An anti-wear additive, its preparation method and application in oil products

Abstract

An anti-wear additive, which contains a compound shown in structural formula 1: wherein R1 and R2 are single bonds or C1-C20 hydrocarbon groups, R3 and R4 are independently hydrogen or C1-C10 hydrocarbon groups, and X and Y groups are independently hydrogen or C1-C50 hydrocarbon groups, oxygen-containing functional groups or nitrogen-containing functional groups. The anti-wear agent product is added in a small amount in oil products, can significantly improve the lubrication performance of oil products, has good stability, is not easy to oxidize and deteriorate, and can maintain a good anti-wear effect for a long time.

Description

Technical Field

[0001] The present invention relates to the field of oil additives, in particular to an additive for improving the lubricating performance of oil and an oil composition containing the additive. Background Art

[0002] In order to meet environmental protection requirements, low-sulfur or ultra-low-sulfur diesel has become the goal pursued by countries around the world. With the continuous improvement of hydrorefining technology, other lubricating components such as oxygen-containing nitrogen-containing compounds and polycyclic aromatic hydrocarbons will be removed while producing low-sulfur diesel. The lubrication performance of diesel will deteriorate, which will cause wear when the diesel engine is working, making it difficult to ensure the normal operation of the engine. In order to improve the lubrication performance of diesel, adding anti-wear agents with lubricating properties to low-sulfur diesel is currently the simplest, most effective and economical method.

[0003] CN109576063A discloses a low-sulfur diesel antiwear agent and a preparation method, which comprises mixing the esterification product of maleic anhydride, a vegetable oil fatty acid having a non-conjugated double bond, and a catalyst in proportion, reacting for a certain time at 180-220°C under stirring conditions, cooling after the reaction, recovering the catalyst, and obtaining an antiwear agent product after vacuum distillation. Although the antiwear agent product prepared by this process exhibits good antiwear performance, the source of raw materials is relatively limited, thus greatly increasing the production cost of the antiwear agent product, which is not conducive to industrial production. On the other hand, the prepared antiwear agent product has poor oxidation stability, is difficult to maintain a stable antiwear effect, is not conducive to the storage of the antiwear agent product, and has high storage requirements for the product.

[0004] CN103540369B discloses a low-sulfur diesel antiwear agent composition, which is composed of the following components by mass fraction: 30-50 parts of glyceryl stearate, 10-20 parts of isocetyl palmitate, 10-20 parts of cetyl ethylhexanoate, and 10-20 parts of lanolin alcohol polyether-25. Although the antiwear agent product provided can improve the lubrication performance of low-sulfur diesel, the source of raw materials is limited, resulting in high preparation costs of the antiwear agent product.

[0005] CN101768480B discloses a diesel antiwear agent, which is composed of raw materials (A) at least one amide component, (B) at least one amine oiliness agent component, (C) at least one ester oiliness agent component, (D) at least one rust inhibitor, (E) at least one demulsifier, and (F) at least one organic solvent. Although the antiwear agent product can improve the lubrication performance of low-sulfur diesel, the antiwear agent product contains nitrogen-containing components such as amines and amide compounds. Adding them to diesel will lead to the generation of nitrogen oxides, which is not in line with the concept of green chemistry.

[0006] CN109929624B discloses a fatty acid diesel antiwear agent and a formula, which is specifically composed of 80 parts by weight of fatty acid diesel antiwear agent and 20 parts by weight of organic nitrogen molybdenum fullerene lubricant. However, on the one hand, the antiwear agent product has a general effect of improving the lubricity of low-sulfur diesel, and on the other hand, since one of the components of the additive is organic nitrogen molybdenum fullerene, the preparation cost of the antiwear agent product is greatly increased, and the industrialization prospect is relatively small.

[0007] EP1404726A2 discloses a polymer antiwear agent that can be used to improve the lubricity of low-sulfur diesel. The additive is composed of a polyisobutenyl succinic anhydride derivative with a number average molecular weight of 300 to 1000 or a polyisobutenyl succinic anhydride derivative with a number average molecular weight of 2000 to 20000. However, the polymerization reaction conditions are relatively harsh and the requirements for production equipment are relatively high. In addition, the polymerization reaction is difficult to control. If the molecular weight of the polymer is too high, it is difficult to dissolve in diesel and it is difficult to show good antiwear performance. Summary of the invention

[0008] The present invention provides an anti-wear agent product capable of improving the lubricating performance of oil products. The anti-wear agent product can exhibit good anti-wear performance in fuel oil products and lubricating oil products and has good stability.

[0009] The invention also provides a preparation method of the antiwear agent.

[0010] The present invention also provides an oil product composition containing the anti-wear agent and an application method of the anti-wear agent product in oil products.

[0011] In order to achieve the above object, the present invention provides an anti-wear additive for improving the lubrication performance of oil products, wherein the additive is a compound having a structural formula 1:

[0012] (Structural Formula 1)

[0013] Among them, R1 and R2 are single bonds or C1-C20 hydrocarbon groups, R3 and R4 are each independently hydrogen or C1-C10 hydrocarbon groups, and X and Y groups are each independently hydrogen or C1-C50 hydrocarbon groups, oxygen-containing functional groups or nitrogen-containing functional groups.

[0014] The hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, such as normal alkanes, isoalkanes, cycloalkanes, aromatic hydrocarbons, normal olefins, isoolefins, cycloolefins, and the like.

[0015] Preferably, R1 and R2 are single bonds or C1-C10 alkanes or alkenes, R3 and R4 are hydrogen or C1-C5 alkanes or alkenes; the X group and the Y group are hydrogen or C4-30 alkanes, alkenes, oxygen-containing functional groups or nitrogen-containing functional groups.

[0016] Further preferably, R1 and R2 are single bonds or C1-C4 alkanes or alkenes, R3 and R4 are hydrogen or C1-C2 alkanes or alkenes; the X group and the Y group are hydrogen or C4-C20 normal alkanes, alkenes, oxygen-containing functional groups, and nitrogen-containing functional groups.

[0017] Most preferably, R1 and R2 are single bonds, and R3 and R4 are hydrogen or C1-C2 normal alkanes.

[0018] When R1 and R2 are single bonds, and R3 and R4 are hydrogen, the antiwear agent is a compound structure shown in Structural Formula 2:

[0019] (Structural Formula 2)

[0020] In structural formula 2, it is further preferred that the X group is hydrogen, and the Y group is a C4-C20 normal alkane, normal olefin, isoalkane, isoolefin, oxygen-containing functional group, or nitrogen-containing functional group.

[0021] In structural formula 2, when the Y group is a normal alkane or an isoalkane, it may specifically include but is not limited to n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl, isodecyl, n-dodecyl, isododecyl, n-tetradecyl, isomeric tetradecyl, n-hexadecyl, isomeric hexadecyl, n-octadecyl, isomeric octadecyl, n-eicosyl, isomeric eicosyl, and the like; when the Y group is a normal alkenyl or an isomeric alkenyl, it may specifically include but is not limited to n-butenyl, isobutenyl, n-pentenyl, isopentenyl, n-alkenylhexyl, isohexenyl, n-heptenyl, isoheptenyl, n-octenyl, isooctenyl, n-nonenyl, isononenyl, n-decenyl, isodecenyl, n-dodecenyl, isododecenyl, n-tetradecenyl, isomeric tetradecenyl, n-hexadecenyl, isomeric hexadecenyl, , n-octadecene, isooctadecene, n-eicosenyl, isoicosenyl, etc.; when the Y group is a cycloalkane, it includes but is not limited to cyclopentane, cyclohexane, methylcycloalkyl, methylcyclohexane, etc.; when the Y group is a cycloolefin, it includes but is not limited to cyclopentene, cyclohexene, methylcyclopentene, methylcyclohexene, etc.; when the Y group is an oxygen-containing functional group, it includes but is not limited to hydroxyl (-OH), carboxyl (-COOH), ester group (-COOR), ether group (ROR) and hydroxyl (-OH), and the specific structure may include but is not limited to: -C8H16OH, -C8H16COOH, -C8H16COOCH=CH2, -C2H4OC7H14CH3, -C17H34COOCH3, -C17H34COOH, -C17H32COOH, -C17H32COOCH3, etc.

[0022] When the Y group is a nitrogen-containing functional group, it includes but is not limited to amino (-HNx), amide (-NOH), etc. It includes but is not limited to: -C8H16NH2, -C2H4NHOC8H16, -(C2H4)2NOC8H16, etc.

[0023] Specifically, the compound of the structural formula 1 may include but is not limited to the following compounds: mono-n-butyl epoxysuccinate, mono-isobutyl epoxysuccinate, mono-n-pentyl epoxysuccinate, mono-isopentyl epoxysuccinate, mono-n-octyl epoxysuccinate, mono-isooctyl epoxysuccinate, mono-n-nonyl epoxysuccinate, mono-isononyl epoxysuccinate, mono-lauryl epoxysuccinate, mono-octadecyl epoxysuccinate, mono-oleyl epoxysuccinate, etc.; Epoxysuccinic acid monocyclopentanol ester, epoxysuccinic acid monocyclohexanol ester, epoxysuccinic acid monopolyethylene glycol monomethyl ether ester, epoxysuccinic acid monopolyethylene glycol ester, epoxysuccinic acid polypropylene glycol ester, epoxysuccinic acid polypropylene glycol monobutyl ether ester, epoxysuccinic acid monoricinoleic acid ester, epoxysuccinic acid monoricinoleic acid methyl ester, 12-hydroxystearic acid monoepoxysuccinic acid ester, 12-hydroxystearic acid methyl ester epoxysuccinic acid ester, and the like.

[0024] The present invention provides two methods for preparing the antiwear agent. The first method comprises the following steps:

[0025] (1) a half-esterification reaction is carried out between an unsaturated dibasic acid or anhydride and a hydroxyl-containing compound to obtain a reaction intermediate;

[0026] (2) The reaction intermediate is then subjected to epoxidation reaction with a peroxide in the presence of a catalyst to obtain a product.

[0027] Wherein, in step (1), the half-esterification reaction temperature is 20 to 200° C., preferably 50 to 150° C., most preferably 75 to 120° C.; the reaction time is 0.5 to 20 hours, preferably 1 to 10 hours, most preferably 1 to 4 hours; and the molar ratio of the unsaturated dibasic acid or anhydride to the hydroxyl-containing compound is 1:0.1 to 5, preferably 1:0.5 to 3, most preferably 1:1 to 2.

[0028] In step (2), the molar ratio of the reaction intermediate to the peroxide is 1:0.1 to 10, preferably 1:0.5 to 5, and most preferably 1:1 to 3; the reaction time is 0.5 to 20 hours, preferably 1 to 10 hours; the reaction temperature is 0 to 180°C, more preferably 20 to 150°C, and most preferably 30 to 100°C.

[0029] The second preparation method comprises the following steps:

[0030] (1) an unsaturated dibasic acid or anhydride is subjected to an epoxidation reaction with a peroxide in the presence of a catalyst to obtain a reaction intermediate;

[0031] (2) The reaction intermediate is then subjected to a half-esterification reaction with a hydroxyl-containing compound to obtain a product.

[0032] Wherein, in step (1), the temperature of the epoxidation reaction is 0°C to 180°C, preferably 20°C to 150°C, and most preferably 30°C to 100°C. The epoxidation reaction time is 0.5h to 30h, preferably 1h to 20h, and most preferably 6h to 10h. The molar ratio of the unsaturated dibasic acid or anhydride to the peroxide is 1:0.1 to 10, preferably 1:0.5 to 5, and most preferably 1:1 to 3.

[0033] In step (2), the half-esterification reaction temperature is 20-200°C, preferably 50-150°C, and most preferably 75-120°C; the reaction time is 0.5h-20h, preferably 1h-10h, and most preferably 1h-4h; the molar ratio of the epoxide intermediate to the hydroxyl-containing compound is 1:0.1-5, preferably 1:0.5-3, and most preferably 1:1-2.

[0034] According to the two preparation methods of the present invention, the unsaturated dibasic acid or anhydride includes but is not limited to: maleic acid, fumaric acid, maleic anhydride (maleic anhydride), fumaric anhydride (fumaric anhydride), 2,3-dimethylmaleic acid, 2,3-dimethylmaleic anhydride, 2-methylmaleic acid, 2-methylmaleic anhydride, glutaric acid, glutaric anhydride, 3-methylglutaric acid, decanedioic acid, decanedioic anhydride, hexadienedioic acid, dodecenedioic acid, octadecenedioic acid, eicosenedioic acid, etc.

[0035] According to the two preparation methods of the present invention, the hydroxy compound can be selected from fatty alcohols, hydroxy fatty acids, hydroxy fatty acid esters, hydroxy fatty amines, hydroxy amides, ether alcohols, and phenolic compounds of C1 to C50, preferably C4 to C30, and further preferably C4 to C20. Among them, the fatty alcohols include but are not limited to n-butanol, isobutanol, n-pentanol, isopentanol, n-octanol, isooctyl alcohol, n-nonanol, isononyl alcohol, lauryl alcohol, tetradecanol, octadecyl alcohol, oleyl alcohol, eicosanol, pentenol, hexenol, polyethylene glycol, polypropylene glycol, cyclohexanol, cyclopentanol, cyclohexenol, cyclopentenol, etc.; the hydroxy fatty acids include but are not limited to ricinoleic acid, 12-hydroxystearic acid, etc.; the hydroxy fatty acid esters include but are not limited to 12-hydroxystearic acid methyl ester, ricinoleic acid methyl ester Ester, ricinoleic acid ethyl ester, ricinoleic acid butyl ester, and biodiesel containing ricinoleic acid methyl ester; the hydroxy fatty amines include but are not limited to N-methyl dioctanolamine and octanolamine; the hydroxy amides are preferably octyl hydroxyacetamide; the ether alcohols include but are not limited to polyethylene glycol monomethyl ether, polypropylene glycol monobutyl ether, etc.; the phenolic compounds include but are not limited to amylphenol, heptylphenol, octylphenol, nonylphenol, decylphenol, dodecylphenol, pentadecylphenol, alkylphenol polyoxyethylene ether, etc.

[0036] According to the two preparation methods of the present invention, the peroxide includes but is not limited to hydrogen peroxide, peroxy acid, alkyl peroxide, and the hydrogen peroxide is a hydrogen peroxide solution with a mass fraction of 0.1% to 50%, preferably a hydrogen peroxide solution of 10% to 40%. The alkyl peroxide includes but is not limited to dimethyl peroxide, diethyl peroxide, tert-butyl methyl peroxide, di-sec-butyl peroxide, di-tert-butyl peroxide, tert-butyl tert-amyl peroxide, tert-butyl peroxide isopropyl benzene, 2,5-dimethyl-2,5-bis(tert-butyl peroxy)hexane, 2,5-dimethyl-2,5-bis(tert-butyl peroxy)-3-hexyne, diisopropyl benzene peroxide, 1,4-di(2-tert-butyl peroxyisopropyl)benzene, cyclohexyl hydroperoxide, isopropyl benzene hydroperoxide, etc.

[0037] In the epoxidation reaction described in step 1 of the first method or step 2 of the second method, the catalyst includes but is not limited to an inorganic acid catalytic system, a cation exchange resin catalytic system, an organic acid catalytic system, an aluminum sulfate catalytic system, a meta-chloroperoxybenzoic acid catalytic system, a tert-butyl peroxide catalytic system, an enzyme catalytic system, a titanium silicon molecular sieve catalyst, a heteropoly compound catalytic system, a metal complex catalytic system, a methyl trioxide rhenium catalytic system, a metal organic complex catalytic system, etc., preferably a tungsten compound, a titanium silicon molecular sieve catalyst and a phosphorus compound catalytic system, respectively tungstic acid or sodium tungstate and aminomethylphosphonic acid, phosphoric acid, sodium dihydrogen phosphate or potassium dihydrogen phosphate, a titanium silicon molecular sieve with an MFI topological structure, etc., and the total amount of the catalyst is 0.01% to 10.0% of the total mass of the reactants, preferably 0.05% to 5%.

[0038] According to the present invention, the peroxide and the catalyst can be added in the following three ways: (1) The peroxide can be added dropwise to the reaction intermediate solution together with the catalyst, and the dropwise addition rate is controlled at 1 to 20 drops / second, preferably 1 to 10 drops / second, and most preferably 1 to 5 drops / second. (2) The catalyst is first added to the reaction system, and then the peroxide is added dropwise to the reaction intermediate solution alone, and the dropwise addition rate is controlled at 1 to 20 drops / second, preferably 1 to 10 drops / second, and most preferably 1 to 5 drops / second. (3) The peroxide and the catalyst are added to the reaction system together, and the reaction is carried out in a "one-pot method". The second reactant addition method is preferred.

[0039] The reaction system of the two preparation methods of the present invention may use a solvent or not use a solvent. The solvent used may be a polar solvent or a non-polar solvent. The amount of the solvent used may be 1 to 300% by mass ratio to the mass of the reactants, preferably 10% to 150%, and more preferably 30% to 100%. Specifically, it may include but is not limited to aromatic hydrocarbons, solvent oil, alkylene oxides, cycloalkanes, normal alkanes, isoalkanes, petroleum ether, etc.; the solvent is preferably one or more of aromatic hydrocarbons, solvent oil, normal pentane, normal hexane, petroleum ether, carbon disulfide, carbon dioxide, methyl formate, methyl tert-butyl ether, dimethoxyethane, dimethyl ether, dimethoxymethane, ethyl methyl ether, diethyl ether and acetone.

[0040] The preparation process provided by the present invention can be carried out under normal pressure or under pressure, and the pressure range can be in the range of 0.01Mpa to 10Mpa. It is preferred to carry out the reaction under normal pressure.

[0041] The present invention provides a method for applying the anti-wear additive in fuel oil, which comprises: adding the anti-wear agent to the fuel oil, and the amount of the anti-wear agent added to the fuel oil is 10 to 5000 mg / kg, preferably 50 to 1000 mg / kg, and further preferably 100 to 500 mg / kg, based on the base fuel without the additive.

[0042] The present invention provides a method for applying the anti-wear additive in lubricating oil, wherein the amount of the anti-wear additive added to the lubricating oil is 0.01% to 30%, preferably 0.05% to 20%, and more preferably 0.1% to 10%, based on the mass of the lubricating oil base oil.

[0043] The present invention also provides a fuel oil composition, which includes a base fuel and the anti-wear agent of the present invention, wherein the amount of the anti-wear agent added to the fuel oil is 10 to 5000 mg / kg, preferably 50 to 1000 mg / kg, and further preferably 100 to 500 mg / kg, based on the base fuel.

[0044] The present invention also provides a lubricating oil composition, which includes a lubricating oil base oil and the anti-wear agent of the present invention, wherein the amount of the anti-wear agent added to the lubricating oil is 0.01% to 30%, preferably 0.05% to 20%, and further preferably 0.1% to 10%, based on the mass of the lubricating oil base oil.

[0045] The base fuel may include all petroleum-based fuels, such as middle distillate fuels, diesel fuels, gasoline, jet fuels, kerosene, marine fuels and other low-sulfur fuels, high-asphalt fuels, liquefied petroleum gas fuels, etc.; biorenewable fuels, such as biodiesel fuels, biomass-to-liquid (BTL) fuels, etc.; synthetic fuels, such as natural gas-to-liquid (GTL) fuels and other synthetic fuels, etc.; coal-based fuels, such as alcohols, ethers, FT synthetic fuels, coal-to-liquid (CTL) fuels, fuels derived from coal and / or petroleum coke; other fuels, such as genetically engineered biofuels and crops and their extract fuels, and natural gas, etc. Preferred fuels include gasoline fuel and diesel fuel.

[0046] The lubricating oil base oil includes but is not limited to mineral base oil, synthetic base oil and biological base oil.

[0047] According to the use requirements, the additive provided by the present invention can also be used together with other additives, such as detergent dispersants, metal deactivators, preservatives, etc.

[0048] Compared with the prior art, the anti-wear agent provided by the present invention has the following outstanding features:

[0049] (1) The synthesis process is simple, the synthesis steps are short and easy to operate, the reaction conditions are mild, and the reaction process is easy to control;

[0050] (2) The anti-wear agent product is added in a small amount in the oil product and can significantly improve the lubrication performance of the oil product.

[0051] (3) The product has good stability, is not easy to oxidize or deteriorate, and can maintain good anti-wear effect for a long time.

[0052] (4) The raw materials are widely available and inexpensive, so the production cost is low. BRIEF DESCRIPTION OF THE DRAWINGS

[0053] Figure 1 This is the wear spot image of blank diesel.

[0054] Figure 2 This is the wear spot image of Example 3 when 200 mg / kg dosage is added to blank diesel.

[0055] Figure 3 It is the infrared spectrum of the anti-wear agent product obtained in the preparation example. DETAILED DESCRIPTION

[0056] The present invention will be described in detail below by way of examples. It should be understood that the present invention can have various variations in different embodiments without departing from the scope of the present invention, and the descriptions therein are essentially for the purpose of illustration rather than for limiting the present invention.

[0057] The following examples will further illustrate the present invention.

[0058] Preparation Example 1

[0059] 49g (0.5mol) of maleic anhydride (analytical grade, Beijing Inokai Technology Co., Ltd.) and 65.5g (0.5mol) of isooctyl alcohol (analytical grade, Beijing Inokai Technology Co., Ltd.) were placed in a reactor equipped with an electric stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube, and nitrogen was introduced for 5 to 10 minutes, and a weak nitrogen flow was maintained during the reaction. The temperature was heated and stirred to 100°C, the molar ratio of maleic anhydride to isooctyl alcohol was about 1:1, and the reaction time was 1.5 hours. The reaction intermediate of monoisooctyl maleate was prepared to obtain about 113.6g of the reaction intermediate.

[0060] 113.6g of the reaction intermediate was placed in a reactor with a three-necked flask, 12g of sodium tungstate was added as a catalyst, the mass of sodium tungstate accounted for about 10% of the mass of the reaction intermediate, the temperature was raised to 65°C, 85g of hydrogen peroxide (mass fraction 30%, Shanghai Aladdin Biochemical Technology Co., Ltd.) was slowly added dropwise while stirring, the molar ratio of monoisooctyl maleate to hydrogen peroxide was about 1:3, the drop rate was controlled to be 2 drops / second, the reaction was carried out for 3 hours, the product was cooled, dried, and filtered to obtain about 196.4g of the product, and the reaction process was shown in Reaction Formula 1.

[0061]

[0062] (Reaction 1)

[0063] Preparation Example 2

[0064] 49g (0.5mol) of maleic anhydride (analytical grade, Beijing Inokai Technology Co., Ltd.) and 61.3 (0.6mol) of n-hexanol (analytical grade, Beijing Inokai Technology Co., Ltd.) were placed in a reactor equipped with an electric stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube, and nitrogen was introduced for 5 to 10 minutes, and a weak nitrogen flow was maintained during the reaction. The temperature was heated and stirred to 85°C, the molar ratio of maleic anhydride to n-hexanol was about 1:1.2, and the reaction time was 1.5 hours. The reaction intermediate of maleic acid mono-n-hexyl ester was prepared to obtain about 109.6g of the reaction intermediate.

[0065] 109.6 g of the reaction intermediate was placed in a reactor with a three-necked flask, and 11 g of titanium silicalite was added as a catalyst, the mass of the titanium silicalite catalyst accounting for about 10% of the mass of the reaction intermediate. The temperature was raised to 65° C., and 37.5 g of hydrogen peroxide (mass fraction 30%, Shanghai Aladdin Biochemical Technology Co., Ltd.) was slowly added dropwise with stirring. The molar ratio of mono-n-hexyl maleate to hydrogen peroxide was about 1:2. The drop acceleration rate was controlled to be 2 drops / second. The reaction was carried out for 6 hours. The product was cooled, dried, and filtered to obtain about 139.3 g of the product. The reaction process is shown in Reaction Formula 2.

[0066]

[0067] (Reaction 2)

[0068] Preparation Example 3

[0069] 49g (0.5mol) of maleic anhydride (analytical grade, Beijing Inokai Technology Co., Ltd.) was placed in a three-necked flask reactor equipped with a stirrer, a dropper, a reflux condenser, a thermometer and a heating device, 2.5g of sodium tungstate (analytical grade, Beijing Inokai Technology Co., Ltd.) was added, nitrogen was introduced for 5 to 10 minutes, and a weak nitrogen flow was maintained during the reaction, the temperature was raised to 70°C until the maleic anhydride was completely melted into a liquid, 51g (1.5mol) of 30% hydrogen peroxide solution (Beijing Inokai Technology Co., Ltd.) was weighed and added dropwise to the maleic anhydride solution, the dropping speed was controlled to be about 2 to 5 drops / s, the temperature was maintained at 70°C, and the reaction was carried out for 6 hours. The epoxy maleic anhydride reaction intermediate was obtained, and the product was about 96.5g after filtration and standing.

[0070] 96.5g of epoxidized maleic anhydride was placed in a three-necked flask reactor equipped with a stirrer, a dropper, a reflux condenser, a thermometer and a heating device, 183g of isononyl alcohol (analytical grade, Beijing Inokai Technology Co., Ltd.) was weighed and added to the reaction system, the temperature was raised to 150°C, and the reaction was carried out for 2.5h to prepare epoxidized monoisononyl maleate. The product was subjected to rotary distillation to purify the epoxidized monoisononyl maleate to obtain about 267.9g of the product, that is, the desired epoxysuccinic acid monoisononyl ester.

[0071] Preparation Example 4

[0072] 49g (0.5mol) of maleic anhydride (analytical grade, Beijing Inokai Technology Co., Ltd.) and 157.3g (0.5mol) of 12-hydroxystearic acid methyl ester (99%, Shanghai Aladdin Biochemical Technology Co., Ltd.) were placed in a reactor equipped with an electric stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube, 50g of petroleum ether with a boiling range of 90°C to 120°C was used as a solvent, nitrogen was introduced for 5 to 10 minutes, and a weak nitrogen flow was maintained during the reaction, heated and stirred to 110°C, the molar ratio of maleic anhydride to 12-hydroxystearic acid methyl ester was about 1:1, and the reaction time was 2.5 hours. Prepare 12-hydroxystearic acid methyl ester maleic acid monoester reaction intermediate, distill off the solvent, and obtain about 205.7g of reaction intermediate.

[0073] 205.7g of the reaction intermediate was placed in a reactor with a three-necked flask, 10g of sodium tungstate was added as a catalyst, the mass of sodium tungstate accounted for about 10% of the mass of the reaction intermediate, the temperature was raised to 65°C, 85g of hydrogen peroxide (mass fraction 30%, Shanghai Aladdin Biochemical Technology Co., Ltd.) was slowly added dropwise while stirring, the molar ratio of 12-hydroxystearic acid methyl maleate to hydrogen peroxide was about 1:5, the drop rate was controlled to be 2 drops / second, the reaction was performed for 8 hours, the product was cooled, dried, and filtered to obtain about 285.1g of the product. The reaction formula is shown in Formula 3.

[0074]

[0075] (Reaction 3)

[0076] Example 1

[0077] The anti-wear agent product prepared as described in Preparation Example 1 was added to blank diesel at 75 mg / kg, and the lubrication performance of the added diesel was evaluated using a high frequency reciprocating test machine (HFRR).

[0078] Example 2

[0079] The anti-wear agent product prepared as described in Preparation Example 1 was added to blank diesel at 100 mg / kg, and the lubrication performance of the added diesel was evaluated using a high frequency reciprocating test machine (HFRR).

[0080] Example 3

[0081] The anti-wear agent product prepared as described in Preparation Example 1 was added to blank diesel at 200 mg / kg, and the lubrication performance of the added diesel was evaluated using a high frequency reciprocating test machine (HFRR).

[0082] Example 4

[0083] The anti-wear agent product prepared as described in Preparation Example 2 was added to blank diesel at 75 mg / kg, and the lubrication performance of the added diesel was evaluated using a high frequency reciprocating test machine (HFRR).

[0084] Example 5

[0085] The anti-wear agent product prepared as described in Preparation Example 2 was added to blank diesel at 100 mg / kg, and the lubrication performance of the added diesel was evaluated using a high frequency reciprocating test machine (HFRR).

[0086] Example 6

[0087] The anti-wear agent product prepared as described in Preparation Example 2 was added to blank diesel at 200 mg / kg, and the lubrication performance of the added diesel was evaluated using a high frequency reciprocating test machine (HFRR).

[0088] Example 7

[0089] The anti-wear agent product prepared in Preparation Example 3 was added to blank diesel at a concentration of 100 mg / kg, and the lubrication performance of the added diesel was evaluated using a high frequency reciprocating test machine (HFRR).

[0090] Example 8

[0091] The anti-wear agent product prepared in Preparation Example 4 was added to blank diesel at 200 mg / kg, and the lubrication performance of the added diesel was evaluated using a high frequency reciprocating test machine (HFRR).

[0092] Example 9

[0093] The anti-wear agent product prepared in Preparation Example 1 was added to 10W / 40 lubricating oil at 2% (mass fraction). The anti-wear and friction-reducing properties of the lubricating oil were evaluated using a four-ball friction and wear tester at 75°C, 40kg, and 1200rpm.

[0094] Comparative Example 1

[0095] 49g (0.5mol) of maleic anhydride (analytical grade, Beijing Inokai Technology Co., Ltd.) and 143.5g (1.1mol) of isooctyl alcohol (analytical grade, Beijing Inokai Technology Co., Ltd.) were placed in a reactor equipped with an electric stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube, and nitrogen was introduced for 5 to 10 minutes, and a weak nitrogen flow was maintained during the reaction. The temperature was heated and stirred to 120°C, the molar ratio of maleic anhydride to isooctyl alcohol was about 1:2.2, and the reaction time was 4 hours. Prepare diisooctyl maleate reaction intermediate, and obtain about 190.6g of reaction intermediate.

[0096] 190.6g of the reaction intermediate was placed in a reactor with a three-necked flask, 19g of sodium tungstate was added as a catalyst, the mass of sodium tungstate accounted for about 10% of the mass of the reaction intermediate, the temperature was raised to 65°C, 57.3g of hydrogen peroxide (mass fraction 30%, Shanghai Aladdin Biochemical Technology Co., Ltd.) was slowly added dropwise while stirring, the molar ratio of diisooctyl maleate to hydrogen peroxide was about 1:3, the drop acceleration rate was controlled to 2 drops / second, the reaction was carried out for 8 hours, the product was cooled, dried, and filtered to obtain about 245.7g of the product.

[0097] The product was added into blank diesel at a dosage of 200 mg / kg to investigate the lubrication performance of the added diesel.

[0098] Comparative Example 2

[0099] 49g (0.5mol) of maleic anhydride (analytical grade, Beijing Inokai Technology Co., Ltd.) and 78.5 (0.6mol) of isooctyl alcohol (analytical grade, Beijing Inokai Technology Co., Ltd.) were placed in a reactor equipped with an electric stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube, and nitrogen was introduced for 5 to 10 minutes, and a weak nitrogen flow was maintained during the reaction. The temperature was heated and stirred to 105°C, the molar ratio of maleic anhydride to isooctyl alcohol was about 1:1.2, and the reaction time was 2.5 hours. About 126.6g of maleic acid monoisooctanol ester was prepared.

[0100] Monoisooctanol maleate was added to blank diesel at dosages of 200 mg / kg, 100 mg / kg and 75 mg / kg to investigate the lubrication properties of the added diesel.

[0101] Comparative Example 3

[0102] Will Afton 4140 (a commercial diesel anti-wear agent produced by Afton Corporation, USA) was added to blank diesel at a dosage of 200 mg / kg to examine the lubrication performance of the added diesel.

[0103] Table 1 shows the basic physical and chemical properties of blank diesel. The selected blank diesel has a typical characteristic in that the lubricity (WS1.4) of the blank diesel is 640 μm, which does not meet the lubricity requirements of diesel.

[0104] Table 1 Physical and chemical properties of diesel

[0105]

[0106]

[0107] Table 2 Evaluation results of diesel lubricity

[0108] Oil Sample <![CDATA[Additional dose / mg·kg -1 > WS1.4 / μm Blank Diesel 0 640 Example 1 75 422 Example 2 100 337 Example 3 200 172 Example 4 75 395 Example 5 100 224 Example 6 200 218 Example 7 100 354 Example 8 200 204 Comparative Example 1 200 644 Comparative Example 2 75 552 Comparative Example 2 100 375 Comparative Example 2 200 237 Comparative Example 3 200 424

[0109] As can be seen from Table 2, the anti-wear agent product prepared in the blank diesel is small in dosage, and can significantly improve the lubrication performance of low-sulfur diesel. In addition, by comparing Examples 1 to 3 with Comparative Example 2, it can be found that the anti-wear effect of epoxidized maleic acid monoisooctyl ester is better than that of maleic acid monoisooctyl ester. When the same dosage is added, the anti-wear effect of epoxidized maleic acid monoisooctyl ester is better than that of maleic acid monoisooctyl ester. Especially when the dosage is 75 mg / kg, the anti-wear effect of maleic acid monoisooctyl ester is poor, while epoxidized maleic acid monoisooctyl ester can still maintain a good anti-wear effect. This discovery is unexpected.

[0110] By comparing Examples 1 to 3 with Comparative Example 1, it can be found that the anti-wear effect of the epoxidized monoester compound is absolutely better than that of the epoxidized diester compound, that is, under the premise of the same dosage, the epoxidized monoester compound can significantly improve the lubrication performance of diesel, but the epoxidized diester compound does not have any anti-wear effect.

[0111] On the other hand, the prepared anti-wear agent product is superior to the anti-wear agent products currently on the market. Under the premise of maintaining similar anti-wear effects, the amount of the anti-wear agent product provided by the present invention added to diesel is less than that of the anti-wear agent products on the market.

[0112] Table 3 Stability study of antiwear agents

[0113] Oil Sample Storage duration Lubrication performance (WS1.4) / μm Example 3 1 day 172 Example 3 7 days 197 Example 3 15 days 209 Example 3 30 days 206 Comparative Example 1 1 day 644 Comparative Example 1 7 days 659 Comparative Example 1 15 days 670 Comparative Example 1 30 days 660

[0114] It can be seen from Table 3 that the anti-wear agent product provided by the present invention can maintain good anti-wear performance for a long time under storage conditions.

[0115] Table 4 Lubricity evaluation results of lubricating oil

[0116] Oil Sample Wear spot diameter / mm Friction coefficient Commercially available oil 0.4 0.107 Example 9 0.36 0.103

[0117] It can be seen from Table 4 that by adding the anti-wear agent product provided by the present invention to the lubricating oil, the wear spot diameter and the friction coefficient are reduced, and the friction reduction performance of the lubricating oil can be improved.

Claims

1. A fuel oil composition comprising a base fuel and an anti-wear additive as shown in structural formula 1, wherein the amount of the anti-wear additive added to the fuel oil is 50 to 500 mg / kg based on the base fuel. in, R1 and R2 are single bonds, R3 and R4 are hydrogen, one of the X and Y groups is hydrogen, and the other is C4~C 20 Hydrocarbon or oxygen-containing functional groups.

2. The composition according to claim 1, wherein The amount of the anti-wear additive added to the fuel oil is 75-200 mg / kg based on the base fuel.

3. The composition according to claim 1, wherein The anti-wear additive of structural formula 1 is selected from the following compounds: mono-n-butyl epoxysuccinate, mono-isobutyl epoxysuccinate, mono-n-pentyl epoxysuccinate, mono-isopentyl epoxysuccinate, mono-n-octyl epoxysuccinate, mono-isooctyl epoxysuccinate, mono-n-nonyl epoxysuccinate, mono-isononyl epoxysuccinate, mono-lauryl epoxysuccinate, mono-octadecyl epoxysuccinate, mono-oleyl epoxysuccinate; mono-cyclopentanol epoxysuccinate, mono-cyclohexanol epoxysuccinate, mono-ricinoleyl epoxysuccinate, mono-ricinoleyl epoxysuccinate, 12-hydroxystearic acid mono-epoxysuccinate, and 12-hydroxystearic acid methyl-epoxysuccinate.

4. A method for applying an anti-wear additive in fuel oil, comprising: The anti-wear additive of structural formula 1 in claim 1 is added to the fuel oil, and the amount of the anti-wear additive added to the fuel oil is 50-500 mg / kg based on the base fuel.

5. The method of use according to claim 4, wherein: Calculated on the basis fuel, the anti-wear additive is added in an amount of 75-200 mg / kg in the fuel oil.

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