A method and oil composition for improving the rust-preventive properties of oils

Abstract

This invention relates to a method for improving the rust-preventive properties of oil products. The method includes adding an oil rust inhibitor to a base oil product, said oil rust inhibitor having a structure shown in formula (I) or formula (II), wherein each R1 is independently -CH2-, -CH2CH2-, -CH(CH3)CH2-, or -CH2CH(CH3)-; n is an integer selected from 1 to 15; and each R2 is independently a substituted or unsubstituted C1-C 40 The invention also relates to an oil composition with improved rust-preventive properties using the above-described method. The invention improves the rust-preventive properties of base oils by adding methyl oleate-succinic acid monoether alcohol esters. These rust inhibitors can form an adsorption film on metal surfaces, and even small dosages in the base oil can significantly improve the oil's corrosion resistance. Furthermore, the methyl oleate-succinic acid monoether esters prepared by the invention have a low freezing point and can be used to improve the rust-preventive properties of oils under low-temperature conditions.

Description

Technical Field

[0001] This application belongs to the field of oil processing, and specifically relates to a method and an oil composition for improving the rust-preventive properties of oils. Background Technology

[0002] During storage, transportation, and use, petroleum products can corrode materials and machinery they come into contact with, causing a series of hazards. For example, they can damage metal parts of oil storage containers and engine fuel systems, shortening the lifespan of these metal parts; they can also cause fuel contamination, corrode rubber seals, reduce fuel stability, and accelerate the wear and tear of machine parts.

[0003] The reasons why fuel oil corrodes metals can be categorized as follows: First, fuel oil contains dissolved water or a small amount of free water. When water-containing fuel oil comes into contact with containers, pipelines, oil pumps, etc., it may cause rust on the metal. Second, sulfur and sulfur-containing compounds, organic acids, water-soluble acids or alkalis, water additives, and bacteria in the fuel can also cause metal corrosion. Third, alcohol compounds added to gasoline fuel have corrosive effects, and mixtures of hydrocarbons and alcohols can reduce the adsorption capacity of surfactants on metal surfaces, thus exacerbating the corrosion of metals by gasoline fuel.

[0004] Rust inhibitors are highly efficient synthetic penetrants that can powerfully penetrate rust, corrosion, and oil stains to remove them. Adding rust inhibitors (corrosion inhibitors) to oils is an effective and feasible way to reduce the corrosion of mechanical equipment caused by oils. The proper use of rust inhibitors is an economical and effective means of preventing the corrosion of metals and their alloys.

[0005] CN1597876A provides a functional additive for inhibiting metal corrosion. The additive is a composition consisting of magnesium-based inorganic compounds, solvent oil, organic acid, and accelerator. Its main component with anti-rust properties is an oil-soluble magnesium salt, which can inhibit corrosion caused by vanadium and sodium metal ions.

[0006] CN102286300A provides a metal corrosion inhibitor composed of ethylene glycol monomethyl ether, methacrylate oligomer and polypropylene glycol. It is an ashless additive with an addition amount of 0.02-0.03% in fuel. It requires a small amount and has low cost.

[0007] CN115304485A provides an oil rust inhibitor additive, which is an acidic additive prepared from unsaturated fatty acids or unsaturated fatty acid esters through addition and hydrolysis reactions.

[0008] However, existing rust inhibitors added to oils still have problems such as poor rust prevention performance of the oils and high pour point of the rust inhibitors. Summary of the Invention

[0009] The purpose of this invention is to further improve the rust-preventive properties of oils.

[0010] To achieve the above objectives, a first aspect of the present invention provides a method for improving the rust-preventive properties of oils, the method comprising adding an oil rust inhibitor to a base oil, said oil rust inhibitor having a structure as shown in formula (I) or formula (II).

[0011]

[0012] Wherein, each R1 is independently -CH2-, -CH2CH2-, -CH(CH3)CH2-, or -CH2CH(CH3)-; n is an integer selected from 1 to 15; each R2 is independently selected from substituted or unsubstituted C1-C 40 The hydrocarbon group; the amount of the oil rust inhibitor added to the base oil is 0.1-10000 μg / g.

[0013] Optionally, each R1 is independently -CH2CH2-, -CH(CH3)CH2-, or -CH2CH(CH3)-; n is an integer selected from 1 to 10; each R2 is independently a substituted or unsubstituted C1-C 18 Hydrocarbon group.

[0014] Optionally, each R1 is independently ethyl or propyl; n is an integer selected from 1 to 3; each R2 is independently methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, isooctyl, nonyl, isononyl, decyl, isoundecyl, and isotridecyl.

[0015] Optionally, the amount of the oil rust inhibitor added to the base oil is 10-5000 μg / g.

[0016] Optionally, the base oil is mineral oil or biomass fuel; the mineral oil is selected from one or more of crude oil, naphtha, gasoline, kerosene, light oil, lubricating oil, lubricating grease, base oil for blending lubricating oil and grease, heavy oil, jet fuel oil, FCC slurry, asphalt, bitumen, extra-heavy oil, tar, gas liquefaction oil, coal liquefaction oil, alkylation oil, black oil, synthetic crude oil, reformed gasoline, isomerized gasoline, recycled heavy oil, residual oil, white oil, and wax; the biomass fuel is selected from one or more of biomass liquefaction oil, bioethanol fuel, bioETBE fuel, and biogasoline.

[0017] A second aspect of the present invention provides an oil composition comprising the oil whose rust-preventive properties are improved by the method described in the first aspect of the present invention.

[0018] Optionally, the oil is gasoline, and the amount of the rust inhibitor added to the gasoline is 1-300 μg / g, preferably 10-200 μg / g, and more preferably 20-100 μg / g.

[0019] Optionally, the oil is a lubricating oil or a grease, and the amount of the rust inhibitor added to the lubricating oil or grease is 20-3000 μg / g, preferably 50-2000 μg / g, and more preferably 100-1000 μg / g.

[0020] Optionally, the oil is selected from one or more of the following: total loss system oil, mold release oil, gear oil, compressor oil, internal combustion engine oil, bearing oil, clutch oil, guide rail oil, hydraulic oil, metalworking oil, electrical insulating oil, pneumatic tool oil, heat transfer oil, corrosion-resistant oil, turbine oil, heat treatment oil, lubricating grease, and steam cylinder oil.

[0021] Optionally, the oil composition further contains a base additive selected from at least one of lubricants, detergents, antioxidants, and demulsifiers.

[0022] Through the above technical solution, the oleate methyl succinate monoether alcohol ester oil rust inhibitor added to the base oil of the present invention can form an adsorption film on the metal surface. Even a small dosage added to the base oil can significantly improve the rust resistance of the oil. Moreover, the oleate methyl succinate alcohol ester prepared by the present invention has a low freezing point and is suitable for improving the rust prevention performance of the oil under low temperature environment conditions.

[0023] Other features and advantages of the present invention will be described in detail in the following detailed description section. Attached Figure Description

[0024] The accompanying drawings are provided to further illustrate the invention and form part of the specification. They are used together with the following detailed description to explain the invention, but do not constitute a limitation thereof. In the drawings:

[0025] Figure 1 The mass spectrum of the product prepared in Example 2 is shown.

[0026] Figure 2 The infrared spectrum of the product prepared in Example 2.

[0027] Figure 3 The image shows the corrosion test results of the metal rods of the product prepared in Example 3. In the image, A is the metal rod for the corrosion test of blank gasoline, and B is the metal rod for the corrosion test of gasoline with the rust inhibitor product of Example 3 added. The corrosion test lasted for 8 hours.

[0028] Figure 4The image shows the corrosion test results of the metal rods of the product prepared in Example 4. In the image, C is the metal rod of the blank lubricating oil corrosion test, and D is the metal rod of the lubricating oil with the rust inhibitor product of Example 4 added. The corrosion test lasted for 8 hours. Detailed Implementation

[0029] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0030] A first aspect of the present invention provides a method for improving the rust-preventive properties of oil products, the method comprising adding an oil rust inhibitor to a base oil product, said oil rust inhibitor having a structure as shown in formula (I) or formula (II).

[0031]

[0032] Wherein, each R1 is independently -CH2-, -CH2CH2-, -CH(CH3)CH2-, or -CH2CH(CH3)-; n is an integer selected from 1 to 15; each R2 is independently selected from substituted or unsubstituted C1-C 40 The hydrocarbon group; the amount of the oil rust inhibitor added to the base oil is 0.1-10000 μg / g.

[0033] The oleic acid methyl succinic acid monoether alcohol ester rust inhibitor added to the base oil of this invention can form an adsorption film on the metal surface. Even a small amount added to the base oil can significantly improve the rust resistance of the oil.

[0034] In this invention, hydrocarbon groups refer to alkyl, alkenyl, alkynyl, cycloalkyl, aryl, etc. C1-C 40 The hydrocarbon group can be a normal or isomeric alkyl group with 1-40 carbon atoms, a straight-chain or branched alkenyl or alkynyl group with 2-40 carbon atoms, a substituent with a saturated carbon ring with 3-40 carbon atoms, or a substituent with one or more aromatic rings or fused rings with 6-40 carbon atoms, or may contain multiple of the above groups.

[0035] Wherein, each R1 is independently -CH2CH2-, -CH(CH3)CH2-, or -CH2CH(CH3)-; n is an integer selected from 1 to 10; each R2 is independently a substituted or unsubstituted C1-C 18 Hydrocarbon group.

[0036] Wherein, each R1 is independently ethyl or propyl; n is an integer selected from 1 to 3; each R2 is independently methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, isooctyl, nonyl, isononyl, decyl, isoundecyl, or isotridecyl.

[0037] In one specific embodiment of the present invention, n is 1, R1 is selected from ethyl or propyl, and R2 is selected from methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, isooctyl, nonyl, isononyl, decyl, isoundecyl, and isotridecyl.

[0038] In another specific embodiment of the present invention, n is 2, R1 is selected from ethyl or propyl, and R2 is selected from methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl, isooctyl, nonyl, isononyl, isoundecyl, and isotridecyl.

[0039] In another specific embodiment of the present invention, n is 3, R1 is selected from ethyl or propyl, and R2 is selected from methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl, isooctyl, nonyl, isononyl, isoundecyl, and isotridecyl.

[0040] The amount of the oil-based rust inhibitor added to the base oil is 10-5000 μg / g. In some specific embodiments of the present invention, the amount of the oil-based rust inhibitor added to the base oil can be 10 μg / g, 20 μg / g, 40 μg / g, 60 μg / g, 80 μg / g, 100 μg / g, 120 μg / g, 140 μg / g, 160 μg / g, 180 μg / g, 200 μg / g, 240 μg / g, 280 μg / g, 300 μg / g, 400 μg / g, 500 μg / g, 600 μg / g, 700 μg / g, 800 μg / g, 900 μg / g, 1000 μg / g, 2000 μg / g, 5000 μg / g, or any value within the aforementioned range.

[0041] In this invention, the preparation method of the oil-based rust inhibitor includes the following steps:

[0042] (1) Methyl oleate and maleic anhydride reacted under olefin reaction conditions to prepare methyl oleate-based succinic anhydride intermediate;

[0043] (2) The intermediate of methyl oleate succinic anhydride is esterified with alcohol ether under esterification reaction conditions to obtain methyl oleate succinic anhydride ester.

[0044] The structural formula of the alcohol ether is R2[OR1]. n OH;

[0045] Wherein, R1 is selected from -CH2-, -CH2CH2-, -CH(CH3)CH2-, -CH2CH(CH3)-; n is selected from integers from 1 to 15; R2 is selected from substituted or unsubstituted C1-C 40Hydrocarbon group.

[0046] The method for preparing oil rust inhibitors according to the present invention is simple and easy to operate, and there is no pollutant emission during the preparation process. Moreover, the methyl oleate-based succinate alcohol ether ester of the present invention uses methyl oleate as a raw material, which is widely available, biodegradable, and environmentally friendly.

[0047] In a preferred embodiment of the present invention, the structural formula is R2[OR1]. n In the OH alcohol ether, n is 1, and the alcohol ether is selected from ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monoisobutyl ether, ethylene glycol monotert-butyl ether, ethylene glycol monopentyl ether, ethylene glycol monohexyl ether, ethylene glycol monoheptyl ether, ethylene glycol monoisooctyl ether, ethylene glycol monononyl ether, ethylene glycol monoisononyl ether, ethylene glycol monodecyl ether, ethylene glycol monoisodecyl ether, ethylene glycol monoisodecaether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monoisobutyl ether, propylene glycol monotert-butyl ether, propylene glycol monopentyl ether, propylene glycol monohexyl ether, propylene glycol monoheptyl ether, propylene glycol monoisooctyl ether, propylene glycol monononyl ether, propylene glycol monoisononyl ether, propylene glycol monoisodecaether, and propylene glycol monoisodecaether.

[0048] In a preferred embodiment of the present invention, the structural formula is R2[OR1]. n In the OH alcohol ether, n is 2, and the alcohol ether is selected from diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monotert-butyl ether, diethylene glycol monopentyl ether, diethylene glycol monohexyl ether, diethylene glycol monooctyl ether, diethylene glycol monoisooctyl ether, diethylene glycol monononyl ether, diethylene glycol monoisononyl ether, diethylene glycol monoisoundeether, diethylene glycol monoisotridecyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monoisobutyl ether, dipropylene glycol monotert-butyl ether, dipropylene glycol monopentyl ether, dipropylene glycol monohexyl ether, dipropylene glycol monooctyl ether, dipropylene glycol monoisooctyl ether, dipropylene glycol monoisononyl ether, dipropylene glycol monoisoundeether, and dipropylene glycol monoisotridecyl ether.

[0049] In a preferred embodiment of the present invention, the structural formula is R2[OR1]. nIn the OH alcohol ether, n is 3, and the alcohol ether is selected from triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol mono-n-butyl ether, triethylene glycol monoisobutyl ether, triethylene glycol monotert-butyl ether, triethylene glycol monopentyl ether, triethylene glycol monohexyl ether, triethylene glycol monooctyl ether, triethylene glycol monoisooctyl ether, triethylene glycol monononyl ether, triethylene glycol monoisononyl ether, triethylene glycol monoisoundeether, triethylene glycol monoisotridecyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monoisobutyl ether, tripropylene glycol monotert-butyl ether, tripropylene glycol monopentyl ether, tripropylene glycol monohexyl ether, tripropylene glycol monooctyl ether, tripropylene glycol monoisooctyl ether, tripropylene glycol monoisononyl ether, tripropylene glycol monoisoundeether, and tripropylene glycol monoisotridecyl ether.

[0050] In order to enable the methyl oleate succinic anhydride intermediate to react and generate methyl oleate succinic anhydride alcohol ether ester, the molar ratio of the methyl oleate succinic anhydride intermediate to the alcohol ether is 1:(0.5-3), the esterification reaction temperature is 40-180℃, and the reaction time is 10min-10h.

[0051] Preferably, in order to generate as much monool ether ester product as possible during the esterification reaction, the molar ratio of the methyl oleate succinic anhydride intermediate to the alcohol ether is 1:(0.5-1.2), the esterification reaction temperature is 50-120℃, and the reaction time is 0.5-2h.

[0052] To accelerate the reaction rate, a catalyst is added to the esterification reaction; the catalyst is selected from one or more of aluminum chloride, sulfuric acid, hydrochloric acid, boron trifluoride, solid superacids, cation exchange resins, and heteropolyacids. While adding a catalyst to the esterification reaction of methyl oleate succinic anhydride with alcohol ethers can accelerate the reaction rate, it can also trigger side reactions; therefore, it is preferable not to add a catalyst.

[0053] To maximize the formation of monool ether esters during the esterification reaction, an inhibitor is added to reduce or eliminate the formation of diol ether esters. The inhibitor is one or more of triethylamine and pyridine.

[0054] Depending on the reaction requirements, a reaction solvent may be added to the esterification reaction, which may be one or more of toluene, xylene, and ethylbenzene.

[0055] The methyl oleate-based succinic anhydride intermediate is prepared by an alder(-ene) reaction between methyl oleate and maleic anhydride. Based on the positional differences of the C=C double bond activation sites on the methyl oleate backbone, the alder(-ene) reaction between methyl oleate and succinic anhydride follows the following reaction formula:

[0056]

[0057] In order to ensure that methyl oleate reacts fully to generate methyl oleate-based succinic anhydride intermediate, the molar ratio of methyl oleate to maleic anhydride is 1:(0.1-10), preferably 1:(0.5-5); the reaction conditions of the olefin include: a reaction temperature of 50-300℃, preferably 150-250℃; and a reaction time of 1-20h, preferably 6-12h.

[0058] Depending on the reaction requirements, a reaction solvent may be added to the olefin reaction, which may be one or more of toluene, petroleum ether, hexane, xylene, and ethylbenzene.

[0059] In this process, because the chemical bonds of the reactants break under the influence of light, heat, or oxygen, reactive free radicals and hydroperoxides are generated, which may then trigger a free radical chain reaction. To prevent the free radical reaction, an antioxidant is added to the alkene reaction. The antioxidant is one or more of phenolic antioxidants, amine antioxidants, and heterocyclic antioxidants. The phenolic antioxidant is selected from isooctyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)acrylate, antioxidant 1010, antioxidant 2246, and antioxidant 107. 6 and one or more of antioxidant 300; the amine antioxidant is selected from one or more of N',N-diphenyl-p-phenylenediamine, N,N'-hexamethylene-bis-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide, phenothiazine (diphenylamine sulfide), antioxidant DNP, antioxidant H and antioxidant 4010; the heterocyclic antioxidant is selected from one or more of benzotriazole, alkyl-substituted imidazoline, 2-mercaptobenzothiazole, 2,5-dimercapto-1,3,4-thiadiazole and their derivatives.

[0060] Wherein, the base oil is mineral oil or biomass fuel; the mineral oil is selected from one or more of crude oil, naphtha, gasoline, kerosene, light oil, lubricating oil, lubricating grease, base oil for blending lubricating oil and grease, heavy oil, jet fuel oil, FCC slurry, asphalt, bitumen, extra heavy oil, tar, gas liquefied oil (GTL), coal liquefied oil (CTL), alkylated oil, black oil, synthetic crude oil, reformed gasoline, isomerized gasoline, recycled heavy oil, residual oil, white oil, and wax; the biomass fuel is selected from one or more of biomass liquefied oil, bioethanol fuel, bioETBE fuel, and biogasoline.

[0061] A second aspect of the present invention provides an oil composition comprising the oil with improved rust-preventive properties according to the first aspect of the present invention.

[0062] The oil is gasoline, and the amount of rust inhibitor added to the gasoline is 1-300 μg / g, preferably 10-200 μg / g, and more preferably 20-100 μg / g.

[0063] In some specific embodiments of the present invention, the amount of the oil-based rust inhibitor added to the gasoline can be 10 μg / g, 20 μg / g, 30 μg / g, 40 μg / g, 50 μg / g, 60 μg / g, 70 μg / g, 80 μg / g, 90 μg / g, 100 μg / g, 110 μg / g, 120 μg / g, 130 μg / g, 140 μg / g, 150 μg / g, 160 μg / g, 170 μg / g, 180 μg / g, 190 μg / g, 200 μg / g, or any value within the aforementioned range.

[0064] In this invention, gasoline refers to refined petroleum fractions with or without additives that have a boiling range of 30-220°C and are suitable as fuel for spark-ignition engines, including automotive gasoline and aviation piston engine fuel (also known as aviation gasoline).

[0065] In this invention, the gasoline can be automotive gasoline, automotive ethanol gasoline, and aviation gasoline that meet the requirements of GB 17930, GB 18351, and GB 1787.

[0066] Automotive gasoline is mainly composed of catalytic cracking gasoline, reformed gasoline, aromatics, alkylated gasoline, and isomerized gasoline. The gasoline described in this invention may also contain various oxygen-containing compounds, such as methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE), tert-amyl methyl ether (TAME), diisopropyl ether (DIPE), methanol, ethanol, and butanol.

[0067] The oil is a lubricating oil or grease, and the amount of rust inhibitor added to the lubricating oil or grease is 20-3000 μg / g, preferably 50-2000 μg / g, and more preferably 100-1000 μg / g.

[0068] In some specific embodiments of the present invention, the amount of the oil-based rust inhibitor added to the lubricating oil or grease is 20 μg / g, 50 μg / g, 100 μg / g, 200 μg / g, 300 μg / g, 400 μg / g, 500 μg / g, 600 μg / g, 700 μg / g, 800 μg / g, 900 μg / g, 1000 μg / g, 1200 μg / g, 1400 μg / g, 3000 μg / g, or any value within the aforementioned range.

[0069] In this invention, lubricating oil refers to an oil product composed of lubricating oil base oil and additives, specifically including internal combustion engine oil, gear oil, hydraulic oil, automatic transmission oil, compressor oil, bearing oil, clutch oil, guide rail oil, metalworking oil, electrical insulating oil, pneumatic tool oil, heat transfer oil, turbine oil, heat treatment oil, and other lubricating oils.

[0070] In this invention, the lubricating oil base oil can be mineral base oil, synthetic base oil, bio-based base oil, paraffinic base oil, intermediate base oil, naphthenic base oil, etc. The synthetic oil can be ester oil, polyolefin oil, ether oil, Fischer-Tropsch synthetic oil, etc., or Group I oil, Group II oil, Group III oil, Group IV oil, Group V oil, etc.

[0071] In this invention, lubricating grease refers to a product composed of thickeners, base oils, and additives, such as soap-based grease, hydrocarbon-based grease, inorganic grease, and organic grease. Depending on the composition and applicable environment, it can also be lithium-based grease, calcium-based grease, aluminum-based grease, complex lithium-based grease, complex aluminum-based grease, high-temperature grease, wheel and axle bearing grease, multi-functional lubricating grease, electric motorcycle grease, insulating grease, bearing grease, and other lubricating greases.

[0072] The oil-based rust inhibitor of this invention has a wide range of applications, such as for the prevention of rust in total loss system oils, mold release oils, gear oils, compressor oils (including refrigeration and gear pumps), internal combustion engine oils, spindle, bearing and clutch oils, guide rail oils, hydraulic oils, metalworking oils, electrical insulating oils, pneumatic tool oils, heat transfer oils, temporary protective corrosion-resistant oils, turbine oils, heat treatment oils, greases, steam cylinder oils, special lubricant application oils, and other oils in various applications.

[0073] The present invention will be further described in detail below through examples, but these examples do not constitute any limitation on the invention. All raw materials used in the examples are commercially available.

[0074] In the following embodiments and comparative examples of the present invention, methyl oleate (content 96%) was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., maleic anhydride (content 99.5%) was purchased from Beijing Innocare Technology Co., Ltd., ethylene glycol monomethyl ether (content 98%), ethylene glycol mono-n-butyl ether (content 99.7%) and ethylene glycol tert-butyl ether (content 98%) were purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., and n-propanol (99.5%) and n-hexanol (98%) were purchased from Beijing Chemical Reagent Company.

[0075] In this invention, the acid value of the prepared oil rust inhibitor product is determined according to the method of GB / T 7304, and the freezing point is determined according to the method of GB / T 510.

[0076] Example 1

[0077] This embodiment prepares a reaction intermediate of methyl oleate-based succinic anhydride, and the preparation method includes the following steps:

[0078] Prepare a 3000mL reactor equipped with an electric stirrer, thermometer, reflux condenser and nitrogen inlet tube. Weigh 1500g of methyl oleate (96% by mass) and 745g of maleic anhydride (the molar ratio of methyl oleate to maleic anhydride is about 1:1.5) and place them in the reactor. Purge with nitrogen for 5-10 minutes, heat and stir to 200℃, and react for 8 hours. Remove excess maleic anhydride by vacuum distillation to obtain the methyl oleate-based succinic anhydride reaction intermediate.

[0079] Example 2

[0080] Preparation of methyl oleate succinate mono(ethylene glycol monomethyl ether) ester:

[0081] After the methyl oleate-based succinic anhydride reaction intermediate prepared in Example 1 is cooled to 70°C or below, 200g of the methyl oleate-based succinic anhydride reaction intermediate is weighed and placed in a 500mL reactor equipped with an electric stirrer, thermometer, reflux condenser and nitrogen inlet tube. Then, 38.4g of ethylene glycol monomethyl ether (the molar ratio of methyl oleate-based succinic anhydride reaction intermediate to ethylene glycol monomethyl ether is 1:1) is added, nitrogen is introduced for 5-10 minutes, and the mixture is stirred and refluxed at a constant temperature of 60°C for 1 hour. Then, the ethylene glycol monomethyl ether is removed by vacuum distillation and cooled to obtain the methyl oleate-based succinic acid mono(ethylene glycol monomethyl ether) ester product, whose acid value is determined to be 65mgKOH / g.

[0082] Figure 1 The image shows the mass spectrum of the rust inhibitor product prepared in Example 2. In the image, m / z = 493 is the mass addition peak of sodium ions of methyl oleate succinate monoethylene glycol methyl ether ester.

[0083] Figure 2 The infrared spectrum of the rust inhibitor product prepared in Example 2 is shown below, with the peaks assigned as follows:

[0084] 2800cm -1 -3000cm -1 and 1450cm -1 The peak indicates an aliphatic hydrocarbon structure; 1782 cm⁻¹ -1 The peak indicates an ester carbonyl group close to the carboxyl group; 1736 cm⁻¹ -1 The peak represents the ester group at the end of the long chain; 1710 cm⁻¹ -1 The peak represents a carboxylic acid; 1217 cm⁻¹ -1 The nearby peak indicates the presence of a CO structure; 3000 cm⁻¹ -1 Nearby and 1640cm -1 The nearby peaks represent carbon-carbon double bonds; 2830 cm⁻¹ -1 -2815cm -1 The peak indicates the presence of an ether structure.

[0085] Example 3

[0086] Preparation of methyl oleate succinate mono(ethylene glycol mono-n-butyl ether) ester:

[0087] 200g of the methyl oleate succinic anhydride reaction intermediate prepared in Example 1 was weighed and placed in a 500mL reactor equipped with an electric stirrer, thermometer, reflux condenser and nitrogen inlet tube. Then 59.8g of ethylene glycol mono-n-butyl ether (the molar ratio of methyl oleate succinic anhydride reaction intermediate to ethylene glycol mono-n-butyl ether was 1:1) was added. Nitrogen gas was introduced for 5-10 minutes, and the mixture was stirred and refluxed at a constant temperature of 110℃ for 2 hours. Then, ethylene glycol mono-n-butyl ether was removed by vacuum distillation and cooled to obtain the methyl oleate succinic acid mono(ethylene glycol mono-n-butyl ether) ester product. Its acid value was determined to be 45mgKOH / g.

[0088] Example 4

[0089] Preparation of methyl oleate succinate (monoethylene glycol tert-butyl ether) ester:

[0090] Weigh 500g of the methyl oleate succinic anhydride reaction intermediate obtained in Example 1 and place it in a 1000mL reactor equipped with an electric stirrer, thermometer, reflux condenser and nitrogen inlet tube. Add 149.7g of ethylene glycol tert-butyl ether (the molar ratio of methyl oleate succinic anhydride reaction intermediate to ethylene glycol tert-butyl ether is 1:1). Purge with nitrogen for 5-10 minutes and stir and reflux at a constant temperature of 110℃ for 2 hours. Then remove ethylene glycol tert-butyl ether by vacuum distillation and cool to obtain methyl oleate succinic acid mono(ethylene glycol monotert-butyl ether) ester product. Its acid value was determined to be 40mgKOH / g.

[0091] Comparative Example 1

[0092] 200g of the methyl oleate succinic anhydride reaction intermediate prepared in Example 1 was weighed and placed in a 500mL reactor equipped with an electric stirrer, thermometer, reflux condenser and nitrogen inlet tube. 34.3g of propanol was added (the molar ratio of methyl oleate succinic anhydride reaction intermediate to propanol was 1:1.2). Nitrogen gas was introduced for 5-10 minutes, and the mixture was stirred and refluxed at a constant temperature of 80°C for 2 hours. Then, propanol was removed by vacuum distillation and cooled to room temperature to obtain methyl oleate succinate monopropyl ester, whose acid value was determined to be 63mgKOH / g.

[0093] Comparative Example 2

[0094] 200g of the methyl oleate succinic anhydride reaction intermediate prepared in Example 1 was weighed and placed in a 500mL reactor equipped with an electric stirrer, thermometer, reflux condenser and nitrogen inlet tube. 61.8g of n-hexanol was added (the molar ratio of methyl oleate succinic anhydride reaction intermediate to n-hexanol was 1:1.2). Nitrogen gas was introduced for 5-10 minutes, and the mixture was stirred and refluxed at a constant temperature of 110℃ for 3 hours. Then, the n-hexanol was removed by vacuum distillation and cooled to room temperature to obtain methyl oleate succinic acid monohexyl ester, whose acid value was determined to be 47mgKOH / g.

[0095] Comparative Example 3

[0096] 200g of the oleate methyl succinic anhydride reaction intermediate prepared in Example 1 was weighed and placed in a 500mL reactor equipped with an electric stirrer, thermometer, reflux condenser, water separator and nitrogen inlet tube. 115.2g of ethylene glycol monomethyl ether (the molar ratio of oleate methyl succinic anhydride reaction intermediate to ethylene glycol monomethyl ether was 1:3) and 1.58g of phosphotungstic acid catalyst were added. Nitrogen gas was introduced and the mixture was stirred at 110°C for 6 hours. The catalyst was separated, and ethylene glycol monomethyl ether and water were removed by distillation. After cooling, the oleate methyl succinic acid diethylene glycol monomethyl ether ester product was obtained. Its acid value was determined to be 7.5mgKOH / g.

[0097] Corrosion test

[0098] The oil rust inhibitors prepared in Examples 2-4 and Comparative Examples 1-3 were added to base oils to evaluate their rust-preventing effects. The physicochemical properties of the base oil, gasoline, are shown in Table 1.

[0099] Table 1. Basic physicochemical properties of gasoline used for evaluation

[0100]

[0101]

[0102] The physicochemical properties of base oils for lubricating oils are shown in Table 2.

[0103] Table 2 Physicochemical Properties of Lubricating Oil Base Oils

[0104] project data <![CDATA[Viscosity, mm 2 / s (cSt), 100 °C]]> 19.4 <![CDATA[Viscosity, mm 2 / s (cSt), 40 °C]]> 221.6 <![CDATA[Density, g / cm 3 (kg / L)]]> 914.8 Pour point / ℃ -14 Appearance clear

[0105] The oil rust inhibitors prepared in Examples 2-4, the oil rust inhibitors prepared in Comparative Examples 1-3, and the industrial rust inhibitor product T747 (dodecenyl succinate half ester) produced by Shenyang Northern Petroleum Group were added to base oils at certain amounts, and the rust-preventive effect of the oil rust inhibitors was statistically analyzed. The test results are shown in Table 3.

[0106] Test Method: The rust resistance test of the oil-based rust inhibitor was conducted according to GB / T 11143. 300 mL of the sample was mixed with 30 mL of distilled water, and the cylindrical stainless steel rod was completely immersed in the mixture. The mixture was stirred at 36℃ (gasoline) or 60℃ (base lubricating oil). The test cycle was 8 or 72 hours. After the test cycle, the rust marks and degree of rust on the stainless steel rod were observed.

[0107] Table 3 Rust prevention results of rust inhibitors

[0108] oil sample <![CDATA[Added dose / mg·kg -1 > Test temperature / ℃ Corrosion test duration / h Corrosion evaluation Blank gasoline 0 36 8 Severe corrosion Blank lubricating oil 0 60 8 Severe corrosion Blank gasoline + Example 2 20 36 8 No rust Blank gasoline + Example 2 20 36 72 No rust Blank lubricating oil + Example 2 500 60 8 No rust Blank lubricating oil + Example 2 500 60 72 No rust Blank gasoline + Example 3 20 36 8 No rust Blank gasoline + Example 3 20 36 72 No rust Blank gasoline + Example 4 20 36 8 No rust Blank gasoline + Example 4 20 36 72 No rust Blank gasoline + T747 20 36 8 No rust Blank gasoline + T747 20 36 72 There are 27 rust spots Blank lubricating oil + T747 500 60 8 No rust Blank lubricating oil + T747 500 60 72 There are 11 rust spots Blank gasoline + Comparative Example 1 20 36 8 Severe corrosion Blank gasoline + Comparative Example 1 20 36 72 Severe corrosion Blank gasoline + Comparative Example 2 20 36 8 Severe corrosion Blank gasoline + Comparative Example 2 20 36 72 Severe corrosion Blank gasoline + Comparative Example 3 20 36 8 Severe corrosion Blank gasoline + Comparative Example 3 20 36 72 Severe corrosion

[0109] As shown in Table 3, when the oil rust inhibitor prepared by the present invention is used to improve the rust prevention performance of base oils, gasoline and lubricating oil have good rust prevention performance, and a small amount of additive in the base oil can significantly improve the rust prevention performance of the oil.

[0110] By comparing the rust-preventive effects of the oil-based rust inhibitor prepared in Examples 2-4 of this invention with those of the industrial rust inhibitor T747, it can be seen that the rust-preventive effect of the rust inhibitor product of this invention is better than that of the industrial rust inhibitor.

[0111] Freezing point test

[0112] The solidification points of the oil rust inhibitors prepared in Examples 2-4 and Comparative Examples 1-3 were tested using the GB / T510 method, and the test results are shown in Table 4.

[0113] Table 4. Freezing points of rust inhibitors

[0114] Rust inhibitor Freezing point / °C Example 2 ＜-50℃ Example 3 ＜-50℃ Example 4 ＜-50℃ Comparative Example 1 -28℃ Comparative Example 2 -30℃ Comparative Example 3 ＜-50℃

[0115] The rust inhibitor product provided by this invention has a freezing point below -50℃, which makes it widely applicable and suitable for use in oil rust prevention at ultra-low temperatures and high altitudes.

[0116] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all fall within the protection scope of the present invention.

[0117] It should also be noted that the various specific technical features described in the above embodiments can be combined in any suitable manner without contradiction. To avoid unnecessary repetition, the present invention will not describe the various possible combinations separately.

[0118] Furthermore, various different embodiments of the present invention can be combined in any way, as long as they do not violate the spirit of the present invention, they should also be regarded as the content disclosed by the present invention.

Claims

1. A method for improving the rust-preventive properties of oil, characterized in that, The method includes adding an oil rust inhibitor to a base oil, said oil rust inhibitor having a structure as shown in formula (I) or formula (II). Each R1 is independently -CH2-, -CH2CH2-, -CH(CH3)CH2-, or -CH2CH(CH3)-; n is an integer selected from 1 to 15; Each R2 is independently selected from substituted or unsubstituted C1-C. 40 hydrocarbon group; The amount of the oil-based rust inhibitor added to the base oil is 0.1-10000 μg / g.

2. The method according to claim 1, wherein, Each R1 is independently -CH2CH2-, -CH(CH3)CH2-, or -CH2CH(CH3)-; n is an integer selected from 1 to 10; Each R2 is independently a substituted or unsubstituted C1-C 18 Hydrocarbon group.

3. The method according to claim 1, wherein, Each R1 is independently ethyl or propyl; n is an integer selected from 1 to 3; Each R2 is independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isoundecyl, or isotridecyl.

4. The method according to claim 1, wherein, The amount of the oil rust inhibitor added to the base oil is 10-5000 μg / g.

5. The method according to claim 1, wherein, The base oil is mineral oil or biomass fuel; The mineral oil is selected from one or more of the following: crude oil, naphtha, kerosene, lubricating oil, lubricating grease, base oil for blending lubricating oil and grease, jet fuel oil, FCC slurry, asphalt, bitumen, extra-heavy oil, tar, gas liquefaction oil, coal liquefaction oil, alkylated oil, black oil, synthetic crude oil, reformed gasoline, isomerized gasoline, recycled heavy oil, residual oil, white oil, and wax. The biomass fuel is selected from one or more of biomass liquefied oil, bioethanol fuel, bioETBE fuel, and biogas.

6. An oil composition, characterized in that, It includes oils whose rust-preventive properties are improved by the method described in any one of claims 1-5.

7. The oil composition according to claim 6, wherein, The oil is gasoline, and the amount of rust inhibitor added to the gasoline is 1-300 μg / g.

8. The oil composition according to claim 7, wherein, The amount of the oil rust inhibitor added to the gasoline is 10-200 μg / g.

9. The oil composition according to claim 8, wherein, The amount of the oil rust inhibitor added to the gasoline is 20-100 μg / g.

10. The oil composition according to claim 6, wherein, The oil is a lubricating oil or grease, and the amount of rust inhibitor added to the lubricating oil or grease is 20-3000 μg / g.

11. The oil composition according to claim 10, wherein, The amount of the oil-based rust inhibitor added to the lubricating oil or grease is 50-2000 μg / g.

12. The oil composition according to claim 11, wherein, The amount of the oil-based rust inhibitor added to the lubricating oil or grease is 100-1000 μg / g.

13. The oil composition according to claim 6, wherein, The oil is selected from one or more of the following: total loss system oil, mold release oil, gear oil, compressor oil, internal combustion engine oil, bearing oil, clutch oil, guide rail oil, hydraulic oil, metalworking oil, electrical insulating oil, pneumatic tool oil, heat transfer oil, anti-corrosion oil, turbine oil, heat treatment oil, lubricating grease, and steam cylinder oil.

14. The oil composition according to claim 6, wherein, The oil composition also contains a basic additive selected from at least one of lubricants, detergents, antioxidants, and demulsifiers.

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