CN112707817B - Ester compound and preparation method and application thereof - Google Patents
Ester compound and preparation method and application thereof Download PDFInfo
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- CN112707817B CN112707817B CN201911017553.7A CN201911017553A CN112707817B CN 112707817 B CN112707817 B CN 112707817B CN 201911017553 A CN201911017553 A CN 201911017553A CN 112707817 B CN112707817 B CN 112707817B
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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
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- 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
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- 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
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- 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
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- 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
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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
Technical Field
The invention relates to an ester compound, in particular to an ester compound which can be used as a lubricating oil additive or a lubricating oil 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, the base oil and additives which form the lubricating oil are mostly from petroleum raw materials, are difficult to regenerate under the specific time condition in the nature at the present stage, and the components of the lubricating oil are mostly isoalkanes, cyclanes, aromatic hydrocarbons and trace metal substances, so that the biodegradability of the lubricating oil is poor.
The environmentally friendly lubricating oil means a lubricating oil having excellent biodegradability, renewability, and no 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, 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 open environment. However, unsaturated double bonds in vegetable fat molecules are easily oxidized, which causes problems such as increased viscosity and acidic corrosion.
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 changing the structure of the fatty side chain in the triglyceride structure of vegetable oils, 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 produce triglyceride partially substituted with branched fatty acids and polyol ester partially substituted with long chain fatty acids.
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 environmentally friendly base oils and additives with superior properties.
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:
wherein each L is 1 Each independently selected from the group consisting of H atom and a group represented by formula (II), and at least one L 1 The group is selected from the group shown in the formula (II),
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 Linear or branched alkylene); r is 0 The groups are the same or different from each other and are independently selected from H and 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-, methylene and ethylene, and at least one a group is selected from the group represented by formula (III);
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);
L 2 the radicals being selected from C 1-10 A hydrocarbon group and a group of the formula (IV) (preferably selected from C) 1-6 Straight or branched chain alkyl and a group of formula (IV),
-R 1 -O-L 1 (IV)
in the formula (IV), R 1 The radicals being selected from C 1-10 Alkylene (preferably C) 1-5 Straight or branched alkylene, more preferably C 1-3 Linear or branched alkylene); l is a radical of an alcohol 1 The group is selected from a H atom and a group represented by the formula (II) (the A group in the group represented by the formula (II) is selected from a group represented by the formula (III)).
The ester compound with a specific structure comprises one or more of the following compounds:
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),
in the formula (. Alpha.), L 2 The group being selected from C 1-10 Hydrocarbyl or-R 1 -OH (preferably selected from C) 1-6 Straight or branched alkyl or-R 1 -OH) wherein R is 1 The radicals being selected from C 1-10 Alkylene (preferably C) 1-5 Straight or branched alkylene, more preferably C 1-3 Linear or branched alkylene);
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 Straight or branched chain alkylene); r 0 The groups are the same or different from each other and are independently selected from H and 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-, methylene, ethylene, and at least one a group is selected from the group represented by formula (γ);
in the formula (. Gamma.), 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 compound represented by the formula (α) can be selected from one or more of the following specific compounds: trimethylolpropane, pentaerythritol.
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.),
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 independently selected from H and 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 formula-C = C-, methylene, ethylene, 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 butyl 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 present invention, a catalyst may or may not be added to the reaction of the compound represented by the formula (δ) with the compound represented by the formula (ε). 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 perchloric 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 (δ).
According to the invention, the compound represented by the formula (δ) can be selected from one or more of the following specific compounds: eicosenoic acid, oleic acid, linoleic acid, linolenic acid, hexadecenoic acid, decatetraenoic acid, dodecenoic acid, undecylenic 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, tetradecenoic acid, dodecenoic acid, undecylenic acid, decenoic acid, octenoic acid.
According to the invention, the reaction equivalence ratio between the compound of formula (α) (calculated as OH) and the compound of formula (β) (calculated as Y) is preferably 0.1 to 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 may not be 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 butyl 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. The solvent may also function as a water-carrying agent to promote the smooth progress 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), 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 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 ester compound accounts for 0.1-100% of the lubricating oil composition by mass, 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, amine or sulfur-phosphorus antioxidants, carboxylate, sulfonate or alkylphenate detergents, succinimide type ashless dispersants, polyester, polyolefin or alkylnaphthalene type pour point depressants, methacrylate copolymers, ethylene-propylene copolymers, polyisobutylene, hydrogenated styrene/butadiene copolymer type viscosity index improvers, sulfur/phosphorus type friction modifiers, sulfur/phosphorus, boric acid type extreme pressure agents, silicon type and non-silicon type antifoaming agents, and the like. The type 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 one or more applications of the ester compound as lubricating oil base oil, lubricating oil viscosity index improver and lubricating oil friction improver.
The ester compound has excellent viscosity temperature, low temperature, oxidation resistance and antifriction performance.
The ester compound disclosed by the invention 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, can be used as an antiwear agent to obviously reduce the wear-scar diameter of the base oil, and can be used as a friction improver to obviously reduce the friction coefficient of the base oil.
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" is meant that the group is absent. For example, assume the structural 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 connection, 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 -*、
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: preparation of isomerate A
The reaction was carried out in a high pressure autoclave equipped with a vent, stirrer and thermocouple. 565g of oleic acid is gradually pumped into a reaction kettle containing 1200g 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 cut off by adopting a distillation mode, the reaction kettle is cooled to room temperature, and the reaction kettle is washed by alkali, water and organic phases with potassium dihydrogen phosphate with the pH =3.7 for three times, and after drying by anhydrous sodium sulfate, filtering and the like, unreacted oleic acid is cut off 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 the following.
Example 2: preparation of ester Compound A-1
171g of isoacid A, 22g of trimethylolpropane, 1.8g of p-toluenesulfonic acid catalyst and water carrying agent (petroleum ether at 90-120 ℃) are added into a 500mL three-neck glass flask, heated to 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-1.
Example 3: preparation of ester Compound A-2
171g of isoacid A, 17g of pentaerythritol, 1.8g of paratoluenesulfonic acid catalyst and a water carrying agent (petroleum ether at the temperature of 90-120 ℃) are added into a 500mL 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 A-2.
Example 4: preparation of ester Compound A-3
67g of threeAdding hydroxymethyl propane, 0.5g of p-toluenesulfonic acid catalyst and toluene as a water carrying agent into a 500mL three-neck glass flask, heating to reflux temperature, gradually dropwise adding 85g of isoacid A into the three-neck flask within 3H, and collecting H generated in the reaction process by using a water separator 2 And O, stopping the reaction when the actual water yield is the same as the theoretical value, and distilling to remove the excessive trimethylolpropane. 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-3.
Comparative example 1: preparation of ester Compound D-1
D-1 was prepared in the same manner as A-1 except that the isomeric acid A was replaced with an equimolar amount of oleic acid.
Comparative example 2: preparation of ester Compound D-2
D-2 was prepared in the same manner as A-1 except that trimethylolpropane was replaced with an equimolar amount of glycerol.
Example 5: preparation of isomeric acid B
The reaction was carried out in a high pressure autoclave equipped with a vent, stirrer and thermocouple. 560g of linoleic acid is pumped into a reaction kettle filled with 1800g of acetic acid and 10g of perchloric acid with the concentration of 70 percent, the reaction is carried out for 18 hours at 70 ℃, the heating is stopped, the reaction is finished, the residual acetic acid is cut off by adopting a distillation mode, the reaction kettle is cooled to room temperature, the reaction kettle is washed by alkali, water and organic phase with potassium dihydrogen phosphate with Ph =3.7 for three times, after drying by anhydrous sodium sulfate and filtration treatment, unreacted linoleic acid is cut off by molecular distillation, and the addition product of acetic acid and linoleic acid, namely, the isomeric acid B, is obtained, and the structure of the addition product is shown as the following.
Example 6: preparation of ester Compound B-1
Adding 201g of isoacid B, 22g of trimethylolpropane, 3.2g of p-toluenesulfonic 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 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 7: preparation of ester Compound B-2
Adding 121g of isoacid B, 10g of pentaerythritol, 2.5g of p-toluenesulfonic acid catalyst and water carrying agent (petroleum ether at 90-120 ℃) into a 250mL three-neck glass flask, heating to 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. 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.
Example 8: preparation of ester Compound B-3
134g of trimethylolpropane, 2g of p-toluenesulfonic acid catalyst and toluene as a water carrying agent are added into a 500mL three-neck glass flask, the flask is heated to the reflux temperature, 201g of isoacid B is gradually added into the three-neck flask dropwise within 5H, and H generated in the reaction process is collected by a water separator 2 And O, stopping the reaction when the actual water yield is the same as the theoretical value, and distilling to remove excessive trimethylolpropane. 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-3.
Comparative example 3: preparation of ester compound DM-1
The preparation method of the DM-1 is the same as that of the B-1 except that the trimethylolpropane is replaced by the ethanol with the same mole, and the ester compound DM-1 is obtained.
The physical and chemical properties of the ester compounds of examples A-1 to A-3, B-1 to B-2, D-1 and D-2 were examined by GB/T265 kinematic viscosity determination of petroleum products and dynamic viscometer algorithm, GB/T1995 petroleum product viscosity index calculation method, GB/T3535 pour point determination of petroleum products, SH/T0074 gasoline engine oil thin layer oxygen absorption oxidation stability test method, and the results are shown in Table 1.
TABLE 1
The ester compounds of examples A-3, B-3 and DM-1 were examined for their anti-wear properties by the SH/T0762 lubricating oil friction coefficient measurement method (four-ball method), the results of which are shown in Table 2.
TABLE 2
| Sample(s) | Steel ball grinding spot diameter/mum |
| A-3 | 331 |
| B-3 | 285 |
| DM-1 | 585 |
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 should 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; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present disclosure.
Claims (23)
1. An ester compound having the structure:
wherein each L is 1 Each independently selected from the group consisting ofThe group shown in the figure is,
in the formula (II), m is an integer between 1 and 6; 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 A linear or branched alkylene group; r is 0 The radicals, equal to or different from each other, are each independently selected from C 1-5 A linear or branched alkyl group; m A groups, equal to or different from each other, are each independently selected from the group represented by formula (III);
in the formula (III), R 0 The group being selected from C 1-17 An alkyl group;
L 2 the radicals being selected from C 1-6 A linear or branched alkyl group and a group of formula (IV),
-R 1 -O-L 1 (IV)
in the formula (IV), R 1 The radicals being selected from C 1-5 A linear or branched alkylene group; l is 1 The group is selected from the group shown in formula (II).
2. An ester compound according to claim 1,
in the formula (III), R 0 The group being selected from C 1-15 Straight or branched chain alkyl.
3. An ester compound according to claim 1, wherein,
in the formula (II), m is an integer of 1-5; m + 1R groups are each independently selected from single bond, C 1-10 A linear or branched alkylene group; r 0 Each independently selected from C 1-3 A linear or branched alkyl group;
in the formula (III), R 0 The group being selected from C 1-11 Straight or branched chain alkanesA group;
in the formula (IV), R 1 The radicals being selected from C 1-3 Straight or branched chain alkylene.
4. An ester compound as claimed in claim 1, wherein the ester compound comprises one or more of the following compounds:
5. a preparation method of ester compounds comprises the step of reacting compounds shown as a formula (alpha) with compounds shown as a formula (beta),
in the formula (. Alpha.), L 2 The group being selected from C 1-6 Straight or branched alkyl or-R 1 -OH, wherein R 1 The radicals being selected from C 1-5 A linear or branched alkylene group;
in the formula (β), m is an integer of 1 to 6; 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 A linear or branched alkylene group; r 0 The radicals, equal to or different from each other, are each independently selected from C 1-5 A linear or branched alkyl group; 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);
in the formula (. Gamma.), R 0 The group being selected from C 1-17 An alkyl group.
6. The method of claim 5,
in the formula (. Gamma.), R 0 The group being selected from C 1-15 Straight or branched chain alkyl.
7. The method of claim 5,
in the formula (. Alpha.), wherein R is 1 The radicals being selected from C 1-3 A linear or branched alkylene group;
in the formula (β), m is an integer of 1 to 5; m + 1R groups are independently selected from single bond and C 1-10 A linear or branched alkylene group; r is 0 Each independently selected from C 1-3 A linear or branched alkyl group;
in the formula (. Gamma.), R 0 The group being selected from C 1-11 Straight or branched chain alkyl.
8. The method according to claim 5, wherein the compound represented by the formula (α) is one or more of the following specific compounds: trimethylolpropane, pentaerythritol.
9. A process according to claim 5, wherein the compound of formula (. Beta.) is obtained by reacting a compound of formula (. Delta.) with a compound of formula (. Epsilon.),
in the formula (δ), m is an integer between 1 and 6; 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 A linear or branched alkylene group; r is 0 The radicals, equal to or different from each other, are each independently selected from C 1-5 A linear or branched alkyl group; the Y group is selected from H, F, cl, br and I; m a' groups are selected from formula-CH = CH-;
in the formula (. Epsilon.), R 0 The group being selected from C 1-17 An alkyl group.
10. The method of claim 9,
in the formula (. Epsilon.), R 0 The group being selected from C 1-15 Straight or branched chain alkyl.
11. The method of claim 9,
in the formula (δ), m is an integer between 1 and 5; m + 1R groups are independently selected from single bond and C 1-10 A linear or branched alkylene group; r 0 Each independently selected from C 1-3 A linear or branched alkyl group; in the formula (. Epsilon.), R 0 The group being selected from C 1-11 Straight or branched chain alkyl.
12. The process according to claim 9, wherein the equivalent ratio of the reaction between the compound of formula (δ) and the compound of formula (e) is 0.05 to 20, in terms of-C = C-, and the compound of formula (e) is in terms of carboxyl groups: 1; the reaction temperature is 0-200 ℃; the reaction time is 0.5 to 72 hours.
13. The process according to claim 9, wherein the equivalent ratio of the reaction between the compound of formula (δ) and the compound of formula (e) is 0.1 to 10, in terms of-C = C-, and the compound of formula (e) is in terms of carboxyl groups: 1; the reaction temperature is 50-160 ℃; the reaction time is 3 to 48 hours.
14. A process according to claim 9, 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 heteropolyacid, an acidic ionic liquid, an acidic resin, an acidic molecular sieve, a metal chloride and a metal oxide.
15. The process according to claim 9, 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 resins, phosphotungstic heteropoly acids, acidic ionic liquids and acidic molecular sieves.
16. The method according to claim 9, wherein the compound represented by the formula (δ) is selected from one or more of the following compounds: eicosenoic acid, oleic acid, linoleic acid, linolenic acid, hexadecenoic acid, tetradecenoic acid, dodecenoic acid, undecenoic acid, decenoic acid, octenoic acid.
17. The method according to claim 9, wherein the compound of formula (e) is selected from one or more of the following compounds: acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid.
18. The process according to claim 5, wherein the compound of formula (α) is calculated as OH and the compound of formula (β) is calculated as Y, and the reaction equivalent 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.
19. The process according to claim 5, wherein the compound of formula (α) is calculated as OH and the compound of formula (β) is calculated as Y, and the reaction equivalent ratio between the compound of formula (α) and the compound of formula (β) is 0.2 to 5:1; the reaction temperature is 90-200 ℃; the reaction time is 2 to 15 hours.
20. A process according to claim 5, wherein a catalyst is added to the reaction of the compound of formula (α) with the compound of formula (β), said catalyst being one or more of an inorganic acid, an organic acid, a heteropolyacid, an acidic ionic liquid, an acidic resin, an acidic molecular sieve, a metal chloride and a metal oxide.
21. A process according to claim 5, wherein a catalyst is added to the reaction of the compound of formula (α) with the compound of formula (β), said catalyst being one or more of sulphuric acid, tin chloride, n-butyl tin oxide, p-toluenesulphonic acid, an acidic resin and a phosphotungstic heteropoly acid.
22. A lubricating oil composition comprising the ester compound according to any one of claims 1 to 4 or the ester compound produced by the method according to any one of claims 5 to 21, and a lubricating oil base oil.
23. Use of the ester compound according to any one of claims 1 to 4 or the ester compound obtained by the process according to any one of claims 5 to 21 as one or more of a lubricant base oil, a lubricant viscosity index improver and a lubricant friction improver.
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| US17/755,075 US20230012456A1 (en) | 2019-10-24 | 2020-10-23 | Ester compound and preparation method therefor and uses thereof |
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| Effect of branching in hyperbranched alkyd on the performance of alkyd polyurethane coating;Tirthankar Jana et al.;《J. APPL. POLYM. SCI.》;20171101;第135卷(第9期);第45835（1-11）页 * |
| 酯类润滑油的结构对性能影响研究;姜会泽等;《当代化工》;20150731;第44卷(第7期);第1570-1572页 * |
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