Long-acting rust preventive oil and its preparation method

Abstract

The application discloses a long-acting rust-proof oil and a preparation method thereof. The long-acting rust-proof oil comprises the following components in percentage by mass: base oil 50-80%, solvent 10-30%, cashew phenol-based polyether sulfate metal salt composite rust-proof agent 5-15%, film forming agent 1-3%, and auxiliary agent 1-3%. The rust-proof oil does not use traditional petroleum sulfonate rust-proof agents, but uses a cashew phenol-based polyether sulfate metal salt composite rust-proof agent, has excellent rust-proof performance, and has the characteristics of low cost and biodegradability.

Description

Technical Field

[0001] This invention belongs to the field of rust-preventive oil technology, and specifically relates to a long-lasting rust-preventive oil and its preparation method. Background Technology

[0002] Metal corrosion causes enormous losses and damage to social production and daily life. In industrial production and metal processing, rust-preventive oils containing oil-soluble corrosion inhibitors are often used to prevent metal from rusting. Rust-preventive oils consist of base oils and rust-preventive additives. The performance of rust-preventive additives plays a decisive role in the rust-preventive performance of solvent-based rust-preventive oils, and most of them are added to the base oil at a concentration of 5% to 15%.

[0003] Petroleum sulfonates were selected as corrosion inhibitors as early as the 1930s and remain one of the preferred oil-soluble rust inhibitors today, with typical addition levels in domestic rust-preventive greases below 10%. However, existing sulfonates have poor demulsification properties, are prone to decomposition in water, and their poor stability significantly limits their application. Furthermore, with the global resource and ecological crisis, petroleum prices are soaring, leading to increased costs for fine chemicals. In addition, the widespread use of petroleum sulfonates and other petrochemical products in the market pollutes the environment during raw material production processes and is difficult to degrade in nature after use.

[0004] Cashew nut shell extract, derived from cashew nut shells, is biodegradable and serves as an intermediate for green and environmentally friendly materials. Cashew nut shell polyether sulfate metal salt is obtained by modifying cashew nut shell, offering advantages such as low cost, environmental friendliness, and renewable raw material availability. Similar to petroleum sulfonates, which are commonly used in surfactants, the emulsifying properties of cashew nut shell and its derivatives in surfactant products have been reported. As an oil-water system surfactant, cashew nut shell polyether sulfate metal salt is suitable for applications in detergents and oil displacement agents, but there are no reports of its application in rust prevention. Summary of the Invention

[0005] To address the aforementioned technical problems, the present invention aims to provide a long-lasting rust-preventive oil and its preparation method. This rust-preventive oil does not use traditional petroleum sulfonate rust inhibitors, but instead employs a cashew phenol-based polyether sulfate metal salt composite rust inhibitor, exhibiting excellent rust-preventive performance while also being low-cost and biodegradable.

[0006] To achieve the above-mentioned technical objectives and effects, the present invention is implemented through the following technical solution:

[0007] This invention provides a long-lasting rust-preventive oil, comprising the following components by weight percentage: 50-80% base oil, 10-30% solvent, 5-15% cashew phenol-based polyether sulfate metal salt composite rust inhibitor, 1-3% film-forming agent, and 1-3% additives.

[0008] Wherein, the cashew phenolic sulfate metal salt composite rust inhibitor is one or a mixture of two or more of the cashew phenol polyether sulfate metal salt shown in formula (I-1) or formula (I-2) and the cashew phenol Gemini polyether sulfate metal salt shown in formula (II-1) or formula (II-2); in formula (I-1) or formula (I-2), the group R is a long-chain hydrocarbon with different saturation containing 15 carbons, M1 is one of the metals K, Ca, Mg, and Ba, and n1 is a positive integer between 1 and 10; in formula (II-1) or formula (II-2), M2 is one of the metals K, Ca, Mg, and Ba, and n2 is a positive integer between 1 and 10;

[0009]

[0010]

[0011] Furthermore, the cashew phenol polyether sulfate metal salt shown in formula (I-1) or formula (I-2) is prepared by using cashew phenol as raw material, modifying it with polyoxyethylene or polyoxypropylene, reacting it with aminosulfonic acid to obtain cashew phenol-based polyether ammonium sulfate, and finally neutralizing it.

[0012] Furthermore, the preparation process of cashew phenol Gemini polyether sulfate metal salt shown in formula (II-1) or formula (II-2) is as follows: cashew phenol is used as raw material, and after copolymerization with formaldehyde, it is modified by polyoxyethylene or polyoxypropylene to obtain cashew phenol-based Gemini polyoxyethylene ether or polyoxypropylene ether. Then, after sulfonation reaction, cashew phenol-based Gemini polyoxyethylene ether sulfate ammonium or cashew phenol-based Gemini polyoxypropylene ether sulfate ammonium is obtained. Finally, cashew phenol Gemini polyether sulfate metal salt is obtained by neutralization reaction.

[0013] Preferably, the base oil is one or a mixture of two or more of mineral oil, synthetic oil, or hydrocarbon solvent oil.

[0014] Preferably, the solvent is selected from one or a mixture of two or more of ethylene glycol methyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol propyl ether, propylene glycol butyl ether, diethylene glycol methyl ether, dipropylene glycol methyl ether, and dipropylene glycol butyl ether.

[0015] Preferably, the additive is one or a mixture of two or more of the following: thickener, antioxidant, and defoamer.

[0016] Preferably, the film-forming agent is selected from one or a mixture of two or more of oxidized wax esters, acrylic resins, and petroleum resins.

[0017] The antioxidant is selected from one or a mixture of two or more of benzotriazole, N-phenyl-α-naphthylamine, 2,6-di-tert-butyl-4-methylphenol (BHT), butylated hydroxyanisole, and butylated hydroxytoluene.

[0018] The thickener is selected from one or a mixture of two or more of polyacrylic acid, polytetrafluoroethylene, and polyacrylamide.

[0019] The defoamer is preferably a polydimethylsiloxane defoamer.

[0020] Another aspect of the present invention provides a method for preparing the long-lasting rust-preventive oil, comprising the following steps:

[0021] (1) Pour the base oil into the reaction vessel, heat and stir. After the temperature rises to 60-80℃, add the solvent, additives and cashew phenolic polyether sulfate metal salt composite rust inhibitor into the reaction vessel in sequence and mix.

[0022] (2) The reaction vessel after step (1) is heated to 80-150°C and stirred thoroughly to completely dissolve the mixture;

[0023] (3) When the reaction vessel after step (2) is cooled to 60-70°C at room temperature, the film-forming agent is slowly added and stirred thoroughly to obtain the rust-preventive oil;

[0024] (4) Pour the rust-preventive oil obtained in step (3) into the packaging machine and seal it after filling.

[0025] The beneficial effects of this invention are:

[0026] The rust-preventive oil of this invention does not use traditional petroleum sulfonate rust inhibitors, but instead uses a cashew phenol-based polyether sulfate metal salt composite rust inhibitor, which has excellent rust-preventive performance, and is also low in cost and biodegradable.

[0027] Specifically, the cashew phenol-based polyether sulfate metal salt added to the rust-preventive oil of the present invention has high-temperature resistance. It contains benzene rings and long carbon chains with double bonds, which can endow the system with excellent toughness and oleophilicity, making it stable in the rust-preventive oil system. Moreover, the cashew phenol Gemini polyether sulfate metal salt is formed by the reaction of cashew phenol with formaldehyde to form Gemini dimers, which further enhances its hydrophobic properties, increases molecular polarity, increases adsorption force on metal surfaces, and enhances the rust-preventive protection effect.

[0028] The cashew phenol-based polyether sulfate metal salt used in this invention has enhanced polarity through polyoxyethylene ether modification of the phenolic hydroxyl chain, further enhancing its adsorption force on the metal surface. It can form a tight monomolecular or multimolecular protective layer on the metal surface, which can prevent corrosive media from contacting the metal. In addition, its certain hydrophilicity can solubilize water and some corrosive substances, solubilizing them in micelles, thereby dispersing or deactivating corrosive substances and eliminating the corrosion of metal by corrosive substances.

[0029] This invention utilizes bio-based cashew nut shell extract to replace petroleum-based refined chemical products, reducing dependence on petrochemical raw materials while also being environmentally friendly. At the same time, the rust-preventive oil produced by this invention is inexpensive, giving it a strong competitive advantage in the market. Detailed Implementation

[0030] The technical solutions of the present invention will be clearly and completely described below with reference to specific embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0031] This invention provides a long-lasting rust-preventive oil, comprising the following components by weight percentage: 50-80% base oil, 10-30% solvent, 5-15% cashew phenol-based polyether sulfate metal salt composite rust inhibitor, 1-3% film-forming agent, and 1-3% additives.

[0032] The cashew phenolic sulfate metal salt composite rust inhibitor is one or a mixture of two or more of the cashew phenol polyether sulfate metal salt shown in formula (I-1) or formula (I-2) and the cashew phenol Gemini polyether sulfate metal salt shown in formula (II-1) or formula (II-2).

[0033]

[0034] In formula (I-1) or formula (I-2), group R is a long-chain hydrocarbon with different degrees of saturation containing 15 carbons, M1 is one of the metals K, Ca, Mg, and Ba, and n1 is a positive integer between 1 and 10; R may preferably be one of the following groups:

[0035]

[0036] In formula (Ⅱ-1) or formula (Ⅱ-2), M2 is one of the metals K, Ca, Mg, and Ba, and n2 is a positive integer between 1 and 10;

[0037] Among them, the cashew phenol polyether sulfate metal salt shown in formula (I-1) or formula (I-2) is prepared by using cashew phenol as raw material, modifying it with polyoxyethylene or polyoxypropylene, reacting it with aminosulfonic acid to obtain cashew phenol-based polyether ammonium sulfate, and finally neutralizing it.

[0038] The preparation process of cashew phenol Gemini polyether sulfate metal salt as shown in formula (II-1) or formula (II-2) is as follows: cashew phenol is used as raw material, and after copolymerization with formaldehyde, it is modified by polyoxyethylene or polyoxypropylene to obtain cashew phenol-based Gemini polyoxyethylene ether or polyoxypropylene ether. Then, after sulfonation reaction, cashew phenol-based Gemini polyoxyethylene ether sulfate ammonium or cashew phenol-based Gemini polyoxypropylene ether sulfate ammonium is obtained. Finally, cashew phenol Gemini polyether sulfate metal salt is obtained by neutralization reaction.

[0039] The base oil is one or a mixture of two or more of mineral oil, synthetic oil, or hydrocarbon solvent oil.

[0040] The solvent is selected from one or a mixture of two or more of ethylene glycol methyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol propyl ether, propylene glycol butyl ether, diethylene glycol methyl ether, dipropylene glycol methyl ether, and dipropylene glycol butyl ether.

[0041] The additive is one or a mixture of two or more of the following: thickener, antioxidant, and defoamer.

[0042] The film-forming agent in the rust-preventive oil is selected from one or more of the following: oxidized wax esters, acrylic resins, and petroleum resins.

[0043] The antioxidant is selected from one or a mixture of two or more of benzotriazole, N-phenyl-α-naphthylamine, 2,6-di-tert-butyl-4-methylphenol (BHT), butylated hydroxyanisole, and butylated hydroxytoluene.

[0044] The thickener is selected from one or a mixture of two or more of polyacrylic acid, polytetrafluoroethylene, and polyacrylamide.

[0045] The defoamer is preferably a polydimethylsiloxane defoamer.

[0046] The preparation method of this long-lasting rust-preventive oil includes the following steps:

[0047] (1) Pour the base oil into the reaction vessel, heat and stir. After the temperature rises to 60-80℃, add the solvent, additives and cashew phenolic polyether sulfate metal salt composite rust inhibitor into the reaction vessel in sequence and mix.

[0048] (2) The reaction vessel after step (1) is heated to 80-150°C and stirred thoroughly to completely dissolve the mixture for 1-2 hours;

[0049] (3) When the reaction vessel after step (2) is cooled to 60-70°C at room temperature, the film-forming agent is slowly added and stirred thoroughly to obtain the rust-preventive oil;

[0050] (4) Pour the rust-preventive oil obtained in step (3) into the packaging machine, and after filling and sealing, obtain the rust-preventive oil product, and then store it in a cool place.

[0051] To further illustrate the present invention, the following describes in detail, with reference to embodiments, a long-lasting rust-preventive oil and its preparation method provided by the present invention.

[0052] The preparation method of barium cashew phenol Gemini polyether sulfate used in the examples is as follows:

[0053] 15.2 g of saturated cashew phenol (a saturated long-chain hydrocarbon containing 15 carbons) and 30 mL of cyclohexane were placed in a three-necked flask and stirred under nitrogen atmosphere until the temperature reached 50 °C. Then, a mixture of 2.5 g of 37% formaldehyde solution and 1.6 g of 35.4% hydrochloric acid solution was added dropwise. After the addition was complete, the temperature was raised to 85 °C, and the reaction was refluxed and condensed under nitrogen atmosphere until the amount of water separated in the separator remained constant. The reaction was then stopped, and the mixture was distilled under reduced pressure to obtain the product.

[0054] A certain amount of the above product and catalyst KOH (mass fraction of 5% in the reactants) were heated to (100±5)℃ in a high-pressure reactor, and the pressure was evacuated to -0.08MPa using a vacuum pump. The pipeline and reactor were purged twice with nitrogen. The temperature was stirred and raised to (120±5)℃. A certain amount of ethylene oxide or propylene oxide was slowly added, and the reaction temperature was controlled at (130±5)℃. When the pressure inside the reactor no longer changed, the product was cooled and discharged to obtain cashew phenol Gemini polyether.

[0055] Cashew phenol Gemini polyether was mixed thoroughly with urea (mass fraction 1.5–2.5%) to obtain a mixed solution. Sulfamic acid was added to the mixed solution at a molar ratio of 1.8–2.2 to the cashew phenol Gemini polyether, and the mixture was stirred at 150°C and atmospheric pressure for 4–8 hours. Barium hydroxide was then added to the solution, and the mixture was stirred at 150°C and atmospheric pressure for 2 hours. The resulting solution was dried and centrifuged to obtain the cashew phenol Gemini polyether barium sulfate salt.

[0056] The preparation method of cashew phenol polyether sulfate calcium salt is as follows:

[0057] Commercially available cashew phenol ethylene oxide (or propane) and urea (mass fraction 1.5–2.5%) were mixed thoroughly to obtain a mixed solution. Aminosulfonic acid was added to the mixed solution at a molar ratio of 0.9–1.1 to the cashew phenol ethylene oxide (or propane), and the mixture was stirred at 150°C and atmospheric pressure for 4–8 hours. Calcium hydroxide was added to the solution, and the mixture was stirred at 150°C and atmospheric pressure for 2 hours. The resulting solution was dried and centrifuged to obtain the cashew phenol polyether sulfate calcium salt.

[0058] The preparation method for barium cashew phenol polyether sulfate is the same as described above.

[0059] Example 1

[0060] 70% of the total solvent oil D60 was poured into the reaction vessel, heated and stirred. After the temperature rose to 60°C, 11% diethylene glycol methyl ether, 1.5% benzotriazole, 0.4% polytetrafluoroethylene (Teflon PTFE), 0.1% polydimethylsiloxane (Foam Star SI 2210), and 15% barium salt of cashew phenol Gemini polyether sulfate were added to the reaction vessel and mixed. The temperature was raised to 80°C and stirred thoroughly for 1-2 hours. After cooling to 60°C at room temperature, 2% of oxidized wax ester (Lubrizol 2148) was slowly added and stirred thoroughly to obtain the rust-preventive oil.

[0061] Example 2

[0062] 70% of the total solvent oil D60 was poured into the reaction vessel, heated and stirred. After the temperature rose to 60°C, 13% diethylene glycol methyl ether, 1.5% butylated hydroxytoluene, 0.4% polytetrafluoroethylene (Teflon PTFE), 0.1% polydimethylsiloxane (Foam Star SI 2210), and 13% cashew phenol Gemini polyether sulfate calcium salt were added to the reaction vessel and mixed. The temperature was raised to 100°C and stirred thoroughly for 1-2 hours. After cooling to 70°C at room temperature, 2% of oxidized wax ester (TLOY 2108s) was slowly added and stirred thoroughly to obtain the rust-preventive oil.

[0063] Example 3

[0064] 60% of the total solvent oil D60 was poured into the reactor and heated with stirring. After the temperature rose to 80°C, 25% diethylene glycol methyl ether, 1.5% benzotriazole, 0.4% polytetrafluoroethylene (Teflon), 0.1% polydimethylsiloxane (Foam Star SI 2210), 6% barium cashew nut shell phenolate (Gemini) polyether sulfate, and 6% calcium cashew nut shell phenolate (Gemini) polyether sulfate were added to the reactor and mixed. The temperature was raised to 120°C and stirred thoroughly for 1–2 hours. After cooling to 60°C at room temperature, 1% of oxidized wax ester TLOY was slowly added.

[0065] Stir thoroughly for 2108 seconds to obtain rust-preventive oil.

[0066] Example 4

[0067] 60% of the total solvent oil D60 was poured into a reaction vessel, heated and stirred. After the temperature rose to 80°C, 25% diethylene glycol methyl ether, 1.5% butylated hydroxytoluene, 0.4% polytetrafluoroethylene (Teflon) PTFE, 0.1% polydimethylsiloxane (Foam Star SI 2210), and 12% barium salt of cashew phenol polyether sulfate were added to the reaction vessel and mixed. The temperature was raised to 120°C and stirred thoroughly for 1-2 hours. After cooling to 60°C at room temperature, 1% of oxidized wax ester TLOY2108s was slowly added and stirred thoroughly to obtain the rust-preventive oil.

[0068] Example 5

[0069] 55% of the total solvent oil D60 was poured into a reaction vessel, heated and stirred. After the temperature rose to 70°C, 25% diethylene glycol methyl ether, 1.5% benzotriazole, 0.3% polytetrafluoroethylene (Teflon) PTFE, 0.2% polydimethylsiloxane (Foam Star SI 2210), and 15% cashew phenol polyether sulfate calcium salt were added to the reaction vessel and mixed. The temperature was raised to 120°C and stirred thoroughly for 1-2 hours. After cooling to 60°C at room temperature, 3% of oxidized wax ester TLOY 2108s was slowly added and stirred thoroughly to obtain the rust-preventive oil.

[0070] Comparative Example 1

[0071] 70% of the total solvent oil D60 was poured into a reaction vessel, heated and stirred. After the temperature rose to 60°C, 11% diethylene glycol methyl ether, 1.5% butylated hydroxytoluene, 0.4% polytetrafluoroethylene (Teflon) PTFE, 0.1% polydimethylsiloxane (Foam Star SI 2210), and 15% barium dinonylnaphthalene sulfonate (T705A) were added to the reaction vessel in sequence and mixed. The temperature was raised to 80°C and stirred thoroughly for 1-2 hours. After cooling to 60°C at room temperature, 2% of oxidized wax ester (TLOY 2108s) was slowly added and stirred thoroughly to obtain the rust-preventive oil.

[0072] Comparative Example 2

[0073] 65% of the total solvent oil D60 was poured into a reaction vessel, heated and stirred. After the temperature rose to 60°C, 16% diethylene glycol methyl ether, 1.5% butylated hydroxytoluene, 0.4% polytetrafluoroethylene (Teflon) PTFE, 0.1% polydimethylsiloxane (Foam Star SI 2210), and 15% barium petroleum sulfonate (T701) were added to the reaction vessel in sequence and mixed. The temperature was raised to 80°C and stirred thoroughly for 1-2 hours. After cooling to 60°C at room temperature, 2% of TLOY 2108s oxidized wax ester was slowly added and stirred thoroughly to obtain the rust-preventive oil.

[0074] The performance of the rust-preventive oils obtained in the above embodiments and comparative examples was tested, and the test results are shown in Table 1 below:

[0075] Table 1. Test results of rust-preventive oil performance in each embodiment and comparative example.

[0076]

[0077] As shown in Table 1, the rust-preventive oil of the present invention has better rust-preventive effect than Comparative Example 1 and Comparative Example 2 under humid heat and salt spray conditions, indicating that the rust-preventive oil of the present invention has a superior rust-preventive effect.

[0078] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

[0079] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A long-lasting rust-preventive oil, characterized in that, The product comprises the following components by weight percentage: 50-80% base oil, 10-30% solvent, 5-15% cashew nut phenol-based polyether sulfate metal salt composite rust inhibitor, 1-3% film-forming agent, and 1-3% additives; wherein the additives are one or a mixture of two or more of thickeners, antioxidants, and defoamers; and the base oil is a hydrocarbon solvent oil. The cashew phenol-based polyether sulfate metal salt composite rust inhibitor is one or a mixture of two or more cashew phenol Gemini polyether sulfate metal salts shown in formula (Ⅱ-1) or formula (Ⅱ-2); in formula (Ⅱ-1) or formula (Ⅱ-2), M2 is one of the metals K, Ca, Mg, and Ba, and n2 is a positive integer between 1 and 10. 。 2. The long-lasting rust-preventive oil according to claim 1, characterized in that, The preparation process of cashew phenol Gemini polyether sulfate metal salt shown in formula (II-1) or formula (II-2) is as follows: cashew phenol is used as raw material, and after copolymerization with formaldehyde, it is modified by polyoxyethylene or polyoxypropylene to obtain cashew phenol-based Gemini polyoxyethylene ether or polyoxypropylene ether. Then, after sulfonation reaction, cashew phenol-based Gemini polyoxyethylene ether sulfate ammonium or cashew phenol-based Gemini polyoxypropylene ether sulfate ammonium is obtained. Finally, cashew phenol Gemini polyether sulfate metal salt is obtained by neutralization reaction.

3. The long-lasting rust-preventive oil according to claim 1, characterized in that, The solvent is selected from one or a mixture of two or more of ethylene glycol methyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol propyl ether, propylene glycol butyl ether, diethylene glycol methyl ether, dipropylene glycol methyl ether, and dipropylene glycol butyl ether.

4. A method for preparing the long-lasting rust-preventive oil according to any one of claims 1-3, characterized in that, Includes the following steps: (1) Pour the base oil into the reactor, heat and stir. After the temperature rises to 60-80°C, add the solvent, additives and cashew phenolic polyether sulfate metal salt composite rust inhibitor into the reactor in sequence and mix. (2) The reaction vessel after step (1) is heated to 80-150°C and stirred thoroughly to completely dissolve the mixture; (3) When the reaction vessel after step (2) is cooled to 60-70°C at room temperature, the film-forming agent is slowly added and stirred thoroughly to obtain the rust-preventive oil; (4) Pour the rust-preventive oil obtained in step (3) into the packaging machine and seal it after filling.

Images