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-(0))所示：其中各基团的定义见说明书。本发明的酯类化合物具有非常优异的润滑性、扩散性、抗磨性、清净性能,能够用作润滑基础油或添加剂,适宜用作石油产品的清净剂、扩散剂、抗磨剂、减摩剂,特别适宜用于船用气缸油。(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) 0 ) Shown in the figure:)

1. The structure of the ester compound is shown as the formula (I)₀) Shown in the figure:

in the formula (I)₀) In the formula, n is an integer of 1 to 10 (preferably an integer of 1 to 8, more preferably an integer of 1 to 5); the L radical being n-valent C_1-50Is preferably n-valent C_1-30More preferably n-valent C_1-20Straight or branched chain alkyl);

n A groups, which are the same or different from each other, are each independently selected from the group represented by formula (I), C_1-50Is preferably selected from the group consisting of the group represented by the formula (I), C_1-30More preferably selected from the group consisting of a group represented by the formula (I), C_1-20And at least one a group is selected from the group represented by 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);

each R is₀The radicals, equal to or different from each other, are each independently selected from H, C_1-20A hydrocarbon group (preferably H,C_1-12Straight or branched alkyl, more preferably C_1-8Straight or branched chain alkyl);

each m is the same or different and is independently selected from 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 one 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. An ester compound according to claim 1, wherein the ester compound has a structure represented by 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);

each R is₀The radicals, equal to or different from each other, are each independently selected from H, C_1-20Hydrocarbyl (preferably H, C)_1-12Straight or branched alkyl, more preferably C_1-8Straight or branched chain alkyl);

each m is the same or different and is independently selected from 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 one 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～C₄Straight-chain or branched alkylene), Ar group is selected fromFrom 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).

3. 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).

4. 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:

TABLE I

Number of ester Compounds A B 1 Benzoate, cyclopentyl formate Acetate group 2 Acetate group Benzoate, cyclopentyl formate 3 Benzoate and cyclohexanecarboxylate groups Butyrate radical 4 Butyrate radical Benzoate and cyclohexanecarboxylate groups 5 1-naphthyl formate, cyclopentyl formate Propionate group 6 Butyrate radical Benzoate and cyclohexanecarboxylate groups

The structure of the C, D group in the formula is shown in Table II:

TABLE II

Number of ester Compounds C D 7 Benzoate and cyclohexanecarboxylate groups Butyrate radical 8 Acetate group Benzoate, cyclopentyl formate 9 1-naphthyl formate, cyclopentyl formate Acetate group 10 Butyrate radical Benzoate and cyclohexanecarboxylate groups 11 Benzoate, cyclopentyl formate Propionate group 12 Butyrate radical Benzoate and cyclohexanecarboxylate groups

The structure of the E, F group in the formula is shown in Table III:

TABLE III

Number of ester Compounds E F 13 Benzoate, cyclopentyl formate Acetate group 14 Acetate group Benzoate, cyclopentyl formate 15 Benzoate and cyclohexanecarboxylate groups Butyrate radical 16 Butyrate radical Benzoate and cyclohexanecarboxylate groups 17 1-naphthyl formate, cyclopentyl formate Propionate group 18 Butyrate radical Benzoate and cyclohexanecarboxylate groups

。

5. 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);

each R is₀The radicals, equal to or different from each other, are each independently selected from H, C_1-20Hydrocarbyl (preferably H, C)_1-12Straight or branched alkyl, more preferably C_1-8Straight or branched chain alkyl);

each m is the same or different and is independently selected from 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); each X group, equal to or different from each other, is independently selected from OH, F, Cl, Br, I (preferably from OH, Cl, B)_r)。

6. The method according to claim 5, wherein the compound represented by the formula (α) is one or more selected from the group consisting of epoxidized vegetable oil, epoxidized glyceryl trioleate and epoxidized glyceryl trilinolate; and/or the presence of a gas in the gas,

the compound shown in the formula (beta) is selected from 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 cyclopentanecarboxylic acid, cyclopentanecarbonyl chloride, cyclohexanecarboxylic acid, cyclohexanecarbonyl chloride, cycloheptanecarboxylic acid and cycloheptanecarbonyl chloride; and/or the presence of a gas in the gas,

the compound represented by the formula (delta) and/or a self-condensate thereof is selected from one or more of formic acid, acetic acid, propionic acid, butyric acid, formic anhydride, acetic anhydride, propionic anhydride and butyric anhydride.

7. The process according to claim 5, wherein the reaction equivalent ratio of the compound represented by the formula (α) (in terms of the amount of epoxy groups) to one or more compounds selected from the compounds represented by the formulae (β), (γ), (δ) and the compounds represented by the formulae (β), (γ), (δ) themselves or their condensates with each other is 1: 0.1 to 10; the reaction temperature is 50-200 ℃.

8. The process according to claim 5, wherein 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 as an intercondensate.

9. The process according to claim 5, wherein the compound of the formula (α) (in terms of the amount of epoxy groups) is reacted with one or more compounds selected from the group consisting of the compounds of the formulae (β) and (γ) and the compounds of the formulae (β) and (γ) themselves or their condensates, and then with the compound of the formula (δ) and/or its condensate.

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

11. A lubricating oil composition, comprising the ester compound of any one of claims 1 to 4 or the ester compound prepared by the method of any one of claims 5 to 10, an optional lubricating oil additive, and a lubricating oil base oil.

12. The lubricating oil composition of claim 11, wherein the optional lubricating oil additive comprises one or more of a detergent, preferably an ultra-high base number detergent and/or a high base number detergent, an antioxidant, preferably one or more of an alkylated diphenylamine, di-tert-butyl-p-cresol, di-tert-butylphenol, N-phenyl-alpha-naphthylamine, a phenolic ester, and a sulfurized alkylphenol, and a dispersant, preferably a polyisobutylene succinimide ashless dispersant.

Technical Field

The invention relates to the field of petroleum products, in particular to an ester compound suitable for being used as base oil or an additive of lubricating oil.

Background

The marine cylinder oil is mainly used for lubricating a low-speed crosshead diesel engine, and currently, the base number of the cylinder oil is generally 10-100mgKOH/g, wherein the cylinder oil with the base numbers of 40TBN and 70TBN is used in the largest amount. The formula of the cylinder oil generally takes a detergent as a main component and takes other additives as auxiliary components, wherein the high-temperature detergency, the anti-wear property and the diffusivity are important indexes. Therefore, the development of cylinder oil with better performance is a research and development hotspot in recent years.

CN101570712, a high base number marine cylinder lubricating oil, is a 40TBN high base number marine cylinder lubricating oil with base oil as middle base oil and metal detergent mainly calcium naphthenate. In the formula, the calcium naphthenate accounts for 0.2-25%, the calcium alkylphenol sulfide accounts for 0.2-20%, the succinimide accounts for 0.2-20%, the tricresyl phosphate or the benzotriazole fatty amine salt accounts for 0.05-15%, the zinc carbamate accounts for 0.1-18%, the alkyl naphthalene accounts for 0.1-16%, the dimethyl silicon accounts for 0.0001-0.1%, the polyether accounts for 0.01-5%, and the balance is base oil, so that the water-based paint has the performances of good diffusivity, water resistance, corrosion and abrasion resistance, detergency and the like.

U.S. Pat. No. 4,2016/0130522 (Marine Diesel Cylinder oil composition) describes a marine cylinder oil, wherein one of the detergents with a base number of 100 and 250mgKOH/g and containing hydroxyl is adopted, the other detergent does not contain hydroxyl, the base number of the cylinder oil is 5-120mgKOH/g, and the obtained 70TBN marine cylinder oil has lower dosage and the performance of the formula with high dosage of other detergents is equivalent.

US8980805 "marine lubricant for high sulphur fuels" describes a 40TBN marine cylinder oil containing 0.1% to 2% of a metal detergent, having better acid neutralisation on combustion of high sulphur fuels and forming fewer deposits on combustion of low sulphur fuels.

US8334245 "two-stroke marine cylinder oil" describes a marine cylinder oil of 40TBN or more, comprising at least one lubricant base oil, at least one detergent, in particular one or more neutral detergents, having a strong neutralising ability towards sulphuric acid formed on combustion of high sulphur fuels, inhibiting the formation of deposits when using low sulphur fuels.

The above studies report that the cylinder oil 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 the existing marine cylinder oil on biodegradability is higher and higher, and the existing technology can not completely meet the requirement, so that further improvement is needed.

The currently used lubricating oil base oil is generally petroleum base oil, wherein the lubricating oil base oil is classified into API I oil, II oil, III oil and the like according to different processing technologies, and the renewable plant base oil is adopted as the lubricating oil along with the improvement of environmental protection requirements, so that the development direction in the future is the direction. The present research focus on improving the performance of the vegetable-based base oil by epoxidizing double bonds in the vegetable oil and further adding other functional groups is the present plant-based lubricating oil.

Chinese patent CN101928628A "alkyl ether modified rapeseed oil lubricant additive, lubricant and preparation method thereof" introduces an alkyl ether modified rapeseed oil lubricant additive, which is prepared by adding ROH and a catalyst into a reaction kettle, then gradually adding epoxy rapeseed oil, reacting at constant temperature, separating and purifying by distillation, filtration and other methods, and the obtained viscous liquid is the target product. The modified vegetable oil is degradable, contains no sulfur, phosphorus, nitrogen, boron and other elements, has no pungent smell and has good lubricating performance.

Chinese patent CN103087797A 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 as raw material, uses solid super acid to catalyze isomerization to carry out chemical modification under the condition of ultrasonic wave assistance, and uses fatty acid to open unstable epoxy bonds in the epoxy biodiesel by an esterification method to form isomeric modified biodiesel monoester containing hydroxyl.

Chinese patent CN107541307A, a vegetable oil-based amine antioxidant additive and preparation thereof, discloses a vegetable oil-based amine antioxidant additive and a preparation method thereof, wherein p-aminodiphenylamine is added into epoxy soybean oil, the reaction temperature is raised to 60-90 ℃, then the reaction is carried out for 4-8 h under heat preservation, reduced pressure filtration is carried out after the reaction is finished, and a brown viscous product is collected. 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.

US5368776 describes the preparation of epoxy-based rust inhibiting additives by 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.

USRE421313E describes chemical modification of bio-based industrial lubricating oil, wherein epoxy ring is opened by reaction of epoxidized soybean oil and organic acid anhydride to obtain modified soybean oil containing ester group and alcohol group, which improves the oxidation resistance and low temperature performance of oil products and reduces the generation of high temperature deposit.

The epoxidized soybean oil is used as industrial lubricating oil to improve some properties of the lubricant, but the epoxidized soybean oil is not reported in documents as a base oil of marine cylinder oil to achieve the purpose of improving the formulation properties.

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)₀) Shown in the figure:

in the formula (I)₀) In the formula, n is an integer of 1 to 10 (preferably an integer of 1 to 8, more preferably an integer of 1 to 5); the L radical being n-valent C_1-50Is preferably n-valent C_1-30More preferably n-valent C_1-20Straight or branched chain alkyl);

n A groups, which are the same or different from each other, are each independently selected from the group represented by formula (I), C_1-50Is preferably selected from the group consisting of the group represented by the formula (I), C_1-30More preferably selected from the group consisting of a group represented by the formula (I), C_1-20Straight or branched chain ofAlkyl) and at least one A group is selected from the group represented by 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);

each R is₀The radicals, equal to or different from each other, are each independently selected from H, C_1-20Hydrocarbyl (preferably H, C)_1-12Straight or branched alkyl, more preferably C_1-8Straight or branched chain alkyl);

each m is the same or different and is independently selected from 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 one 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).

According to the present invention, preferably, the ester compound of the present invention has a structure represented by 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);

each R is₀The radicals, equal to or different from each other, are each independently selected from H, C_1-20Hydrocarbyl (preferably H, C)_1-12Straight or branched alkyl, more preferably C_1-8Straight or branched chain alkyl);

each m is the same or different and is independently selected from 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 one G group is selected from the group represented by formula (II);

wherein G is₁Radical, G₂The radicals being selected fromA group of formula (III), a group of formula (IV) and a group of 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, the R radicals in the formula (I) are preferably identical to one another or different and are each independently preferably selected from C_1-12Straight or branched alkylene, more preferably selected from C_1-8Straight-chain or branched alkylene, each R₀The radicals, equal to or different from each other, are each independently preferably chosen from H, C_1-12Straight or branched alkyl, more preferably selected from C_1-8A linear or branched alkyl group; each m is the same or different from each other, and each m is independently preferably an integer of 1 to 8, more preferably an integer of 1 to 5; each G group is preferably independently selected from the group represented by the formula (II) wherein G is₁Radical, G₂Each independently selected from the group of formula (III), the group of formula (IV) and the group of formula (V), wherein the R' group is preferably selected from the group consisting of a single bond, C₁～C₄Linear or branched alkylene, the Ar group preferably being selected from C₆～C₁₀Aryl, preferably selected from C₆～C₁₅Aryl, more preferably phenyl, naphthyl, anthracenyl or C₁～C₈Alkyl-substituted phenyl/naphthyl/anthracenyl, the R' group preferably being selected from C₅～C₈CycloalkanesAnd more preferably cyclopentyl, cyclohexyl, the radical R' "being preferably chosen from C₁～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:

epoxidized soybean oil is used as a raw material and reacts with benzoic acid, 1-naphthyl formic acid, methylcyclopentanoic acid, methylcyclohexanoic acid, acetic anhydride and other raw materials to obtain a product which mainly comprises a mixture of ester compounds 1-6, wherein the structures of the ester compounds 1-6 are shown as the following structural formulas:

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

TABLE I

Number of ester Compounds	A	B
			1	Benzoate, cyclopentyl formate	Acetate group
2	Acetate group	Benzoate radical, ringGlutaric acid formate group
			3	Benzoate and cyclohexanecarboxylate groups	Butyrate radical
4	Butyrate radical	Benzoate and cyclohexanecarboxylate groups
			5	1-naphthyl formate, cyclopentyl formate	Propionate group
6	Butyrate radical	Benzoate and cyclohexanecarboxylate groups

The method comprises the following steps of taking epoxy peanut oil as a raw material, and reacting the epoxy peanut oil with benzoic acid, 1-naphthyl formic acid, methylcyclopentanoic acid, methylcyclohexanoic acid, acetic anhydride and other raw materials to obtain a product, wherein the obtained product mainly comprises a mixture of ester compounds 7-12, and the structures of the ester compounds 7-12 are shown as the following structural formulas:

the structure of the C, D group in the formula is shown in Table II:

TABLE II

Number of ester Compounds	C	D
			7	Benzoate and cyclohexanecarboxylate groups	Butyrate radical
8	Acetate group	Benzoate, cyclopentyl formate
			9	1-naphthyl formate, cyclopentyl formate	Acetate group
10	Butyrate radical	Benzoate and cyclohexanecarboxylate groups
			11	Benzoate, cyclopentyl formate	Propionate group
12	Butyrate radical	Benzoate and cyclohexanecarboxylate groups

The method comprises the following steps of taking linseed oil as a raw material, and reacting the linseed oil with benzoic acid, 1-naphthyl formic acid, methylcyclopentanoic acid, methylcyclohexanoic acid, acetic anhydride and other raw materials to obtain a product, wherein the product mainly comprises a mixture of ester compounds 13-18, and the structures of the ester compounds 13-18 are shown as the following structural formulas:

the structure of the E, F group in the formula is shown in Table III:

TABLE III

Number of ester Compounds	E	F
			13	Benzoate, cyclopentyl formate	Acetate group
14	Acetate group	Benzoate, cyclopentyl formate
			15	Benzoate and cyclohexanecarboxylate groups	Butyrate radical
16	Butyrate radical	Benzoate and cyclohexanecarboxylate groups
			17	1-naphthyl formate, cyclopentyl formate	Propionate group
18	Butyrate radical	Benzoate and cyclohexanecarboxylate groups

。

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);

each R is₀The radicals, equal to or different from each other, are each independently selected from H, C_1-20Hydrocarbyl (preferably H, C)_1-12Straight or branched alkyl, more preferably C_1-8Straight or branched chain alkyl);

each m is the same or different and is independently selected from 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 fromMethylene, ethylene, propylene and at least one G' group 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).

According to the preparation method of the present invention, the compound represented by the formula (α) may be one or more selected from epoxidized vegetable oil, epoxidized triolein and linolenic anhydride glycerol trioleate, or a mixed glyceride of epoxidized oleic acid, linoleic acid and linolenic acid, for example, one or more selected from epoxidized soybean oil, epoxidized peanut oil, epoxidized palm oil, epoxidized rapeseed oil, epoxidized sunflower oil, epoxidized olive oil and epoxidized corn oil, preferably one or more selected from epoxidized soybean oil, epoxidized peanut oil and epoxidized palm oil.

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 catalyst, a molecular sieve, a solid acidic sulfate catalyst, and an acidic ionic liquid catalyst, such as an alkyl imidazole or an alkyl pyridine as a cation of the acidic ionic liquid, and one or more of tetrafluoroborate, trifluoromethylsulfonate, hexafluorophosphate, p-toluenesulfonate, nitrate, perchlorate, methanesulfonate, oxalate, and hydrogensulfate as an anion of the acidic ionic liquid. 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, a solvent may be optionally added 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), (δ) and the compounds represented by the formulae (β), (γ), (δ) themselves or the mutual condensates. The solvent is not particularly limited as it is conventionally known.

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: 0.2-5 ℃, 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.

According to the production method of the present invention, in 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 their mutual condensates, the reaction product can be washed and purified with a solvent, and the solvent which can be washed and purified is preferably a hydrocarbon solvent. The solvent may be removed by conventional techniques such as drying, evaporation, distillation, and the like.

The ester compound has excellent lubricating property, diffusivity, abrasion resistance and cleaning performance, can be used as lubricating base oil or an additive, is suitable for being used as a detergent, a diffusant, an antiwear agent and an antifriction agent of a petroleum product, and is particularly suitable for being used for marine cylinder oil.

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 3-50%, more preferably 5-40% of the total mass of the lubricating oil composition; the optional lubricating oil additive accounts for 0-40%, preferably 1-35%, more preferably 5-30% of the total mass of the lubricating oil composition; the lubricating oil base oil accounts for 40-99%, preferably 45-95% and more preferably 50-90% of the total mass of the lubricating oil composition.

In accordance with the lubricating oil composition of the present invention, the optional lubricating oil additives include one or more of detergents, antioxidants and dispersants.

The lubricating oil composition according to the present invention, the detergent is preferably an ultra-high base number detergent and/or an overbased detergent, wherein the ultra-high base number detergent is preferably selected from the group consisting of ultra-high base number calcium sulfonates having a base number greater than 590 mgKOH/g; the high-base number detergent is preferably selected from synthetic calcium alkyl benzene sulfonate 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 sulfurized calcium alkyl phenate with a base number of 250-400 mgKOH/g. The detergent is preferably a mixture of an ultra-high base number detergent and a high base number detergent, wherein the mass ratio between the ultra-high base number detergent and the high base number detergent is preferably 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%.

According to the lubricating oil composition of the present invention, the antioxidant is preferably selected from one or more of alkylated diphenylamine, di-tert-butyl-p-cresol, di-tert-butylphenol, N-phenyl-alpha-naphthylamine, phenol esters and sulfurized alkylphenols, preferably one or more of alkylated diphenylamine, di-tert-butyl-p-cresol, N-phenyl-alpha-naphthylamine and phenol esters, more preferably alkylated diphenylamine and/or 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, the dispersant is preferably selected from polyisobutylene succinimide ashless dispersant, and one or more of mono-polyisobutylene succinimide, di-polyisobutylene succinimide and polyisobutylene succinimide can be selected, wherein the number average molecular weight of polyisobutylene part is 500-4000, preferably 1000-3000. The dispersant is most preferably a mono-polyisobutylene succinimide and/or a di-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%.

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, and has a viscosity index of above 120 and a kinematic viscosity of 100 DEG CIn the range of 1 to 40mm²Between/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.

Preferred lubricating oil compositions of the present invention have excellent detergency, anti-wear properties, diffusibility, acid-neutralizing properties, dispersibility and biodegradability. The ester compound of the invention shows excellent detergency and abrasion resistance in the marine lubricating oil, and the diffusivity of the marine cylinder oil is unexpectedly found to be improved, probably because the special structure of the ester compound of the invention enables the lubricating oil and the metal surface of an engine to have better adsorbability, and meanwhile, the ester compound of the invention enables the acid neutralization of the lubricating oil composition to be improved, which is related to the synergistic effect of an ester group introduced into the ester compound and a detergent, so that a basic component in the detergent can quickly react with an acidic substance, and the normal work of an engine cylinder sleeve is ensured.

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。

In the context of the present specification, the expression "number + valence + group" or the like refers to the position of the basic structure (e.g. chain, etc.) from which the group corresponds,Ring or combination thereof, etc.) from which the number of hydrogen atoms represented by the number has been removed, preferably refers to a group obtained from a carbon atom (preferably a saturated carbon atom and/or a non-identical carbon atom) contained in the structure from which the number of hydrogen atoms represented by the number has been removed. For example, "3-valent straight or branched alkyl" refers to a group obtained by removing 3 hydrogen atoms from a straight or branched alkane (i.e., the base chain to which the straight or branched alkyl corresponds), and "2-valent straight or branched heteroalkyl" refers to a group obtained by removing 2 hydrogen atoms from a straight or branched heteroalkane (preferably from a carbon atom contained in the heteroalkane, or further, from a non-identical carbon atom). For example, the 2-valent propyl group may be-CH₂-CH₂-CH₂-*、The 3-valent propyl group may be The 4-valent propyl group may be Wherein represents a binding end in the group that may be bonded to other groups.

Example 1 epoxidized Soybean oil Mixed ester A₁Preparation of

100g of epoxidized soybean oil (molecular weight: Mn: 961.44, epoxy value 6.2g/100g, light yellow viscous oily liquid, viscosity 325mPa.s, refractive index 1.473 and density 0.985 g/cm) was added into a 500mL three-neck flask³0.104mol), 31 g of benzoic acid (Mn: 122.12, 0.25mol), 30 g of cyclopentanecarboxylic acid (Mn: 114.14, 0.26mol), the molar ratio of benzoic acid, cyclopentanecarboxylic acid and epoxidized soybean oil being 5.1:1, heating to 100 ℃ with stirring and then adding 3.3 g of sulfurSodium hydrogen sulfate, reacting for 9h, stopping the reaction when the epoxidation value is close to 0, neutralizing an oil phase by using 2% NaOH aqueous solution, extracting residual benzoic acid and cyclopentanecarboxylic acid in the oil phase by using methanol aqueous solution, separating the oil phase, washing the oil phase by using distilled water until the oil phase is neutral, distilling the oil phase, and removing organic acid and water to obtain a pale yellow intermediate product A₀' 158 g. The infrared analysis result showed 823cm in wave number^-1And 842cm^-1The disappearance of the absorption peaks at the left and right, indicating that the three-membered ring in the epoxidized soybean oil 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.

The intermediate product A obtained is₀' 158 g was charged into a 500mL three-necked flask, 28 g of acetic anhydride (0.27mol, Mn 102.09) was added in a molar ratio of acetic anhydride to epoxidized soybean oil of 2.6:1, heated to 100 ℃ with stirring, and then 3.0 g of benzenesulfonic acid was added and reacted for 8 hours, and infrared analysis of the sample showed 3500cm wave number^-1The absorption peaks on the left and the right disappear, which shows that the hydroxyl in the esterification products of the epoxidized soybean oil, the benzoic acid and the cyclopentanecarboxylic acid completely carry out the esterification reaction with the anhydride, at the moment, the reaction is stopped, 2 percent NaOH aqueous solution is used for neutralizing the oil phase, then methanol aqueous solution is used for extracting the residual acetic anhydride 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 epoxidized soybean oil, the benzoic acid, the cyclopentanecarboxylic acid and the acetic acid is obtained₁178 g, its kinematic viscosity at 100 ℃ is 46.26mm²(s) kinematic viscosity at 40 ℃ of 580.81mm²Viscosity index 132 per second.

Example 2 epoxidized Soybean oil Mixed ester B₁Preparation of

100g of epoxidized soybean oil (molecular weight: Mn: 961.44, epoxy value 6.2g/100g, light yellow viscous oily liquid, viscosity 325mPa.s, refractive index 1.473 and density 0.985 g/cm) was added into a 500mL three-neck flask³0.104mol), 30 g of cyclopentanecarboxylic acid (Mn: 114.14, 0.265mol), 45 g of 1-naphthylcarboxylic acid (Mn: 172.18, 0.265mol), the molar ratio of cyclopentanecarboxylic acid and 1-naphthylcarboxylic acid to epoxidized soybean oil being 5.1:1,heating to 100 deg.C under stirring, adding Amberlyst15 catalyst (cation exchange resin, import) 3.0 g, reacting for 8h, stopping reaction when epoxidation value is close to 0, neutralizing oil phase with 2% NaOH aqueous solution, extracting residual cyclopentanecarboxylic acid and 1-naphthoic acid in oil phase with methanol aqueous solution, separating oil phase, washing with distilled water until neutral, distilling oil phase, removing organic acid and water to obtain light yellow intermediate product B₀168 grams. The infrared analysis result showed 823cm in 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 soybean oil had occurred at 1740cm^-1And 3500cm^-1Carboxylate absorption peaks appear to the left and right, indicating conversion of the three membered ring to alcohol and ester.

Intermediate product B obtained₀168 g of the mixture was placed in a 500mL three-necked flask, 45 g (0.28mol, Mn 158.2) of butyric anhydride was added thereto at a molar ratio of butyric anhydride to epoxidized soybean oil of 2.7:1, the mixture was heated to 100 ℃ under stirring, 3.0 g of sodium hydrogen sulfate was added thereto, and the mixture was 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 esterification products of the epoxidized soybean oil, the cyclopentanecarboxylic acid and the 1-naphthoic acid is completely esterified with anhydride, at the moment, the reaction is stopped, 2 percent NaOH aqueous solution is used for neutralizing the oil phase, then methanol aqueous solution is used for extracting residual butyric anhydride 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 a light yellow mixed esterification product B of the epoxidized soybean oil, the cyclopentanecarboxylic acid, the 1-naphthoic acid and the butyric acid is obtained₁202 g and the kinematic viscosity at 100 ℃ of 38.52mm²(s) kinematic viscosity at 40 ℃ of 471.92mm²Viscosity index of 126.

EXAMPLE 3 epoxidized Soybean oil Mixed ester C₁Preparation of

100g of epoxidized soybean oil (molecular weight: Mn: 961.44, epoxy value 6.2g/100g, light yellow viscous oily liquid, viscosity 325mPa.s, refractive index 1.473 and density 0.985 g/cm) was added into a 500mL three-neck flask³0.104mol), 24 g of benzoic acid (Mn 122.12, 0.20mol), cyclohexanecarboxylic acid32 g (Mn: 128.17, 0.25mol), the molar ratio of benzoic acid and cyclohexanecarboxylic acid to epoxidized soybean oil is 4.3:1, heating to 100 ℃ under stirring, then adding 4 g of sodium hydrogensulfate, reacting for 8h, stopping the reaction when the epoxidation value is close to 0, neutralizing the oil phase with 2% NaOH aqueous solution, then extracting the residual benzoic acid and cyclohexanecarboxylic acid in the oil phase with methanol aqueous solution, separating the oil phase, washing with distilled water until neutral, distilling the oil phase, removing the organic acid and water to obtain a pale yellow intermediate product C₀152 grams. The infrared analysis result showed 823cm in wave number^-1And 842cm^-1The disappearance of the absorption peaks at the left and right, indicating that the three-membered ring in the epoxidized soybean oil 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.

The intermediate product C obtained is₀152 g of acetic anhydride (molar ratio of acetic anhydride to epoxidized soybean oil: 3.3: 1) was added into a 500mL three-necked flask, 35 g of acetic anhydride (Mn: 102.09) was added thereto, the mixture was heated to 100 ℃ under stirring, 3.0 g of concentrated sulfuric acid was added thereto, and the mixture was reacted for 12 hours, whereby 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 esterification products of the epoxidized soybean oil, the benzoic acid and the cyclohexanecarboxylic acid completely carry out esterification reaction with acid anhydride, at the moment, the reaction is stopped, 2 percent NaOH aqueous solution is used for neutralizing the oil phase, then methanol aqueous solution is used for extracting residual acetic anhydride 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 C of the epoxidized soybean oil, the benzoic acid, the cyclohexanecarboxylic acid and the acetic acid is obtained₁182 g, and the kinematic viscosity at 100 ℃ of the product is 42.59mm²(s) kinematic viscosity at 40 ℃ of 530.34mm²(ii)/s, viscosity index 129.

Example 4 epoxidized Soybean oil Mixed ester D₁Preparation of

100g of epoxidized soybean oil (molecular weight: Mn: 961.44, epoxy value 6.2g/100g, light yellow viscous oily liquid, viscosity 325mPa.s, refractive index 1.473 and density 0.985 g/cm) was added into a 500mL three-neck flask³0.104mol) of 1-naphthylcarboxylic acid34 g (Mn: 172.18, 0.2mol), 43 g cyclohexanecarboxylic acid (Mn: 128.17, 0.34mol), 5.2:1 molar ratio of 1-naphthyl formic acid and cyclohexanecarboxylic acid to epoxidized soybean oil, heating to 100 ℃ under stirring, then adding 3.6 g of sodium hydrogen sulfate, reacting for 8h, stopping the reaction when the epoxidation value is close to 0, neutralizing the oil phase with 2% NaOH aqueous solution, extracting the remaining 1-naphthyl formic acid and cyclohexanecarboxylic acid in the oil phase with methanol aqueous solution, separating the oil phase, washing with distilled water until the oil phase is neutral, distilling the oil phase, removing organic acid and water to obtain pale yellow intermediate product D₀172 g. The infrared analysis result showed 823cm in wave number^-1And 842cm^-1The disappearance of the absorption peaks at the left and right, indicating that the three-membered ring in the epoxidized soybean oil 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.

The intermediate product D obtained₀172 g of propionic anhydride (0.31mol, Mn: 130.14) was added to a 500mL three-necked flask, 40 g of propionic anhydride (3: 1 molar ratio) to epoxidized soybean oil was added thereto, the mixture was heated to 100 ℃ under stirring, 3.0 g of concentrated sulfuric acid was added thereto, and the mixture was reacted for 8 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 esterification products of the epoxidized soybean oil, the 1-naphthyl formic acid and the cyclohexanecarboxylic acid completely carry out the esterification reaction with acid anhydride, at the moment, the reaction is stopped, 2 percent NaOH aqueous solution is used for neutralizing the oil phase, then methanol aqueous solution is used for extracting the residual propionic anhydride 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 D of the epoxidized soybean oil, the 1-naphthoic acid, the cyclohexanecarboxylic acid and the propionic acid is obtained₁206 g, with a kinematic viscosity at 100 ℃ of 41.43mm²(s) kinematic viscosity at 40 ℃ of 556.83mm²(ii) a viscosity index of 120.

Example 5 epoxidized Soybean oil Mixed ester A₀Preparation of

100g of epoxidized soybean oil (molecular weight: Mn: 961.44, epoxy value 6.2g/100g, pale yellow viscous oily liquid, viscosity 325mPa.s, refractive index 1.473,density 0.985g/cm³0.104mol), 31 g of benzoic acid (Mn is 122.12, 0.25mol), 30 g of cyclopentanecarboxylic acid (Mn is 114.14, 0.26mol), the molar ratio of benzoic acid, cyclopentanecarboxylic acid and epoxidized soybean oil is 5.1:1, 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, neutralizing the oil phase with 2% NaOH aqueous solution, extracting the residual benzoic acid and cyclopentanecarboxylic acid in the oil phase with methanol aqueous solution, separating the oil phase, washing with distilled water until the oil phase is neutral, distilling the oil phase, and removing the organic acid and water to obtain a pale yellow product A₀158 g, kinematic viscosity at 100 ℃ of 35.8mm²(s) kinematic viscosity at 40 ℃ of 387.6mm²Viscosity index 136/s. The infrared analysis result showed 823cm in wave number^-1And 842cm^-1The disappearance of the absorption peaks at the left and right, indicating that the three-membered ring in the epoxidized soybean oil 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.

Example 6 epoxidized Soybean oil Mixed ester A_1-1Preparation of

100g of epoxidized soybean oil (molecular weight: Mn: 961.44, epoxy value 6.2g/100g, light yellow viscous oily liquid, viscosity 325mPa.s, refractive index 1.473 and density 0.985 g/cm) was added into a 500mL three-neck flask³0.104mol), 62 g of benzoic acid (Mn is 122.12, 0.5mol), 60 g of cyclopentanecarboxylic acid (Mn is 114.14, 0.52mol), the molar ratio of the benzoic acid, the cyclopentanecarboxylic acid and the epoxidized soybean oil is 10.2:1, the mixture is heated to 100 ℃ under stirring, then 3.3 g of sodium bisulfate is added for reaction for 9h, when the epoxidation value is close to 0, the reaction is stopped, 2% NaOH aqueous solution is used for neutralizing the oil phase, then methanol aqueous solution is used for extracting the residual benzoic acid and the cyclopentanecarboxylic 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 the water are removed, and a pale yellow esterified product A of the epoxidized soybean oil, the benzoic acid and the cyclopentanecarboxylic acid is obtained_1-1218 g, and the kinematic viscosity at 100 ℃ of the product is 40.1mm²(s) kinematic viscosity at 40 ℃ of 476.9mm²(ii) a viscosity index of 131. The infrared analysis result showed 823cm in wave number^-1And 842cm^-1The disappearance of the absorption peaks at the left and right, indicating that the three-membered ring in the epoxidized soybean oil had reacted, at 1740cm^-1The carboxylate absorption peaks appear to the left and right, indicating the conversion of the three-membered ring to an ester.

Example 7 epoxidized Soybean oil Mixed ester A_1-2Preparation of

100g of epoxidized soybean oil (molecular weight: Mn: 961.44, epoxy value 6.2g/100g, pale yellow viscous oily liquid, viscosity 325mPa.s, refractive index 1.473 and density 0.985 g/cm) was added into a 500mL three-necked flask³0.104mol), 54 g of acetic anhydride (0.53mol, Mn 102.09) in a molar ratio of acetic anhydride to epoxidized soybean oil of 5.1:1, heating to 100 ℃ with stirring, then adding 3.0 g of benzenesulfonic acid, reacting for 10h, and stopping the reaction when the epoxidation number approaches 0. Neutralizing oil phase with 2% NaOH water solution, extracting residual acetic anhydride with methanol water solution, separating oil phase, washing with distilled water until neutral, distilling oil phase, removing organic acid and water to obtain light yellow esterified product A of epoxidized soybean oil, acetic acid and benzenesulfonic acid_1-2149 g, with a kinematic viscosity at 100 ℃ of 28.1mm²(s) kinematic viscosity at 40 ℃ of 270.2mm²Viscosity index 138/s. The infrared analysis result of the product shows that the wave number is 823cm^-1And 842cm^-1The disappearance of the absorption peaks at the left and right, indicating that the three-membered ring in the epoxidized soybean oil had reacted, at 1740cm^-1And carboxylate absorption peaks around, indicating conversion of the three membered ring to an ester.

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

SH/T0251 Petroleum products base number determination method (perchloric acid potentiometric titration 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 5000DSC 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

The acid neutralization test is used for simulating the neutralization reaction of alkaline components (mainly calcium carbonate) in the oil and sulfuric acid generated in the combustion process of sulfur-containing fuel in the process of using the marine cylinder oil. 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 progress of the reaction is indicated by the change in the pressure of the generated carbon dioxide gas, and when the carbon dioxide pressure reached the maximum, the completion of the neutralization reaction is indicated, and the time required for completion of the neutralization reaction is indicated by the degree of the acid neutralization rate. The shorter the time, the stronger the acid neutralizing ability.

Diffusion test

The diffusion test was used to simulate the diffusion of cylinder oil at the cylinder surface. 20mL of test oil was dropped onto a bright iron plate at a constant temperature of 120 ℃ to measure the diameter of oil droplet diffusion. The larger the diffusion diameter, the better the oil diffusivity.

Gel test

The gel test was 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.

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 triangular flask, 80mL mineral medium and 15. mu.L of test oil were added, and 4mL of LB medium solution without inoculated wastewater was added as a blank control flask. 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 for the tests

3. The main additives used in the tests are shown in Table 2.

TABLE 2 major additives for the tests

4. The main marine cylinder oils used in the tests are shown in table 3.

TABLE 3 marine cylinder oil for testing

Examples 8 to 16 and comparative examples 1 to 4, in which 70TBN marine cylinder oils were prepared according to API50 viscosity grade, were formulated as shown in Table 4. Two commercially available TBN70 marine cylinder oils (5070 cylinder oils from two companies at home and abroad) were used as comparative examples 5 and 6. The evaluation tests were carried out on these marine cylinder oils and the test results are shown in tables 5 and 6.

TABLE 470 TBN examples and comparative examples of marine cylinder oils

TABLE 570 Performance test results for marine cylinder oil examples of TBN

TABLE 670 TBN Performance test results for marine cylinder oil comparative examples

Examples 17 to 25 and comparative examples 7 to 10 of 40TBN marine cylinder oil prepared according to API50 viscosity grade, the formulation composition of which is shown in Table 7. Two commercially available TBN40 marine cylinder oils (5040 cylinder oils from two companies at home and abroad) were used as comparative examples 11 and 12. The evaluation results are shown in tables 8 and 9.

TABLE 740 TBN examples and comparative examples of marine cylinder oils

TABLE 840 TBN Performance test results for marine cylinder oil embodiments

TABLE 940 TBN Performance test results for marine cylinder oil comparative examples

As can be seen from tables 4 to 6, the 5070 marine cylinder oil formulations of examples 8 to 13 are low in dosage and have excellent detergency, wear resistance, diffusibility, acid neutrality, dispersibility and biodegradability.

As is apparent from tables 7 to 9, the 5040 marine cylinder oil formulations prepared in examples 17 to 22 were low in dosage and excellent in detergency, anti-wear properties, diffusibility, acid-neutralizing properties, dispersibility and biodegradability.