CN112707819B - 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
CN112707819B
CN112707819B CN201911018298.8A CN201911018298A CN112707819B CN 112707819 B CN112707819 B CN 112707819B CN 201911018298 A CN201911018298 A CN 201911018298A CN 112707819 B CN112707819 B CN 112707819B
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formula
compound
acid
reaction
catalyst
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CN112707819A (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 CN201911018298.8A priority Critical patent/CN112707819B/en
Priority to EP20879644.1A priority patent/EP4049994A4/en
Priority to PCT/CN2020/123197 priority patent/WO2021078249A1/en
Priority to US17/755,075 priority patent/US20230012456A1/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
    • C10M105/38—Esters of polyhydroxy compounds
    • 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
    • C10M129/74—Esters of polyhydroxy compounds
    • 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
    • C10M2207/283—Esters of polyhydroxy compounds
    • 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
    • C10M2207/283—Esters of polyhydroxy compounds
    • C10M2207/2835—Esters of polyhydroxy compounds used as base material

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: L-O-L' -O-L (I) wherein each group is defined in the specification. The ester compound has excellent viscosity temperature, low temperature, oxidation resistance and antifriction performance.

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.
Background
Lubricating oil is an indispensable component in the operation of machinery, plays roles of reducing friction and wear, protecting machinery, cooling, cleaning, sealing, prolonging service life and the like, but causes serious harm to the natural environment due to factors such as lubricating oil leakage, overflow, evaporation or improper treatment and the like, so that higher requirements are put on the environmental friendliness of the lubricating oil. 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 oil is achieved by changing the structure of the fatty side chain in the triglyceride structure of vegetable oil glycerol acid, comprising two steps of reactions: (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 oils and additives can improve the environmental friendliness of lubricating oils, there is much 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:
L-O-L'-O-L (I)
wherein the L' group is C 2～100 Alkylene (preferably C) 2～50 Straight or branched alkylene of (2), more preferably C 2～20 Linear or branched alkylene groups of (a);
wherein each L group is independently selected from the group represented by formula (II),
Figure BDA0002246391480000021
in formula (II), m is an integer of 1 to 10 (preferably an integer of 1 to 6, more preferably an integer of 1 to 5); m + 1R groups, equal to or different from each other, are each independently selected from the group consisting of a single bond, C 1-10 Alkylene (preferably C) 1-5 Straight or branched alkylene, more preferably C 1-3 Straight or branched chain alkylene); r 0 The groups are the same or different from each other and are each independently selected from H, C 1-10 Hydrocarbyl (preferably C) 1-5 Straight or branched alkyl, more preferably C 1-3 Straight or branched chain alkyl); m a groups, equal to or different from each other, are each independently selected from the group represented by formula (III), -C = C-, a single bond, a methylene group and an ethylene group, and at least one a group is selected from the group represented by formula (III);
Figure BDA0002246391480000022
in the formula (III), R 0 The group being selected from C 1-17 Hydrocarbyl (preferably C) 1-15 Straight or branched alkyl, more preferably C 1-11 Straight or branched chain alkyl).
The ester compound with a specific structure comprises one or more of the following compounds:
Figure BDA0002246391480000031
Figure BDA0002246391480000041
Figure BDA0002246391480000051
Figure BDA0002246391480000061
Figure BDA0002246391480000071
Figure BDA0002246391480000081
Figure BDA0002246391480000091
Figure BDA0002246391480000101
Figure BDA0002246391480000111
Figure BDA0002246391480000121
Figure BDA0002246391480000131
Figure BDA0002246391480000141
Figure BDA0002246391480000151
Figure BDA0002246391480000161
Figure BDA0002246391480000171
the invention also provides a preparation method of the ester compound, which comprises the step of reacting the compound shown in the formula (alpha) with the compound shown in the formula (beta),
HO-L'-OH (α)，
Figure BDA0002246391480000181
in formula (. Alpha.), the L' group is C 2～100 Alkylene (preferably C) 2～50 Straight or branched alkylene of (2), more preferably C 2～20 Linear or branched alkylene groups of (a);
in the formula (. Beta.), m is an integer of 1 to 10 (preferably an integer of 1 to 6, more preferably an integer of 1 to 5); m + 1R groups, equal to or different from each other, are each independently selected from the group consisting of a single bond, C 1-10 Alkylene (preferably C) 1-5 Straight or branched alkylene, more preferably C 1-3 Linear or branched alkylene); r 0 The groups are the same or different from each other and are each independently selected from H, C 1-10 Hydrocarbyl (preferably C) 1-5 Straight or branched alkyl, more preferably C 1-3 Straight or branched chain alkyl); the Y group is selected from H, F, cl, br and I; m a groups, equal to or different from each other, are each independently selected from the group represented by formula (γ), -C = C-, a single bond, a methylene group and an ethylene group, and at least one a group is selected from the group represented by formula (γ);
Figure BDA0002246391480000182
in the formula (gamma)，R 0 ' selected from C 1-17 Hydrocarbyl (preferably C) 1-15 Straight or branched alkyl, more preferably C 1-11 Straight or branched chain alkyl).
According to the invention, the compound of formula (α) may be selected from one or more of the following specific compounds: ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, heptylene glycol, octylene glycol, nonylene glycol, decylene glycol, undecylene glycol, dodecylene glycol, tridecylene glycol, tetradecylene glycol, pentadecylene glycol.
According to the invention, alternatively, the compound represented by the formula (. Beta.) can be obtained by reacting a compound represented by the formula (. Delta.) with a compound represented by the formula (. Epsilon.),
Figure BDA0002246391480000183
in formula (δ), m is an integer between 1 and 10 (preferably an integer between 1 and 6, more preferably an integer between 1 and 5); m + 1R groups, equal to or different from each other, are each independently selected from the group consisting of a single bond, C 1-10 Alkylene (preferably C) 1-5 Straight or branched alkylene, more preferably C 1-3 Linear or branched alkylene); r 0 The groups are the same or different from each other and are each independently selected from H, C 1-10 Hydrocarbyl (preferably C) 1-5 Straight or branched alkyl, more preferably C 1-3 Straight or branched chain alkyl); the Y group is selected from H, F, cl, br and I; m a 'groups, equal to or different from each other, are each independently selected from-C = C-, a single bond, a methylene group, an ethylene group, and at least one a' group is-C = C-; in the formula (. Epsilon.), R 0 The group being selected from C 1-17 Hydrocarbyl (preferably C) 1-15 Straight or branched alkyl, more preferably C 1-11 Straight or branched chain alkyl).
According to the invention, the reaction equivalence ratio between the compound of formula (δ) (calculated as-C = C-) and the compound of formula (∈) (calculated as 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 preferably 0.5 to 72 hours, more preferably 3 to 48 hours.
According to the present invention, a solvent may or may not be added, preferably a solvent is added, in the reaction of the compound represented by the formula (δ) and the compound represented by the formula (ε). 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, and is preferably such that the reaction is smoothly progressed.
According to the present invention, a catalyst may or may not be added to the reaction of the compound represented by the formula (. Delta.) with the compound represented by the formula (. Epsilon.). 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 selected 3 One 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 (δ).
According to the invention, the compound represented by the formula (δ) 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 invention, the compound of formula (ε) may 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.
According to the invention, the equivalent ratio of the reaction between the compound of formula (α) (calculated as OH) and the compound of formula (β) (calculated as Y) is preferably between 0.1 and 10:1, more preferably 0.2 to 5:1; the reaction temperature is preferably 70-250 ℃, and more preferably 90-200 ℃; the reaction time is preferably 0.5 to 24 hours, more preferably 2 to 15 hours.
According to the present invention, a solvent may be added or not added, preferably a solvent is added in the reaction of the compound represented by the formula (α) and the compound represented by the formula (β). 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 present invention, a catalyst may or may not be added in the reaction of the compound represented by the formula (α) and the compound represented by the formula (β). 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 selected 3 One 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 (. Beta.). The catalyst may be removed by a method known in the art (e.g., a method of alkali washing and water washing), and is not particularly limited.
According to the present invention, in the reaction of the compound represented by the formula (α) and the compound represented by the formula (β), the reaction product is preferably washed and purified with 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 present invention, the reaction of the compound represented by the formula (. Alpha.) with the compound represented by the formula (. Beta.) 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, etc.
The invention also provides a lubricating oil composition which comprises the ester compound or the ester compound prepared by the method and lubricating oil 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%, 0.5-5%.
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 invention also provides the application of the ester compound as one or more of lubricating oil base oil, lubricating oil viscosity index improver and lubricating oil friction improver.
The ester compound and the lubricating oil composition have excellent viscosity-temperature, low-temperature, oxidation resistance and antifriction performance.
The ester compound has excellent viscosity-temperature performance and low-temperature performance as base oil, has excellent viscosity-temperature performance and low-temperature performance as a viscosity index improver, and can obviously reduce the friction coefficient of the base oil as a friction 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-CH 2 -A-CH 3 Wherein 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-CH 2 -CH 3 。
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-CH 2 -CH 2 -CH 2 -*、
Figure BDA0002246391480000211
The 3-valent propyl group may be
Figure BDA0002246391480000212
The 4-valent propyl group may be
Figure BDA0002246391480000213
Wherein represents inThe binding end of the group to which other groups may be bonded.
Example 1: preparation of isomerate A
The reaction is carried out in a high-pressure reaction kettle provided with a vent, a stirrer, a thermocouple and a thermocouple. 565g of oleic acid is gradually pumped into a reaction kettle filled with 1000g of acetic acid and 10g of perchloric acid with the concentration of 70%, the reaction is carried out for 24 hours at 70 ℃, heating is stopped, the reaction is finished, the residual acetic acid is removed by distillation, the reaction kettle is cooled to room temperature, the reaction kettle is washed by alkali, water and organic phase potassium dihydrogen phosphate with the pH =3.7 for three times, and after the treatment of drying by anhydrous sodium sulfate, filtration and the like, unreacted oleic acid is removed by molecular distillation, so that the addition product of acetic acid and oleic acid, namely the isomeric acid A, is obtained, wherein the structure of the addition product is shown as follows.
Figure BDA0002246391480000221
Example 2: preparation of ester Compound A-1
171g of isoacid A, 15.5g of ethylene glycol, 1.3g of concentrated sulfuric acid catalyst and a water carrying agent (petroleum ether at the temperature of 90-120 ℃) are added into a 500mL three-neck glass flask, the mixture is heated to the reflux temperature, and a water separator is utilized to collect H generated in the reaction process 2 And O, stopping the reaction until the actual water yield is the same as the theoretical value. And (3) washing the crude product with alkali to remove the catalyst, washing with water to neutrality, and removing the reaction solvent to obtain the ester compound A-1.
Example 3: preparation of ester Compound A-2
171g of isoacid A, 30g of hexanediol, 2g of concentrated sulfuric acid catalyst and a water carrying agent (petroleum ether at 90-120 ℃) are added into a 500mL three-neck glass flask, the mixture is heated to the reflux temperature, and H generated in the reaction process is collected by a water separator 2 And O, stopping the reaction until the actual water yield is the same as the theoretical value. And (3) washing the crude product with alkali to remove the catalyst, washing with water to neutrality, and removing the reaction solvent to obtain the ester compound A-2.
Comparative example 1: preparation of ester Compound D-1
The preparation method of the D-1 is the same as that of the A-1 except that the isomeric acid A is replaced by the equimolar oleic acid, and the ester compound D-1 is obtained.
Comparative example 2: preparation of ester Compound D-2
The preparation method of D-2 is the same as that of A-1 except that the ethylene glycol is replaced by the glycerol with the same mole, and the ester compound D-2 is obtained.
Example 4: preparation of isomeric acid B
The method comprises the following steps of filling 10g of HCl-washed strong-acid ion exchange resin in a fixed bed reactor, controlling the temperature of the reactor at 60 ℃, preheating weighed hexadecenoic acid and caproic acid (molar ratio of 1 to 20) to the same temperature, and pumping the preheated hexadecenoic acid and caproic acid into the reactor, wherein the space velocity is 0.4h -1 Collecting effluent product, removing residual caproic acid by primary distillation, and further removing unreacted hexadecenoic acid by molecular distillation to obtain caproic acid-hexadecenoic acid addition product isomeric acid B, the structure of which is shown in the following.
Figure BDA0002246391480000231
Example 5: preparation of ester Compound B-1
370g of isoacid B, 90g of decanediol, 3g of concentrated sulfuric acid catalyst and a water carrying agent (petroleum ether at 90-120 ℃) are added into a 1000mL three-neck glass flask, heated to the reflux temperature, and H generated in the reaction process is collected by a water separator 2 And O, stopping the reaction until the actual water yield is the same as the theoretical value. And (3) washing the crude product with alkali to remove the catalyst, washing with water to neutrality, and removing the reaction solvent to obtain the ester compound B-1.
Example 6: preparation of ester Compound B-2
370g of isoacid B, 45g of butanediol, 3g of concentrated sulfuric acid catalyst and a water carrying agent (petroleum ether at 90-120 ℃) are added into a 1000mL three-neck glass flask, the flask is heated to the reflux temperature, and a water separator is used for collecting H generated in the reaction process 2 And O, stopping the reaction until the actual water yield is the same as the theoretical value. And (3) washing the crude product with alkali to remove the catalyst, washing with water to neutrality, and removing the reaction solvent to obtain the ester compound B-2.
Comparative example 3: preparation of ester Compound D-3
The preparation method of the D-3 is the same as that of the B-2 except that the isovaleric acid B is replaced by the palmitic acid with the same mole, and the ester compound D-3 is obtained.
The physicochemical properties of the ester compounds A-1, A-2, D-1, D-2, B-1, B-2 and D-3 are considered, the determination methods are GB/T265 petroleum product kinematic viscosity determination method and dynamic viscometer algorithm, GB/T1995 petroleum product viscosity index calculation method, GB/T3535 petroleum product pour point determination method, SH/T0074 gasoline engine oil thin layer oxygen absorption oxidation stability test method and SH/T0762 lubricating oil friction coefficient determination method (four-ball method), and the determination results are shown in Table 1.
TABLE 1
Figure BDA0002246391480000241
Example 7: preparation of the Iso acid C
The reaction was carried out in a high pressure autoclave equipped with a vent, stirrer and thermocouple. Pumping 280g of linoleic acid into a reaction kettle filled with 600g of acetic acid and 5g of perchloric acid with the concentration of 70%, reacting at 70 ℃ for 18 hours, stopping heating, finishing the reaction, removing residual acetic acid by distillation, cooling to room temperature, washing with alkali, washing with water, washing an organic phase with potassium dihydrogen phosphate with the pH =3.7 for three times, drying with anhydrous sodium sulfate, filtering, and finally removing unreacted linoleic acid by molecular distillation to obtain an acetic acid-linoleic acid addition product, namely an isomerized acid C, wherein the structure is shown as the following.
Figure BDA0002246391480000242
Example 8: preparation of ester Compound C-1
Adding 81g of isoacid C, 12g of hexanediol, 1.4g of concentrated sulfuric acid catalyst and a water carrying agent (petroleum ether at 90-120 ℃) into a 500mL three-neck glass flask, heating to the reflux temperature, and collecting H generated in the reaction process by using a water separator 2 And O, stopping the reaction until the actual water yield is the same as the theoretical value. The crude product is washed by alkali to remove the catalyst, washed by water to be neutral, and the reaction solvent is removed to obtain the ester compoundC-1。
Comparative example 4: preparation of ester Compound D-4
The preparation method of D-4 is the same as that of C-1 except that the isoacid C is replaced by linoleic acid with the same mol, and the ester compound D-4 is obtained.
Example 9: preparation of the isomeric acids E
The method comprises the following steps of filling 10g of HCl-washed strong-acid ion exchange resin in a fixed bed reactor, controlling the temperature of the reactor at 65 ℃, preheating weighed linoleic acid, caproic acid and butyric acid (molar ratio of 1 to 5) -1 And 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 and butyric acid-oleic acid, namely an isomerized acid E, wherein the structure of the addition product is shown as follows.
Figure BDA0002246391480000251
Example 10: preparation of ester Compound E-1
242g of isoacid E, 44g of decanediol, 4.5g of concentrated sulfuric acid catalyst and a water carrying agent (petroleum ether at 90-120 ℃) are added into a 500mL three-neck glass flask, heated to the reflux temperature, and a water separator is used for collecting H generated in the reaction process 2 And O, stopping the reaction until the actual water yield is the same as the theoretical value. And (3) washing the crude product with alkali to remove the catalyst, washing with water to neutrality, and removing the reaction solvent to obtain the ester compound E-1.
Example 11: preparation of ester Compound E-2
242g of isoacid E, 22.5g of butanediol, 4.4g of concentrated sulfuric acid catalyst and a water carrying agent (petroleum ether at 90-120 ℃) are added into a 1000mL three-neck glass flask, the mixture is heated to the reflux temperature, and a water separator is utilized to collect H generated in the reaction process 2 And O, stopping the reaction until the actual water yield is the same as the theoretical value. And (3) washing the crude product with alkali to remove the catalyst, washing with water to neutrality, and removing the reaction solvent to obtain the ester compound E-2.
The physical and chemical properties of the ester compounds C-1, D-4, E-1 and E-2 are examined, and the measurement results are shown in Table 2.
TABLE 2
Figure BDA0002246391480000252
In the description of the present invention, numerous specific details are disclosed. It is understood, however, that certain embodiments of the invention may be practiced without these specific details. Moreover, in some embodiments, methods, structures and techniques known in the art have not been described in detail so as not to obscure any aspects of the present invention to those of ordinary skill in the art.
Similarly, it should be appreciated that in the description of exemplary embodiments of the disclosure above, various features are sometimes grouped together in a single embodiment or description thereof for the purpose of streamlining the disclosure and aiding in the understanding of one or more of the disclosed aspects. However, the disclosure should not be construed to reflect the intent: that the invention as claimed requires more features than are expressly recited in each claim. Rather, as the following claims reflect, claimed subject matter may lie in less than all features of a single disclosed embodiment. Thus, the claims following the detailed description are hereby expressly incorporated into this detailed description, with each claim standing on its own as a separate embodiment of this invention.
The above embodiments are only used to illustrate the technical solutions of the embodiments of the present disclosure, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present disclosure.

Claims (11)

1. The ester compound is as follows:
Figure DEST_PATH_IMAGE001
。
2. a method for preparing an ester compound according to claim 1, comprising the step of reacting a compound represented by the formula (. Alpha.) with a compound represented by the formula (. Beta.),
Figure DEST_PATH_IMAGE003
（α），
Figure DEST_PATH_IMAGE005
（β），
the compound represented by the formula (. Beta.) is obtained by reacting a compound represented by the formula (. Delta.) with a compound represented by the formula (. Epsilon.),
Figure DEST_PATH_IMAGE007
（δ），
Figure DEST_PATH_IMAGE008
（ε），
the compound shown in the formula (alpha) is decanediol, the compound shown in the formula (delta) is hexadecenoic acid, and the compound shown in the formula (epsilon) is hexanoic acid.
3. The process according to claim 2, wherein the molar ratio between the compound of formula (δ) and the compound of formula (ε) is between 0.1 and 10:1; the reaction temperature is 50-160 ℃; the reaction time is 3 to 48 hours.
4. A process according to claim 2, wherein a catalyst is added to the reaction of the compound of formula (δ) with the compound of formula (e), the catalyst being one or more of an inorganic acid, an organic acid, a solid acid, a heteropolyacid, an acidic ionic liquid, an acidic resin, an acidic molecular sieve, a metal chloride and a metal oxide.
5. The process according to claim 2, wherein a catalyst is added to the reaction of the compound of formula (δ) with the compound of formula (e), the catalyst being sulfuric acid, perchloric acid, alCl 3 One or more of tin chloride, n-butyl tin oxide, dibutyl tin oxide, p-toluenesulfonic acid, acidic resin, phosphotungstic heteropoly acid, acidic ionic liquid and acidic molecular sieve.
6. The process according to claim 2, wherein the molar ratio between the compound of formula (α) and the compound of formula (β) is from 0.1 to 10:1; the reaction temperature is 70-250 ℃; the reaction time is 0.5 to 24 hours.
7. The process according to claim 2, wherein the molar ratio between the compound of formula (α) and the compound of formula (β) is between 0.2 and 5:1; the reaction temperature is 90-200 ℃; the reaction time is 2 to 15 hours.
8. A process according to claim 2, wherein a catalyst is added to the reaction of the compound of formula (α) with the compound of formula (β), the catalyst being one or more of an inorganic acid, an organic acid, a solid acid, a heteropolyacid, an acidic ionic liquid, an acidic resin, an acidic molecular sieve, a metal chloride and a metal oxide.
9. The process according to claim 2, wherein a catalyst is added to the reaction of the compound of formula (α) with the compound of formula (β), and the catalyst is sulfuric acid, perchloric acid, alCl 3 One 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.
10. A lubricating oil composition comprising the ester compound of claim 1 or the ester compound produced by the process of any one of claims 2~9, and a lubricating oil base oil.
11. Use of the ester compound of claim 1 or prepared according to the process of any one of claims 2~9 as one or more of a lubricant base oil, a lubricant viscosity index improver, and a lubricant friction modifier.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010123492A1 (en) * 2009-04-21 2010-10-28 Dow Global Technologies Inc. Double esters and lubricants thereof
CN105254493A (en) * 2014-07-08 2016-01-20 Sk新技术株式会社 Estolide compound and method for preparing the same

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CA2948777C (en) * 2015-11-16 2023-10-31 Trent University Branched diesters and methods of making and using the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010123492A1 (en) * 2009-04-21 2010-10-28 Dow Global Technologies Inc. Double esters and lubricants thereof
CN105254493A (en) * 2014-07-08 2016-01-20 Sk新技术株式会社 Estolide compound and method for preparing the same

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