme pressure and anti-wear properties, and anti-rust and anti-corrosion properties, and are widely used in fields such as metallurgy, mining, transportation, and food processing. However, existing composite calcium sulfonate-based greases generally do not have antibacterial and anti-microbial properties. Using antibacterial greases in lubricating parts of food processing equipment, medical devices, and ships can reduce the risk of bacterial and microbial contamination during food processing, improve the antibacterial cleanliness of medical devices, and reduce the amount of microorganisms attached during ship navigation. Therefore, it is extremely necessary to develop an energy-saving antibacterial composite calcium sulfonate grease. Summary of the Invention

[0004] The present invention provides an antibacterial composite calcium sulfonate grease composition and a preparation method thereof to solve the problems of single functionality and insufficient antibacterial property of existing greases.

[0005] According to the first aspect of the present invention, the present invention provides an antibacterial composite calcium sulfonate grease composition, and the raw materials for preparing the grease composition include the following components in parts by weight:

[0006]

[0007] The surfactant is one or more of cationic surfactants, zwitterionic surfactants and nonionic surfactants; the cationic surfactant is a quaternary ammonium salt; the zwitterionic surfactant is a betaine-type amphoteric surfactant; the nonionic surfactant is a polyoxyethylene-type surfactant and / or a fatty acid polyol ester; the conversion promoter is selected from one or more of methanol, ethanol, isopropanol, propylene glycol, n-butanol, hexanol and hexanediol.

[0008] In the above solution, the raw materials for preparing the antibacterial composite calcium sulfonate grease composition of the present invention include calcium sulfonate, conversion promoter, surfactant, chitosan, small molecule acid, fatty acid, calcium hydroxide, additive and base oil. In the process of preparing the composite calcium sulfonate grease composition, the conversion promoter is used as a solvent for chitosan, and the high temperature and high pressure in the autoclave process are utilized to enable chitosan and the surfactant to form a chitosan-type bactericide with antibacterial properties, which can effectively improve the antibacterial effect of the grease, effectively inhibit the growth and reproduction of Gram-positive Staphylococcus aureus, Gram-negative Escherichia coli, large algal spores, barnacles, etc. Applying such a grease composition to industries such as ship transportation, food processing and medical devices can reduce the risk of bacterial and microbial contamination during food processing, improve the antibacterial cleanliness of medical devices, and reduce the attachment amount of microorganisms during ship navigation, having great practical application value and market prospects. At the same time, the formed chitosan-type bactericide has a thickening effect and can be used as a thickener to make the formed composite calcium sulfonate grease composition have a suitable viscosity.

[0009] Furthermore, by selecting a surfactant with a quaternary ammonium salt, the surfactant reacts with chitosan to generate chitosan quaternary ammonium salt, which not only has antibacterial properties, but is also non-toxic, has good biocompatibility and is biodegradable.

[0010] Even further, by limiting the amounts of calcium sulfonate, conversion promoter, surfactant, chitosan, small molecule acid, fatty acid, calcium hydroxide, additive and base oil within reasonable range values, better synergistic effects can be achieved among the components, so that the prepared composite calcium sulfonate grease composition not only has antibacterial properties, but also has excellent shear stability and extreme pressure and anti-wear properties compared with existing antibacterial greases.

[0011] Furthermore, the chitosan is selected from one or more of α-chitosan, β-chitosan, γ-chitosan; preferably, the chitosan is β-chitosan with a molecular weight between 1.5×10 4 ~6.7×10 4 and a deacetylation degree of not less than 86%.

[0012] In the above solution, by selecting a suitable type of chitosan, the prepared chitosan quaternary ammonium salt has more excellent antibacterial properties.

[0013] Further, the cationic surfactant accounts for 50-90% of the total amount of the surfactant.

[0014] In the above solution, by limiting the proportion of the cationic surfactant in the total amount of the surfactant within a reasonable range value, it is beneficial to form a chitosan quaternary ammonium salt with more excellent antibacterial properties. When the proportion of the cationic surfactant in the total amount of the surfactant is less than 50%, the prepared calcium sulfonate grease composition is weak. When the proportion of the cationic surfactant in the total amount of the surfactant exceeds 90%, the stability of the calcium sulfonate grease composition will be affected.

[0015] Further, the surfactant is one or more of cetyltrimethylammonium bromide, dodecyldimethylethylbenzylammonium chloride, dodecyldimethylbenzylammonium chloride, p-alkylphenyltrimethylammonium chloride, 2,3-epoxypropyltrimethylammonium chloride, dodecyl betaine, sodium N-lauroylglutamate, polyoxyethylene sorbitan ester, polyethyleneglycol octylphenyl ether, and polyvinylpyrrolidone.

[0016] In the above solution, by selecting a suitable type of surfactant, the prepared chitosan quaternary ammonium salt has more excellent antibacterial properties.

[0017] Preferably, isopropanol accounts for 40-90% of the volume of the conversion promoter.

[0018] In the above solution, by reasonably selecting the type of the conversion promoter, it is more beneficial to the dissolution of chitosan and more beneficial to the reaction between chitosan and the surfactant to form a chitosan-type bactericide. Isopropanol has good solubility and can effectively disperse chitosan in the solvent without destroying the structure and properties of chitosan. By reasonably limiting the amount of isopropanol in the conversion promoter, it is more beneficial to the dissolution of chitosan and more beneficial to the reaction between chitosan and the surfactant to form a chitosan-type bactericide.

[0019] Further, the calcium sulfonate is a high-base synthetic calcium sulfonate; preferably, the total base number of the calcium sulfonate is 155-425 mgKOH / g; and / or, in the high-base synthetic calcium sulfonate, the carbon number distribution of alkylbenzene sulfonic acid C 10 -C 45 is a mixture, wherein the content of alkylbenzene sulfonic acid with carbon number C 12 -C 20 accounts for 20-40% of the total content of alkylbenzene sulfonic acid, and the content of alkylbenzene sulfonic acid with carbon number C 20 -C 26 accounts for 5-20% of the total content of alkylbenzene sulfonic acid.

[0020] In the above solution, by reasonably limiting the type of calcium sulfonate and the carbon number distribution therein, it is more conducive to preparing a complex calcium sulfonate grease composition with excellent shear stability and extreme pressure and anti-wear performance.

[0021] Furthermore, the base oil is selected from one or more of polyalphaolefin oil, alkylnaphthalene base oil, ester oil, and polybutene; the polyalphaolefin oil is selected from one or more of PAO8, PAO10, and PAO40; the ester oil is selected from one or more of trimellitate, phthalate, and complex ester; and / or, the pour point of the base oil is not higher than -30 °C;

[0022] In the above solution, by selecting the above suitable type of base oil, it has a more excellent oxidation induction period compared with common base oils, and can significantly improve the grease life.

[0023] Preferably, the base oil is obtained by blending and compounding the polyalphaolefin oil and the ester oil or the polybutene, and the mass fraction of the polyalphaolefin oil is 30-60%.

[0024] Furthermore, the small molecule acid is selected from one or more of formic acid, glacial acetic acid, propionic acid, oxalic acid, succinic acid, boric acid, and monobasic aromatic acid;

[0025] and / or, the fatty acid is hydrogenated castor oil, cottonseed oil, 12-hydroxystearic acid, or stearic acid, preferably 12-hydroxystearic acid;

[0026] and / or, the additive includes an antioxidant.

[0027] In the above solution, by selecting suitable types of small molecule acids, fatty acids, and additives, these components can achieve better synergistic effects with calcium sulfonate, conversion promoter, surfactant, chitosan, calcium hydroxide, and base oil, and improve the overall performance of the complex calcium sulfonate grease composition.

[0028] According to the second aspect of the present invention, the present invention provides a method for preparing the above grease composition, including the following steps:

[0029] Step 1), mixing and stirring calcium sulfonate and base oil, and heating to 75-90 °C;

[0030] Step 2), mixing and stirring chitosan, surfactant, conversion promoter, and an appropriate amount of water, controlling the temperature between 80-85 °C, stirring and reacting for 1-8 h, and then adding to the mixture in Step 1) and stirring;

[0031] Step 3), adding small molecule acid, calcium hydroxide, and fatty acid, and stirring for 15-30 min;

[0032] Step 4), close the pressure relief valve, seal the reaction system, heat up to 105 - 130 °C, control the reaction pressure not exceeding 0.4 Mpa, and maintain for 30 - 360 min;

[0033] Step 5), open the pressure relief valve, continue to heat up to 150 - 200 °C and keep it constant for 10 - 15 min, then add the remaining base oil;

[0034] Step 6), when the temperature drops below 150 °C, add the additive, stir and then thicken it, and obtain the product after rolling oil.

[0035] In the preparation method of the above composite calcium sulfonate grease composition, by strictly controlling the addition sequence, reaction temperature and reaction time of each raw material, the finally obtained composite calcium sulfonate grease composition has excellent antibacterial properties, lubricity, extreme pressure and anti-wear properties, long-term storage stability, shear stability and other properties.

[0036] Further, in Step 2), the feeding sequence is: first add the conversion promoter, then add chitosan, stir for 10 - 30 min, and then add the surfactant pre-dissolved in water;

[0037] And / or, in Step 3), the addition sequence of the small molecule acid, calcium hydroxide and fatty acid is: first add the small molecule acid, stir for 5 - 10 min, then add calcium hydroxide, continue to stir for 5 - 10 min, and then add the fatty acid.

[0038] In the above solution, by strictly defining the feeding sequence in Steps 2) and 3), each step reaction can be made more sufficient, and the obtained composite calcium sulfonate grease composition has more excellent comprehensive properties.

[0039] The technical solution provided by the present invention has the following beneficial effects:

[0040] An antibacterial composite calcium sulfonate grease composition of the present invention introduces a cationic surfactant and chitosan, uses the conversion promoter in the preparation process of the composite calcium sulfonate grease composition as the solvent of chitosan, and utilizes the high temperature and high pressure in the autoclave process to form a water-soluble chitosan quaternary ammonium salt with antibacterial function, which can effectively improve the antibacterial effect of the grease, and is very suitable for industries such as ship transportation, food processing and medical devices, and has great practical application value and market prospect.

[0041] The preparation method of an antibacterial composite calcium sulfonate grease composition of the present invention adopts a preparation process and raw materials with special requirements. During the reaction process, a surfactant and chitosan are used to form chitosan quaternary ammonium salt, endowing the composite calcium sulfonate grease with antibacterial properties. By using the JIS Z2801 method, through antibacterial tests, it can be obtained that after introducing the above new components, the grease has antibacterial properties, and the antibacterial activity value can reach 2.5, meeting the antibacterial requirements. Detailed implementation manners

[0042] To make the objectives, technical solutions and advantages of the present invention clearer, the technical solutions in the present invention will be clearly and completely described below. Apparently, the described embodiments are some, but not all, of the embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without making creative efforts shall fall within the protection scope of the present invention.

[0043] In the present invention, instruments and the like not indicating the manufacturer can all be conventional products that can be obtained through regular channels. The raw materials used in the present invention can all be conveniently purchased in the domestic product market. In the analysis and testing of the embodiments of the present invention, the evaluation method for the antibacterial effect adopts JIS Z2801.

[0044] Embodiment 1

[0045] This embodiment provides an antibacterial composite calcium sulfonate grease composition, and its preparation raw materials include the following components in parts by weight:

[0046] Calcium sulfonate: 39 parts;

[0047] Conversion promoter: 1 part;

[0048] Surfactant: 1 part;

[0049] Chitosan: 0.1 part;

[0050] Small molecule acid: 0.5 part;

[0051] Fatty acid: 1 part;

[0052] Calcium hydroxide: 1 part;

[0053] Additive: 0.2 part;

[0054] Base oil: 56.2 parts;

[0055] Among them, the base oil is PAO40, the conversion promoter is 0.8 parts of isopropyl alcohol and 0.2 parts of n-butanol, the surfactant is 0.5 parts of dodecyl dimethyl benzyl ammonium chloride and 0.5 parts of polyoxyethylene sorbitan fatty acid ester, the small molecule acid is 0.3 parts of boric acid and 0.2 parts of acetic acid, the fatty acid is 12-hydroxy stearic acid, and the chitosan is selected from β-chitosan with a molecular weight between 1.5×10 4 ~6.7×10 4 and a deacetylation degree of not less than 86%, and the antioxidant is diphenylamine.

[0056] The preparation method of the above antibacterial composite calcium sulfonate grease composition is as follows:

[0057] Put the overbased synthetic calcium sulfonate with a base number of 405mg KOH / g (the content of alkyl benzene sulfonic acid with carbon number C 12 -C 20 is 25%, and the content of alkyl benzene sulfonic acid with carbon number C 20 -C 26 is 20%) and 40% of PAO40 into the reaction kettle for mixing, stir evenly, and heat up to 75-90°C; sequentially add the conversion promoter, chitosan, surfactant and 5-25% of water based on the total weight of the above preparation raw materials into the reaction kettle, heat up to 85-95°C, stir for 1-8h and then add it into the reaction kettle; then add the small molecule acid (diluted with 1 times of water), calcium hydroxide (diluted with 2 times of water) and fatty acid into the reaction kettle; close the pressure relief valve, seal the reaction kettle, heat up to 105-130°C, control the pressure at 0.2-0.3 Mpa, and keep the temperature constant for 120 min; open the pressure relief valve, release the pressure at a constant temperature, heat up to 150-200°C and keep the temperature constant for 10-15 min, and add the remaining base oil; when the temperature drops below 150°C, add the additive and stir for 0.5 h, then thicken to the appropriate penetration, and fill the finished product after rolling the oil three times with a three-roll mill. The sample is numbered A, and it is analyzed and tested, and the results are shown in Table 1.

[0058] Example 2

[0059] This example provides an antibacterial composite calcium sulfonate grease composition, and its preparation raw materials include the following components in parts by weight:

[0060] Calcium sulfonate: 37 parts;

[0061] Conversion promoter: 2 parts;

[0062] Surfactant: 2 parts;

[0063] Chitosan: 0.3 parts;

[0064] Small molecule acid: 1 part;

[0065] Fatty acid: 1.5 parts;

[0066] Calcium hydroxide: 1 part;

[0067] Additive: 0.5 part;

[0068] Base oil: 54.7 parts;

[0069] Among them, the base oil is PAO40, the conversion promoter is 1 part of isopropyl alcohol and 1 part of n-butanol, the surfactant is 1 part of dodecyldimethylbenzylammonium chloride and 1 part of polyoxyethylene sorbitan fatty acid ester, the small molecule acid is 0.4 part of boric acid and 0.6 part of acetic acid, the fatty acid is 12-hydroxystearic acid, and the chitosan is selected from β-chitosan with a molecular weight between 1.5×10 4 ~6.7×10 4 and a deacetylation degree of not less than 86%, and the additive is antioxidant diphenylamine.

[0070] The preparation method of the above antibacterial composite calcium sulfonate grease composition is as follows:

[0071] Put the overbased synthetic calcium sulfonate with a base number of 385mg KOH / g (the content of alkylbenzene sulfonic acid with carbon number C 12 -C 20 is 30% and the content of alkylbenzene sulfonic acid with carbon number C 20 -C 26 is 20%) and 40% of PAO40 into the reaction kettle for mixing, stir evenly, and heat up to 75-90°C; sequentially add the conversion promoter, chitosan, surfactant and 5-25% of water based on the total weight of the above preparation raw materials into the reaction kettle, heat up to 85-95°C, stir for 1-8h and then add it into the reaction kettle; then add the small molecule acid (diluted with 1 times of water), add calcium hydroxide (diluted with 2 times of water) and fatty acid into the reaction kettle; close the pressure relief valve, seal the reaction kettle, heat up to 105-130°C, control the pressure at 0.2-0.3 Mpa, and keep the temperature constant for 120 min; open the pressure relief valve, keep the temperature and relieve the pressure, heat up to 150-200°C and keep the temperature constant for 10-15 min, and add the remaining base oil; when the temperature drops below 150°C, add the additive and stir for 0.5 h, then thicken to the appropriate penetration, and fill the finished product after rolling the oil three times with a three-roll mill. The sample is numbered B and analyzed and tested, and the results are shown in Table 1.

[0072] Example 3

[0073] This example provides an antibacterial composite calcium sulfonate grease composition, and its preparation raw materials include the following components in parts by weight:

[0074] Calcium sulfonate: 32 parts;

[0075] Conversion promoter: 4 parts;

[0076] Surfactant: 3 parts;

[0077] Chitosan: 0.5 parts;

[0078] Small molecule acid: 2 parts;

[0079] Fatty acid: 2 parts;

[0080] Calcium hydroxide: 1.5 parts;

[0081] Additive: 1 part;

[0082] Base oil: 54 parts;

[0083] Among them, the base oil is PAO40, the conversion promoter is 3 parts of isopropyl alcohol and 1 part of n-butanol, the surfactant is 2 parts of dodecyldimethylbenzylammonium chloride and 1 part of polyoxyethylene sorbitan fatty acid ester, the small molecule acid is 1.5 parts of boric acid and 0.5 part of acetic acid, the fatty acid is 12-hydroxystearic acid, and the chitosan is selected from β-chitosan with a molecular weight between 1.5×10 4 ~6.7×10 4 and a deacetylation degree of not less than 86%, and the additive is antioxidant diphenylamine.

[0084] The preparation method of the above antibacterial composite calcium sulfonate grease composition is as follows:

[0085] Mix a high-base synthetic calcium sulfonate with a base number of 380 mg KOH / g (the content of alkylbenzene sulfonic acid with carbon number C 12 -C 20 is 25% and the content of alkylbenzene sulfonic acid with carbon number C 20 -C 26 is 20%) and 40% of PAO40 in a reaction kettle, stir evenly, and heat up to 75-90°C; sequentially add the conversion promoter, chitosan, surfactant and 5-25% of water based on the total weight of the above preparation raw materials into the reaction kettle, heat up to 85-95°C, stir for 1-8 h and then add it into the reaction kettle; then add small molecule acid (diluted with 1 times of water), add calcium hydroxide (diluted with 2 times of water) and fatty acid into the reaction kettle; close the pressure relief valve, seal the reaction kettle, heat up to 105-130°C, control the pressure at 0.2-0.3 Mpa, and keep the temperature constant for 120 min; open the pressure relief valve, relieve the pressure at a constant temperature, heat up to 150-200°C and keep the temperature constant for 10-15 min, and add the remaining base oil; when the temperature drops below 150°C, add the additive and stir for 0.5 h, then adjust the consistency to the appropriate penetration degree, and fill the finished product after rolling the oil three times with a three-roll mill. The sample is numbered C and analyzed and tested, and the results are shown in Table 1.

[0086] Example 4

[0087] This example provides an antibacterial composite calcium sulfonate grease composition, and its preparation raw materials include the following components in parts by weight:

[0088] Calcium sulfonate: 30 parts;

[0089] Conversion promoter: 6 parts;

[0090] Surfactant: 4 parts;

[0091] Chitosan: 1 part;

[0092] Small molecule acid: 3 parts;

[0093] Fatty acid: 2 parts;

[0094] Calcium hydroxide: 2 parts;

[0095] Additive: 1 part;

[0096] Base oil: 51 parts;

[0097] Among them, the base oil is PAO40, the conversion promoter is 5 parts of isopropyl alcohol and 1 part of n-butanol, the surfactant is 2 parts of dodecyl dimethyl benzyl ammonium chloride and 2 parts of polyoxyethylene sorbitan fatty acid ester, the small molecule acid is 2.5 parts of boric acid and 0.5 part of acetic acid, the fatty acid is 12-hydroxystearic acid, the chitosan is β-chitosan selected from those with a molecular weight between 1.5×10 4 ~6.7×10 4 and a deacetylation degree of not less than 86%, and the additive is antioxidant diphenylamine.

[0098] The preparation method of the above antibacterial composite calcium sulfonate grease composition is as follows:

[0099] Put the overbased synthetic calcium sulfonate with a base number of 400mg KOH / g (the content of alkylbenzene sulfonic acid with carbon number C 12 -C 20 is 25%, and the content of alkylbenzene sulfonic acid with carbon number C 20 -C 26 is 20%) and 40% of PAO40 into a reaction kettle for mixing, stir evenly, and heat up to 75-90°C; sequentially add the conversion promoter, chitosan, surfactant and 5-25% of water based on the total weight of the above preparation raw materials into the reaction kettle, heat up to 85-95°C, stir for 1-8h and then add it into the reaction kettle; then add small molecule acid (diluted with 1 times water), add calcium hydroxide (diluted with 2 times water) and fatty acid into the reaction kettle; close the pressure relief valve, seal the reaction kettle, heat up to 105-130°C, control the pressure at 0.2-0.3 Mpa, keep the temperature constant for 120 min; open the pressure relief valve, relieve the pressure at a constant temperature, heat up to 150-200°C and keep the temperature constant for 10-15 min, and add the remaining base oil; when the temperature drops below 150°C, add the additive and stir for 0.5 h, then adjust the consistency to the appropriate penetration degree, and fill the finished product after rolling the oil three times with a three-roll mill. The sample is numbered D and analyzed and tested, and the results are shown in Table 1.

[0100] Example 5

[0101] This example provides an antibacterial composite calcium sulfonate grease composition, and its preparation raw materials include the following components in parts by weight:

[0102] Calcium sulfonate: 29 parts;

[0103] Conversion promoter: 6 parts;

[0104] Surfactant: 4 parts;

[0105] Chitosan: 1 part;

[0106] Small molecule acid: 3.5 parts;

[0107] Fatty acid: 3 parts;

[0108] Calcium hydroxide: 2.5 parts;

[0109] Additive: 1 part;

[0110] Base oil: 50 parts;

[0111] Among them, the base oil is PAO40, the conversion promoter is 5 parts of isopropyl alcohol and 1 part of n-butanol, the surfactant is 2.5 parts of dodecyl dimethyl benzyl ammonium chloride and 1.5 parts of polyoxyethylene sorbitan ester, the small molecule acid is 3 parts of boric acid and 0.5 part of acetic acid, the fatty acid is 12-hydroxystearic acid, the chitosan is β-chitosan selected from those with a molecular weight between 1.5×10 4 ~6.7×10 4 and a deacetylation degree of not less than 86%, and the additive is antioxidant diphenylamine.

[0112] The preparation method of the above antibacterial composite calcium sulfonate grease composition is as follows:

[0113] High-base synthetic calcium sulfonate with a base number of 420mg KOH / g (alkylbenzene sulfonic acid with a carbon number of C 12 -C 20 has a content of 25%, and alkylbenzene sulfonic acid with a carbon number of C 20 -C 2620% of alkyl benzene sulfonic acid content and 40% of PAO40 are put into a reaction kettle and mixed, stirred evenly, and heated to 75 - 90 °C; a conversion promoter, chitosan, a surfactant, and 5 - 25% of water based on the total weight of the above - mentioned preparation raw materials are successively added to the reaction kettle, heated to 85 - 95 °C, stirred for 1 - 8 h and then added to the reaction kettle; subsequently, a small - molecule acid (diluted with 1 - fold water), calcium hydroxide (diluted with 2 - fold water), and fatty acid are added into the reaction kettle; the pressure - relief valve is closed, the reaction kettle is sealed, heated to 105 - 130 °C, the pressure is controlled at 0.2 - 0.3 Mpa, and kept at a constant temperature for 120 min; the pressure - relief valve is opened, the pressure is released at a constant temperature, heated to 150 - 200 °C and kept at a constant temperature for 10 - 15 min, and the remaining base oil is added; when the temperature drops below 150 °C, additives are added, stirred for 0.5 h, and then thickened to a suitable penetration degree, and the finished product is filled after rolling the oil three times with a three - roll mill. The sample is numbered E, and it is analyzed and tested, and the results are shown in Table 1.

[0114] Example 6

[0115] This example provides an antibacterial composite calcium sulfonate grease composition, and its preparation raw materials include the following components in parts by weight:

[0116] Calcium sulfonate: 26 parts;

[0117] Conversion promoter: 7 parts;

[0118] Surfactant: 3.5 parts;

[0119] Chitosan: 1 part;

[0120] Small - molecule acid: 3.5 parts;

[0121] Fatty acid: 4 parts;

[0122] Calcium hydroxide: 2.7 parts;

[0123] Additive: 1 part;

[0124] Base oil: 51.3 parts;

[0125] Among them, the base oil is PAO40, the conversion promoter is 5 parts of isopropyl alcohol and 2 parts of n - butyl alcohol, the surfactant is 2.5 parts of dodecyl dimethyl benzyl ammonium chloride and 1.0 part of polyoxyethylene sorbitan ester, the small - molecule acid is 3 parts of boric acid and 0.5 part of acetic acid, the fatty acid is 12 - hydroxystearic acid, the chitosan is β - chitosan selected from those with a molecular weight between 1.5×10 4 ~6.7×10 4 and a deacetylation degree of not less than 86%, and the additive is antioxidant diphenylamine.

[0126] The preparation method of the above - mentioned antibacterial composite calcium sulfonate grease composition is as follows:

[0127] The overbased synthetic calcium sulfonate with a base number of 420 mg KOH / g (the content of alkylbenzene sulfonic acid with carbon number C 12 -C 20 is 25%, and the content of alkylbenzene sulfonic acid with carbon number C 20 -C 26 is 20%) and 40% of PAO40 are put into a reaction kettle for mixing, stirred evenly, and heated to 75 - 90 °C; a conversion promoter, chitosan, a surfactant, and 5 - 25% of water based on the total weight of the above - prepared raw materials are successively added to the reaction kettle, heated to 85 - 95 °C, stirred for 1 - 8 h and then added to the reaction kettle; subsequently, a small - molecule acid (diluted with 1 - fold water), calcium hydroxide (diluted with 2 - fold water), and fatty acid are added into the reaction kettle; the pressure - relief valve is closed, the reaction kettle is sealed, heated to 105 - 130 °C, the pressure is controlled at 0.2 - 0.3 Mpa, and kept at a constant temperature for 120 min; the pressure - relief valve is opened, the pressure is released at a constant temperature, heated to 150 - 200 °C and kept at a constant temperature for 10 - 15 min, and the remaining base oil is added; when the temperature drops below 150 °C, additives are added and stirred for 0.5 h, and then thickened to a suitable penetration degree, and the finished product is filled after being rolled three times through a three - roll mill. The sample is numbered F, and it is analyzed and tested, and the results are shown in Table 1.

[0128] Example 7

[0129] This example provides an antibacterial composite calcium sulfonate grease composition, and its preparation raw materials include the following components in parts by weight:

[0130] Calcium sulfonate: 30 parts;

[0131] Conversion promoter: 8 parts;

[0132] Surfactant: 4 parts;

[0133] Chitosan: 1.5 parts;

[0134] Small - molecule acid: 4 parts;

[0135] Fatty acid: 4 parts;

[0136] Calcium hydroxide: 3 parts;

[0137] Additive: 1.5 parts;

[0138] Base oil: 44 parts;

[0139] Among them, the base oil is PAO40, the conversion promoter is 7 parts of isopropyl alcohol and 1 part of n - butyl alcohol, the surfactant is 3.0 parts of dodecyl dimethyl benzyl ammonium chloride and 1.0 part of polyoxyethylene sorbitan ester, the small - molecule acid is 3.0 parts of boric acid and 1.0 part of acetic acid, the fatty acid is 12 - hydroxystearic acid, and the chitosan is selected from those with a molecular weight of 1.5×10 4 ~6.7×104 Between, the degree of deacetylation of β-chitosan is not less than 86%, and the additive is antioxidant diphenylamine.

[0140] The preparation method of the above antibacterial composite calcium sulfonate grease composition is as follows:

[0141] Put medium-base synthetic calcium sulfonate with a base number of 165mg KOH / g (the content of alkylbenzene sulfonic acid with carbon number C 12 -C 20 is 25%, and the content of alkylbenzene sulfonic acid with carbon number C 20 -C 26 is 20%) and 40% of PAO40 into the reaction kettle for mixing, stir evenly, and heat up to 75-90°C; add a conversion promoter, chitosan, surfactant and 5-25% of water based on the total weight of the above preparation raw materials into the reaction kettle in turn, heat up to 85-95°C, stir for 1-8h and then add it into the reaction kettle; then add small molecule acid (diluted with 1 times water), calcium hydroxide (diluted with 2 times water) and fatty acid into the reaction kettle; close the pressure relief valve, seal the reaction kettle, heat up to 105-130°C, control the pressure at 0.2-0.3 Mpa, keep the temperature constant for 120 min; open the pressure relief valve, relieve the pressure at a constant temperature, heat up to 150-200°C and keep the temperature constant for 10-15 min, and add the remaining base oil; when the temperature drops below 150°C, add the additive and stir for 0.5h, then thicken to the appropriate penetration, and fill the finished product after rolling the oil three times with a three-roll mill. The sample is numbered G, and it is analyzed and tested. The results are shown in Table 1.

[0142] Example 8

[0143] This example provides an antibacterial composite calcium sulfonate grease composition, which is different from Example 1 in that this example uses α-chitosan instead of β-chitosan. The sample is numbered H, and it is analyzed and tested. The results are shown in Table 1.

[0144] Example 9

[0145] This example provides an antibacterial composite calcium sulfonate grease composition, which is different from Example 1 in that this example uses γ-chitosan instead of β-chitosan. The sample is numbered I, and it is analyzed and tested. The results are shown in Table 1.

[0146] Example 10

[0147] This example provides an antibacterial composite calcium sulfonate grease composition, which is different from Example 1 in that this example uses cetyltrimethylammonium bromide instead of dodecyldimethylbenzylammonium chloride. The sample is numbered J, and it is analyzed and tested. The results are shown in Table 1.

[0148] Example 11

[0149] This embodiment provides an antibacterial composite calcium sulfonate grease composition, which is different from that of Example 1 in that this embodiment uses dodecyl betaine to replace dodecyl dimethyl benzyl ammonium chloride. The sample is numbered K, and it is analyzed and tested. The results are shown in Table 1.

[0150] Comparative Example 1

[0151] This comparative example provides a grease composition, and its preparation raw materials include the following components in parts by weight:

[0152] Calcium sulfonate: 40 parts;

[0153] Conversion promoter: 2 parts;

[0154] Small molecule acid: 5 parts;

[0155] Fatty acid: 3 parts;

[0156] Calcium hydroxide: 1 part;

[0157] Antioxidant: 1.5 parts;

[0158] Base oil: 47.5 parts;

[0159] Among them, the base oil is PAO40, the conversion promoter is n-butanol, the small molecule acid is 3 parts of boric acid and 2 parts of acetic acid, the fatty acid is 12-hydroxy stearic acid, and the antioxidant is diphenylamine.

[0160] The preparation method is as follows: Put the overbased synthetic calcium sulfonate with a base number of 420 mg KOH / g (the content of alkylbenzene sulfonic acid with carbon number C 15 -C 30 is 50%) and 40% of PAO40 and 10-20% of water based on the total weight of the above preparation raw materials into the reaction kettle and mix, stir evenly, and heat up to 75-95 °C; add small molecule acid (diluted 2-3 times with water), stir for 5 min and then add the conversion promoter, stir, and keep the temperature constant at 75-95 °C for 1-2 hours; then control the temperature to 90-100 °C, add calcium hydroxide (pre-diluted with 1-3 times of water), stir for 10 min and then add fatty acid, and keep for 30-90 min; heat up to 110-140 °C, keep for 20-30 min, continue to heat up to 150-200 °C and keep constant for 10-15 min, and add the remaining base oil; when the temperature drops below 150 °C, add the additive and stir for 0.5 h, then thicken to the appropriate penetration degree, and fill the finished product after rolling the oil three times with a three-roll mill. The sample is numbered L, and it is analyzed and tested. The results are shown in Table 1.

[0161] Comparative Example 2

[0162] This comparative example provides a grease composition, and its preparation raw materials include the following components in parts by weight:

[0163] Calcium sulfonate: 40 parts;

[0164] Conversion promoter: 2 parts;

[0165] Small molecule acid: 3 parts;

[0166] Fatty acid: 5 parts;

[0167] Calcium hydroxide: 3 parts;

[0168] Antioxidant: 1.5 parts;

[0169] Base oil: 45.5 parts;

[0170] Among them, the base oil is PAO40, the conversion promoter is n-butanol, the small molecule acid is 1 part of boric acid and 2 parts of acetic acid, the fatty acid is 12-hydroxystearic acid, and the antioxidant is diphenylamine.

[0171] The preparation method is as follows: Put the overbased synthetic calcium sulfonate with a base number of 395 mg KOH / g (the content of alkylbenzene sulfonic acid with carbon number C 15 -C 30 is 50%), 40% of PAO40 and 10-20% of water based on the total weight of the above preparation raw materials into the reaction kettle for mixing, stir evenly, and heat up to 75-95°C; add small molecule acid (diluted 2-3 times with water), stir for 5 min and then add the conversion promoter, stir, and keep the temperature constant at 75-95°C for 1-2 hours; then control the temperature to 90-100°C, add calcium hydroxide (pre-diluted 1-3 times with water), stir for 10 min and then add the fatty acid, and keep it for 30-90 min; heat up to 110-140°C, keep it for 20-30 min, continue to heat up to 150-200°C and keep it constant for 10-15 min, and add the remaining base oil; when the temperature drops below 150°C, add the additive and stir for 0.5 h, then thicken to the appropriate penetration, and fill the finished product after rolling the oil three times with a three-roll mill. The sample is numbered M, and it is analyzed and tested. The results are shown in Table 1.

[0172] Table 1 Comparison of analysis and test data of each example and comparative example

[0173]

[0174] Table 2 Comparison of antibacterial test data of each example and comparative example

[0175]

[0176] By comparing the data in Table 1, the following conclusions can be drawn: From the extended cone penetration test, it can be seen that the calcium sulfonate complex grease composition of the present invention has excellent shear stability; from the extreme pressure performance test and anti-wear performance test, it can be seen that the calcium sulfonate complex grease composition of the present invention has good extreme pressure and anti-wear performance; using the JIS Z2801 test method, from the antibacterial test in Table 2, it can be seen that the calcium sulfonate complex grease composition of the present invention has good antibacterial performance and can play an antibacterial role in lubricating parts such as ship transportation, food processing, and medical devices.

[0177] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. An antibacterial composite calcium sulfonate grease composition, characterized in that, The raw materials for preparing the grease composition include the following components in parts by weight: Calcium sulfonate: 15 - 40 parts; Conversion promoter: 1 - 8 parts; Surfactant: 1 - 4 parts; Chitosan: 0.1 - 1.5 parts; Small molecule acid: 0.5 - 4 parts; Fatty acid: 1 - 4 parts; Calcium hydroxide: 1 - 3 parts; Additive: 0.2 - 1.5 parts; Base oil: 44 - 57 parts; The surfactant consists of a cationic surfactant and a non-ionic surfactant; the cationic surfactant is a quaternary ammonium salt; the non-ionic surfactant is a polyoxyethylene type surfactant and / or a fatty acid polyol ester; the conversion promoter is selected from one or more alcohol compounds such as methanol, ethanol, propylene glycol, n-butanol, hexanol, and hexanediol and isopropanol; in the conversion promoter, isopropanol accounts for 40 - 90% of the volume of the conversion promoter; The chitosan is selected from β-chitosan with a molecular weight between 1.5×10 4 ~6.7×10 4 and a deacetylation degree of not less than 86%. The cationic surfactant accounts for 50 - 90% of the total weight of the surfactant; The preparation method of the grease composition includes the following steps: Step 1), mix and stir calcium sulfonate and base oil, and heat up to 75 - 90 °C; Step 2), mix and stir chitosan, surfactant, conversion promoter and appropriate amount of water, control the temperature between 80 - 85 °C, stir and react for 1 - 8 h, then add to the mixture in Step 1) and stir; Step 3), add small molecule acid, calcium hydroxide and fatty acid, and stir for 15 - 30 min; Step 4), close the pressure relief valve, seal the reaction system, heat up to 105 - 130 °C, control the reaction pressure not exceeding 0.4 Mpa, and maintain for 30 - 360 min; Step 5), open the pressure relief valve, continue to heat up to 150 - 200 °C and keep it constant for 10 - 15 min, and add the remaining base oil; Step 6), when the temperature drops below 150 °C, add the additive, stir and thicken, and obtain the product after rolling oil.

2. The grease composition according to claim 1, wherein The cationic surfactant is one or more of cetyltrimethylammonium bromide, dodecyldimethylbenzylammonium chloride, p-alkylphenyltrimethylammonium chloride, and 2,3-epoxypropyltrimethylammonium chloride; the non-ionic surfactant is one or two of polyoxyethylene sorbitan ester and polyethyleneglycol octylphenyl ether.

3. The grease composition according to claim 1, characterized in that, The calcium sulfonate is a high-base synthetic calcium sulfonate.

4. The grease composition according to claim 3, characterized in that, The total base number of the calcium sulfonate is 155 - 425 mgKOH / g.

5. The grease composition according to claim 3 or 4, characterized in that, The carbon number distribution C of alkylbenzene sulfonic acid in the overbased synthetic calcium sulfonate 10 -C 45 in the mixture, wherein the content of alkylbenzene sulfonic acid with carbon number C 12 -C 20 accounts for 20-40% of the total weight of alkylbenzene sulfonic acid, and the content of alkylbenzene sulfonic acid with carbon number C 20 -C 26 accounts for 5-20% of the total weight of alkylbenzene sulfonic acid.

6. The grease composition according to claim 1, characterized in that, The base oil is selected from one or more of polyalphaolefin oil, alkylnaphthalene base oil, ester oil, and polybutene; the polyalphaolefin oil is selected from one or more of PAO8, PAO10, and PAO40; the ester oil is selected from one or more of trimellitate, phthalate, and complex ester; and / or, the pour point of the base oil is not higher than -30 °C.

7. The grease composition according to claim 6, characterized in that, The base oil is obtained by blending and compounding the polyalphaolefin oil and the ester oil or the polybutene, and the mass fraction of the polyalphaolefin oil is 30 - 60%.

8. The grease composition according to claim 1, wherein The small molecule acid is selected from one or more of formic acid, glacial acetic acid, propionic acid, oxalic acid, succinic acid, boric acid, and monobasic aromatic acid; and / or, the fatty acid is hydrogenated castor oil, cottonseed oil, 12-hydroxystearic acid, or stearic acid; And / or, the additive includes an antioxidant.

9. The grease composition according to claim 8, wherein, The fatty acid is 12-hydroxy stearic acid.

10. A method for preparing the grease composition according to any one of claims 1-9, characterized in that, It includes the following steps: Step 1), mix and stir calcium sulfonate and base oil, and heat up to 75 - 90 °C; Step 2), mix and stir chitosan, surfactant, conversion promoter and appropriate amount of water, control the temperature between 80 - 85 °C, after stirring and reacting for 1 - 8 h, add it to the mixture in Step 1), and stir; Step 3), add small molecule acid, calcium hydroxide and fatty acid, and stir for 15 - 30 min; Step 4), close the pressure relief valve, seal the reaction system, heat up to 105 - 130 °C, control the reaction pressure not exceeding 0.4 Mpa, and keep it for 30 - 360 min; Step 5), open the pressure relief valve, continue to heat up to 150 - 200 °C and keep it at a constant temperature for 10 - 15 min, and add the remaining base oil; Step 6), when the temperature drops below 150 °C, add the additive, stir and thicken, and obtain the product after rolling oil.

11. The preparation method according to claim 10, wherein, In Step 2), the feeding order is: first add the conversion promoter, then add chitosan, stir for 10 - 30 min, and then add the surfactant pre-dissolved in water; And / or, in Step 3), the order of adding small molecule acid, calcium hydroxide and fatty acid is: first add small molecule acid, stir for 5 - 10 min, then add calcium hydroxide, continue to stir for 5 - 10 min, and then add fatty acid.

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