Methyl oleate succinic acid alcohol ether ester and preparation method and application thereof

Abstract

The invention relates to methyl oleate succinic acid alcohol ether ester with a structure as shown in a formula (I) or a formula (II), and in the formula (I), R1 is selected from-CH2-,-CH2CH2-,-CH (CH3) CH2-and-CH2CH (CH3)-; n is an integer selected from 1-15; and R2 is selected from substituted or unsubstituted C1-C40 alkyl groups. The invention also relates to a preparation method of the methyl oleate succinic acid alcohol ether ester and a diesel oil composition containing the methyl oleate succinic acid alcohol ether ester. The methyl oleate succinic acid alcohol ether ester provided by the invention can obviously improve the lubricating property of low-sulfur diesel oil, has an excellent effect of improving the lubricating property of the diesel oil by adding the methyl oleate succinic acid alcohol ether ester into the diesel oil, has a low freezing point and can be normally used under a low-temperature environment condition. # imgabs0 #

Description

Technical Field

[0001] The invention belongs to the field of petroleum processing, and in particular relates to methyl oleate succinate alcohol ether ester and a preparation method and application thereof. Background Art

[0002] As environmental issues become increasingly prominent, environmental regulations are becoming more and more stringent. For example, my country's National V and National VI diesel standards stipulate that the sulfur content of diesel is 10μg / g or less. Refineries generally use hydrofining to produce low-sulfur diesel to meet environmental protection requirements. However, while hydrodesulfurizing diesel, aromatics, polycyclic aromatic hydrocarbons and other components with lubricating properties in diesel will also be removed, resulting in poor lubrication performance of diesel. In order to avoid wear and damage to diesel engines as the sulfur content in diesel decreases, adding anti-wear agents to low-sulfur diesel is the simplest and most widely used method to improve the lubrication performance of low-sulfur diesel.

[0003] The lubrication form of diesel in the engine fuel system belongs to adsorption lubrication, which mainly relies on the diesel itself to form an adsorption film on the metal surface to achieve lubrication. In order to improve the lubrication performance of diesel, the anti-wear agent molecules need to meet the requirements of being able to quickly adsorb on the metal surface and form an adsorption film. At present, the improvers used to improve the lubrication performance of diesel in China are fatty acid compounds. This type of oxygen-containing compound has a strong polarity and is easily adsorbed by the friction surface to form an adsorption film, which has a good anti-wear effect. However, there are many problems when fatty acid compounds are used to improve the lubrication performance of diesel. For example, there are compatibility issues between fatty acid compounds and other additives of diesel, especially fatty acids are easy to react with nitrogen-containing compounds in diesel detergents, resulting in a double decrease in the anti-wear and detergency performance of diesel. In addition, the interaction between fatty acid anti-wear agents and high-base dispersants of diesel will cause the problem of fuel filter clogging, and if the acidity of the anti-wear agent is too strong, it will also corrode the metal.

[0004] Compared with fatty acid anti-wear agents, fatty acid alkyl ester anti-wear agents not only avoid the above problems, but also under the same additive dosage conditions, the lubrication performance of fatty acid alkyl ester anti-wear agents is more excellent, and there is no compatibility problem with other diesel additives, which is the best substitute for fatty acid anti-wear agents. For example, EP0605857A1 discloses a method of directly using fatty acid alkyl esters such as rapeseed oil, sunflower oil, castor oil as a diesel anti-wear agent. EP0739970A1 discloses a mixture of glycerides as an anti-wear agent for low-sulfur diesel, and the mixture contains glycerides with different degrees of esterification. US6511520 discloses a diesel anti-wear agent whose main components are fatty acid monoglyceride and fatty acid diglyceride.

[0005] WO2002100987A1 discloses a fatty amine-fatty acid alkyl ester-fatty acid mixture diesel antiwear agent, the preparation method of which comprises: esterifying a high melting point fatty acid with an unsaturated refined fusel oil to obtain a fatty acid alkyl ester, and reacting a high melting point fatty acid with a diamine compound or a lactam, N,N-dimethylamine or N,N-diethylamine to obtain a fatty acid amine.

[0006] CN106929112A discloses a method for improving the anti-wear property of low-sulfur diesel. The diesel anti-wear agent is a product of the esterification reaction of alkenyl succinic anhydride and monohydric fatty alcohol.

[0007] CN112779065A discloses a low-sulfur diesel antiwear agent and a preparation method thereof. The low-sulfur diesel antiwear agent is a product containing alkenyl succinic acid monoester compounds, which is prepared by an addition reaction of unsaturated fatty acid alkyl ester and unsaturated dicarboxylic acid anhydride, followed by an esterification reaction with fatty alcohol.

[0008] However, the effect of existing fatty acid ester antiwear agents in improving the lubricity of low-sulfur diesel still needs to be improved. Summary of the invention

[0009] The present invention aims to further improve the lubrication performance of low-sulfur diesel.

[0010] In order to achieve the above object, the first aspect of the present invention provides a methyl oleate succinate alcohol ether ester, wherein the methyl oleate succinate alcohol ether ester has a structure as shown in formula (I) or formula (II):

[0011]

[0012] wherein R1 is selected from -CH2-, -CH2CH2-, -CH(CH3)CH2-, -CH2CH(CH3)-; n is selected from an integer of 1 to 15; R2 is selected from substituted or unsubstituted C1 to C 40 of hydrocarbon groups.

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

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

[0015] The second aspect of the present invention provides a method for preparing methyl oleate succinate alcohol ether ester, the method comprising the following steps:

[0016] The methyl oleate succinic anhydride and the alcohol ether are subjected to an esterification reaction under esterification reaction conditions to obtain methyl oleate succinic acid alcohol ether ester; the chemical structural formula of the alcohol ether is R2[OR1] n OH; wherein R1 is selected from -CH2-, -CH2CH2-, -CH(CH3)CH2-, -CH2CH(CH3)-; n is selected from an integer of 1 to 15; R2 is selected from substituted or unsubstituted C1 to C 40 of hydrocarbon groups.

[0017] Optionally, the molar ratio of the methyl oleate succinic anhydride to the alcohol ether is 1:(0.5-3), preferably 1:(0.5-1.2); the conditions of the esterification reaction include: the reaction temperature is 40-180°C, preferably 50-120°C; the reaction time is 10min-8h, preferably 50-120°C.

[0018] Optionally, a catalyst and an inhibitor are further 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; the inhibitor is one or more of triethylamine and pyridine.

[0019] Preferably, a reaction solvent is further added in the esterification reaction, and the reaction solvent is one or more of petroleum ether, hexane, toluene, xylene and ethylbenzene.

[0020] Optionally, the methyl oleate succinic anhydride is prepared by olefin reaction of methyl oleate and maleic anhydride; the molar ratio of the methyl oleate to the maleic anhydride is 1:(0.1-10), preferably 1:(0.5-5), and more preferably 1:(1-3); the conditions of the olefin reaction include: the reaction temperature is 50-300°C, preferably 100-250°C, and more preferably 150-250°C; the reaction time is 1-20h, preferably 4-15h, and more preferably 6-12h.

[0021] Optionally, an antioxidant or a reaction solvent is further added to the olefin reaction, and the antioxidant is selected from one or more of phenolic antioxidants, amine antioxidants and heterocyclic antioxidants; based on the total weight of the methyl oleate and maleic anhydride, the amount of the antioxidant added is 0.01 to 10 wt%, preferably 0.05 to 1 wt%, and more preferably 0.1 to 0.5 wt%; preferably, the reaction solvent is one or more of toluene, xylene and ethylbenzene; preferably, the phenolic antioxidant is selected from 3-(3,5-di-tert-butyl-4-hydroxyphenyl) acrylate, antioxidant 10 10. One or more of antioxidant 2246, antioxidant 1076 and antioxidant 300; preferably, 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; preferably, 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.

[0022] The third aspect of the present invention provides a diesel composition, comprising diesel and the methyl oleate succinate alcohol ether ester described in the first aspect of the present invention, wherein the addition amount of the methyl oleate succinate alcohol ether ester to the diesel is 50 to 400 μg / g, preferably 100 to 300 μg / g; the sulfur content of the diesel is less than 500 μg / g.

[0023] Optionally, a basic additive is further added to the diesel composition, and the basic additive is selected from at least one of a flow improver, a cetane number improver, a detergent dispersant, a metal deactivator and a corrosion inhibitor.

[0024] Through the above technical scheme, the present invention introduces a polar group with a certain chain length into the structure of the reaction product of methyl oleate and maleic anhydride to obtain methyl oleate succinate alcohol ether ester, and the methyl oleate succinate alcohol ether ester can quickly form an adsorption film on the metal, and when it is used in diesel, the lubrication performance of low-sulfur diesel can be significantly improved; in addition, the methyl oleate succinate alcohol ether ester prepared by the present invention has the characteristic of a low freezing point and can be used normally under low temperature environmental conditions.

[0025] Other features and advantages of the present invention will be described in detail in the following detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 This is the mass spectrum of methyl oleyl succinic acid mono(ethylene glycol monomethyl ether) ester prepared in Example 2 of the present invention.

[0027] Figure 2This is the infrared spectrum of methyl oleyl succinate mono(ethylene glycol monomethyl ether) ester prepared in Example 2 of the present invention. DETAILED DESCRIPTION

[0028] The specific implementation of the present invention is described in detail below. It should be understood that the specific implementation described here is only used to illustrate and explain the present invention, and is not used to limit the present invention.

[0029] The first aspect of the present invention provides a methyl oleate succinate alcohol ether ester, wherein the methyl oleate succinate alcohol ether ester has a structure as shown in formula (I) or formula (II):

[0030]

[0031]

[0032] wherein R1 is selected from -CH2-, -CH2CH2-, -CH(CH3)CH2-, -CH2CH(CH3)-; n is selected from an integer of 1 to 15; R2 is selected from substituted or unsubstituted C1 to C 40 of hydrocarbon groups.

[0033] The invention introduces a polar group with a certain chain length into the structure of the reaction product of methyl oleate and maleic anhydride to obtain methyl oleate succinic acid alcohol ether ester. The methyl oleate succinic acid alcohol ether ester contains a large number of highly active oxygen atoms and can be stably adsorbed on the metal surface to form a firm protective film. When the methyl oleate succinic acid alcohol ether ester is used in diesel, the lubrication performance of low-sulfur diesel can be significantly improved, and the lubricity of low-sulfur diesel can be improved.

[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 at the same time.

[0035] wherein R1 is selected from -CH2CH2-, -CH(CH3)CH2-, -CH2CH(CH3)-; n is selected from an integer of 1 to 10; R2 is selected from substituted or unsubstituted C1 to C 18 of hydrocarbon groups.

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

[0037] In a specific embodiment of the present invention, R1 is ethyl or propyl, n is 1, 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, R1 is ethyl or propyl, n is 2, 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, R1 is ethyl or propyl, n is 3, and R2 is selected from methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl, isooctyl, nonyl, isononyl, isoundecyl and isotridecyl.

[0040] The second aspect of the present invention provides a method for preparing methyl oleate succinate alcohol ether ester, the method comprising the following steps:

[0041] Allowing methyl oleate succinic anhydride to react with alcohol ether under esterification reaction conditions to obtain methyl oleate succinic alcohol ether ester;

[0042] The chemical structural formula of the alcohol ether is R2[OR1] n OH; wherein R1 is selected from -CH2-, -CH2CH2-, -CH(CH3)CH2-, -CH2CH(CH3)-; n is selected from an integer of 1 to 15; R2 is selected from substituted or unsubstituted C1 to C 40 of hydrocarbon groups.

[0043] Among them, the molar ratio of the methyl oleate succinic anhydride to the alcohol ether is 1: (0.5-3), preferably 1: (0.5-1.2); the conditions of the esterification reaction include: the reaction temperature is 40-180°C, preferably 50-120°C; the reaction time is 10min-8h, preferably 0.5-2h.

[0044] Methyl oleate succinic anhydride and the structural formula R2[OR1] n The alcohol ether of OH undergoes esterification reaction to obtain oleic acid methyl ester succinic acid alcohol ether esters with different structures.

[0045] In a preferred embodiment of the present invention, when n is 1, the structural formula is R2[OR1] nThe alcohol ether of OH can be 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, propylene glycol monoisotridecanyl ether.

[0046] In a preferred embodiment of the present invention, when n is 2, the structural formula is R2[OR1] n The alcohol ether of OH can be diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol mono-tert-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.

[0047] In a preferred embodiment of the present invention, when n is 3, the structural formula is R2[OR1] n The alcohol ether of OH can be 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 mono-tert-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, tripropylene glycol monoisotridecanyl ether.

[0048] In order to accelerate the reaction rate, a catalyst is further added to the esterification reaction, and the catalyst is selected from one or more of aluminum chloride, sulfuric acid, hydrochloric acid, boron trifluoride, solid superacid, cation exchange resin and heteropolyacid. Under the esterification reaction conditions, the catalyst can not only accelerate the reaction rate of the oleyl methyl succinic anhydride and the alcohol ether, but also induce side reactions, so it is preferred not to use a catalyst.

[0049] In the present invention, the solid superacid refers to an acid that is stronger than 100% sulfuric acid, preferably an inorganic salt compound solid superacid (such as AlCl3-Cu-Cl2, etc.), a sulfate ion modified metal oxide solid superacid (such as SO4 2- / TiO2、SO4 2- / ZrO2, etc.) and heteropoly acid solid super acid catalysts, etc.

[0050] In the present invention, the cation exchange resin refers to a strong acid cation exchange resin, which dissociates H + In the esterification reaction of the present invention, the cation exchange resin is preferably a catalyst such as Amberlyst series resin.

[0051] In the present invention, heteropolyacid refers to the general term for condensed oxygen-containing acids obtained by condensing different oxygen-containing acids, which are protonic acids with uniform strength. Due to the low charge density on the surface of heteropolyacid molecules, the activity of protons is quite large, and heteropolyacids thus have strong Bronsted acidity. For example, in a specific embodiment of the present invention, the heteropolyacid used to catalyze the esterification reaction is preferably phosphotungstic acid.

[0052] In order to generate as much monoalcohol ether ester as possible and less or no diol ether ester as possible, an inhibitor may be added during the esterification reaction to inhibit the generation of diol ether ester, and the inhibitor is triethylamine and / or pyridine.

[0053] Wherein, a reaction solvent is also added in the esterification reaction, and the reaction solvent is one or more of toluene, xylene and ethylbenzene. In the esterification reaction process of the present invention, water produced by the reaction can be taken away by continuously introducing nitrogen, thereby avoiding the use of water-carrying agents such as benzene and toluene.

[0054] The methyl oleate succinic anhydride is prepared by reacting methyl oleate with maleic anhydride, wherein the molar ratio of the methyl oleate to the maleic anhydride is 1:(0.1-10), preferably 1:(0.5-5), and more preferably 1:(1-3).

[0055] The conditions for the olefin reaction include: a reaction temperature of 50 to 300° C., preferably 100 to 250° C., more preferably 150 to 250° C.; a reaction time of 1 to 20 h, preferably 4 to 15 h, more preferably 6 to 12 h.

[0056] Methyl oleate and maleic anhydride undergo an Alder-ene reaction, specifically a reaction with the following reaction formula:

[0057]

[0058] According to the position difference of the C=C double bond activation site on the main chain of methyl oleate, the obtained product methyl oleate succinic anhydride has the above two possible structures.

[0059] Wherein, an antioxidant is also added in the olefin reaction. Under the action of heat, light or oxygen, the chemical bonds of the reactants are broken to generate active free radicals and hydroperoxides, and the decomposition reaction of the hydroperoxides can also generate hydrocarbon oxygen free radicals and hydroxyl free radicals. These free radicals can trigger a series of free radical chain reactions, resulting in fundamental changes in the structure and properties of the reactants. Antioxidants can eliminate the free radicals that have just been generated, or promote the decomposition of hydroperoxides to prevent the chain reaction from continuing.

[0060] Wherein, the antioxidant is selected from one or more of phenolic antioxidants, amine antioxidants and heterocyclic antioxidants.

[0061] The phenolic antioxidant may be a monophenolic antioxidant, a bisphenolic antioxidant, a polyphenolic antioxidant or a combination thereof. Specifically, the phenolic antioxidant is selected from one or more of 3-(3,5-di-tert-butyl-4-hydroxyphenyl) acrylate, antioxidant 1010, antioxidant 2246, antioxidant 1076 and antioxidant 300.

[0062] Wherein, 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.

[0063] Wherein, 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.

[0064] In order to ensure the antioxidant performance of the antioxidant, the added amount of the antioxidant is 0.01-10wt%, preferably 0.05-1wt%, and more preferably 0.1-0.5wt%, based on the total weight of the methyl oleate and maleic anhydride.

[0065] Wherein, a reaction solvent is also added in the olefin reaction, and the reaction solvent is one or more of petroleum ether, hexane, toluene, xylene and ethylbenzene. In the present invention, the boiling range of petroleum ether can be 60-90°C, or 90-120°C.

[0066] The third aspect of the present invention provides a diesel composition, comprising diesel and the methyl oleyl succinic acid alcohol ether ester described in the first aspect of the present invention, wherein the amount of the methyl oleyl succinic acid alcohol ether ester added to the diesel is 50 to 400 μg / g, preferably 100 to 300 μg / g; the sulfur content of the diesel is less than 500 μg / g. In some specific embodiments of the present invention, the amount of the methyl oleyl succinic acid alcohol ether ester added to the diesel is 50 μg / g, 100 μg / g, 150 μg / g, 200 μg / g, 250 μg / g, 300 μg / g, 350 μg / g, 400 μg / g or any value within the aforementioned range.

[0067] The diesel fuel composition may also contain other additives, such as flow improvers, cetane number improvers, detergent dispersants, metal deactivators, preservatives, and the like.

[0068] The present invention is further described in detail by the following examples, but the present invention is not limited thereto. The raw materials used in the examples can be obtained through commercial channels unless otherwise specified.

[0069] The sources of the raw materials used in the following examples and comparative examples of the present invention are as follows:

[0070] Methyl oleate (content 96%) is produced by Shanghai Aladdin Biochemical Technology Co., Ltd.; maleic anhydride (content 99.5%) is produced by 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%) are produced by Shanghai Aladdin Biochemical Technology Co., Ltd.; n-propanol (99.5%) and n-hexanol (98%) are produced by Beijing Chemical Reagent Company.

[0071] In the present invention, the acid value of the prepared methyl oleyl succinic acid alcohol ether ester product is determined according to the method of GB / T7304, and the solidification point is determined according to the method of GB / T 510.

[0072] Example 1

[0073] Preparation of methyl oleate succinic anhydride reaction intermediate:

[0074] A 3000 mL reactor equipped with an electric stirrer, a thermometer, a reflux condenser and a nitrogen inlet tube was prepared, 1500 g of methyl oleate (mass fraction 96%) and 745 g of maleic anhydride (the molar ratio of methyl oleate to maleic anhydride was about 1:1.5) were added to the reactor, and then 11.2 g of antioxidant 2246 was added to the reactor, nitrogen was introduced into the reactor for 5 to 10 minutes, heated and stirred to 200°C, refluxed for 6 hours, and the excess maleic anhydride was removed by reduced pressure distillation to obtain a methyl oleate succinic anhydride reaction intermediate.

[0075] Example 2

[0076] Preparation of methyl oleyl succinic acid mono(ethylene glycol monomethyl ether) ester:

[0077] After the methyl oleate succinic anhydride reaction intermediate prepared in Example 1 is cooled to 60°C, 200g of the methyl oleate succinic anhydride reaction intermediate is placed in a 500mL reactor equipped with an electric stirrer, a thermometer, a reflux condenser and a nitrogen inlet tube, 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) is added to the reactor, and then nitrogen is introduced for 5 to 10 minutes. After stirring and reacting at a constant temperature of 60°C for 1 hour, the ethylene glycol monomethyl ether is removed by reduced pressure distillation; the product of the reduced pressure distillation is cooled to room temperature and allowed to stand for 24 hours to obtain a methyl oleate succinic acid mono (ethylene glycol monomethyl ether) ester product, and its acid value is measured to be 65mgKOH / g.

[0078] Figure 1 The mass spectrum of methyl oleyl succinate mono(ethylene glycol monomethyl ether) ester prepared in Example 2 of the present invention is shown in FIG. Figure 1 As shown, m / z=493 is the mass spectrum addition peak of the sodium ion of methyl oleyl succinate mono(ethylene glycol monomethyl ether) ester.

[0079] Figure 2 This is the infrared spectrum of methyl oleyl succinate mono(ethylene glycol monomethyl ether) ester prepared in Example 2 of the present invention, and the peaks in the spectrum are assigned as follows:

[0080] 2800cm -1 ~3000cm -1 and 1450cm -1 The peak indicates the presence of aliphatic hydrocarbon structure in the product structure; 1781cm -1 The peak represents the ester carbonyl group close to the carboxyl group; 1735 cm -1 The peak represents the ester group at the end of the long chain; 1708 cm -1 The peak represents carboxylic acid; 1217 cm -1 The nearby peaks indicate the 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 in the product structure.

[0081] Example 3

[0082] Preparation of methyl oleyl succinic acid mono(ethylene glycol mono-n-butyl ether) ester:

[0083] 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, 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) into the reactor, then introduce nitrogen for 5 to 10 minutes, stir and reflux for 2 hours at a constant temperature of 110°C, and then distill under reduced pressure to remove the ethylene glycol mono-n-butyl ether, cool the product of the reduced pressure distillation, 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.

[0084] Example 4

[0085] Preparation of methyl oleyl succinic acid mono(ethylene glycol mono-tert-butyl ether):

[0086] 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, add 59.8 g of ethylene glycol monotert-butyl ether (the molar ratio of the methyl oleate succinic anhydride reaction intermediate to the ethylene glycol monotert-butyl ether is 1:1) into the reactor, then introduce nitrogen for 5 to 10 minutes, stir and reflux under a constant temperature of 110° C. for 2 hours, and then remove the ethylene glycol monotert-butyl ether by vacuum distillation. Cool the product of the vacuum distillation to obtain the methyl oleate succinic acid mono(ethylene glycol monotert-butyl ether) ester product, which has an acid value of 40 mgKOH / g after being measured.

[0087] Comparative Example 1

[0088] Preparation of methyl oleyl succinate monopropyl ester:

[0089] 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) was added to the reactor, and then nitrogen was introduced for 5 to 10 minutes. After stirring and refluxing at a constant temperature of 80°C for 2 hours, the propanol was removed by distillation under reduced pressure and cooled to room temperature to obtain methyl oleyl succinic acid monopropyl ester, which had an acid value of 63 mgKOH / g after being measured.

[0090] Comparative Example 2

[0091] Preparation of methyl oleyl succinate monohexyl ester:

[0092] 200 g of the methyl oleate 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 oleate succinic anhydride reaction intermediate to n-hexanol was 1:1.2) was added to the reactor, and then nitrogen was introduced for 5 to 10 minutes. After stirring and reflux reaction at a constant temperature of 110° C. for 3 hours, the n-hexanol was removed by reduced pressure distillation and the mixture was cooled to room temperature to obtain methyl oleate succinic acid monohexyl ester, which had an acid value of 47 mgKOH / g after being measured.

[0093] Comparative Example 3

[0094] Preparation of methyl oleyl succinate bis(ethylene glycol monomethyl ether):

[0095] 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 into the reactor, pass nitrogen, stir the reaction at 110°C for 6 hours, separate the catalyst, distill off excess 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.

[0096] Lubricity test

[0097] The lubrication performance test uses hydrorefined low-sulfur diesel A and low-sulfur diesel B as base oils. The sulfur content of low-sulfur diesel A is 6 mg kg -1 The wear spot diameter is 647 μm, and the sulfur content of low-sulfur diesel B is 11 mg kg -1 The wear spot diameter is 545 μm. The specific properties of low-sulfur diesel A and low-sulfur diesel B are shown in Table 1.

[0098] The lubricity of diesel is measured by the wear scar diameter (WSD) at 60°C on a high-frequency reciprocating rig (HFRR) (produced by PCS Instruments, UK) according to the method described in CEC-F-06-A-96 or ISO / FDIS12156-1 (ASTM D6079 in the United States), and the reported result WS1.4 is obtained by correcting the effects of temperature and humidity. The HFRR method (ISO 12156-1) wear scar diameter WS1.4 of diesel before and after adding the oleyl methyl succinic acid alcohol ether ester of the present invention is shown in Table 2, wherein the smaller the wear scar diameter, the better the lubricity of the diesel.

[0099] At present, most diesel standards in the world, such as European standard EN 590 and Chinese automotive diesel standard GB / T 19147, use the wear diameter of less than 460μm (60℃) as the basis for the diesel lubricity qualification standard.

[0100] Table 1 Physical and chemical properties of diesel

[0101]

[0102]

[0103] The methyl oleate succinate alcohol ether ester prepared in Examples 2-4 of the present invention and the product prepared in Comparative Examples 1-3 were added to low-sulfur diesel to conduct a lubrication performance test. The test results are shown in Table 2.

[0104] Table 2 Diesel oil lubricity improvement effect

[0105] Oil Sample <![CDATA[Added dose / mg·kg -1 > WS1.4 / μm Blank Diesel A 0 647 Blank diesel A+Example 2 200 342 Blank diesel A+Example 3 200 380 Blank diesel A+Example 4 200 389 Blank diesel A+Comparative Example 1 200 410 Blank diesel A+Comparative Example 2 200 415 Blank diesel A+Comparative Example 3 200 495 Blank Diesel B 0 545 Blank Diesel B+Example 2 200 325 Blank Diesel B+Example 3 200 345 Blank Diesel B+Example 4 200 362 Blank diesel B+Comparative Example 1 200 395 Blank diesel B+Comparative Example 2 200 403 Blank diesel B+Comparative Example 3 200 487

[0106] As can be seen from Table 2, adding a small dose of the methyl oleyl succinic acid alcohol ether ester of the present invention can greatly improve the lubricity of low-sulfur diesel, so the methyl oleyl succinic acid alcohol ether ester provided by the present invention can significantly improve the lubricity of low-sulfur diesel. Among them, the effect of methyl oleyl succinic acid monoethylene glycol monomethyl ether ester on improving the lubricity of basic diesel is the most obvious, far exceeding the lubricity effect of methyl oleyl succinic acid monoethylene glycol mono-n-butyl ether ester or methyl oleyl succinic acid monoethylene glycol tert-butyl ether ester.

[0107] The methyl oleate succinate alcohol ether esters prepared in Examples 2-4 of the present invention and the products prepared in Comparative Examples 1-3 were subjected to freezing point tests. The test results are shown in Table 3.

[0108] Table 3 Comparison of freezing points

[0109] Methyl oleyl succinate alcohol ether ester Freezing point / ℃ Example 2 ＜-50℃ Example 3 ＜-50℃ Example 4 ＜-50℃ Comparative Example 1 -28℃ Comparative Example 2 -30℃ Comparative Example 3 ＜-50℃

[0110] From Table 3, it can be seen that the methyl oleyl succinic acid alcohol ether ester of the present invention has a low freezing point, which is much lower than that of methyl oleyl succinic acid monomethyl ester. Among them, the freezing points of methyl oleyl succinic acid monoethylene glycol monomethyl ether ester, methyl oleyl succinic acid monoethylene glycol mono-n-butyl ether ester, and methyl oleyl succinic acid monoethylene glycol tert-butyl ether ester are all less than -50°C, and can be widely used in severe cold areas.

[0111] 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.

[0112] 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.

[0113] 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 methyl oleate succinate alcohol ether ester, characterized in that: The methyl oleate succinate alcohol ether ester has a structure as shown in formula (I) or formula (II): wherein R1 is selected from -CH2-, -CH2CH2-, -CH(CH3)CH2-, -CH2CH(CH3)-; n is an integer selected from 1 to 15; R2 is selected from substituted or unsubstituted C1 to C 40 of hydrocarbon groups.

2. The methyl oleate succinate alcohol ether ester according to claim 1, wherein R1 is selected from -CH2CH2-, -CH(CH3)CH2-, -CH2CH(CH3)-; n is an integer selected from 1 to 10; R2 is selected from substituted or unsubstituted C1 to C 18 of hydrocarbon groups.

3. The methyl oleate succinate alcohol ether ester according to claim 2, wherein R1 is selected from ethyl and propyl; n is an integer selected from 1 to 3; R2 is selected from the group consisting of methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, isooctyl, nonyl, isononyl, decyl, isoundecyl and isotridecyl.

4. A method for preparing methyl oleate succinic acid alcohol ether ester, characterized in that: The method comprises the following steps: Allowing methyl oleate succinic anhydride to react with alcohol ether under esterification reaction conditions to obtain methyl oleate succinic alcohol ether ester; The chemical structural formula of the alcohol ether is R2[OR1] n OH; wherein R1 is selected from -CH2-, -CH2CH2-, -CH(CH3)CH2-, -CH2CH(CH3)-; n is an integer selected from 1 to 15; R2 is selected from substituted or unsubstituted C1 to C 40 of hydrocarbon groups.

5. The method according to claim 4, wherein: The molar ratio of the methyl oleate succinic anhydride to the alcohol ether is 1:(0.5-3), preferably 1:(0.5-1.2); The conditions of the esterification reaction include: reaction temperature of 40 to 180° C., preferably 50 to 120° C.; reaction time of 10 min to 8 h, preferably 0.5 to 2 h.

6. The method according to claim 4, wherein: A catalyst and an inhibitor are also added in 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; The inhibitor is one or more of triethylamine and pyridine; Preferably, a reaction solvent is further added in the esterification reaction, and the reaction solvent is one or more of petroleum ether, hexane, toluene, xylene and ethylbenzene.

7. The method according to claim 4, wherein: The methyl oleate succinic anhydride is prepared by reacting methyl oleate and maleic anhydride through ene reaction; The molar ratio of the methyl oleate to the maleic anhydride is 1:(0.1-10), preferably 1:(0.5-5), and more preferably 1:(1-3); The conditions for the olefin reaction include: a reaction temperature of 50 to 300° C., preferably 100 to 250° C., more preferably 150 to 250° C.; a reaction time of 1 to 20 hours, preferably 4 to 15 hours, more preferably 6 to 12 hours.

8. The method according to claim 7, wherein: An antioxidant or a reaction solvent is also added in the ene reaction, wherein the antioxidant is selected from one or more of phenolic antioxidants, amine antioxidants and heterocyclic antioxidants; Based on the total weight of the methyl oleate and maleic anhydride, the amount of the antioxidant added is 0.01 to 10 wt %, preferably 0.05 to 1 wt %, and more preferably 0.1 to 0.5 wt %; Preferably, the phenolic antioxidant is selected from one or more of 3-(3,5-di-tert-butyl-4-hydroxyphenyl) acrylate, antioxidant 1010, antioxidant 2246, antioxidant 1076 and antioxidant 300; Preferably, 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, antioxidant DNP, antioxidant H and antioxidant 4010; Preferably, 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; Preferably, the reaction solvent is one or more of toluene, xylene and ethylbenzene.

9. A diesel composition, characterized in that It comprises diesel and the methyl oleyl succinate alcohol ether ester according to any one of claims 1 to 3, wherein the addition amount of the methyl oleyl succinate alcohol ether ester in the diesel is 50 to 400 μg / g, preferably 100 to 300 μg / g; and the sulfur content of the diesel is less than 500 μg / g.

10. The diesel composition according to claim 9, wherein: The diesel composition is further added with a basic additive, wherein the basic additive is selected from at least one of a flow improver, a cetane number improver, a detergent dispersant, a metal deactivator and a corrosion inhibitor.

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