Methyl oleate-based succinic alcohol ether ester, and preparation method and application thereof

Abstract

The present application relates to the structure of the formula (I) or formula (II) shown in the methyl oleate succinic alcohol ether ester, wherein, R1 It is selected from -CH2-, -CH2CH2-, -CH (CH3) CH2-, -CH2CH (CH3)-; N It is selected from the integer of 1-15; R2 It is selected from the substituted or unsubstituted C1-C 40 Hydrocarbon group. The present application also relates to the preparation method of the methyl oleate succinic alcohol ether ester and the diesel composition comprising the methyl oleate succinic alcohol ether ester. The methyl oleate succinic alcohol ether ester provided by the present application can significantly improve the lubricating property of low sulfur diesel, and has excellent effect of improving the lubricating property of diesel with small addition amount in diesel, and the freezing point of the methyl oleate succinic alcohol ether ester is low, which can be normally used under low temperature environmental conditions.

Description

Technical Field

[0001] This invention belongs to the field of petroleum processing, specifically relating to a methyl oleate succinate alcohol ether ester, its preparation method, and its application. Background Technology

[0002] With increasingly prominent environmental issues and increasingly stringent environmental regulations, for example, my country's National V and National VI diesel standards stipulate that the sulfur content of diesel fuel must be 10 μg / g or below. Refineries generally use hydrorefining to produce low-sulfur diesel fuel to meet environmental requirements. However, hydrodesulfurization of diesel fuel also removes aromatics, polycyclic aromatic hydrocarbons, and other lubricating components, resulting in poor lubrication performance. To avoid wear and damage to diesel engines caused by the reduction in sulfur content, adding anti-wear agents to low-sulfur diesel fuel is the simplest and currently the most widely used method to improve its lubrication performance.

[0003] Diesel fuel lubrication in engine fuel systems is adsorption lubrication, primarily relying on the formation of an adsorption film on metal surfaces. To improve the lubrication performance of diesel fuel, anti-wear agents need to be able to rapidly adsorb onto metal surfaces and form an adsorption film. Currently, fatty acid compounds are used domestically to improve diesel fuel lubrication. These oxygenated compounds have strong polarity, are easily adsorbed by friction surfaces, and form an adsorption film, exhibiting good anti-wear effects. However, using fatty acid compounds to improve diesel fuel lubrication presents several problems. For example, there are compatibility issues between fatty acid compounds and other diesel fuel additives, especially since fatty acids readily react with nitrogen-containing compounds in diesel detergents, leading to a dual decrease in both anti-wear and detergent properties. Furthermore, the interaction between fatty acid anti-wear agents and high-alkalinity dispersants in diesel fuel can cause fuel filter clogging, and if the anti-wear agent is too acidic, it can corrode metals.

[0004] Compared to fatty acid-based anti-wear agents, fatty acid alkyl ester-based anti-wear agents not only avoid the aforementioned problems, but also exhibit superior lubrication performance under the same dosage conditions. Furthermore, they do not have compatibility issues with other diesel fuel additives, making them the optimal alternative to fatty acid-based anti-wear agents. For example, EP0605857A1 discloses a method for directly using fatty acid alkyl esters such as rapeseed oil, sunflower oil, and castor oil as diesel fuel anti-wear agents. EP0739970A1 discloses a mixture of glycerol esters as an anti-wear agent for low-sulfur diesel fuel, the mixture containing glycerol esters with different degrees of esterification. US6511520 discloses a diesel fuel anti-wear agent whose main components are fatty acid glycerol monoesters and fatty acid glycerol dieesters.

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

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

[0007] CN112779065A discloses a low-sulfur diesel anti-wear agent and its preparation method. The low-sulfur diesel anti-wear agent is a product containing an alkenyl succinic acid monoester compound, which is prepared by adding an unsaturated fatty acid alkyl ester to an unsaturated dicarboxylic acid anhydride and then esterifying it with a fatty alcohol.

[0008] However, the effectiveness of existing fatty acid ester-based anti-wear agents in improving the lubricity of low-sulfur diesel fuel still needs to be improved. Summary of the Invention

[0009] The purpose of this invention is to further improve the lubrication performance of low-sulfur diesel fuel.

[0010] To achieve the above objectives, a first aspect of the present invention provides a methyl oleate succinate ether ester having a structure as shown in formula (I) or formula (II):

[0011]

[0012] Wherein, R1 is selected from -CH2-, -CH2CH2-, -CH(CH3)CH2-, and -CH2CH(CH3)-; n is selected from integers from 1 to 15; R2 is selected from substituted or unsubstituted C1 to C2. 40 Hydrocarbon group.

[0013] Optionally, R1 is selected from -CH2CH2-, -CH(CH3)CH2-, and -CH2CH(CH3)-; n is selected from integers from 1 to 10; and R2 is selected from substituted or unsubstituted C1 to C2. 18 Hydrocarbon group.

[0014] Optionally, R1 is selected from ethyl and propyl; n is selected from integers from 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] A second aspect of the present invention provides a method for preparing methyl oleate succinate alcohol ether ester, the method comprising the following steps:

[0016] Oleate methyl succinic anhydride is reacted with an alcohol ether under esterification conditions to obtain oleate methyl 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 integers from 1 to 15; R2 is selected from substituted or unsubstituted C1 to C2. 40 Hydrocarbon group.

[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 esterification reaction conditions include: a reaction temperature of 40-180℃, preferably 50-120℃; and a reaction time of 10 min-8 h, preferably 50-120℃.

[0018] Optionally, a catalyst and an inhibitor are 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 added to the esterification reaction, and the reaction solvent is one or more of petroleum ether, hexane, toluene, xylene and ethylbenzene.

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

[0021] Optionally, an antioxidant or reaction solvent is added to the olefin reaction. 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 antioxidant added is 0.01–10 wt%, preferably 0.05–1 wt%, more preferably 0.1–0.5 wt%. Preferably, the reaction solvent is one or more of toluene, xylene, and ethylbenzene. Preferably, the phenolic antioxidant is selected from isooctyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)acrylate and antioxidant 10. 10. One or more of antioxidants 2246, 1076, and 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 (diphenylamine sulfide), 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] A third aspect of the present invention provides a diesel composition comprising diesel oil and the methyl oleate succinate ether ester described in the first aspect of the present invention, wherein the methyl oleate succinate ether ester is added to the diesel oil in an amount of 50 to 400 μg / g, preferably 100 to 300 μg / g; and the sulfur content of the diesel oil is less than 500 μg / g.

[0023] Optionally, the diesel composition may further contain a base additive selected from at least one of flow improvers, cetane number improvers, detergents and dispersants, metal deactivators, and preservatives.

[0024] Through the above technical solution, 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-based succinic acid alcohol ether ester. This methyl oleate-based succinic acid alcohol ether ester can rapidly form an adsorption film on metals, and when used in diesel fuel, it can significantly improve the lubrication performance of low-sulfur diesel fuel. In addition, the methyl oleate-based succinic acid alcohol ether ester prepared by the present invention has the characteristic of low freezing point and can be used normally under low temperature environment conditions.

[0025] Other features and advantages of the present invention will be described in detail in the following detailed description section. Attached Figure Description

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

[0027] Figure 2The infrared spectrum of methyl oleate succinate mono(ethylene glycol monomethyl ether) ester prepared in Example 2 of this invention. Detailed Implementation

[0028] 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.

[0029] A first aspect of the present invention provides a methyl oleate succinate having a structure as shown in formula (I) or formula (II):

[0030]

[0031]

[0032] Wherein, R1 is selected from -CH2-, -CH2CH2-, -CH(CH3)CH2-, and -CH2CH(CH3)-; n is selected from integers from 1 to 15; R2 is selected from substituted or unsubstituted C1 to C2. 40 Hydrocarbon group.

[0033] This 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-based succinic acid alcohol ether ester. This methyl oleate-based succinic acid alcohol ether ester contains a large number of highly active oxygen atoms, which can stably adsorb onto the metal surface to form a strong protective film. When used in diesel fuel, it can significantly improve the lubrication performance of low-sulfur diesel fuel and enhance its lubricity.

[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. It can also contain multiple of the above groups at the same time.

[0035] Wherein, R1 is selected from -CH2CH2-, -CH(CH3)CH2-, and -CH2CH(CH3)-; n is selected from integers from 1 to 10; R2 is selected from substituted or unsubstituted C1 to C2. 18 Hydrocarbon group.

[0036] Wherein, R1 is selected from ethyl and propyl; n is selected from integers from 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 one 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] A second aspect of the present invention provides a method for preparing methyl oleate succinate alcohol ether ester, the method comprising the following steps:

[0041] Oleate methyl succinic anhydride is esterified with an alcohol ether under esterification reaction conditions to obtain oleate methyl succinic anhydride 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 integers from 1 to 15; R2 is selected from substituted or unsubstituted C1 to C2. 40 Hydrocarbon group.

[0043] 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 esterification reaction conditions include: a reaction temperature of 40-180℃, preferably 50-120℃; and a reaction time of 10 min-8 h, preferably 0.5-2 h.

[0044] Oleate methyl succinic anhydride and structural formula R2[OR1] n OH alcohol ethers undergo esterification to yield methyl oleate succinate 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 ethers 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 monotert-butyl ether, ethylene glycol monopentyl ether, ethylene glycol monohexyl ether, ethylene glycol monoheptyl ether, ethylene glycol monooctyl ether, ethylene glycol monononyl ether, ethylene glycol monoisononyl ether, ethylene glycol monodecyl ether, ethylene glycol monoisodecyl ether, ethylene glycol monoisodecyl 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 monononyl ether, propylene glycol monoisononyl ether, propylene glycol monoisodecyl ether, and propylene glycol monoisodecyl 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 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, dipropylene glycol monoisotridecyl ether.

[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 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, tripropylene glycol monoisotridecyl ether.

[0048] 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. Under the esterification reaction conditions, the catalyst not only accelerates the reaction rate of the methyl oleate succinic anhydride with the alcohol ether but also triggers side reactions. Therefore, it is preferable not to use a catalyst.

[0049] In this invention, a solid superacid refers to an acid stronger than 100% sulfuric acid, preferably an inorganic salt complex type solid superacid (such as AlCl3-Cu-Cl2, etc.) or a sulfate ion modified metal oxide type solid superacid (such as SO4). 2- / TiO2、SO4 2- (e.g., ZrO2) and heteropolyacid solid superacid catalysts, etc.

[0050] In this invention, the cation exchange resin refers to a strong acid type cation exchange resin, which dissociates into H+ in solution. + Therefore, it exhibits acidity. In the esterification reaction of this invention, the cation exchange resin is preferably an Amberlyst series resin or other catalyst.

[0051] In this invention, heteropolyacids refer to the general term for condensed oxyacids obtained by condensing different oxyacids, and are proton acids with uniform strength. Due to the low charge density on the surface of heteropolyacid molecules, the protons are highly reactive, and therefore heteropolyacids exhibit strong bronsted acidity. For example, in one specific embodiment of this invention, the heteropolyacid used to catalyze the esterification reaction is preferably phosphotungstic acid.

[0052] In order to generate as many monool ether esters as possible and generate as few or no diol ether esters as possible, an inhibitor may be added during the esterification reaction to suppress the formation of diol ether esters. The inhibitor is triethylamine and / or pyridine.

[0053] The esterification reaction also includes the addition of a reaction solvent, which is one or more of toluene, xylene, and ethylbenzene. In the esterification reaction process of this invention, the water produced in the reaction can be carried away by continuously introducing nitrogen gas, thereby avoiding the use of dehydrating agents such as benzene and toluene.

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

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

[0056] Methyl oleate and maleic anhydride undergo an Alder-ene reaction, specifically as shown in the following reaction equation:

[0057]

[0058] Based on the difference in the position of the C=C double bond activation sites on the methyl oleate backbone, the resulting product, methyl oleate succinic anhydride, has the two possible structures mentioned above.

[0059] In this process, antioxidants are added to the alkene reaction. Under the influence of heat, light, or oxygen, the chemical bonds of the reactants break, generating reactive free radicals and hydroperoxides. The hydroperoxides then decompose, generating hydrocarbon oxygen radicals and hydroxyl radicals. These free radicals can initiate a series of free radical chain reactions, leading to fundamental changes in the structure and properties of the reactants. Antioxidants can eliminate newly generated free radicals or promote the decomposition of hydroperoxides, thus preventing the chain reaction from continuing.

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

[0061] The phenolic antioxidant can 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] 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] 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] To ensure the antioxidant properties, the amount of antioxidant added is 0.01 to 10 wt%, preferably 0.05 to 1 wt%, and more preferably 0.1 to 0.5 wt%, based on the total weight of the methyl oleate and maleic anhydride.

[0065] In this process, a reaction solvent is added to the olefin reaction. The reaction solvent is one or more selected from petroleum ether, hexane, toluene, xylene, and ethylbenzene. In this invention, the boiling range of petroleum ether can be 60–90°C or 90–120°C.

[0066] A third aspect of the present invention provides a diesel composition comprising diesel fuel and the methyl oleate succinate described in the first aspect of the present invention, wherein the methyl oleate succinate is added to the diesel fuel in an amount of 50–400 μg / g, preferably 100–300 μg / g; and the sulfur content of the diesel fuel is less than 500 μg / g. In some specific embodiments of the present invention, the amount of the methyl oleate succinate added to the diesel fuel 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 composition may also contain other additives, such as flow improvers, cetane number improvers, detergents and dispersants, metal deactivators, and preservatives.

[0068] The present invention will be further described in detail below through examples, but these examples do not constitute any limitation on the invention. Unless otherwise specified, all raw materials used in the examples are commercially available.

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

[0070] Methyl oleate (96%) was produced by Shanghai Aladdin Biochemical Technology Co., Ltd.; maleic anhydride (99.5%) was produced by Beijing Innocare Technology Co., Ltd.; ethylene glycol monomethyl ether (98%), ethylene glycol monobutyl ether (99.7%), and ethylene glycol tert-butyl ether (98%) were produced by Shanghai Aladdin Biochemical Technology Co., Ltd.; n-propanol (99.5%) and n-hexanol (98%) were produced by Beijing Chemical Reagent Company.

[0071] In this invention, the acid value of the prepared methyl oleate succinate alcohol ether ester product was determined according to the method of GB / T7304, and the freezing point was determined according to the method of GB / T 510.

[0072] Example 1

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

[0074] Prepare a 3000mL reactor equipped with an electric stirrer, thermometer, reflux condenser, and nitrogen inlet. Add 1500g of methyl oleate (96% by mass) and 745g of maleic anhydride (the molar ratio of methyl oleate to maleic anhydride is approximately 1:1.5) to the reactor. Then add 11.2g of antioxidant 2246 to the reactor. Purge the reactor with nitrogen for 5-10 minutes, heat and stir to 200℃, and reflux for 6 hours. Remove excess maleic anhydride by vacuum distillation to obtain the methyl oleate-based succinic anhydride reaction intermediate.

[0075] Example 2

[0076] Preparation of methyl oleate succinate mono(ethylene glycol monomethyl ether) ester:

[0077] After the methyl oleate-based succinic anhydride reaction intermediate prepared in Example 1 was cooled to 60°C, 200g of the methyl oleate-based succinic anhydride reaction intermediate was placed in a 500mL reactor equipped with an electric stirrer, thermometer, reflux condenser and nitrogen inlet tube. 38.4g of ethylene glycol monomethyl ether (the molar ratio of methyl oleate-based succinic anhydride reaction intermediate to ethylene glycol monomethyl ether was 1:1) was added to the reactor. Nitrogen gas was then introduced for 5-10 minutes, and the reaction was stirred at a constant temperature of 60°C for 1 hour. After that, the ethylene glycol monomethyl ether was removed by vacuum distillation. The product obtained by vacuum distillation was cooled to room temperature and allowed to stand for 24 hours to obtain the methyl oleate-based succinic acid mono(ethylene glycol monomethyl ether) ester product. Its acid value was determined to be 65mgKOH / g.

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

[0079] Figure 2 The infrared spectrum of methyl oleate succinate mono(ethylene glycol monomethyl ether) ester prepared in Example 2 of this invention is shown below. 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 structures in the product; 1781 cm⁻¹ -1 The peak indicates an ester carbonyl group close to the carboxyl group; 1735 cm⁻¹ -1 The peak represents the ester group at the end of the long chain; 1708 cm⁻¹ -1 The peak represents a carboxylic acid; 1217 cm⁻¹ -1 The nearby peaks indicate the 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 in the product.

[0081] Example 3

[0082] Preparation of methyl oleate succinate mono(ethylene glycol mono-n-butyl ether) ester:

[0083] 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. 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 to the reactor. Nitrogen gas was then introduced for 5-10 minutes. The mixture was stirred and refluxed at a constant temperature of 110°C for 2 hours. After that, the ethylene glycol mono-n-butyl ether was removed by vacuum distillation. The product obtained by vacuum distillation was cooled to obtain methyl oleate succinic acid mono(ethylene glycol mono-n-butyl ether) ester. Its acid value was determined to be 45mgKOH / g.

[0084] Example 4

[0085] Preparation of methyl oleate succinate mono(ethylene glycol monotert-butyl ether) ester:

[0086] 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. 59.8g of ethylene glycol monotert-butyl ether (the molar ratio of methyl oleate succinic anhydride reaction intermediate to ethylene glycol monotert-butyl ether was 1:1) was added to the reactor. Nitrogen gas was then introduced for 5-10 minutes. The mixture was stirred and refluxed at a constant temperature of 110°C for 2 hours. After removing the ethylene glycol monotert-butyl ether by vacuum distillation, the product obtained by vacuum distillation was cooled to obtain methyl oleate succinic acid mono(ethylene glycol monotert-butyl ether) ester. Its acid value was determined to be 40mgKOH / g.

[0087] Comparative Example 1

[0088] Preparation of methyl oleate monopropyl succinate:

[0089] 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 (the molar ratio of methyl oleate succinic anhydride reaction intermediate to propanol was 1:1.2) was added to the reactor, and then nitrogen was introduced for 5-10 minutes. The mixture was stirred and refluxed at a constant temperature of 80°C for 2 hours. After that, the propanol was removed by vacuum distillation. After cooling to room temperature, monopropyl methyl oleate succinate was obtained. Its acid value was determined to be 63mgKOH / g.

[0090] Comparative Example 2

[0091] Preparation of methyl oleate monohexyl succinate:

[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. 61.8g of n-hexanol (the molar ratio of methyl oleate succinic anhydride reaction intermediate to n-hexanol was 1:1.2) was added to the reactor, and then nitrogen was introduced for 5-10 minutes. The mixture was stirred and refluxed at a constant temperature of 110°C for 3 hours. After that, the n-hexanol was removed by vacuum distillation. After cooling to room temperature, methyl oleate succinic acid monohexyl ester was obtained. Its acid value was determined to be 47mgKOH / g.

[0093] Comparative Example 3

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

[0095] 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, water separator and nitrogen inlet pipe. 115.2g of ethylene glycol monomethyl ether (the molar ratio of methyl oleate succinic anhydride reaction intermediate to ethylene glycol monomethyl ether was 1:3) and 1.58g of phosphotungstic acid catalyst were added to the reactor. Nitrogen gas was introduced and the reaction was stirred at 110°C for 6 hours. The catalyst was separated, and excess ethylene glycol monomethyl ether and water were removed by distillation. After cooling, the diethylene glycol monomethyl ether ester of methyl oleate succinic acid was obtained. Its acid value was determined to be 7.5mgKOH / g.

[0096] Lubricity test

[0097] The lubrication performance test used hydrotreated low-sulfur diesel A and low-sulfur diesel B as base oils, with low-sulfur diesel A having a sulfur content of 6 mg·kg⁻¹. -1 The wear scar diameter is 647 μm, and the sulfur content of low-sulfur diesel B is 11 mg·kg⁻¹. -1 The wear scar 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 fuel was determined according to the method described in CEC-F-06-A-96 or ISO / FDIS12156-1 (the American method is ASTM D6079) using a High-Frequency Reciprocating Rig (HFRR) (manufactured by PCS Instruments, UK) at 60°C. The reported result, WS1.4, was obtained after correcting for the effects of temperature and humidity. Table 2 shows the HFRR method (ISO 12156-1) wear scar diameters (WS1.4) of diesel fuel before and after adding the methyl oleate succinate alcohol ether ester of this invention. A smaller wear scar diameter indicates better lubricity of the diesel fuel.

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

[0100] Table 1. Physicochemical properties of diesel fuel

[0101]

[0102]

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

[0104] Table 2. Effects of Diesel Lubricity Improvement

[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 fuel B + Comparative Example 1 200 395 Blank diesel fuel B + Comparative Example 2 200 403 Blank diesel fuel B + Comparative Example 3 200 487

[0106] As shown in Table 2, adding a small dose of the methyl oleate succinate alcohol ether ester of the present invention can greatly improve the lubrication performance of low-sulfur diesel fuel. Therefore, the methyl oleate succinate alcohol ether ester provided by the present invention can significantly improve the lubrication performance of low-sulfur diesel fuel. Among them, the methyl oleate succinate monoethylene glycol monomethyl ether ester has the most significant effect on improving the lubrication performance of base diesel fuel, far exceeding the lubrication effect of methyl oleate succinate monoethylene glycol monobutyl ether ester or methyl oleate succinate monoethylene glycol tert-butyl ether ester.

[0107] The solidification point of the methyl oleate succinate alcohol ether ester prepared in Examples 2-4 of the present invention and the products prepared in Comparative Examples 1-3 were tested, and the test results are shown in Table 3.

[0108] Table 3 Comparison of Freezing Points

[0109] methyl oleate succinate alcohol ether ester Freezing point / °C Example 2 ＜-50℃ Example 3 ＜-50℃ Example 4 ＜-50℃ Comparative Example 1 -28℃ Comparative Example 2 -30℃ Comparative Example 3 ＜-50℃

[0110] As shown in Table 3, the methyl oleate-based succinic acid alcohol ether ester of the present invention has a low freezing point, which is much lower than that of methyl oleate-based monomethyl succinate. Among them, methyl oleate-based ethylene glycol monomethyl ether ester, methyl oleate-based ethylene glycol mono-n-butyl ether ester, and methyl oleate-based ethylene glycol monotert-butyl ether ester all have freezing points < -50℃, making them widely applicable to extremely cold regions.

[0111] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details of 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.

[0112] 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.

[0113] 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 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): ； Among them, R1 is selected from -CH2-, -CH2CH2-, -CH(CH3)CH2-, and -CH2CH(CH3)-; n is an integer selected from 1 to 15; R2 is selected from unsubstituted C1~C1. 18 Hydrocarbon group.

2. The methyl oleate succinate alcohol ether ester according to claim 1, wherein, R1 is selected from -CH2CH2-, -CH(CH3)CH2-, and -CH2CH(CH3)-. n is an integer selected from 1 to 10.

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 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 succinate alcohol ether ester according to any one of claims 1-3, characterized in that, The method includes the following steps: Oleate methyl succinic anhydride is esterified with an alcohol ether under esterification reaction conditions to obtain oleate methyl succinic anhydride alcohol ether ester. The chemical structural formula of the alcohol ether is R2[OR1]. n OH; Among them, R1 is selected from -CH2-, -CH2CH2-, -CH(CH3)CH2-, and -CH2CH(CH3)-; n is an integer selected from 1 to 15; R2 is selected from unsubstituted C1~C1. 18 Hydrocarbon group.

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); The conditions for the esterification reaction include: a reaction temperature of 40~180℃ and a reaction time of 10min~8h.

6. The method according to claim 5, wherein, The molar ratio of the methyl oleate succinic anhydride to the alcohol ether is 1:(0.5~1.2); The conditions for the esterification reaction include: a reaction temperature of 50~120℃ and a reaction time of 0.5~2h.

7. The method according to claim 4, wherein, The esterification reaction also includes the addition of catalysts and inhibitors; 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.

8. The method according to claim 7, wherein, The esterification reaction also includes the addition of a reaction solvent, which is one or more of petroleum ether, hexane, toluene, xylene, and ethylbenzene.

9. The method according to claim 4, wherein, The methyl oleate-based succinic anhydride is prepared by reacting methyl oleate and maleic anhydride with an olefin reaction. The molar ratio of methyl oleate to maleic anhydride is 1:(0.1~10); The conditions for the olefin reaction include: a reaction temperature of 50~300℃ and a reaction time of 1~20h.

10. The method according to claim 9, wherein, The molar ratio of methyl oleate to maleic anhydride is 1:(0.5~5); The conditions for the olefin reaction include: a reaction temperature of 100~250℃ and a reaction time of 4~15h.

11. The method according to claim 10, wherein, The molar ratio of methyl oleate to maleic anhydride is 1:(1~3); The conditions for the olefin reaction include: a reaction temperature of 150~250℃ and a reaction time of 6~12h.

12. The method according to claim 9, wherein, The olefin reaction also involves the addition of an antioxidant or a reaction solvent, 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 antioxidant added is 0.01~10 wt%.

13. The method according to claim 12, wherein, Based on the total weight of the methyl oleate and maleic anhydride, the amount of antioxidant added is 0.05~1 wt%.

14. The method according to claim 13, wherein, Based on the total weight of the methyl oleate and maleic anhydride, the amount of antioxidant added is 0.1~0.5 wt%.

15. The method according to any one of claims 12-14, wherein, 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; 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; 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; The reaction solvent is one or more of toluene, xylene, and ethylbenzene.

16. A diesel fuel composition, characterized in that, The mixture includes diesel fuel and methyl oleate succinate as described in any one of claims 1-3, wherein the amount of methyl oleate succinate added to the diesel fuel is 50-400 μg / g; and the sulfur content of the diesel fuel is less than 500 μg / g.

17. The diesel composition according to claim 16, wherein, The amount of methyl oleate succinate added to the diesel fuel is 100~300 μg / g.

18. The diesel composition according to claim 16 or 17, wherein, The diesel composition also contains a basic additive selected from at least one of flow improvers, cetane number improvers, detergents and dispersants, metal deactivators, and preservatives.

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