Method for improving antirust performance of oil product and oil product composition

Abstract

The invention relates to a method for improving the anti-rust performance of an oil product, the method comprises the following steps: adding an oil product anti-rust agent into a base oil product, the oil product anti-rust agent has a structure represented by a formula (I) or a formula (II), each R1 is independently-CH2-,-CH2CH2-,-CH (CH3) CH2-or-CH2CH (CH3)-, and each R2 is independently-CH2-,-CH2CH2-,-CH (CH3) CH2-or-CH2CH (CH3)-. N is an integer selected from 1-15; and each R2 is independently a substituted or unsubstituted hydrocarbon group of C1 to C40. The invention also relates to an oil product composition for improving the anti-rust performance by using the method. According to the invention, the methyl oleate succinic acid monoether alcohol ester compound is added into the base oil product to improve the anti-rust property of the oil product, the anti-rust agent can form an adsorption film on the metal surface, and the additive amount of the anti-rust agent in the base oil product is small, so that the anti-rust property of the oil product can be obviously improved; in addition, the prepared methyl oleate succinic acid alcohol ether ester is low in freezing point and can be used for improving the anti-rust performance of oil products under the low-temperature environment condition. # imgabs0 #

Description

Technical Field

[0001] The present application belongs to the field of oil processing, and in particular, relates to a method for improving the anti-rust performance of oil products and an oil product composition. Background Art

[0002] During storage, transportation and use, petroleum products will corrode the materials, mechanical equipment, etc. they come into contact with, causing a series of hazards. For example, they will damage the metal parts of oil storage containers and engine fuel systems and shorten the life of metal parts. They will also cause fuel pollution, corrode rubber and damage seals, reduce fuel stability and accelerate wear of machine parts.

[0003] The reasons why fuel oil causes corrosion to metals are divided into the following categories: First, fuel oil contains dissolved water or a small amount of free water. When the water-containing fuel oil comes into contact with containers, pipelines, oil pumps, etc., it may cause rust to the metal; Second, sulfur and sulfur-containing compounds, organic acids, water-soluble acids or alkalis, moisture additives and bacteria in the oil can also cause metal corrosion; Third, the alcohol compounds added to gasoline fuel are corrosive, and the mixture of hydrocarbons and alcohols will reduce the adsorption capacity of surfactants on the metal surface, aggravating the corrosion of gasoline fuel to metals.

[0004] Rust inhibitor is a highly effective synthetic penetrant that can penetrate rust, corrosion and oil stains to remove them. Adding rust inhibitor (corrosion inhibitor) to oil is an effective and feasible way to reduce the corrosion of oil to mechanical equipment. The rational use of rust inhibitor is an economical and effective means to prevent metals and their alloys from rusting.

[0005] CN1597876A provides a functional additive for inhibiting metal corrosion. The additive is a composition composed of a magnesium inorganic compound, solvent oil, an organic acid and an accelerator. The main component with anti-rust performance 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. The metal corrosion inhibitor is an ashless additive, and the amount added to the fuel is 0.02-0.03%. The amount added is small and the cost is low.

[0007] CN115304485A provides an oil antirust additive, which is an acid type additive, which is prepared by using unsaturated fatty acid or unsaturated fatty acid ester as raw material through addition reaction and hydrolysis reaction.

[0008] However, the existing rust inhibitors added to oil products still have the problems of poor anti-corrosion performance of the oil products and high freezing point of the rust inhibitors. Summary of the invention

[0009] The purpose of the present invention is to further improve the anti-corrosion performance of oil products.

[0010] In order to achieve the above object, the first aspect of the present invention provides a method for improving the anti-rust performance of oil products, the method comprising adding an oil product rust inhibitor to a base oil product, wherein the oil product rust inhibitor has 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 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 1-10; each R2 is independently substituted or unsubstituted C1-C 18 of hydrocarbon groups.

[0014] Optionally, each R1 is independently ethyl or propyl; n is an integer selected from 1-3; 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 oil rust inhibitor is added to the base oil in an amount of 10-5000 μg / g.

[0016] Optionally, the base oil product 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, grease, base oil for blended lubricating oil and grease, heavy oil, jet fuel oil, FCC slurry, asphalt, asphalt, extra heavy oil, tar, gas liquefied oil, coal liquefied oil, alkylate, 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, bio-ETBE fuel and biogasoline.

[0017] The second aspect of the present invention provides an oil composition, which comprises the oil with improved anti-rust performance according to the method of the first aspect of the present invention.

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

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

[0020] Optionally, the oil product is selected from one or more of total loss system oil, 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, grease and steam cylinder oil.

[0021] Optionally, the oil composition further contains a basic additive, and the basic additive is selected from at least one of a lubricant, a detergent, an antioxidant and a demulsifier.

[0022] Through the above technical scheme, the methyl oleate succinic acid monoether alcohol ester oil rust inhibitor added to the base oil of the present invention can form an adsorption film on the metal surface, and a small amount of the additive in the base oil has the effect of significantly improving the anti-corrosion performance of the oil; moreover, the methyl oleate succinic acid monoether alcohol ester prepared by the present invention has a low freezing point and is suitable for improving the anti-rust 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. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] The accompanying drawings are used to provide a further understanding of the present invention and constitute a part of the specification. Together with the following specific embodiments, they are used to explain the present invention but do not constitute a limitation of the present invention. In the accompanying drawings:

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

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

[0027] Figure 3 The figure is a metal rod corrosion test effect diagram of the product prepared in Example 3, wherein A is a metal rod subjected to a corrosion test of blank gasoline, and B is a metal rod subjected to a corrosion test of gasoline added with the rust inhibitor product of Example 3; the corrosion test duration is 8 hours.

[0028] Figure 4This is a diagram showing the effect of a metal rod rust test of the product prepared in Example 4, wherein C is a metal rod rusted with a blank lubricant, and D is a metal rod rusted with a lubricant to which the rust inhibitor product of Example 4 is added; the rust test lasts for 8 hours. DETAILED DESCRIPTION

[0029] The specific embodiments of the present invention are described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention, and are not used to limit the present invention.

[0030] The first aspect of the present invention provides a method for improving the anti-rust performance of oil products, the method comprising adding an oil product rust inhibitor to a base oil product, wherein the oil product rust inhibitor has 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 amount of the oil rust inhibitor added to the base oil is 0.1-10000 μg / g.

[0033] The methyl oleate 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, and a small amount of the additive in the base oil has the effect of significantly improving the anti-rust performance of the oil.

[0034] In the present invention, the hydrocarbon group refers to an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, etc. 40 The hydrocarbon group can be a normal or isomeric alkyl group having 1 to 40 carbon atoms, a straight-chain or branched alkenyl or alkynyl group having 2 to 40 carbon atoms, a substituent having a saturated carbon ring having 3 to 40 carbon atoms, or a substituent having 6 to 40 carbon atoms and containing one or more aromatic rings or condensed rings, or it can 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 substituted or unsubstituted C1-C 18 of hydrocarbon groups.

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

[0037] In a 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] Wherein, the amount of the oil 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 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 the present invention, the preparation method of the oil rust inhibitor comprises the following steps:

[0042] (1) reacting methyl oleate and maleic anhydride under olefin reaction conditions to prepare a methyl oleate succinic anhydride intermediate;

[0043] (2) allowing the methyl oleate succinic anhydride intermediate to undergo an esterification reaction with an alcohol ether under esterification reaction conditions to obtain a methyl oleate succinic acid alcohol ether ester;

[0044] Wherein, 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 an integer of 1-15; R2 is selected from substituted or unsubstituted C1-C 40of hydrocarbon groups.

[0046] The method for preparing the oil rust inhibitor of the present invention is simple and easy to operate, and no pollutants are discharged during the preparation process. In addition, the methyl oleate succinic acid alcohol ether ester of the present invention uses methyl oleate as a raw material, which has a wide source of raw materials, is degradable, and has no pollution to the environment.

[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 mono-tert-butyl ether, ethylene glycol monopentyl ether, ethylene glycol monohexyl ether, ethylene glycol monoheptyl ether, ethylene glycol monooctyl ether, ethylene glycol monoisooctyl ether, ethylene glycol monononyl ether, ethylene glycol monoisononyl ether, ethylene glycol monodecyl ether, ethylene glycol monoisoundecyl ether, ethylene glycol monoisotridecanyl ether, 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 monooctyl ether, propylene glycol monoisooctyl ether, propylene glycol monononyl ether, propylene glycol monoisononyl ether, propylene glycol monoisoundecyl ether and propylene glycol monoisotridecanyl ether.

[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 monoisoundecyl ether, diethylene glycol monoisotridecathode, 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 monoisoundecyl ether, and dipropylene glycol monoisotridecathode.

[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 mono-tert-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 monoisoundecyl ether, triethylene glycol monoisotridecanyl 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 monoisoundecyl ether, and tripropylene glycol monoisotridecanyl ether.

[0050] In order to allow the methyl oleate succinic anhydride intermediate to react to form methyl oleate succinic 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°C, and the reaction time is 10min-10h.

[0051] Preferably, in order to generate monoalcohol ether ester products as much 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°C, and the reaction time is 0.5-2h.

[0052] In order to accelerate the reaction rate, a catalyst is also added to the esterification reaction; the catalyst is selected from one or more of aluminum chloride, sulfuric acid, hydrochloric acid, boron trifluoride, solid superacid, cation exchange resin and heteropolyacid. Although adding a catalyst to the esterification reaction of methyl oleyl succinic anhydride and alcohol ether can accelerate the reaction rate, it will also induce side reactions, so it is preferably not to add a catalyst.

[0053] In order to generate as much monoalcohol ether ester as possible during the esterification reaction, an inhibitor is added to the esterification reaction to generate less or no diol ether ester, and the inhibitor is one or more of triethylamine and pyridine.

[0054] Wherein, according to the reaction requirements, a reaction solvent is further added in the esterification reaction, and the reaction solvent is one or more of toluene, xylene and ethylbenzene.

[0055] The methyl oleate succinic anhydride intermediate is prepared by olefin reaction (Alder(-ene) reaction) of methyl oleate and maleic anhydride. According to the position difference of the C=C double bond activation site on the main chain of methyl oleate, the olefin reaction of methyl oleate and succinic anhydride has the following reaction formula:

[0056]

[0057] Among them, in order to make methyl oleate react fully to form methyl oleate succinic anhydride intermediate, the molar ratio of methyl oleate to maleic anhydride is 1: (0.1-10), preferably 1: (0.5-5); the conditions of the ene reaction include: the reaction temperature is 50-300°C, preferably 150-250°C; the reaction time is 1-20h, preferably 6-12h.

[0058] Wherein, according to the reaction requirements, a reaction solvent is further added in the olefin reaction, and the reaction solvent is one or more of toluene, petroleum ether, hexane, xylene and ethylbenzene.

[0059] In which, due to the breakage of chemical bonds of reactants under the action of light, heat or oxygen, active free radicals and hydroperoxides are generated, which may further trigger a free radical chain reaction. In order to prevent the free radical reaction, an antioxidant is also added to the ene reaction, and the antioxidant is one or more of a phenolic antioxidant, an amine antioxidant and a heterocyclic antioxidant; the phenolic antioxidant is selected from 3-(3,5-di-tert-butyl-4-hydroxyphenyl) acrylate, antioxidant 1010, antioxidant 2246, 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 (sulfurized diphenylamine), 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 derivatives thereof.

[0060] The base oil product 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, grease, base oil for blended lubricating oil and grease, heavy oil, jet fuel oil, FCC slurry, asphalt, asphalt, extra heavy oil, tar, gas to liquids (GTL), coal to liquids (CTL), alkylate, 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, bio-ETBE fuel and biogasoline.

[0061] The second aspect of the present invention provides an oil composition, which comprises the oil with improved anti-rust performance according to the first aspect of the present invention.

[0062] Wherein, the oil product is gasoline, and the amount of the oil 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 rust inhibitor added to the gasoline can be 10μg / g, 20μg / g, 30μg / g, 40μg / g, 50μg / g, 60μg / g, 70μg / g, 80μg / g, 90μg / g, 100μg / g, 110μg / g, 120μg / g, 130μg / g, 140μg / g, 150μg / g, 160μg / g, 170μg / g, 180μg / g, 190μg / g, 200μg / g or any value within the aforementioned range.

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

[0065] In the present invention, the gasoline may be vehicle gasoline, vehicle ethanol gasoline and aviation gasoline meeting the requirements of GB 17930, GB 18351 and GB 1787.

[0066] Motor gasoline is mainly composed of catalytic cracking gasoline, reformed gasoline, aromatics, alkylated gasoline, isomerized gasoline, etc. The gasoline of the present 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, butanol, etc.

[0067] Wherein, the oil product is lubricating oil or grease, and the amount of the oil 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 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 the present invention, lubricating oil refers to an oil product composed of a lubricating oil base oil and additives, and specifically can be 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 the present invention, the lubricating oil base oil can be a mineral base oil, a synthetic base oil, a biological base oil, a paraffin base oil, an intermediate base oil, a cycloalkyl base oil, among which the synthetic oil can be an ester oil, a polyolefin oil, an ether oil, a Fischer-Tropsch synthetic oil or the like, and can also be a Class I oil, a Class II oil, a Class III oil, a Class IV oil, a Class V oil or the like.

[0071] In the present invention, lubricating grease refers to a product composed of a thickener, a base oil and an additive, such as soap-based grease, hydrocarbon-based grease, inorganic grease, and organic grease. Depending on the composition and applicable environment, lubricating grease may also be lithium-based grease, calcium-based grease, aluminum-based grease, composite lithium-based grease, composite aluminum-based grease, high-temperature grease, wheel bearing grease, multifunctional grease, grease for electric motorcycles, insulating grease, bearing grease, and the like.

[0072] The oil rust inhibitor of the present invention has a wide range of applications, for example, it can be used for total loss system oil, demoulding oil, gear oil, compressor oil (including refrigerator and gear pump), internal combustion engine oil, spindle, bearing and clutch oil, guide rail oil, hydraulic oil, metal processing oil, electrical insulating oil, pneumatic tool oil, heat transfer oil, temporary protection anti-corrosion oil, turbine oil, heat treatment oil, grease, steam cylinder oil, special lubricant application oil and other application occasions of oil rust prevention.

[0073] The present invention is further described in detail by the following examples, but they do not constitute any limitation to the present invention. The raw materials used in the examples can be obtained through commercial channels.

[0074] Among them, methyl oleate (content 96%) used in the following embodiments and comparative examples of the present invention was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., maleic anhydride (content 99.5%) was purchased from Beijing Inokai 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 the present invention, the acid value of the prepared oil rust inhibitor product is measured according to the method of GB / T 7304, and the solidification point is measured according to the method of GB / T 510.

[0076] Example 1

[0077] In this embodiment, a reaction intermediate of methyl oleate succinic anhydride is prepared, and the preparation method comprises the following steps:

[0078] A reactor with a specification of 3000 mL equipped with an electric stirrer, a thermometer, a reflux condenser and a nitrogen inlet tube was prepared, 1500 g of methyl oleate (mass fraction of 96%) and 745 g of maleic anhydride (the molar ratio of methyl oleate to maleic anhydride was about 1:1.5) were weighed and placed in the above reactor, nitrogen was introduced for 5-10 minutes, heated and stirred to 200° C., and after reacting for 8 hours, the excess maleic anhydride was removed by reduced pressure distillation to obtain a methyl oleate succinic anhydride reaction intermediate.

[0079] Example 2

[0080] Preparation of methyl oleyl succinic acid mono(ethylene glycol monomethyl ether) ester:

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

[0082] Figure 1 This is the mass spectrum of the rust inhibitor product prepared in Example 2, in which m / z=493 is the mass spectrum addition peak of the sodium ion of methyl oleyl succinate monoethylene glycol methyl ether.

[0083] Figure 2 This is the infrared spectrum of the rust inhibitor product prepared in Example 2. The peaks in the figure are attributed as follows:

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

[0085] Example 3

[0086] Preparation of methyl oleyl succinic acid mono(ethylene glycol mono-n-butyl ether) ester:

[0087] Weigh 200 g of the methyl oleate succinic anhydride reaction intermediate obtained in Example 1 and place it in a 500 mL reactor equipped with an electric stirrer, a thermometer, a reflux condenser and a nitrogen inlet tube, then add 59.8 g of ethylene glycol mono-n-butyl ether (the molar ratio of the methyl oleate succinic anhydride reaction intermediate to the ethylene glycol mono-n-butyl ether is 1:1), pass nitrogen for 5-10 minutes, stir and reflux for 2 hours at a constant temperature of 110°C, then distill under reduced pressure to remove the ethylene glycol mono-n-butyl ether, cool, and obtain the methyl oleate succinic acid mono-(ethylene glycol mono-n-butyl ether) ester product, which has an acid value of 45 mgKOH / g after being measured.

[0088] Example 4

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

[0090] Weigh 500 g of the methyl oleate succinic anhydride reaction intermediate obtained in Example 1 and place it in a 1000 mL reactor equipped with an electric stirrer, a thermometer, a reflux condenser and a nitrogen inlet tube, add 149.7 g of ethylene glycol tert-butyl ether (the molar ratio of the methyl oleate succinic anhydride reaction intermediate to ethylene glycol tert-butyl ether is 1: 1), pass nitrogen for 5-10 minutes, stir and reflux for 2 hours at a constant temperature of 110° C., then distill under reduced pressure to remove ethylene glycol tert-butyl ether, cool, and obtain a methyl oleate succinic acid mono (ethylene glycol mono-tert-butyl ether) ester product, which has an acid value of 40 mgKOH / g after being measured.

[0091] Comparative Example 1

[0092] 200 g of the methyl oleyl succinic anhydride reaction intermediate obtained in Example 1 was weighed and placed in a 500 mL reactor equipped with an electric stirrer, a thermometer, a reflux condenser and a nitrogen inlet tube, 34.3 g of propanol (the molar ratio of the methyl oleyl succinic anhydride reaction intermediate to the propanol was 1:1.2), nitrogen was introduced for 5-10 minutes, and the reaction was stirred and refluxed at a constant temperature of 80°C for 2 hours, and then the propanol was removed by distillation under reduced pressure, and the mixture was cooled to room temperature to obtain methyl oleyl succinic acid monopropyl ester, which had an acid value of 63 mgKOH / g after measurement.

[0093] Comparative Example 2

[0094] 200 g of the methyl oleyl succinic anhydride reaction intermediate obtained in Example 1 was weighed and placed in a 500 mL reactor equipped with an electric stirrer, a thermometer, a reflux condenser and a nitrogen inlet tube, 61.8 g of n-hexanol (the molar ratio of the methyl oleyl succinic anhydride reaction intermediate to the n-hexanol was 1:1.2), nitrogen was introduced for 5-10 minutes, and the reaction was stirred and refluxed at a constant temperature of 110°C for 3 hours, and then the n-hexanol was removed by distillation under reduced pressure, and the mixture was cooled to room temperature to obtain methyl oleyl succinic acid monohexyl ester, which had an acid value of 47 mgKOH / g after measurement.

[0095] Comparative Example 3

[0096] Weigh 200g of the methyl oleate succinic anhydride reaction intermediate obtained in Example 1 and place it in a 500mL reactor equipped with an electric stirrer, a thermometer, a reflux condenser, a water separator and a nitrogen inlet tube, add 115.2g of ethylene glycol monomethyl ether (the molar ratio of methyl oleate succinic anhydride reaction intermediate to ethylene glycol monomethyl ether is 1:3) and 1.58g of phosphotungstic acid catalyst, pass nitrogen, stir and react at a temperature of 110°C for 6 hours, separate the catalyst, distill off ethylene glycol monomethyl ether and water, and cool to obtain a methyl oleate succinic acid diethylene glycol monomethyl ether product, which has an acid value of 7.5mgKOH / g after being measured.

[0097] Rust test

[0098] The oil rust inhibitors prepared in Examples 2-4 and Comparative Examples 1-3 were added to the base oil to evaluate the anti-corrosion effect of the oil rust inhibitors. The physical and chemical performance indicators of the base oil gasoline are shown in Table 1.

[0099] Table 1 Basic physical and chemical properties of gasoline used for evaluation

[0100]

[0101]

[0102] The physical and chemical properties of base oil lubricant base oil are shown in Table 2.

[0103] Table 2 Physical and chemical properties of lubricating oil base oil

[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 and Comparative Examples 1-3, as well as industrial rust inhibitor product T747 (dodecenyl succinic acid half ester) produced by Shenyang Northern Petroleum Group were added to the base oil in a certain amount, and the anti-corrosion effect of the oil rust inhibitors was statistically analyzed. The test results are shown in Table 3.

[0106] Test method: The rust test of oil rust inhibitor is carried out according to GB / T 11143. 300mL of sample and 30mL of distilled water are mixed, and the cylindrical stainless steel rod is completely immersed in it, and stirred at 36℃ (gasoline) or 60℃ (base lubricating oil). The test cycle is 8 or 72 hours. After the test cycle, observe the traces and degree of rust on the stainless steel rod.

[0107] Table 3 Anti-corrosion results of rust inhibitors

[0108] Oil Sample <![CDATA[Added dose / mg·kg -1 > Test temperature / ℃ Rust test duration / h Corrosion evaluation Blank gasoline 0 36 8 Severe rust Blank lubricating oil 0 60 8 Severe rust 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 lubricant + T747 500 60 8 No rust Blank lubricant + T747 500 60 72 There are 11 rust spots Blank gasoline + comparative example 1 20 36 8 Severe rust Blank gasoline + comparative example 1 20 36 72 Severe rust Blank gasoline + comparative example 2 20 36 8 Severe rust Blank gasoline + comparative example 2 20 36 72 Severe rust Blank gasoline + comparative example 3 20 36 8 Severe rust Blank gasoline + comparative example 3 20 36 72 Severe rust

[0109] It can be seen from Table 3 that when the oil rust inhibitor prepared by the present invention is used to improve the rust resistance of base oil products, the rust resistance of gasoline and lubricating oil is good, and a small amount of additive in the base oil product can significantly improve the rust resistance of the oil product.

[0110] By comparing the anti-rust effects of the oil rust inhibitors prepared in Examples 2-4 of the present invention and the industrial rust inhibitor T747, it can be seen that the anti-rust effect of the rust inhibitor product of the present invention is better than that of the industrial rust inhibitor.

[0111] Freezing point test

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

[0113] Table 4 Solidification point of rust inhibitor

[0114] Rust inhibitor Freezing point / ℃ 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 the invention has a freezing point lower than -50°C, a low freezing point, and a wide application range, and can be used for rust prevention of oil products at ultra-low temperatures and high altitudes.

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

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

[0118] In addition, various embodiments of the present invention may be arbitrarily combined, and as long as they do not violate the concept of the present invention, they should also be regarded as the contents disclosed by the present invention.

Claims

1. A method for improving the anti-rust performance of oil products, characterized in that: The method comprises adding an oil rust inhibitor to a base oil, wherein the oil rust inhibitor has a structure as 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; 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.

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 substituted or unsubstituted C1-C 18 of hydrocarbon groups.

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, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, isooctyl, nonyl, isononyl, 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 product 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, grease, base oil for blended lubricating oil and grease, heavy oil, jet fuel oil, FCC slurry, asphalt, bitumen, extra heavy oil, tar, gas liquefied oil, coal liquefied oil, alkylate, 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, bio-ETBE fuel and bio-gasoline.

6. An oil composition, characterized in that: The invention comprises an oil product whose anti-rust performance is improved by the method described in any one of claims 1 to 5.

7. The oil composition according to claim 6, wherein: The oil product is gasoline, and the amount of the oil rust inhibitor added to the gasoline is 1-300 μg / g, preferably 10-200 μg / g, and more preferably 20-100 μg / g.

8. The oil composition according to claim 6, wherein: The oil product is lubricating oil or grease, and the amount of the oil 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.

9. The oil composition according to claim 6, wherein: The oil product is selected from one or more of total loss system oil, demoulding oil, gear oil, compressor oil, internal combustion engine oil, bearing oil, clutch oil, guide rail oil, hydraulic oil, metal processing oil, electrical insulating oil, pneumatic tool oil, heat transfer oil, anti-corrosion oil, turbine oil, heat treatment oil, grease and steam cylinder oil.

10. The oil composition according to claim 6, wherein: The oil composition further contains a basic additive, and the basic additive is selected from at least one of a lubricant, a detergent, an antioxidant and a demulsifier.

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