阅读说明：本技术 酯类化合物及其制备方法、用途和润滑油组合物 (Ester compound, preparation method and application thereof, and lubricating oil composition ) 是由 刘依农 段庆华 马静 于 2020-06-30 设计创作，主要内容包括：本发明提供了一种酯类化合物及其制备方法、用途和包含该酯类化合物的润滑油组合物。本发明的酯类化合物,其结构如式(I)所示：其中各基团和符号的定义见说明书。本发明的酯类化合物具有非常优异的润滑性、抗氧化性、抗磨性、清净性能,能够用作润滑油基础油或添加剂,适宜用作石油产品的清净剂、抗磨剂、减摩剂,特别适宜用于船用发动机油。(The invention provides an ester compound, a preparation method and application thereof, and a lubricating oil composition containing the ester compound. The structure of the ester compound is shown as the formula (I):)

1. The structure of the ester compound is shown as the formula (I):

in formula (I), each R group is the same or different from each other and is independently selected from the group consisting of a single bond, C_1-20Alkylene (preferably C)_1-12Straight or branched alkylene, more preferably C_1-8Linear or branched alkylene);

R₀the group is selected from H, C_1-20Hydrocarbyl (preferably H, C)_1-12Straight or branched alkyl, more preferably C_1-8Straight or branched chain alkyl); r₀' group is selected from C_1-20Hydrocarbyl (preferably C)_1-12Straight or branched alkyl, more preferably C_1-8Straight or branched chain alkyl);

m is an integer of 1 to 12 (preferably an integer of 1 to 8, more preferably an integer of 1 to 5); each G group, which may be the same or different from each other, is independently selected from the group consisting of a group represented by the formula (II) — CH ═ CH —, a group represented by the formula (II),Methylene, ethylene, propylene, and at least oneEach G group is selected from the group represented by formula (II);

wherein G is₁Radical, G₂The group is selected from the group represented by formula (III), the group represented by formula (IV) and the group represented by formula (V),

wherein the R' group is selected from single bond, C₁～C₁₀Straight or branched alkylene (preferably selected from single bond, C)₁～C₄Linear or branched alkylene), Ar group is selected from C₆～C₂₀Aryl (preferably selected from C)₆～C₁₅Aryl, more preferably phenyl, naphthyl, anthracenyl or C₁～C₈Alkyl substituted phenyl/naphthyl/anthracenyl); the R' group is selected from C₃～C₁₀Cycloalkyl (preferably selected from C)₅～C₈Cycloalkyl, more preferably cyclopentyl, cyclohexyl); r' "group is selected from C₁～C₁₀Straight or branched alkyl (preferably selected from C)₁～C₄Straight or branched chain alkyl).

2. Esters according to claim 1, characterized in that in the radical of formula (II), G₁Radical, G₂One of the groups is selected from the group represented by formula (III) or formula (IV), and the other group is represented by formula (V).

3. An ester compound as claimed in claim 1, wherein the ester compound comprises one or more of the following compounds:

the structure of the A, B group in the structural formula is shown in Table I:

substituents in the structural formulae of Table I

4. A process for producing an ester compound, which comprises reacting a compound represented by the formula (alpha) with one or more compounds selected from the group consisting of compounds represented by the formulae (beta), (gamma), (delta) and compounds represented by the formulae (beta), (gamma), (delta) themselves or a condensate thereof,

in the formula (. alpha.), each R group is the same or different from each other and is independently selected from the group consisting of a single bond, C_1-20Alkylene (preferably C)_1-12Straight or branched alkylene, more preferably C_1-8Linear or branched alkylene);

R₀the group is selected from H, C_1-20Hydrocarbyl (preferably H, C)_1-12Straight or branched alkyl, more preferably C_1-8Straight or branched chain alkyl); r₀' group is selected from C_1-20Hydrocarbyl (preferably C)_1-12Straight or branched alkyl, more preferably C_1-8Straight or branched chain alkyl);

m is an integer of 1 to 12 (preferably an integer of 1 to 8, more preferably an integer of 1 to 5);

each G' group, which may be the same or different from each other, is independently selected from-CH ═ CH-, methylene-, ethylene-, propylene-, and at least one G' group is selected from

In the formulae (. beta., (. gamma.), (. delta.), the R' group is selected from a single bond and C₁～C₁₀Straight or branched alkylene (preferably selected from single bond, C)₁～C₄Linear or branched alkylene), Ar group is selected from C₆～C₂₀Aryl (preferably selected from C)₆～C₁₅Aryl, more preferably phenyl, naphthyl, anthracenyl or C₁～C₈Alkyl substituted phenyl/naphthyl/anthracenyl); the R' group is selected from C₃～C₁₀Cycloalkyl (preferably selected from C)₅～C₈Cycloalkyl, more preferably cyclopentyl, cyclohexyl); r' "group is selected from C₁～C₁₀Straight or branched alkyl (preferably selected from C)₁～C₄Straight or branched chain alkyl); the X groups, equal to or different from each other, are each independently selected from OH, F, Cl, Br, I (preferably from OH, Cl, Br).

5. The method according to claim 4, wherein the compound represented by the formula (α) is one or more selected from the group consisting of epoxidized methyl oleate, epoxidized methyl linoleate, epoxidized methyl linolenate, epoxidized methyl erucate, epoxidized methyl cis-13-eicosenoate, epoxidized methyl cis-9, cis-12, cis-15-eicosatrienoate, epoxidized methyl cis-9, cis-12, cis-15-docosatrienoate; and/or the presence of a gas in the gas,

the compound shown in the formula (beta) is selected from one or more of the following compounds: one or more of benzoic acid, phenylacetic acid, phenylpropionic acid, benzoyl chloride, 1-naphthoic acid, 1-naphthylacetic acid, 1-naphthylpropionic acid, 1-naphthoyl chloride, 2-naphthoic acid, 2-naphthylacetic acid and 2-naphthylpropionic acid; and/or the presence of a gas in the gas,

the compound shown in the formula (gamma) is selected from one or more of the following compounds: one or more of cyclopentanecarboxylic acid, cyclopentanecarbonyl chloride, cyclohexanecarboxylic acid, cyclohexanecarbonyl chloride, cycloheptanecarboxylic acid and cycloheptanecarboxylic acid chloride; and/or the compound represented by the formula (delta) and/or the self-condensate thereof is selected from one or more of the following compounds: one or more of formic acid, acetic acid, propionic acid, butyric acid, formic anhydride, acetic anhydride, propionic anhydride, and butyric anhydride.

6. The process according to claim 4, wherein the equivalent ratio of the compound of formula (α) to one or more compounds selected from the group consisting of compounds of formulae (β), (γ), (δ) and compounds of formulae (β), (γ), (δ) themselves or their condensates with each other is 1: 0.1-10 ℃, and the reaction temperature is 50-200 ℃.

7. A process according to claim 4, characterized in that a catalyst, preferably an acidic catalyst, is added to the reaction of the compound of formula (α) with the compound of formula (β), (γ), (δ) and one or more compounds of the compounds of formula (β), (γ), (δ) themselves or in the intercondensates.

8. A process according to claim 4, wherein the compound of formula (α) (in terms of the amount of epoxy groups) is reacted with one or more compounds selected from the group consisting of compounds of formulae (β), (γ) and compounds of formulae (β), (γ) themselves or with one another, and then with the compound of formula (δ) and/or its condensate.

9. The process according to claim 8, wherein the equivalent ratio of the compound of formula (α) to one or more compounds selected from the group consisting of the compounds of formulae (β), (γ) and the compounds of formulae (β), (γ) themselves or their condensates with each other is 1: 0.1-10 ℃, the reaction temperature is 50-200 ℃, and the reaction time is 1-24 hours; the reaction equivalent ratio of the reaction product of the reaction of the compound represented by the formula (α) with the compound represented by the formula (β) or (γ) and the compound represented by the formula (β) or (γ) itself or a condensate thereof with the compound represented by the formula (δ) and/or a condensate thereof is 1: 0.1-10 ℃, the reaction temperature is 50-200 ℃, and the reaction time is 1-24 h.

10. A lubricating oil composition comprising the ester compound according to any one of claims 1 to 3 or the ester compound obtained by the method according to any one of claims 4 to 9, an optional lubricating oil additive, and a lubricating oil base oil.

11. The composition of claim 10, wherein the optional lubricating oil additive comprises one or more of a detergent, preferably selected from the group consisting of ultra-high base number detergents, high base number detergents and low base number detergents, an antioxidant, preferably selected from one or more of dialkyl dithiophosphates, alkylated diphenylamines, di-t-butyl-p-cresols, di-t-butylphenols, N-phenyl-alpha-naphthylamines, phenolic esters and sulfurized alkylphenols, a dispersant, preferably selected from the group consisting of polyisobutylene succinate ester, polyisobutylene succinimide ashless dispersants, and a demulsifier, preferably selected from the group consisting of polyether lubricating oil demulsifiers, non-polyether lubricating oil demulsifiers.

12. A method for preparing the lubricating oil composition of claim 10 or 11, comprising the step of mixing the ester compound, optional lubricating oil additives, and lubricating oil base oil.

Technical Field

The invention relates to an ester compound, in particular to an ester compound suitable for marine diesel engine lubricating oil.

Background

With the economic development of China and the rapid development of the marine transportation industry, the demand of marine oil for large ships is continuously increased, and the quality of oil products is continuously improved. The oil products mainly comprise two-stroke low-speed crosshead cylinder oil, system oil, four-stroke medium-speed cylinder-shaped piston diesel oil and the like. Although the working conditions of the system oil and the four-stroke medium-speed cylindrical piston diesel engine oil are not as harsh as those of marine cylinder oil, the diesel oil with high sulfur content is used, and water exists in the engine during working, so that the system oil and the medium-speed engine oil are required to have good high-temperature detergency, oxidation resistance, acid neutralization performance, water separation performance and anti-emulsification performance, wherein the high-temperature detergency, the water separation performance and the anti-emulsification performance are two important indexes. In recent years, there have been many studies on medium speed engine oils and system oils.

CN 1203263 & lt & ltmarine crankcase oil composition containing demulsifier & gt introduces a marine crankcase oil composition, which comprises a large amount of mineral oil base oil, a small amount of sulfurized alkylphenate, salicylate, polyisobutylene succinimide, dialkyl dithiophosphate, ethylene propylene oxide alkyl block copolyether, alcohols and dimethyl silicone oil, can be prepared into 3-40 mgKOH/g marine crankcase oil according to the requirement of oil products on the base number, and can meet the lubricating requirements of a low-speed crosshead marine engine crankcase system and a medium-speed crosshead cylindrical piston engine.

CN 1253542 "lubricating oil composition" describes a lubricating oil composition for four-stroke plunger type medium-speed compression ignition marine engine, which comprises: (A) an oil of lubricating viscosity; and (B) an oil-soluble overbased metal detergent additive in the form of a complex in which detergent base stock is stabilized with one or more surfactants; the composition is substantially free of dispersant, or contains 1% or less than 1% dispersant based on the mass of the composition; the TBN value of the composition is 3.5 to 100 mgKOH/g. The composition has good high-temperature detergency.

CN 1257255 "lubricating oil composition", which describes a lubricating oil composition suitable for lubricating a low-speed, medium-speed 4-stroke cylinder piston or a 2-stroke crosshead engine, comprising: a major amount of an oil of lubricating viscosity, and at least one oil-soluble or oil-dispersible ashless organic compound having at least two adjacent substitutable carbon atoms which are part of an aromatic residue or are linked by a double bond, wherein the carbon atoms bear oxygen-containing or oxygen-and nitrogen-containing functional groups, respectively, both groups being derived from carboxyl groups, solves primarily the problem of dispersion of fuels incorporated into lubricating oils.

The lubricating oil composition introduced in CN 1257256 method for lubricating four-stroke medium-speed compression ignition marine engine and CN 1322797 lubricating oil composition comprises (1) at least 60% of lubricating oil, and 100 kinematic viscosity of the lubricating oil is 2-40 mm²(s), (2) 2.55-30% of calcium salicylate, the base number of which is 100-450 mgKOH/g, and the calcium salicylate is used as the only overbased metal detergent, and (3) 0.1-1.5% of zinc dihydrocarbyl dithiophosphate, wherein the composition does not contain a dispersant, and the base number of the composition is 25-100 mgKOH/g, and the composition has better high-temperature detergency.

US 4358386 (crankcase lubricating oil for ships) introduces a low-speed crankcase oil for ships with a base number of 3-10 TBN, which has better wear resistance, antifriction, demulsification and water diversion properties, wherein the crankcase oil comprises 1-5% of high-base-number calcium alkyl phenate, 0.1-1% of dialkyl dithiophosphate, 0.2-0.4% of epoxy alkyl phenol and 0.75-2% of N-alkyl glycine derivatives.

US 5753598 "lubricating oil compositions with improved water-dividing properties" describes a lubricating oil composition with improved water-dividing properties, the demulsifier of which uses alkylene oxides and heterocyclic compounds, such as dimercaptothiadiazole, in a ratio of 0.1: 1-0.5: the proportion of 1 is added into lubricating oil, and the synergistic demulsification effect and the better water-separating property are shown.

The above studies report that the lubricating fluid used can meet the working requirements of the engine in most occasions. However, the addition amount of the detergent used in the formulation is large, and the formulation cost is high. And the base oil used in the formulation is a conventional petroleum-based base oil. Along with the increase of engine power and the extension of oil change period of oil products, the requirements of the original oil products on detergency, wear resistance, oxidation resistance, dispersibility and wear resistance are further improved, and the detergency and various performances in the existing formula can not meet the requirements sometimes. In addition, with the improvement of environmental protection requirements, the requirement of biodegradability of the existing marine cylinder oil is higher and higher, and the existing technology cannot completely meet the requirement, so that further improvement is needed.

CN 103087797A 'preparation method of biodegradable lubricating oil', relates to a preparation method of alcohol ester type environment-friendly lubricating oil base oil, which takes epoxy biodiesel (epoxy fatty acid methyl ester) as a raw material, and uses solid super acid to catalyze isomerization to carry out chemical modification on the raw material under the ultrasonic wave auxiliary condition, and adopts an esterification method to open unstable epoxy bonds in the epoxy biodiesel to form isomeric modified biodiesel monoester containing hydroxyl.

CN 107541307A discloses a plant oil-based amine antioxidant additive and a preparation method thereof, and discloses a plant oil-based amine antioxidant additive and a preparation method thereof, wherein the method comprises the steps of adding p-aminodiphenylamine into epoxy fatty acid methyl ester, reacting for 4-8 h at 60-90 ℃, carrying out reduced pressure suction filtration after the reaction is finished, and collecting to obtain a brown viscous product. The additive can be mutually soluble with vegetable oil base oil, and further improves the thermal oxidation resistance of the vegetable oil-based lubricating oil.

US 5368776 describes a process for the preparation of epoxy-based rust inhibiting additives using C₂₀～C₂₄The alkyl benzene sulfonic acid reacts with epoxy methyl ester of unsaturated fatty acid to obtain fatty acid methyl ester sulfonate which can be used as a lubricating oil antirust agent.

The epoxidized fatty acid ester improves some properties of the lubricant as an industrial lubricant, but has not been reported as a base oil for a marine medium speed engine oil and a system oil.

Along with the increasingly strict requirements on environmental protection and emission, the working conditions of the internal combustion engine oil engine are increasingly strict, and the high-temperature detergency of the oil is further improved. Meanwhile, along with the increase of the power of an engine and the extension of the oil change period of an oil product, the oxidation resistance, the dispersibility and the abrasion resistance of the original oil product are required to be further improved, and the detergency and various performances in the existing formula cannot meet the requirements, so that the further improvement is required. Meanwhile, the requirement on biodegradability of the internal combustion engine oil is higher and higher, and the traditional internal combustion engine oil cannot meet the requirement on biodegradability and needs to be further improved.

Disclosure of Invention

The invention provides an ester compound, a preparation method and application thereof, and a lubricating oil composition containing the ester compound.

The structure of the ester compound is shown as the formula (I):

in formula (I), each R group is the same or different from each other and is independently selected from the group consisting of a single bond, C_1-20Alkylene (preferably C)_1-12Straight or branched alkylene, more preferably C_1-8Linear or branched alkylene);

R₀the group is selected from H, C_1-20Hydrocarbyl (preferably H, C)_1-12Straight or branched alkyl, more preferably C_1-8Straight or branched chain alkyl); r₀' group is selected from C_1-20Hydrocarbyl (preferably C)_1-12Straight or branched alkyl, more preferably C_1-8Straight or branched chain alkyl);

m is an integer of 1 to 12 (preferably an integer of 1 to 8, more preferably an integer of 1 to 5);

each G group, which may be the same or different from each other, is independently selected from the group consisting of a group represented by the formula (II) — CH ═ CH —, a group represented by the formula (II),Methylene (methylene)And at least one G group is selected from the group consisting of groups represented by formula (II);

wherein G is₁Radical, G₂The group is selected from the group represented by formula (III), the group represented by formula (IV) and the group represented by formula (V),

wherein the R' group is selected from single bond, C₁～C₁₀Straight or branched alkylene (preferably selected from single bond, C)₁～C₄Linear or branched alkylene), Ar group is selected from C₆～C₂₀Aryl (preferably selected from C)₆～C₁₅Aryl, more preferably phenyl, naphthyl, anthracenyl or C₁～C₈Alkyl substituted phenyl/naphthyl/anthracenyl); the R' group is selected from C₃～C₁₀Cycloalkyl (preferably selected from C)₅～C₈Cycloalkyl, more preferably cyclopentyl, cyclohexyl); r' "group is selected from C₁～C₁₀Straight or branched alkyl (preferably selected from C)₁～C₄Straight or branched chain alkyl).

According to the invention, preferably, in the radical of the formula (II), G₁Radical, G₂One of the groups is selected from the group represented by formula (III) or formula (IV), and the other group is represented by formula (V).

The ester compound with a specific structure comprises one or more of the following compounds:

one or more of epoxidized methyl oleate, epoxidized methyl linoleate and epoxidized methyl linolenate are used as raw materials to react with one or more of benzoic acid, 1-naphthyl formic acid, methylcyclopentanoic acid, methylcyclohexanoic acid, acetic acid and acetic anhydride, the obtained product mainly comprises a mixture of ester compounds 1-6, and the structure of the ester compounds 1-6 is shown as the following structural formula:

the structure of the A, B group in the structural formula is shown in Table I:

substituents in the structural formulae of Table I

The invention provides a method for preparing ester compounds, which comprises the step of reacting a compound shown as a formula (alpha) with one or more compounds in compounds shown as formulas (beta), (gamma) and (delta) and compounds shown as formulas (beta), (gamma) and (delta) per se or mutual condensation compounds,

in the formula (. alpha.), each R group is the same or different from each other and is independently selected from the group consisting of a single bond, C_1-20Alkylene (preferably C)_1-12Straight or branched alkylene, more preferably C_1-8Linear or branched alkylene);

R₀the group is selected from H, C_1-20Hydrocarbyl (preferably H, C)_1-12Straight or branched alkyl, more preferably C_1-8Straight or branched chain alkyl); r₀' group is selected from C_1-20Hydrocarbyl (preferably C)_1-12Straight or branched alkyl, more preferably C_1-8Straight or branched chain alkyl);

m is an integer of 1 to 12 (preferably an integer of 1 to 8, more preferably an integer of 1 to 5);

each G' group, which may be the same or different from each other, is independently selected from-CH ═ CH-, methylene-, ethylene-, propylene-, and at least one G' group is selected fromIn the formulae (. beta., (. gamma.), (. delta.), the R' group is selected from a single bond and C₁～C₁₀Straight or branched alkylene (preferably selected from single bond, C)₁～C₄Linear or branched alkylene), Ar group is selected from C₆～C₂₀Aryl (preferably selected from C)₆～C₁₅Aryl, more preferably phenyl, naphthyl, anthracenyl or C₁～C₈Alkyl substituted phenyl/naphthyl/anthracenyl); the R' group is selected from C₃～C₁₀Cycloalkyl (preferably selected from C)₅～C₈Cycloalkyl, more preferably cyclopentyl, cyclohexyl); r' "group is selected from C₁～C₁₀Straight or branched alkyl (preferably selected from C)₁～C₄Straight or branched chain alkyl); the X groups, equal to or different from each other, are each independently selected from OH, F, Cl, Br, I (preferably from OH, Cl, Br).

According to the preparation method of the invention, the compound represented by the formula (alpha) can be one or more of epoxidized methyl oleate, epoxidized methyl linoleate, epoxidized methyl linolenate, epoxidized methyl erucate, epoxidized cis-13-methyl eicosenoate, epoxidized cis-9, cis-12, cis-15-methyl eicosatrienoic acid, epoxidized cis-9, cis-12, cis-15-methyl docosatrienoate, preferably one or more of epoxidized methyl oleate, epoxidized methyl linoleate and epoxidized methyl linolenate.

According to the preparation method of the invention, the compound represented by the formula (β) can be selected from one or more of the following specific compounds: one or more of benzoic acid, phenylacetic acid, phenylpropionic acid, benzoyl chloride, 1-naphthoic acid, 1-naphthylacetic acid, 1-naphthylpropionic acid, 1-naphthoyl chloride, 2-naphthoic acid, 2-naphthylacetic acid and 2-naphthylpropionic acid.

According to the preparation method of the invention, the compound represented by the formula (γ) can be selected from one or more of the following specific compounds: one or more of cyclopentanecarboxylic acid, cyclopentanecarbonyl chloride, cyclohexanecarboxylic acid, cyclohexanecarbonyl chloride, cycloheptanecarboxylic acid and cycloheptanecarboxylic acid chloride.

According to the preparation method of the invention, the compound represented by the formula (δ) and/or the self-condensation compound thereof may be selected from one or more of the following specific compounds: one or more of formic acid, acetic acid, propionic acid, butyric acid, formic anhydride, acetic anhydride, propionic anhydride, and butyric anhydride.

According to the production method of the present invention, it is preferable that the reaction equivalent ratio of the compound represented by the formula (α) (in terms of the amount of epoxy groups) to the compound represented by the formula (β), (γ), (δ) and one or more compounds of the compounds represented by the formula (β), (γ), (δ) themselves or a mutual condensate is 1: 0.1 to 10, more preferably 1: 0.2 to 5; the reaction temperature is preferably 50 to 200 ℃, more preferably 80 to 160 ℃. The reaction time is preferably such that the reaction proceeds smoothly, and generally, the longer the reaction time is, the better the reaction time is, the more preferably 1 to 24 hours, and the more preferably 2 to 16 hours.

According to the production method of the present invention, it is preferable to add a catalyst to the reaction of the compound represented by the formula (α) with one or more compounds selected from the compounds represented by the formulae (β), (γ), and (δ) and the compounds represented by the formulae (β), (γ), and (δ) themselves or the mutual condensates. The catalyst is preferably an acidic catalyst, and can be an organic acid, such as alkylbenzene sulfonic acid, benzoic acid, trifluoromethanesulfonic acid, an inorganic acid, such as concentrated sulfuric acid, concentrated hydrochloric acid, concentrated phosphoric acid, a solid acid, such as acid clay, an ion exchange resin, a molecular sieve, a solid acid sulfate, and an acidic ionic liquid, wherein the cation of the acidic ionic liquid is alkyl imidazole or alkyl pyridine, and the anion of the acidic ionic liquid is one or more of tetrafluoroborate, trifluoromethylsulfonate, hexafluorophosphate, p-toluenesulfonate, nitrate, perchlorate, methanesulfonate, oxalate and hydrogensulfate. The amount of the catalyst to be added is preferably 0.5 to 10%, more preferably 1 to 5% of the compound represented by the formula (α).

According to the preparation process of the present invention, optionally, the compound of the formula (. alpha.) (in terms of the amount of epoxy groups) is reacted with one or more compounds of the formulae (. beta.),. gamma.) (and the compounds of the formulae (. beta.),. gamma.) themselves or with each other, and then with the compound of the formula (. delta.) and/or its condensate. The reaction product of the compound represented by the formula (α) and one or more compounds selected from the compounds represented by the formulae (β) and (γ) and the compounds represented by the formulae (β) and (γ) themselves or their mutual condensates may be purified and then subjected to the next reaction, or may be subjected to the next reaction without purification. The reaction equivalent ratio of the compound represented by the formula (α) (in terms of the amount of epoxy groups) to the compound represented by the formula (β), (γ) and one or more compounds of the compounds represented by the formula (β), (γ) themselves or the mutual condensates thereof is preferably 1: 0.1 to 10, more preferably 1: 0.2 to 5; the reaction temperature is preferably 50-200 ℃, more preferably 80-160 ℃, and the reaction time is preferably 1-24 hours, more preferably 2-16 hours; the reaction equivalent ratio of the reaction product obtained by reacting the compound represented by the formula (α) (in terms of the amount of epoxy groups) with the compound represented by the formula (β) or (γ) and the compound represented by the formula (β) or (γ) itself or one or more compounds among condensates thereof, to the compound represented by the formula (δ) and/or a condensate thereof is preferably 1: 0.1 to 10, more preferably 1: 0.2-5 ℃, the reaction temperature is preferably 50-200 ℃, more preferably 80-160 ℃, and the reaction time is preferably 1-24 hours, more preferably 2-16 hours. In any of the above reactions, the catalyst may or may not be added, preferably the catalyst is added. The catalyst is preferably an acidic catalyst, as described in any of the preceding aspects.

According to the preparation method of the invention, the reaction product of the compound represented by the formula (alpha) and one or more compounds selected from the compounds represented by the formulae (beta), (gamma) and (delta) and the compounds represented by the formulae (beta), (gamma) and (delta) themselves or mutual condensation products is the ester compound of the invention. The ester compound can be a compound with a single structure, and can also be a mixture containing compounds with different structures. For a mixture of compounds of different structures, it is sometimes possible to separate it into compounds of a single structure, and it is sometimes also possible to use the mixture of compounds of different structures as it is without separating it into compounds of a single structure.

The ester compound has excellent lubricating property, oxidation resistance, wear resistance and cleaning property, can be used as base oil or additive of lubricating oil, is suitable for being used as detergent, anti-wear agent and anti-friction agent of petroleum products, and is particularly used as anti-wear agent and detergent of lubricating grease.

The invention also provides a lubricating oil composition which comprises the ester compound or the ester compound prepared by the method, optional lubricating oil additives and lubricating oil base oil. Wherein the ester compound accounts for 1-60%, preferably 8-50%, more preferably 10-40% of the total mass of the lubricating oil composition; the optional lubricating oil additive accounts for 0-40%, preferably 2-35%, more preferably 5-30% of the total mass of the lubricating oil composition; the lubricating oil base oil accounts for 40-99%, preferably 45-90%, and more preferably 50-85% of the total mass of the lubricating oil composition.

The optional lubricating oil additives according to the lubricating oil composition of the present invention include one or more of detergents, antioxidants, dispersants, and demulsifiers.

The lubricating oil composition according to the present invention, the detergent is preferably selected from one or more of an ultra-high base number detergent, an overbased detergent, and a low base number detergent, wherein the ultra-high base number detergent is preferably selected from an ultra-high base number calcium sulfonate having a base number of greater than 590 mgKOH/g; the high-base number detergent is preferably selected from calcium alkyl salicylate with a base number of more than 300mgKOH/g and/or high-base number sulfurized calcium alkyl phenate with a base number of more than 250mgKOH/g, and is more preferably selected from calcium alkyl salicylate with a base number of 250-400 mgKOH/g; the low-base number detergent is preferably selected from one or more of low-base number calcium alkyl salicylate with a base number of 20-150 mgKOH/g and low-base number sulfurized calcium alkyl phenate, and is more preferably selected from low-base number sulfurized calcium alkyl phenate; wherein the mass ratio of the ultrahigh-base-number detergent to the high-base-number detergent to the low-base-number detergent is preferably 1: 0.3-1: 0.1 to 1. The detergent preferably accounts for 0-30% of the total mass of the lubricating oil composition, more preferably 0.2-25%, and most preferably 0.3-15%.

In the lubricating oil composition according to the present invention, the antioxidant is preferably selected from one or more of dialkyldithiophosphates, alkylated diphenylamines, di-t-butyl-p-cresols, di-t-butylphenols, N-phenyl-alpha-naphthylamines, phenol esters and sulfurized alkylphenols, and for example, one or more of zinc dialkyldithiophosphates, copper dialkyldithiophosphates, alkylated diphenylamines, di-t-butyl-p-cresols, N-phenyl-alpha-naphthylamines and phenol esters may be selected, and more preferably one or more of zinc dialkyldithiophosphates, alkylated diphenylamines and phenol esters. The antioxidant accounts for 0-10% of the total mass of the lubricating oil composition, preferably 0.2-6%, and most preferably 0.3-3%.

According to the lubricating oil composition of the invention, the dispersant is preferably selected from polyisobutylene succinate ester and polyisobutylene succinimide ashless dispersant, and can be one or more of mono-polyisobutylene succinimide, di-polyisobutylene succinimide and polyisobutylene succinimide, wherein the number average molecular weight of polyisobutylene part is 500-4000, preferably 1000-3000. The dispersant is most preferably a bis-polyisobutylene succinimide. The dispersant accounts for 0-15% of the total mass of the lubricating oil composition, preferably 0.2-10%, and most preferably 0.3-8%.

The demulsifier is preferably selected from polyether type lubricating oil demulsifiers and non-polyether type lubricating oil demulsifiers, wherein the polyether type lubricating oil demulsifiers can be ethylene oxide-propylene oxide block copolymers, and the non-polyether type lubricating oil demulsifiers can be copolymers of alkyl acrylate and alpha-alkenyl sulfonic acid and sulfurized alkylphenol ethylene oxide-propylene oxide copolymers.

According to the lubricating oil composition of the present invention, the lubricating base oil may be selected from one or more of API group I, II, III, IV and V lubricating base oils, preferably one or more of API group I, II and V lubricating base oils. The I-type lubricating oil base oil is obtained by performing clay refining and solvent refining on distillate oil, the viscosity index of the I-type lubricating oil base oil is 80-100, and the kinematic viscosity of the I-type lubricating oil base oil at 100 ℃ is 1-40 mm²Between/s; the II-type oil is lubricating oil obtained by hydrotreating distillate oil through lubricating oil, the viscosity index of the II-type oil is between 100 and 120, and the kinematic viscosity of the II-type oil at 100 ℃ is 1 to 40mm²Between/s; the III-class oil is lubricating oil obtained by hydrogenating and isomerizing distillate oil, the viscosity index of the III-class oil is more than 120, and the kinematic viscosity at 100 ℃ is 1-40 mm²Between/s; the IV oil is synthetic oil polymerized by alpha-olefin, the viscosity index of the IV oil is 120-150, and the kinematic viscosity at 100 ℃ is 1-40 mm²Between/s; the V-type oil is ester oil, the viscosity index of the V-type oil is 120-150, and the kinematic viscosity at 100 ℃ is 1-40 mm²Is between/s. Preferably, in the lubricating base oil, the API group I lubricating base oil accounts for 10-50%, the API group II lubricating base oil accounts for 10-50%, and the API group V lubricating base oil accounts for 10-50%.

According to the present invention, the method for preparing the lubricating oil composition comprises the step of mixing the ester compound, optional lubricating oil additives and lubricating oil base oil.

The lubricating oil composition has excellent high-temperature detergency, oxidation stability, acid neutralization, wear resistance and friction reduction, especially excellent high-temperature detergency, wear resistance and oxidation resistance, and is suitable for lubricating marine diesel engines, especially four-stroke diesel engine and crankcase.

The lubricating oil composition of the invention uses the ester compound and the ultrahigh base number calcium sulfonate simultaneously, so that the abrasion resistance and the detergency of the composition are improved, and the reason is probably that the special structure of the ester compound of the invention ensures that the lubricating oil and the metal surface of an engine have better adsorbability.

Detailed Description

In the context of the present specification, the term "single bond" is sometimes used in the definition of a group. By "single bond", it is meant that the group is absent. For example, assume the formula-CH₂-A-CH₃Wherein the group a is defined as being selected from the group consisting of a single bond and a methyl group. In this respect, if A is a single bond, this means that the group A is absent, in which case the formula is correspondingly simplified to-CH₂-CH₃。

The invention is further illustrated by the following examples, which are not intended to be limiting.

Example 1 epoxy fatty acid methyl ester Mixed ester A₁Preparation of

In a 500mL three-necked flask, 100 g of epoxy fatty acid methyl ester (purity 82%, average molecular weight: Mn 319, wherein 50% of trans-9, 10-epoxyoctadecanoic acid methyl ester, molecular weight 312, 50% of trans-9, 10-epoxy-12, 13-epoxyoctadecanoic acid methyl ester, molecular weight 326, epoxy value 5.5, pale yellow viscous oily liquid, 0.263mol), benzoic acid 24.4(Mn 122.12, 0.20mol), cyclopentanecarboxylic acid 22.8 g (Mn 114.14, 0.20mol), molar ratio of benzoic acid, cyclopentanecarboxylic acid and epoxy fatty acid methyl ester 823 1.5:1, heating to 100 ℃ under stirring, then adding 3.3 g of sodium hydrogen sulfate to react for 9 hours, when the epoxidation number is close to 0, stopping the reaction, and infrared analysis showed that the epoxidation number is cm^-1And 842cm^-1The absorption peaks on the left and right disappeared, indicating that the three-membered ring in the epoxidized fatty acid methyl ester had reacted, at 1740cm^-1And 3500cm^-1Carboxylate absorption peaks appear to the left and right, indicating conversion of the three membered ring to alcohol and ester. Then 31 g of acetic acid (0.53mol, Mn 60.05) was added, the molar ratio of acetic acid to epoxidized fatty acid methyl ester was 2:1, the mixture was heated to 100 ℃ under stirring and reacted for 9 hours, and the infrared analysis of the sample showed 3500cm in wave number^-1The absorption peaks on the left and the right disappear, which indicates that hydroxyl in the ring-opening product of the epoxy fatty acid methyl ester has completely reacted with acetic acid, at the moment, the reaction is stopped, 2 percent NaOH is used for neutralizing the oil phase, then methanol water solution is used for extracting the residual acetic acid in the oil phase, the oil phase is separated, distilled water is used for washing until the oil phase is neutral, the oil phase is distilled, organic acid and water are removed, and the light yellow mixed esterification product A of the epoxy fatty acid methyl ester, benzoic acid, cyclopentanecarboxylic acid and acetic acid is obtained₁168 g, the kinematic viscosity at 100 ℃ of the mixture is 6.87mm²(s) kinematic viscosity at 40 ℃ of 33.26mm²(ii)/s, viscosity index of 121.

Example 2 epoxy fatty acid methyl ester Mixed ester B₁Preparation of

A500 mL three-necked flask was charged with 100 g of methyl epoxy fatty acid ester (purity: 82%, average molecular weight: Mn: 31)9, wherein 50% of trans-9, 10-epoxyoctadecanoic acid methyl ester, molecular weight 312, 50% of trans-9, 10-epoxy-12, 13-epoxyoctadecanoic acid methyl ester, molecular weight 326, epoxy value 5.5, pale yellow viscous oily liquid, 0.263mol), 27.4 g of cyclopentecarboxylic acid (Mn 114.14, 0.24mol), 34.4 g of 1-naphthylformic acid (Mn 172.18, 0.20mol), a molar ratio of cyclopentecarboxylic acid, 1-naphthylformic acid to epoxy fatty acid methyl ester of 1.67:1, heating to 100 ℃ with stirring, then adding 3.0 g of Amberlyst15 catalyst to react for 10 hours, stopping the reaction when the epoxidation value approaches 0, and infrared analysis shows that the wave number at 823cm is a wave number^-1And 842cm^-1The absorption peaks on the left and right disappeared, indicating that the ring opening reaction of the three-membered ring in the epoxidized fatty acid methyl ester was completed, and was found to be 1740cm^-1And 3500cm^-1Carboxylate absorption peaks appear to the left and right, indicating conversion of the three membered ring to alcohol and ester. 39 g of propionic acid (0.53mol, Mn. multidot.74) with a molar ratio of propionic acid to epoxidized fatty acid methyl ester of 2.0:1 were then added and the mixture was heated to 100 ℃ with stirring and reacted for 8 hours, the infrared analysis of the sample showing 3500cm wave number^-1The absorption peaks on the left and the right disappear, which indicates that the hydroxyl in the esterification ring-opening product of the epoxy fatty acid methyl ester has completely reacted with the propionic acid, at the moment, the reaction is stopped, 2 percent NaOH solution is used for neutralizing the oil phase, then methanol water solution is used for extracting the residual propionic acid in the oil phase, the oil phase is separated, distilled water is used for washing until the oil phase is neutral, the oil phase is distilled, organic acid and water are removed, and the light yellow mixed esterification product B of the epoxy fatty acid methyl ester, cyclopentanecarboxylic acid, 1-naphthoic acid and propionic acid is obtained₁182 g, and the kinematic viscosity at 100 ℃ of the product is 5.92mm²(s) kinematic viscosity at 40 ℃ of 33.12mm²(ii)/s, viscosity index of 125.

Example 3 epoxy fatty acid methyl ester Mixed ester C₁Preparation of

In a 500mL three-necked flask, 100 g of epoxy fatty acid methyl ester (purity 82%, average molecular weight: Mn 319, where trans-9, 10-epoxyoctadecanoic acid methyl ester is 50%, molecular weight 312, trans-9, 10-epoxy-12, 13-epoxyoctadecanoic acid methyl ester is 50%, molecular weight 326, epoxy value 5.5, pale yellow viscous oily liquid, 0.263mol), 26.9 g of benzoic acid (Mn 122.12, 0.22mol), 25.6 g of cyclohexanecarboxylic acid were added(Mn. about. 128.17, 0.20mol), benzoic acid and cyclohexanecarboxylic acid in a molar ratio of 1.67:1 with epoxidized fatty acid methyl ester, heated to 100 ℃ with stirring, 4 g of benzenesulfonic acid was added and the reaction was stopped when the epoxidation number approached 0 for 7h, and infrared analysis showed that the wave number was 823cm^-1And 842cm^-1The absorption peaks on the left and right disappeared, indicating that the three-membered ring in the epoxidized fatty acid methyl ester had reacted, at 1740cm^-1And 3500cm^-1Carboxylate absorption peaks appear to the left and right, indicating conversion of the three membered ring to alcohol and ester. Then 34 g of butyric acid (0.39mol, Mn: 88.11) with a molar ratio of butyric acid to epoxidized fatty acid methyl ester of 1.5:1 was added thereto, the mixture was heated to 100 ℃ under stirring and reacted for 10 hours, and infrared analysis of the sample showed 3500cm wave number^-1The absorption peaks on the left and the right disappear, which indicates that the hydroxyl in the epoxy fatty acid methyl ester has completely reacted with the acid anhydride for esterification, the reaction is stopped at the moment, 2 percent NaOH is used for neutralizing the oil phase, then methanol aqueous solution is used for extracting residual butyric acid in the oil phase, the oil phase is separated, distilled water is used for washing until the oil phase is neutral, the organic acid and water are removed, and a light yellow mixed esterification product C of the epoxy fatty acid methyl ester, benzoic acid, cyclohexanecarboxylic acid and butyric acid is obtained₁168 g, and the kinematic viscosity at 100 ℃ of the product is 5.62mm²(s) kinematic viscosity at 40 ℃ of 31.22mm²(ii)/s, viscosity index of 121.

Example 4 epoxy fatty acid methyl ester Mixed ester D₁Preparation of

In a 500mL three-necked flask, 100 g of epoxy fatty acid methyl ester (purity 82%, average molecular weight: Mn 319, wherein trans-9, 10-epoxyoctadecanoic acid methyl ester is 50%, molecular weight 312, trans-9, 10-epoxy-12, 13-epoxyoctadecanoic acid methyl ester is 50%, molecular weight 326, epoxy value 5.5, pale yellow viscous oily liquid, 0.263mol), 1-naphthylcarboxylic acid 34.4(Mn 172.18, 0.2mol), cyclohexanecarboxylic acid 19.2 g (Mn 128.17, 0.15mol), molar ratio of 1-naphthylcarboxylic acid and cyclohexanecarboxylic acid to epoxy fatty acid methyl ester 1.33:1, heating to 110 ℃ under stirring, then adding 3.5 g of sodium hydrogen sulfate, reacting for 10 hours, stopping the reaction when the epoxidation value approaches 0, and infrared analysis shows that the reaction is stopped at a wave number of cm 823^-1And 842cm^-1Left and right absorption peaksDisappearance, indicating that the three-membered ring in the epoxidized fatty acid methyl ester has reacted, at 1740cm^-1And 3500cm^-1Carboxylate absorption peaks appear to the left and right, indicating conversion of the three membered ring to alcohol and ester. Then 28 g of acetic acid (0.466mol, Mn 60.05) with a molar ratio of acetic acid to epoxidized fatty acid methyl ester of 1.8:1 was added, the mixture was heated to 100 ℃ under stirring and reacted for 12 hours, and infrared analysis of the sample showed 3500cm wave number^-1The absorption peaks on the left and the right disappear, which indicates that the hydroxyl in the epoxy fatty acid methyl ester has completely reacted with the acid anhydride for esterification, the reaction is stopped at the moment, 2 percent NaOH is used for neutralizing the oil phase, then methanol aqueous solution is used for extracting residual acetic acid in the oil phase, the oil phase is separated, distilled water is used for washing until the oil phase is neutral, the organic acid and water are removed, and a light yellow mixed esterification product D of the epoxy fatty acid methyl ester, 1-naphthyl formic acid, cyclohexanecarboxylic acid and acetic acid is obtained₁169 g of a mixture with a kinematic viscosity at 100 ℃ of 6.23mm²(s) kinematic viscosity at 40 ℃ of 36.93mm²(ii)/s, viscosity index of 118.

Example 5 epoxy fatty acid methyl ester Mixed ester A₂Preparation of

In a 500mL three-necked flask, 100 g of epoxy fatty acid methyl ester (purity 82%, average molecular weight: Mn: 319, where trans-9, 10-epoxyoctadecanoic acid methyl ester is 50%, molecular weight: 312, trans-9, 10-epoxy-12, 13-epoxyoctadecanoic acid methyl ester is 50%, molecular weight: 326, epoxy value 5.5, pale yellow viscous oily liquid, 0.263mol), benzoic acid 24.4 (Mn: 122.12, 0.20mol), cyclopentecarboxylic acid 22.8 g (Mn: 114.14, 0.20mol), benzoic acid, cyclopentecarboxylic acid and epoxy fatty acid methyl ester in a molar ratio of 1.5:1, heating to 100 ℃ under stirring, adding 3.3 g of sodium bisulfate, reacting for 9h, stopping the reaction when the epoxidation value is close to 0, and the infrared analysis result shows that the wave number is 823cm^-1And 842cm^-1The absorption peaks on the left and right disappeared, indicating that the three-membered ring in the epoxidized fatty acid methyl ester had reacted, at 1740cm^-1And 3500cm^-1The absorption peaks of carboxylic ester appear on the left and right, which shows that the three-membered ring is converted into alcohol and ester to obtain a light yellow mixed esterification product A of epoxy fatty acid methyl ester, benzoic acid and cyclopentanecarboxylic acid₂151 g, 100 ℃ thereofKinematic viscosity of 4.23mm²(s) kinematic viscosity at 40 ℃ of 19.98mm²(ii)/s, viscosity index of 118.

Example 6 epoxy fatty acid methyl ester Mixed ester A₃Preparation of

In a 500mL three-necked flask, 100 g of epoxy fatty acid methyl ester (purity 82%, average molecular weight: Mn 319, wherein 50% of trans-9, 10-epoxyoctadecanoic acid methyl ester, molecular weight 312, 50% of trans-9, 10-epoxy-12, 13-epoxyoctadecanoic acid methyl ester, molecular weight 326, epoxy value 5.5, pale yellow viscous oily liquid, 0.263mol), benzoic acid 48.4(Mn 122.12, 0.40mol), cyclopentanecarboxylic acid 45.6 g (Mn 114.14, 0.40mol), molar ratio of benzoic acid, cyclopentanecarboxylic acid and epoxy fatty acid methyl ester 3:1, heating to 100 ℃ with stirring, then adding 3.3 g of sodium hydrogensulfate to react for 9 hours, when the epoxidation value approaches 0, stopping the reaction, and infrared analysis showed that the wave number was 823cm^-1And 842cm^-1The absorption peaks at the left and right sides disappear, and the wave number is 3500cm^-1The absorption peaks on the left and the right disappear, which shows that the three-membered ring in the epoxy fatty acid methyl ester has reacted and the hydroxyl in the ring-opening product of the epoxy fatty acid methyl ester has completely reacted, at the moment, the reaction is stopped, 2 percent NaOH is used for neutralizing the oil phase, then methanol aqueous solution is used for extracting residual acetic acid in the oil phase, the oil phase is separated, distilled water is used for washing until the oil phase is neutral, the oil phase is distilled, organic acid and water are removed, and the light yellow mixed esterification product A of the epoxy fatty acid methyl ester, benzoic acid and cyclopentanecarboxylic acid is obtained₃189 g, with a kinematic viscosity at 100 ℃ of 7.21mm²(s) kinematic viscosity at 40 ℃ of 45.71mm²(ii) viscosity index 119.

Example 7 esterification product A of epoxidized fatty acid methyl ester with acetic acid₄Preparation of

In a 500mL three-neck flask, 100 g of epoxy fatty acid methyl ester (purity 82%, average molecular weight: Mn 319, where 50% of trans-9, 10-epoxyoctadecanoic acid methyl ester, molecular weight 312, 50% of trans-9, 10-epoxy-12, 13-epoxyoctadecanoic acid methyl ester, molecular weight 326, epoxy value 5.5, pale yellow viscous oily liquid, 0.263mol) was added, 54 g of acetic acid (0.9mol, Mn 60.05) was added, and the molar ratio of acetic acid to epoxy fatty acid methyl ester was 60.053.4:1, heating to 100 ℃ under stirring, reacting for 9h, and displaying the infrared analysis result of the sample at a wave number of 823cm^-1And 842cm^-1The absorption peaks on the left and right disappeared, indicating that the three-membered ring in the epoxidized fatty acid methyl ester had reacted and the wave number was 3500cm^-1The absorption peaks on the left and the right disappear, which indicates that hydroxyl in the ring-opening product of the epoxy fatty acid methyl ester has completely reacted with acetic acid, at the moment, the reaction is stopped, 2 percent NaOH is used for neutralizing the oil phase, then methanol water solution is used for extracting the residual acetic acid in the oil phase, the oil phase is separated, distilled water is used for washing until the oil phase is neutral, the oil phase is distilled, organic acid and water are removed, and the light yellow esterification product A of the epoxy fatty acid methyl ester and the acetic acid is obtained₄151 g, with a kinematic viscosity at 100 ℃ of 3.92mm²(s) kinematic viscosity at 40 ℃ of 17.57mm²(ii) a viscosity index of 120.

Test method and test material

1. Test methods employed

GB/T265 petroleum product kinematic viscometry and dynamic viscometer algorithm

GB/T2541 petroleum product viscosity index calculation table

Four-ball method for GB/T3142 lubricant bearing capacity determination

GB/T3535 petroleum product pour point determination method

Test method for antirust performance of GB/T11143 mineral oil with inhibitor in presence of water

SH/T0251 Petroleum products base number determination method (perchloric acid potentiometric titration method)

SH/T0619 method for measuring oil-water separation performance of ship

SH/T0649 marine lubricating oil corrosion test method

SRV testing machine method for measuring friction and wear performance of SH/T0847 extreme pressure lubricating oil

High temperature detergency measurement method

The method of assessing high temperature detergency was a paint and coke formation panel test, which was conducted on an L-1 type panel coke former. The coke formation test conditions were: the plate temperature/oil temperature is 320 ℃/100 ℃, the time is 2 hours, the stop/start time is 45 seconds/15 seconds, and the paint forming test conditions are as follows: the plate temperature/oil temperature was 300 ℃/150 ℃ for 2 hours, and the operation was continued.

Method of measuring oxidation resistance

The method for evaluating the antioxidant stability is a PDSC test, which is carried out on a TA 5000 DSC 2910 thermal analyzer, and the test conditions are as follows: the temperature rise speed is 100 ℃/min, the temperature is kept for 60min at 3.5 MPa.

Acid neutralization assay

In the test, 10g of test oil was taken, and 0.2mL of 20% sulfuric acid solution was added thereto at a water bath temperature of 60 ℃ to carry out neutralization reaction. The extent of the progress of the reaction is indicated by the change in the pressure of the generated carbon dioxide gas, and when the carbon dioxide pressure reaches the maximum, the completion of the neutralization reaction is described. The time required for the completion of the neutralization reaction represents the degree of the neutralization rate of the acid. The shorter the time, the stronger the acid neutralizing ability.

Gel test

Used to assess the tendency of cylinder oil to form precipitates and gels after contamination with water. Adding 1mL of distilled water into 99mL of test oil, stirring at a speed for 15min, uniformly mixing, standing for 96h, and measuring the generated precipitation amount and the gel generation amount. The smaller the amount of precipitation and gel, the better the gel resistance of the oil.

Dispersibility test

Putting 1g of sample, 9g of oil sludge and 10g of base oil into a beaker, heating and stirring at a constant temperature of 150 ℃, taking a drop of the test oil to drop on filter paper while the test oil is hot, putting the filter paper into an oven, keeping the temperature of the oven at a constant temperature of 80 ℃ for 1 hour, and measuring the ratio of a diffusion ring to an oil ring, wherein the larger the ratio is, the better the dispersibility of the oil sludge is.

Base number retention test

Adding a certain amount of distilled water and a metal catalyst into a 100 g test oil sample, introducing a certain amount of oxygen, sequentially oxidizing the oil product for 240min at 150 ℃, and measuring the change of the base number of the oxidized oil product. The change rate of the alkali value of the oil after the test is used for representing the alkali value retention rate.

Biodegradability test

80mL of mineral medium specified in the CEC standard and 15. mu.L of test oil were added to the flask, and 4mL of inoculum solution was added. In another 250mL flask, 80mL mineral medium and 15. mu.L of test oil were added, and 4mL non-inoculated soil was addedWater LB medium solution, which was used as a blank control bottle. Shaking at 24 + -3 deg.C in the dark. After the end of the incubation period, 1moL/L HCl, NaCl and 15mLCCl were added to each flask₄Shaking, standing for layering, performing infrared analysis on the test oil extract, and measuring 2930 + -10 cm^-1And (4) calculating the biodegradation rate of the test oil according to the absorbance change rate.

2. The main base oils used in the tests are shown in table 1.

TABLE 1 base oils used in the tests

3. The additives and the marine cylinder oil used in the test are shown in tables 2 and 3.

TABLE 2 additives for the tests

TABLE 3 marine cylinder oil for testing

Preparing 40TBN marine medium-speed engine oil according to API40 viscosity grade, wherein TBN600 ultrahigh base number calcium sulfonate and other additives are adopted, and the base oil adopts the ester compound A₁、B₁、C₁、D₁Formation examples 8 to 11; using ester compounds A₂、A₃、A₄Examples 12 to 14 were formed; epoxy fatty acid methyl ester, 400TBN ultrahigh base number calcium sulfonate and other additives are adopted, API I oil and API II oil are blended into comparative examples 1-4, commercial 40TBN medium-speed engine oil is used as comparative examples 5 and 6, the formula composition is shown in Table 4, and the test results show thatSee table 5.

Preparing No. 8 low-speed crosshead two-stroke marine system oil according to API40 viscosity grade, wherein TBN600 ultrahigh base number calcium sulfonate and other additives are adopted, and the base oil adopts the ester compound A of the invention₁、B₁、C₁、D₁Formation examples 15 to 18; using ester compounds A₂、A₃、A₄Examples 16-18, epoxidized fatty acid methyl ester, 400TBN ultra-high base number calcium sulfonate, and other additives were formed, and API group I oil and API group II oil were blended to comparative examples 7-10, and commercially available No. 8 low-speed crosshead two-cycle marine system oil was used as comparative examples 11 and 12, and the formulation composition and test results are shown in Table 6 and Table 7, respectively.

TABLE 440 TBN four-stroke medium speed trunk piston engine oil examples and comparative examples

TABLE 540 TBN Performance test of four-stroke Medium speed piston oil

As can be seen from tables 4 and 5, the 40TBN marine medium speed engine oils prepared in examples 8 to 11 adopt 600TBN ultrahigh base number calcium sulfonate, and the dosage of the formula is 11.8 to 12.5 percent, compared with the comparative example, the dosage of the additive is reduced by 24 percent, and the detergency, oxidation resistance, wear resistance, water distribution, base number retention and biodegradability are better than those of the comparative example and better than those of the commercial 40TBN marine medium speed engine oil. The mixed esterification product of epoxy fatty acid methyl ester is used as base oil, and 600TBN ultrahigh base number calcium sulfonate can reduce the dosage of the formula, and compared with the formula with 15.5% of dosage in comparative example 4, the formula has equivalent performance and shows better economy.

TABLE 68 example and comparative example of marine system oil

Performance testing of Marine System oil No. Table 78

As can be seen from tables 6 and 7, the marine system oil No. 8 prepared in examples 15 to 18 has a dosage of 7.1 to 7.5% due to the use of 600TBN ultra-high base number calcium sulfonate, and the dosage of the additive is relatively reduced by 13.3% compared with 8.5% in comparative example 10, and the formulations are better in detergency, oxidation resistance, abrasion resistance, water-splitting property, base number retention property and biodegradability.