CN112707818A - Ester compound and preparation method and application thereof - Google Patents

Ester compound and preparation method and application thereof Download PDF

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Publication number
CN112707818A
CN112707818A CN201911018285.0A CN201911018285A CN112707818A CN 112707818 A CN112707818 A CN 112707818A CN 201911018285 A CN201911018285 A CN 201911018285A CN 112707818 A CN112707818 A CN 112707818A
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formula
acid
group
compound represented
compound
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CN112707818B (en
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张耀
段庆华
鱼鲲
李勇
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Priority to CN201911018285.0A priority Critical patent/CN112707818B/en
Priority to EP20879644.1A priority patent/EP4049994A4/en
Priority to US17/755,075 priority patent/US20230012456A1/en
Priority to PCT/CN2020/123197 priority patent/WO2021078249A1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/68—Esters
    • C10M129/78—Complex esters, i.e. compounds containing at least three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compound: monohydroxy compounds, polyhydroxy compounds, monocarboxylic acids, polycarboxylic acids, hydroxy carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/30—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/30—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
    • C10M2207/301—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids used as base material

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides an ester compound and a preparation method and application thereof. The structure of the ester compound of the invention is as follows:

Description

Ester compound and preparation method and application thereof
Technical Field
The invention relates to the field of lubricating oil, in particular to an ester compound suitable for being used as a lubricating oil additive or base oil.
Background
Lubricating oil is an indispensable component in the operation of machinery, plays roles in reducing friction and wear, protecting machinery, cooling, cleaning, sealing, prolonging service life and the like, but because the factors such as lubricating oil leakage, overflow, evaporation or improper treatment and the like cause serious harm to the natural environment, higher requirements on the environmental friendliness of the lubricating oil are put forward. In the prior art, base oil and additives which form lubricating oil are mostly from petroleum raw materials, are difficult to regenerate under the specific time condition of the nature at the present stage, and the components are mostly isoparaffin, cycloparaffin, aromatic hydrocarbon and trace metal substances, which causes poor biodegradability.
The environmentally friendly lubricating oil means a lubricating oil having excellent biodegradability, renewability, and no toxicity or low toxicity. The degradation rate of environmentally friendly lubricating oils is typically more than two times higher than that of petroleum base oils.
The vegetable oil has the advantages of good lubricating property, wide raw material source, lower production cost, good biodegradability (the biodegradation rate can reach 70% -100%), and the like, is suitable for boundary lubrication, can be used for hydrodynamic lubrication, and can be applied to most lubrication working conditions. Compared with mineral oil, the vegetable oil has better lubricating property and viscosity-temperature property, the viscosity change of the vegetable oil is smaller in a wide temperature range, the friction can be better reduced, and the mechanical energy loss can be reduced by 5-15% compared with the mineral oil. The vegetable oil also has higher flash point and lower evaporation loss, can obviously reduce the overflow of organic gas under the high-temperature working condition, and is safer to use in the open environment. However, unsaturated double bonds in vegetable oil molecules are easily oxidized, so that the problems of viscosity increase, acid corrosion and the like are caused.
For this reason, many base oils and additives of ester structure have been developed in the prior art.
US 6051539 reports that the improvement of antioxidant and low temperature properties of vegetable oils is achieved by modifying the fatty side chain structure in the triglyceride structure of vegetable oils, comprising a two-step reaction: (1) carrying out esterification reaction on isomeric fatty acid (such as 2-ethyl hexanoic acid) and methanol or polyol containing branched chain to generate branched chain fatty acid methyl ester or polyol ester; (2) the branched fatty acid methyl ester or polyol ester and triglyceride are subjected to transesterification reaction under the action of a catalyst to generate triglyceride partially substituted by branched fatty acid and polyol ester partially substituted by long-chain fatty acid.
Although the existing ester base oil and additives can improve the environmental friendliness of the lubricating oil, there is a great room for improvement. With the development of environment-friendly lubricating oil, higher requirements are also put forward on the performance of ester base oil and additives. In view of this, there is still a need in the art for more excellent environmentally friendly base oils and additives.
Disclosure of Invention
The invention provides an ester compound and a preparation method and application thereof.
The structure of the ester compound of the invention is as follows:
Figure BDA0002246391920000021
wherein each R' group, which may be the same or different from each other, is independently selected from C1-10Linear or branched alkylene (preferably C)1-6Linear or branched alkylene groups of (a); each L' group, which may be the same or different from each other, is independently selected from C1-16Linear or branched alkylene (preferably C)2-10Linear or branched alkylene groups of (a); n is an integer of 1 to 10 (preferably an integer of 1 to 5); each L group is the same or different from each other and is independently selected from the group consisting of a group represented by the formula (II), a group represented by the formula (III), C1-10Is preferably selected from the group consisting of a group represented by the formula (II), a group represented by the formula (III), C1-6Straight or branched alkyl groups) on each carbon atom to which the L group is attached, at least one L group selected from the group represented by formula (III),
—R'—OH(II)，
Figure BDA0002246391920000022
in formula (II), the R group is selected from C1-10Linear or branched alkylene (preferably C)1-6Linear or branched alkylene groups of (a);
in formula (III), the R' group is selected from C1-10Linear or branched alkylene (preferably C)1-6Linear or branched alkylene groups of (a); each R' group is the same or different from each other and is independently selected from the group consisting of a single bond, C1-10Alkylene (preferably C)1-5Linear or branched alkylene); r0The group is selected from H, C1-10Hydrocarbyl (preferably C)1-5Straight or branched chain alkyl); m is an integer of 1 to 10 (preferably an integer of 1 to 6, more preferably an integer of 1 to 5); m a groups, equal to or different from each other, are each independently selected from the group represented by formula (IV), -C ═ C-, methylene, and ethylene, and at least one a group is selected from the group represented by formula (IV);
Figure BDA0002246391920000031
in the formula (IV), R0The group being selected from C1-17Hydrocarbyl (preferably C)1-15Straight or branched alkyl, more preferably C1-11Straight or branched chain alkyl).
According to the ester compound of the present invention, optionally, each L group is the same as or different from each other, and is independently selected from the group represented by formula (III).
According to the ester compounds of the present invention, optionally, at least one group L selected from C is present on each carbon atom to which the group L is attached1-6Linear or branched alkyl.
According to the ester compounds of the present invention, optionally, at least one group L selected from C is present on each carbon atom to which the group L is attached1-6The other L groups, which are the same or different from each other, are each independently selected from the group represented by the formula (III).
The ester compound with a specific structure comprises one or more of the following compounds:
Figure BDA0002246391920000041
Figure BDA0002246391920000051
Figure BDA0002246391920000061
Figure BDA0002246391920000071
Figure BDA0002246391920000081
Figure BDA0002246391920000091
Figure BDA0002246391920000101
Figure BDA0002246391920000111
Figure BDA0002246391920000121
Figure BDA0002246391920000131
Figure BDA0002246391920000141
Figure BDA0002246391920000151
Figure BDA0002246391920000161
Figure BDA0002246391920000171
Figure BDA0002246391920000181
Figure BDA0002246391920000191
Figure BDA0002246391920000201
Figure BDA0002246391920000211
Figure BDA0002246391920000221
the invention also provides a preparation method of the ester compound, which comprises the step of reacting the compound shown in the formula (alpha), the compound shown in the formula (beta) and the compound shown in the formula (gamma),
Figure BDA0002246391920000231
in formula (. alpha.), the L' group is selected from C1～100Alkylene (preferably C)1～16Straight or branched chain ofAlkalkylene, more preferably C2～10Linear or branched alkylene groups of (a); each X, equal to or different from each other, is independently selected from H, F, Cl, Br or I (preferably H, Cl or Br);
in the formula (. beta.), the respective L' groups, which are the same or different from each other, are each independently selected from the group represented by the formula (. delta.), C1-10Is preferably selected from the group consisting of a group of the formula (delta), C1-6And at least one L "group is selected from the group represented by formula (δ);
—R'—OH(δ)，
in formula (. delta.), the R' group is selected from C1-10Linear or branched alkylene (preferably C)1-6Linear or branched alkylene groups of (a);
in the formula (gamma), m is an integer of 1 to 10 (preferably an integer of 1 to 6, more preferably an integer of 1 to 5); each R' group is the same or different from each other and is independently selected from the group consisting of a single bond, C1-10Alkylene (preferably C)1-5Linear or branched alkylene); r0The group is selected from H, C1-10Hydrocarbyl (preferably C)1-5Straight or branched chain alkyl); the Y group is selected from H, F, Cl, Br or I (preferably H, Cl or Br); m a groups, equal to or different from each other, are each independently selected from the group represented by formula (epsilon), -C ═ C-, methylene, and ethylene, and at least one a group is selected from the group represented by formula (epsilon);
Figure BDA0002246391920000232
in the formula (. epsilon.), R0The group being selected from C1-17Hydrocarbyl (preferably C)1-15Straight or branched alkyl, more preferably C1-11Straight or branched chain alkyl).
According to the preparation process of the present invention, optionally, the respective L' groups, which are the same or different from each other, are each independently selected from the group represented by the formula (. delta.).
According to the preparation process of the present invention, optionally, at least one group L 'is present on each carbon atom to which the group L' is attached, selected from C1-6Linear chain of (2)Or a branched alkyl group.
According to the preparation process of the present invention, optionally, at least one group L 'is present on each carbon atom to which the group L' is attached, selected from C1-6The other L' groups, which are the same or different from each other, are each independently selected from the group represented by the formula (delta).
According to the production method of the present invention, the reaction equivalent ratio between the compound represented by the formula (α) (in terms of X) and the compound represented by the formula (β) (in terms of OH) and the compound represented by the formula (γ) (in terms of Y) is preferably 1: 0.8-2: 0.5 to 10, more preferably 1: 1-2: 1-6; the reaction temperature is preferably 70-250 ℃, and more preferably 90-200 ℃. The reaction time is usually as long as possible, and may be generally 0.5 to 24 hours, preferably 2 to 15 hours.
According to the preparation method of the present invention, a plurality of ester compounds may be contained in the reaction product of the compound represented by the formula (α), the compound represented by the formula (β) and the compound represented by the formula (γ), and these ester compounds may be separated into a single-structure compound by a conventional method, or may be used as a product without separating them.
According to the production method of the present invention, the compound represented by the formula (α), the compound represented by the formula (β) and the compound represented by the formula (γ) may be reacted together, or the compound represented by the formula (α) and the compound represented by the formula (β) may be reacted first, and then the product thereof may be reacted with the compound represented by the formula (γ), or the compound represented by the formula (β) and the compound represented by the formula (γ) may be reacted, and then the product thereof may be reacted with the compound represented by the formula (α).
According to the production method of the present invention, preferably, the compound represented by the formula (α) and the compound represented by the formula (β) are reacted first, and then the product thereof is reacted with the compound represented by the formula (γ). The temperature for the reaction of the compound represented by the formula (alpha) and the compound represented by the formula (beta) and the reaction of the product thereof and the compound represented by the formula (gamma) can be 0-300 ℃ (preferably 50-260 ℃); the reaction time may be 0.5 to 72 hours (preferably 3 to 48 hours).
According to the preparation method of the present invention, a solvent may be added or may not be added, preferably a solvent is added in the reaction of the compound represented by the formula (α), the compound represented by the formula (β) and the compound represented by the formula (γ). The solvent is preferably a hydrocarbon solvent, preferably one or more of alkane, aromatic hydrocarbon and ether, more preferably an alkane solvent, and for example, one or more of hexane, heptane, octane, nonane, decane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, benzene, toluene, xylene, ethylbenzene, propylbenzene, diethyl ether, propyl ether, isopropyl ether and dibutyl ether may be used. The amount of the solvent to be added is not particularly limited, as long as the reaction is promoted to proceed smoothly. The solvent can also play a role of a water carrying agent so as to promote the smooth proceeding of the reaction.
According to the preparation method of the present invention, a catalyst may or may not be added in the reaction of the compound represented by the formula (α), the compound represented by the formula (β), and the compound represented by the formula (γ). The catalyst can be one or more of inorganic acid, organic acid, solid acid, heteropoly acid, acidic ionic liquid, acidic resin, acidic molecular sieve, metal chloride and metal oxide, for example, sulfuric acid, perchloric acid, AlCl can be selected3One or more of stannic chloride, n-butyl stannic oxide, dibutyl stannic oxide, p-toluenesulfonic acid, acidic resins, phosphotungstic heteropoly acids, acidic ionic liquids and acidic molecular sieves, preferably one or more of perchloric acid, stannic chloride, n-butyl stannic oxide, p-toluenesulfonic acid, acidic resins and phosphotungstic heteropoly acids. The amount of the catalyst to be added is preferably 0.1 to 10% by mass based on the compound represented by the formula (. beta.). The catalyst may be removed by a method known in the art (e.g., a method of washing with an alkali or water, or filtration), and is not particularly limited.
According to the production method of the present invention, in the reaction of the compound represented by the formula (α) with the compound represented by the formula (β) or the compound represented by the formula (γ), it is preferable to perform washing and purification operations of the reaction product using a solvent, and the solvent which can be washed is preferably a hydrocarbon solvent. The solvent may be removed by conventional techniques such as drying, evaporation, distillation, and the like.
According to the production method of the present invention, the reaction of the compound represented by the formula (α) with the compound represented by the formula (β) or the compound represented by the formula (γ) may be carried out in a continuous or batch reaction apparatus such as a reaction vessel, a fixed bed, a fluidized bed, a microchannel reactor, or the like.
According to the preparation method of the invention, the compound represented by the formula (α) can be selected from one or more of the following specific compounds: oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid.
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: trimethylolethane, trimethylolpropane and pentaerythritol.
According to the production method of the present invention, alternatively, the compound represented by the formula (. gamma.) may be obtained by reacting a compound represented by the formula (. zeta.) with a compound represented by the formula (. eta.),
Figure BDA0002246391920000251
R′0-COOH(η)，
in the formula (. zeta.) m is an integer of 1 to 10 (preferably an integer of 1 to 6, more preferably an integer of 1 to 5); each R' group is the same or different from each other and is independently selected from the group consisting of a single bond, C1-10Alkylene (preferably C)1-5Linear or branched alkylene); r0The group is selected from H, C1-10Hydrocarbyl (preferably C)1-5Straight or branched chain alkyl); the Y group is selected from H, F, Cl, Br or I (preferably H, Cl or Br); m a 'groups, equal to or different from each other, are each independently selected from-C ═ C-, single bonds, methylene, ethylene, and at least one a' group is-C ═ C —;
in the formula (eta), R0The group being selected from C1-17Hydrocarbyl (preferably C)1-15Straight or branched alkyl, more preferably C1-11Straight or branched chain alkyl).
According to the production method of the present invention, the reaction equivalent ratio between the compound represented by the formula (ζ) (in-C ═ C-) and the compound represented by the formula (η) (in the carboxyl group) is preferably 0.05 to 20: 1, more preferably 0.1 to 10: 1; the reaction temperature is preferably 0-200 ℃, and more preferably 50-160 ℃; the reaction time is generally as long as possible, and is preferably 0.5 to 72 hours, more preferably 3 to 48 hours.
According to the production method of the present invention, a solvent may be added or may not be added, preferably a solvent is added, in the reaction of the compound represented by the formula (ζ) and the compound represented by the formula (η). The solvent is preferably a hydrocarbon solvent, preferably one or more of alkane, aromatic hydrocarbon and ether, more preferably an alkane solvent, and for example, one or more of hexane, heptane, octane, nonane, decane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, benzene, toluene, xylene, ethylbenzene, propylbenzene, diethyl ether, propyl ether, isopropyl ether and dibutyl ether may be used. The amount of the solvent to be added is not particularly limited, as long as the reaction is promoted to proceed smoothly.
According to the production method of the present invention, a catalyst may or may not be added to the reaction of the compound represented by the formula (ζ) and the compound represented by the formula (η). The catalyst can be one or more of inorganic acid, organic acid, solid acid, heteropoly acid, acidic ionic liquid, acidic resin, acidic molecular sieve, metal chloride and metal oxide, for example, sulfuric acid, perchloric acid, AlCl can be selected3One or more of tin chloride, n-butyl tin oxide, dibutyl tin oxide, p-toluenesulfonic acid, acidic resins, phosphotungstic heteropoly acids, acidic ionic liquids and acidic molecular sieves, preferably one or more of sulfuric acid, tin chloride, n-butyl tin oxide, p-toluenesulfonic acid, acidic resins and phosphotungstic heteropoly acids. The amount of the catalyst to be added is preferably 0.1 to 10% by mass based on the compound represented by the formula (. zeta.).
According to the preparation method of the present invention, the compound represented by the formula (ζ) may be selected from one or more of the following specific compounds: eicosenoic acid, oleic acid, linoleic acid, linolenic acid, hexadecenoic acid, tetradecenoic acid, dodecenoic acid, undecenoic acid, decenoic acid, octenoic acid.
According to the preparation method of the invention, the compound represented by the formula (η) can be selected from one or more of the following specific compounds: formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, eicosenoic acid, oleic acid, linoleic acid, linolenic acid, hexadecenoic acid, arachidonic acid, dodecenoic acid, undecylenic acid, decenoic acid, octenoic acid.
The invention also provides a lubricating oil composition which comprises the ester compound or the ester compound prepared by the method and lubricating base oil. Wherein the mass fraction of the ester compound in the lubricating oil composition is 0.1-100%, preferably 0.1-90%, more preferably 1-50%, further optionally 2-30%, and 3-20%.
According to the present invention, the lubricating oil composition may further comprise other components. Examples of the other components include various additives which are allowed to be added to the lubricating oil composition in the art, and specific examples thereof include phenol type, amine type or sulfur phosphorus type antioxidants, carboxylate, sulfonate or alkylphenate detergents, succinimide type ashless dispersants, polyester, polyolefin or alkylnaphthalene type pour point depressants, methacrylate ester copolymers, ethylene-propylene copolymers, polyisobutylene, hydrogenated styrene/butadiene copolymer type viscosity index improvers, sulfur/phosphorus type friction modifiers, sulfur/phosphorus and boric acid type extreme pressure agents, and silicon type or non-silicon type antifoaming agents. The kind and amount of these additives are well known to those skilled in the art and will not be described herein. These additives may be used singly or in combination in any ratio.
The ester compound and the lubricating oil composition have excellent viscosity-temperature and low-temperature performances.
The ester compound has excellent viscosity-temperature performance and low-temperature performance as base oil, and has excellent viscosity-temperature performance and low-temperature performance as a viscosity index improver.
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 a group obtained by removing the number of hydrogen atoms represented by the number from the basic structure (such as a chain, a ring, a combination thereof, or the like) to which the group corresponds, and preferably refers to a group obtained by removing the number of hydrogen atoms represented by the number from a carbon atom (preferably a saturated carbon atom and/or a non-identical carbon atom) contained in the structure. 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-*、
Figure BDA0002246391920000271
The 3-valent propyl group may be
Figure BDA0002246391920000272
The 4-valent propyl group may be
Figure BDA0002246391920000281
Wherein represents a binding end in the group that may be bonded to other groups.
Example 1: preparation of Iso-acid A
The reaction is carried out in a high-pressure reaction kettle provided with a vent, a stirrer and a thermocouple. 565g of oleic acid was pumped gradually into a reaction vessel containing 1000g of acetic acid and 10g of 70% perchloric acid, reacted at 70 ℃ for 24 hours, heating was stopped, the reaction was completed, the remaining acetic acid was removed by distillation, cooled to room temperature, washed with alkali, washed with water and the organic phase with potassium dihydrogen phosphate having a pH of 3.7 three times, dried over anhydrous sodium sulfate and filtered, and unreacted oleic acid was removed by molecular distillation to obtain acetic acid-oleic acid adduct, i.e., isoacid a, whose structure is shown below.
Figure BDA0002246391920000282
Example 2: preparation of ester Compound A-1
Adding 29.2g of adipic acid, 53.6g of trimethylolpropane, 0.3g of concentrated sulfuric acid catalyst and a water carrying agent (petroleum ether at 90-120 ℃) into a 500mL three-neck glass flask, heating to a reflux temperature, and collecting H generated in the reaction process by using a water separator2And O, stopping the reaction until the actual water yield is the same as the theoretical value, and obtaining the composite polyhydroxy compound. Adding 274g of isoacid A into the crude product without treatment, heating to reflux temperature, and collecting H generated in the reaction process by using a water separator2And O, stopping the reaction until the actual water yield is the same as the theoretical value. And (3) removing the catalyst by alkali washing, washing to be neutral by water, and removing the reaction solvent to obtain the compound ester compound A-1.
Example 3: preparation of ester Compound A-2
Adding 23.6 g of succinic acid, 40.8g of pentaerythritol, 0.3g of concentrated sulfuric acid catalyst and a water carrying agent (petroleum ether at 90-120 ℃) into a 500mL three-neck glass flask, heating to a reflux temperature, and collecting H generated in the reaction process by using a water separator2And O, stopping the reaction until the actual water yield is the same as the theoretical value, and obtaining the composite polyhydroxy compound. Adding 272g of isoacid A into the crude product without treatment, heating to reflux temperature, and collecting H generated in the reaction process by using a water separator2And O, stopping the reaction until the actual water yield is the same as the theoretical value. And (3) removing the catalyst by alkali washing, washing to be neutral by water, and removing the reaction solvent to obtain the compound ester compound A-2.
Comparative example 1: preparation of ester Compound D-1
The ester compound D-1 is prepared by the same method as A-1 except that the isoacid A is replaced by the equimolar oleic acid, and the ester compound D-1 is obtained.
Example 4: preparation of Isotropic acid B
10g of strong acid ion exchange resin washed by HCl is filled in a fixed bed reactor, the temperature of the reactor is controlled at 60 ℃, weighed hexadecenoic acid and caproic acid (the molar ratio is 1: 20) are preheated to the same temperature and then pumped into the reactor, and the space velocity is 0.4h-1And collecting effluent products, removing residual caproic acid through preliminary distillation, and further removing unreacted oleic acid through molecular distillation to obtain an addition product, namely an isomeric acid B of caproic acid-oleic acid, wherein the structure of the addition product is shown as the following.
Figure BDA0002246391920000291
Example 5: preparation of ester Compound B-1
Adding 40.4 g of sebacic acid, 33.5g of trimethylolpropane, 0.5g of concentrated sulfuric acid catalyst and a water carrying agent (petroleum ether at 90-120 ℃) into a 500mL three-neck glass flask, heating to a reflux temperature, and collecting H generated in the reaction process by using a water separator2And O, stopping the reaction until the actual water yield is the same as the theoretical value, and obtaining the composite polyhydroxy compound. Adding 129.5g of isoacid B into the crude product without treatment, heating to reflux temperature, and collecting H generated in the reaction process by using a water separator2And O, stopping the reaction until the actual water yield is the same as the theoretical value. And (3) removing the catalyst by alkali washing, washing to be neutral by water, and removing the reaction solvent to obtain the compound ester compound B-1.
Example 6: preparation of ester Compound B-2
Adding 37.6 g of azelaic acid, 27.2g of pentaerythritol, 0.2g of concentrated sulfuric acid catalyst and a water carrying agent (petroleum ether at 90-120 ℃) into a 500mL three-neck glass flask, heating to a reflux temperature, and collecting H generated in the reaction process by using a water separator2And O, stopping the reaction until the actual water yield is the same as the theoretical value, and obtaining the composite polyhydroxy compound. The crude product is not worked up, 162g of the isoacid B are added and the mixture is heated to reflux temperatureCollecting H generated in the reaction process by using a water separator2And O, stopping the reaction until the actual water yield is the same as the theoretical value. And (3) removing the catalyst by alkali washing, washing to be neutral by water, and removing the reaction solvent to obtain the compound ester compound B-2.
Comparative example 2: preparation of ester Compound D-2
The preparation method of the ester compound D-2 is the same as that of the ester compound B-1 except that the isoacid C is replaced by the equimolar oleic acid, so as to obtain the ester compound D-2.
Example 7: preparation of the isomeric acids E
10g of strong acid ion exchange resin washed by HCl is filled in a fixed bed reactor, the temperature of the reactor is controlled at 65 ℃, weighed linoleic acid, caproic acid and butyric acid (the molar ratio is 1: 5: 5) are preheated to the same temperature and then pumped into the reactor, and the space velocity is 0.3h-1And collecting effluent products, removing residual caproic acid and butyric acid through preliminary distillation, and further removing unreacted linoleic acid through molecular distillation to obtain an addition product of caproic acid-linoleic acid, namely an isomerized acid E, wherein the structure of the addition product is shown as follows.
Figure BDA0002246391920000301
Example 8: preparation of ester Compound E-1
Adding 35.7g of azelaic acid, 26.8g of trimethylolpropane, 0.2g of concentrated sulfuric acid catalyst and water carrying agent (petroleum ether at 90-120 ℃) into a 500mL three-neck glass flask, heating to reflux temperature, and collecting H generated in the reaction process by using a water separator2And O, stopping the reaction until the actual water yield is the same as the theoretical value, and obtaining the composite polyhydroxy compound. Adding 107g of isoacid E into the crude product without treatment, heating to reflux temperature, and collecting H generated in the reaction process by using a water separator2And O, stopping the reaction until the actual water yield is the same as the theoretical value. And (3) removing the catalyst by alkali washing, washing to be neutral by water, and removing the reaction solvent to obtain the compound ester compound E-1.
The physicochemical properties of the ester compounds of the examples and the comparative examples were examined by methods including the kinematic viscosity measurement method and dynamic viscosity calculation method for GB/T265 petroleum products, the viscosity index calculation method for GB/T1995 petroleum products, the pour point measurement method for GB/T3535 petroleum products, and the oxygen absorption oxidation stability test method for SH/T0074 gasoline engine oil thin layer, and the results are shown in Table 1.
TABLE 1
Figure BDA0002246391920000302

Claims (18)

1. An ester compound having the structure:
Figure FDA0002246391910000011
wherein each R' group, which may be the same or different from each other, is independently selected from C1-10Linear or branched alkylene (preferably C)1-6Linear or branched alkylene groups of (a); each L' group, which may be the same or different from each other, is independently selected from C1-16Linear or branched alkylene (preferably C)2-10Linear or branched alkylene groups of (a); n is an integer of 1 to 10 (preferably an integer of 1 to 5); each L group is the same or different from each other and is independently selected from the group consisting of a group represented by the formula (II), a group represented by the formula (III), C1-10Is preferably selected from the group consisting of a group represented by the formula (II), a group represented by the formula (III), C1-6Straight or branched alkyl groups) on each carbon atom to which the L group is attached, at least one L group selected from the group represented by formula (III),
—R'—OH (II)，
Figure FDA0002246391910000012
in formula (II), the R group is selected from C1-10Linear or branched alkylene (preferably C)1-6Linear or branched alkylene groups of (a);
in formula (III), the R' group is selected from C1-10Linear or branched alkylene (preferably C)1-6Linear or branched alkylene of) (ii) a Each R' group is the same or different from each other and is independently selected from the group consisting of a single bond, C1-10Alkylene (preferably C)1-5Linear or branched alkylene); r0The group is selected from H, C1-10Hydrocarbyl (preferably C)1-5Straight or branched chain alkyl); m is an integer of 1 to 10 (preferably an integer of 1 to 6, more preferably an integer of 1 to 5); m a groups, equal to or different from each other, are each independently selected from the group represented by formula (IV), -C ═ C-, methylene, and ethylene, and at least one a group is selected from the group represented by formula (IV);
Figure FDA0002246391910000013
in the formula (IV), R0The group being selected from C1-17Hydrocarbyl (preferably C)1-15Straight or branched alkyl, more preferably C1-11Straight or branched chain alkyl).
2. An ester compound according to claim 1, wherein each of the L groups is the same as or different from each other and is independently selected from the group represented by the formula (III).
3. Esters according to claim 1 wherein at least one group L selected from C is present on each carbon atom to which the group L is attached1-6Linear or branched alkyl.
4. Esters according to claim 1 wherein at least one group L selected from C is present on each carbon atom to which the group L is attached1-6The other L groups, which are the same or different from each other, are each independently selected from the group represented by the formula (III).
5. An ester compound as claimed in claim 1, wherein the ester compound comprises one or more of the following compounds:
Figure FDA0002246391910000021
Figure FDA0002246391910000031
Figure FDA0002246391910000041
Figure FDA0002246391910000051
Figure FDA0002246391910000061
Figure FDA0002246391910000071
Figure FDA0002246391910000081
Figure FDA0002246391910000091
Figure FDA0002246391910000101
Figure FDA0002246391910000111
Figure FDA0002246391910000121
Figure FDA0002246391910000131
Figure FDA0002246391910000141
Figure FDA0002246391910000151
Figure FDA0002246391910000161
Figure FDA0002246391910000171
Figure FDA0002246391910000181
Figure FDA0002246391910000191
Figure FDA0002246391910000201
6. a process for producing an ester compound, comprising the step of reacting a compound represented by the formula (alpha), a compound represented by the formula (beta), and a compound represented by the formula (gamma),
Figure FDA0002246391910000211
in formula (. alpha.), the L' group is selected from C1～100Alkylene (preferably C)1～16Straight or branched alkylene of (2), more preferably C2～10Linear or branched alkylene groups of (a); each X, equal to or different from each other, is independently selected from H, F, Cl, Br or I (preferably H, Cl or Br);
in the formula (. beta.), the respective L' groups, which are the same or different from each other, are each independently selected from the group represented by the formula (. delta.), C1-10Is preferably selected from the group consisting of a group of the formula (delta), C1-6And at least one L "group is selected from the group represented by formula (δ);
—R'—OH(δ)，
in formula (. delta.), the R' group is selected from C1-10Linear or branched alkylene (preferably C)1-6Linear or branched alkylene groups of (a);
in the formula (gamma), m is an integer of 1 to 10 (preferably an integer of 1 to 6, more preferably an integer of 1 to 5); each R' group is the same or different from each other and is independently selected from the group consisting of a single bond, C1-10Alkylene (preferably C)1-5Linear or branched alkylene); r0The group is selected from H, C1-10Hydrocarbyl (preferably C)1-5Straight or branched chain alkyl); the Y group is selected from H, F, Cl, Br or I (preferably H, Cl or Br); m a groups, equal to or different from each other, are each independently selected from the group represented by formula (epsilon), -C ═ C-, methylene, and ethylene, and at least one a group is selected from the group represented by formula (epsilon);
Figure FDA0002246391910000212
in the formula (. epsilon.), R0The group being selected from C1-17Hydrocarbyl (preferably C)1-15Straight or branched alkyl, more preferably C1-11Straight or branched chain alkyl).
7. The process according to claim 6, wherein each of the L' groups is the same as or different from each other and is independently selected from the group represented by the formula (δ).
8. The process according to claim 6, wherein at least one group L "is selected from C on each carbon atom to which the group L" is bonded1-6Linear or branched alkyl.
9. The process according to claim 6, wherein at least one group L "is selected from C on each carbon atom to which the group L" is bonded1-6The other L' groups, which are the same or different from each other, are each independently selected from the group represented by the formula (delta).
10. The process according to claim 6, wherein the equivalent ratio of the reaction between the compound represented by the formula (α) (in X) and the compound represented by the formula (β) (in OH), the compound represented by the formula (γ) (in Y) is 1: 0.8-2: 0.5 to 10 (preferably 1: 1 to 2: 1 to 6); the reaction temperature is 70-250 ℃ (preferably 90-200 ℃).
11. The process according to claim 6, wherein the compound represented by the formula (α), the compound represented by the formula (β) and the compound represented by the formula (γ) are reacted together; or reacting the compound represented by the formula (alpha) with the compound represented by the formula (beta) and then reacting the product with the compound represented by the formula (gamma); or reacting a compound represented by the formula (. beta.) with a compound represented by the formula (. gamma.) and then reacting the product with a compound represented by the formula (. alpha.).
12. The process according to claim 6, wherein the compound of formula (α) is reacted with the compound of formula (β) and the product is reacted with the compound of formula (γ); the temperature of the reaction between the compound represented by the formula (alpha) and the compound represented by the formula (beta) and the reaction between the product of the reaction and the compound represented by the formula (gamma) are both 0-300 ℃ (preferably 50-260 ℃); the reaction time is 0.5 to 72 hours (preferably 3 to 48 hours).
13. The process according to claim 6, wherein a catalyst is added to the reaction of the compound of formula (α) with the compound of formula (β) or the compound of formula (γ) (the catalyst may be one or more of inorganic acid, organic acid, solid acid, heteropolyacid, acidic ionic liquid, acidic resin, acidic molecular sieve, metal chloride and metal oxide, such as sulfuric acid, perchloric acid, AlCl3One or more of tin chloride, n-butyl tin oxide, dibutyl tin oxide, p-toluenesulfonic acid, acidic resins, phosphotungstic heteropoly acids, acidic ionic liquids, and acidic molecular sieves, preferably one or more of perchloric acid, tin chloride, n-butyl tin oxide, p-toluenesulfonic acid, acidic resins, and phosphotungstic heteropoly acids).
14. The process according to claim 6, wherein the compound represented by the formula (α) is selected from one or more of the following specific compounds: oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid; or, the compound shown in the formula (beta) is selected from one or more of the following specific compounds: trimethylolethane, trimethylolpropane, trimethylolethane, trimethylolpropane, pentaerythritol; alternatively, the compound represented by the formula (. gamma.) may be obtained by reacting a compound represented by the formula (. zeta.) with a compound represented by the formula (. eta.),
Figure FDA0002246391910000231
R′0-COOH(η)，
in the formula (ζ), the metal salt is,m is an integer of 1 to 10 (preferably an integer of 1 to 6, more preferably an integer of 1 to 5); each R' group is the same or different from each other and is independently selected from the group consisting of a single bond, C1-10Alkylene (preferably C)1-5Linear or branched alkylene); r0The group is selected from H, C1-10Hydrocarbyl (preferably C)1-5Straight or branched chain alkyl); the Y group is selected from H, F, Cl, Br or I (preferably H, Cl or Br); m a 'groups, equal to or different from each other, are each independently selected from-C ═ C-, single bonds, methylene, ethylene, and at least one a' group is-C ═ C —;
in the formula (eta), R0The group being selected from C1-17Hydrocarbyl (preferably C)1-15Straight or branched alkyl, more preferably C1-11Straight or branched chain alkyl).
15. The process according to claim 14, wherein the equivalent ratio of the reaction between the compound represented by the formula (ζ) (in-C ═ C ") and the compound represented by the formula (η) (in the carboxyl group) is 0.05 to 20: 1 (preferably 0.1-10: 1); the reaction temperature is 0-200 ℃ (preferably 50-160 ℃).
16. The process according to claim 15, wherein the compound represented by the formula (ζ) is one or more selected from the group consisting of: eicosenoic acid, oleic acid, linoleic acid, linolenic acid, hexadecenoic acid, tetradecenoic acid, dodecenoic acid, undecenoic acid, decenoic acid, octenoic acid; or, the compound shown in the formula (eta) is selected from one or more of the following compounds: formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, eicosenoic acid, oleic acid, linoleic acid, linolenic acid, hexadecenoic acid, arachidonic acid, dodecenoic acid, undecylenic acid, decenoic acid, octenoic acid.
17. Use of the ester compound of any one of claims 1 to 5 or the ester compound prepared by the method of any one of claims 6 to 16 as a base oil for a lubricating grease or a viscosity index improver.
18. A lubricating oil composition comprising the ester compound according to any one of claims 1 to 5 or the ester compound produced by the method according to any one of claims 6 to 16, and a lubricating base oil.
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