CN111056944B - Phenolic ester compound and preparation method and application thereof - Google Patents

Phenolic ester compound and preparation method and application thereof Download PDF

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CN111056944B
CN111056944B CN201811201072.7A CN201811201072A CN111056944B CN 111056944 B CN111056944 B CN 111056944B CN 201811201072 A CN201811201072 A CN 201811201072A CN 111056944 B CN111056944 B CN 111056944B
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ester compound
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acid
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CN111056944A (en
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陈晓伟
刘辉
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/02Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
    • C07C69/22Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety
    • C07C69/33Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety esterified with hydroxy compounds having more than three hydroxy groups
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32Esters
    • C10M105/38Esters of polyhydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/283Esters of polyhydroxy compounds
    • C10M2207/2835Esters of polyhydroxy compounds used as base material

Abstract

The invention provides a phenolic ester compound and a preparation method and application thereof. The structure of the phenolic ester compound is shown as the general formula (I):
Figure DDA0001830002870000011
wherein the definition of each group is shown in the specification. The phenolic ester compound has excellent viscosity-temperature performance, oxidation resistance, low-temperature performance and lubricating performance, and can replace BS bright stock.

Description

Phenolic ester compound and preparation method and application thereof
Technical Field
The present invention relates to a phenolic ester compound, and particularly to a phenolic ester compound suitable for use as a lubricant base oil.
Background
With the rapid development of modern industry and the increasingly outstanding environmental problems, the requirements on the use performance, the operation reliability, the service life, the biodegradability, the low or non-toxicity and the like of the lubricant are higher and higher, the development of the lubricant at present and in future will face various challenges, and the lubricant is renewable, energy-saving, environment-friendly, low in cost, universal, high in performance and long in service life, and becomes the main direction of the lubricant development. Conventional mineral-based lubricating oils have been difficult to meet these demanding requirements. Furthermore, mineral-based lubricating oils face a double pressure of resource depletion and environmental pollution due to their non-renewability and low biodegradability. With the increasing exhaustion of fossil resources, the increasing concern of people on environmental protection and energy conservation and the coming of laws and regulations with higher requirements on biodegradation rate, the cost advantage of the traditional petroleum-based mineral oil is weakened, and the application field is limited to a certain extent.
The biomass lubricating oil derived from organisms can be recycled repeatedly, cannot cause irreversible damage to the environment, and has outstanding performance, for example, vegetable oil has renewable and biodegradable performance, has the advantages of low volatility, high flash point, high viscosity index, excellent lubricating property and the like compared with the traditional mineral base oil, becomes a main resource of high-quality bio-based lubricating oil base oil, and certainly, the vegetable oil also has the problems of poor oxidation stability and poor low-temperature flowing property. The higher the unsaturated acid content of the vegetable oil, the better its low temperature fluidity, but the poorer the oxidation stability, which is mainly caused by the C ═ C double bonds of the vegetable oil. Therefore, improving the oxidation stability of vegetable oils is critical as lubricating oils. For this reason, many methods have been used to improve the properties of vegetable oils. For example, modern biotechnology has been used to cultivate high oleic vegetable oils, such as canola oil and high oleic sunflower oil, which have oleic acid contents of above 90% but at a higher cost than conventional vegetable oils. In addition, the vegetable oil can be chemically modified by hydrogenation, ester exchange and the like, so that the double bond content of the vegetable oil is reduced, the oxidation stability of the vegetable oil is improved, and the like. CN 104745280a discloses a production process of vegetable oil-based lubricating oil, which adopts high oleic acid sunflower oil and castor oil to mix and use to obtain the lubricating oil base oil with the oxidation resistance meeting the requirement. CN 101892111A discloses a method for obtaining biodegradable, nontoxic and lubricating oil base oil with good lubricating property and oxidation resistance by hydrogenating modified soybean oil A method is provided. CN 106118804a discloses a method for obtaining lubricant base oil with good oxidation stability and lubricity by esterifying modified watermelon seed oil. CN 103154206a discloses a method for obtaining high performance hydrocarbon lubricating oil base oil by hydrolyzing, oligomerizing, hydroisomerizing modified vegetable oil. CN 105189716a discloses a method for obtaining high-performance hydrocarbon lubricating oil base oil by olefin polymerization after removing carbonyl of vegetable oil. However, the methods can only obtain the lubricating base oil with low kinematic viscosity and cannot obtain the kinematic viscosity of more than 20mm at 100 DEG C2A high viscosity lubricant base oil per second. CN 105175698A discloses a lubricant base oil with high viscosity, degradability and good lubricating property obtained by using dicarboxylic acid and diol polymerization modified castor oil, but the base oil obtained by the method has high acid value and pour point, is easy to emulsify, and cannot be used in other types of lubricants such as engine oil, gear oil, hydraulic oil, compressor oil and the like except for being used as metal working fluid.
The high-viscosity base oil is an indispensable component for blending the high-viscosity lubricating oil, only BS bright stock in the mineral oil belongs to the high-viscosity base oil, and at present, products which are low in price and can replace the BS bright stock and the like are hardly available.
Disclosure of Invention
The invention provides a phenolic ester compound and a preparation method and application thereof.
The structure of the phenolic ester compound is shown as the general formula (I):
Figure BDA0001830002850000021
in the general formula (I), the radical R0Is selected from C1-300Straight or branched chain alkyl (preferably C)1-30A linear or branched alkyl group or a polyolefin group having a number average molecular weight Mn of 300-3000); each radical R1、R2、R3、R4、R5Are the same or different from each other and are each independently selected from hydrogen, C1-300Straight or branched chain hydrocarbon radical (preferably C)1-30Straight or branched chain alkyl or radicalsPolyolefin group having an average molecular weight Mn of 300-3000), a group represented by the general formula (II), provided that each group R1、R2、R3、R4、R5At least one group in (a) is a group represented by the general formula (II);
Figure BDA0001830002850000022
in the general formula (II), the group R1' is selected from a single bond, C1-20Straight or branched alkylene (preferably selected from single bond and C)1-4Linear or branched alkylene); each radical R of n repeating units2'、R3' the same or different from each other, each independently selected from
Figure BDA0001830002850000031
Hydrogen (preferably each independently selected from
Figure BDA0001830002850000032
) Wherein R' is selected from C1-30Straight or branched alkyl (preferably selected from C)1-20Straight or branched chain alkyl); in each repeating unit, the radical R2'、R3' at least one group selected from
Figure BDA0001830002850000033
Radicals R in n repeating units4' same or different from each other, each independently selected from the group consisting of a single bond, C 1-20Straight or branched alkylene (preferably each independently selected from the group consisting of a single bond, C1-4Straight or branched chain alkylene); each radical R in n repeating units5'、R6' same or different from each other, each independently selected from hydrogen, C1-20Straight or branched chain alkyl (preferably each independently selected from hydrogen, C1-4Straight or branched chain alkyl); radical R7' is selected from hydrogen, C1-20Straight or branched chain hydrocarbon radicals (preferably selected from hydrogen, C)1-10Straight or branched chain alkyl); n is a positive integer (preferably a positive integer between 1 and 30, more preferably a positive integer between 1 and 5).
In the formula (I), preferably the radical R1、R3、R5Are the same or different from each other and are each independently selected from hydrogen and C1-4A linear or branched alkyl group; radical R2、R4Are the same or different from each other and are each independently selected from hydrogen and C1-300Straight or branched chain hydrocarbon radical (preferably C)1-30A linear or branched alkyl group or a polyolefin group having a number average molecular weight Mn of 300-3000), a group represented by the general formula (II), wherein at least one group is selected from the group represented by the general formula (II).
In the formula (I), further preferably, the group R1、R3、R5Are the same or different from each other and are each independently selected from hydrogen and C1-4A linear or branched alkyl group; radical R2、R4One group is selected from the group represented by the general formula (II) and the other group is selected from hydrogen.
The phenolic ester compound can be a single compound with a structure shown in a general formula (I) or a mixture with a structure shown in the general formula (I); when the phenolic ester compound is a mixture with a structure shown as a general formula (I), the value of n in each group of each compound can be the same or different, and the sum of n in each compound can be the same or different.
The phenolic ester compound of the present invention may be selected from compounds wherein R is0Is ethyl, R2Is independently selected from C2~C18Alkyl of R3Is independently selected from C2~C18The alkyl group of (1).
Figure BDA0001830002850000041
The method for producing a phenol ester compound of the present invention comprises the steps of subjecting a phenol compound represented by the general formula (X) to a first esterification reaction, an epoxidation reaction, and a second esterification reaction,
Figure BDA0001830002850000042
in the general formula (X), the radicals R1”、R2”、R3”、R4”、R5"identical to or different from each other, each independently selected from hydrogen, C1-300Straight or branched chain hydrocarbon radical (preferably C)1-30A linear or branched alkyl group or a polyolefin group having a number average molecular weight Mn of 300-3000), a group represented by the general formula (Y), wherein at least one group is selected from the group represented by the general formula (Y);
Figure BDA0001830002850000043
in the group (Y) of the formula R1' is selected from a single bond, C1-20Straight or branched alkylene (preferably selected from single bond and C)1-4Linear or branched alkylene); radicals R in n repeating units4' same or different from each other, each independently selected from the group consisting of a single bond, C1-20Straight or branched alkylene (preferably each independently selected from the group consisting of single bond, C1-4Linear or branched alkylene); each radical R of n repeating units5'、R6' same or different from each other, each independently selected from hydrogen, C1-20Straight or branched chain alkyl (preferably each independently selected from hydrogen, C 1-4Straight or branched chain alkyl); radical R7' is selected from hydrogen, C1-20Straight or branched chain hydrocarbon radicals (preferably selected from hydrogen, C)1-10Straight or branched chain alkyl); n is a positive integer (preferably a positive integer between 1 and 30, more preferably a positive integer between 1 and 5).
According to the process for producing a phenolic ester compound of the present invention, in the general formula (X), preferably, the group R1”、R3”、R5"identical to or different from each other, each independently selected from hydrogen, C1-4A linear or branched alkyl group; radical R2”、R4"equal to or different from each other, each independently selected from hydrogen, C1-300Straight or branched chain hydrocarbon radical (preferably C)1-30A linear or branched alkyl group or a polyolefin group having a number average molecular weight Mn of 300-3000), a group represented by the general formula (Y), wherein at least one group is selected from the group represented by the general formula (Y)A group of (1).
According to the process for producing a phenol ester compound of the present invention, in the general formula (X), it is further preferred that the group R1”、R3”、R5"are both selected from hydrogen; radical R2”、R4One group in "is selected from the group represented by the general formula (Y), and the other group is selected from hydrogen.
According to the method for producing a phenol ester compound of the present invention, the first esterification reaction is an esterification reaction of a phenol compound represented by the general formula (X) with a first esterifying agent to obtain a phenol ester compound represented by the general formula (Z);
Figure BDA0001830002850000051
In the general formula (Z), each group is as defined above. The first esterification reaction is capable of esterifying the phenolic hydroxyl group in the phenol compound represented by the general formula (X).
According to the preparation method of the phenolic ester compound, the first esterifying agent comprises one or more of alkyl acid anhydride, alkyl halide and alkyl acid, wherein the alkyl is preferably selected from C1-300Straight or branched chain alkyl (more preferably C)1-30Linear or branched alkyl or polyolefin with a number average molecular weight Mn of 300-3000). The first esterifying agent is preferably an alkyl anhydride.
According to the preparation method of the phenolic ester compound, the reaction conditions of the first esterification reaction are as follows: the molar ratio between the phenol compound represented by the general formula (X) and the first esterifying agent is 1: 1 to 10 (preferably 1: 1 to 5); the reaction temperature is 20-120 ℃ (preferably 40-80 ℃); in general, the conversion is higher as the reaction time is longer, and the reaction time is usually 0.5 to 10 hours (preferably 3 to 5 hours). In the first esterification reaction, a catalyst may or may not be added, and preferably a catalyst is added. The catalyst is preferably an inorganic base or a weak acid salt of an inorganic base, and for example, one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate and potassium carbonate can be selected. The amount of the catalyst to be used is 0.1 to 15% (preferably 5 to 10%) by mass of the phenol compound represented by the general formula (X). In the first esterification reaction, a solvent may or may not be added, and preferably a solvent is added. The solvent is preferably one or more of toluene, xylene, petroleum ether and cyclohexane, and for example, toluene and/or xylene may be used. The amount of the solvent to be used is 0.1 to 15% (preferably 5 to 10%) by mass of the phenol compound represented by the general formula (X). The catalyst and the solvent may be removed by one or more methods including acid washing, water washing, distillation, filtration, drying and recrystallization, and are not particularly limited.
According to the method for producing a phenol ester compound of the present invention, the epoxidation reaction is a reaction of a phenol ester compound represented by the general formula (Z) with an epoxidizing agent to obtain an epoxide of the phenol ester compound represented by the general formula (Z). The epoxidizing agent is preferably peroxide, and for example, one or more of hydrogen peroxide, m-chloroperoxybenzoic acid, tert-butyl hydroperoxide, di-tert-butyl peroxide, peracetic acid and benzoyl peroxide can be selected.
According to the method for producing a phenolic ester compound of the present invention, the molar ratio of the phenolic ester compound represented by the general formula (Z) to the epoxidizing agent is preferably 1: 1 to 10, more preferably 1: 2 to 5. The temperature of the epoxidation reaction is 20-100 ℃, preferably 50-80 ℃; generally, the longer the reaction time, the higher the conversion, and the reaction time is generally 0.5 to 10 hours, preferably 3 to 5 hours, in combination of the conversion of the reaction and the economy of the reaction.
According to the method for preparing the phenolic ester compound of the present invention, a catalyst may or may not be added in the epoxidation reaction, and preferably, a catalyst is added. The catalyst is preferably an inorganic acid, and for example, one or more of sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, heteropolyacid and solid acid can be used. The mass of the catalyst is 0.01 to 3%, preferably 0.2 to 0.6% of the mass of the phenol compound represented by the general formula (X). In the epoxidation reaction, a solvent may or may not be added, and preferably a solvent is added. The solvent is preferably one or more of toluene, xylene, petroleum ether and cyclohexane, and for example, toluene and/or xylene may be used. The amount of the solvent to be used is 0.1 to 15% (preferably 5 to 10%) by mass of the phenol compound represented by the general formula (X).
According to the method for producing a phenolic ester compound of the present invention, after the epoxidation reaction is completed, the epoxide of the phenolic ester compound represented by the general formula (Z) may be subjected to a purification treatment by one or more methods selected from water washing, distillation, filtration, drying and recrystallization, without any particular limitation; when the inorganic acid catalyst is added to the epoxidation reaction, the purification treatment may be carried out by one or more of alkali washing, water washing, distillation, filtration, drying and recrystallization.
According to the method for preparing the phenolic ester compound of the present invention, the second esterification reaction is a reaction of an epoxide of the phenolic ester compound represented by the general formula (Z) with a second esterifying agent to obtain the phenolic ester compound of the present invention. The second esterifying agent comprises one or more of fatty acid, fatty acid anhydride and alkyl halide, wherein the alkyl is C1~C30Straight or branched alkyl (more preferably C)1~C20Straight or branched alkyl groups of (iv). The second esterifying agent is preferably C1~C30Linear or branched organic carboxylic acid (more preferably C)1~C20Linear or branched organic carboxylic acids).
According to the preparation method of the phenolic ester compound, the reaction conditions of the second esterification reaction are as follows: the molar ratio between the epoxide and the second esterifying agent of the phenolic ester compound shown by the general formula (Z) is 1: 1 to 10 (preferably 1: 2 to 8); the reaction temperature is 80-260 ℃ (preferably 120-210 ℃); in general, the conversion is higher as the reaction time is longer, and the reaction time is usually 5 to 20 hours (preferably 8 to 18 hours). In the second esterification reaction, a catalyst may or may not be added, and preferably a catalyst is added. The catalyst is preferably an inorganic acid, and for example, one or more of sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid may be used. The amount of the catalyst to be used is 0.1 to 10% (preferably 0.2 to 2%) of the amount of the epoxy compound of the phenol ester compound represented by the general formula (Z). In the second esterification reaction, a solvent may or may not be added, and preferably a solvent is added. The solvent is preferably one or more of toluene, xylene, petroleum ether and cyclohexane, and for example, toluene and/or xylene may be used. The amount of the solvent is 0.1 to 15% (preferably 5 to 10%) of the amount of the epoxy compound of the phenol ester compound represented by the general formula (Z). The catalyst and the solvent may be removed by one or more methods including alkali washing, water washing, distillation, filtration, drying and recrystallization, and are not particularly limited.
The phenol compound represented by the general formula (X) of the present invention is preferably derived from a natural plant cashew nut, contains a large amount of cashew nut shell oil in the cashew nut shell, contains meta-phenol as a main component, is generally called cardanol, and has the following structure:
Figure BDA0001830002850000071
wherein R is C15H31+xAnd x is 0, -2, -4 or-6.
The phenolic ester compound can be used as high-viscosity base oil for lubricating oil and lubricating grease.
The preparation method of the phenolic ester compound is simple, convenient to operate, green and easily available in raw materials, high in product yield and high in purity.
The phenolic ester compound has excellent viscosity-temperature performance, oxidation resistance, low-temperature performance and lubricating performance, and can replace BS bright stock.
Drawings
FIG. 1 is a nuclear magnetic spectrum of the product of example 3.
Detailed Description
The present invention is further illustrated, but is not to be construed as being limited, by the following examples.
The raw materials used were as follows:
cashew nut shell oil, Shanghai Bingshi chemical Co Ltd, Industrial products
Potassium carbonate, national chemical group chemical reagent Limited, analytically pure
Concentrated sulfuric acid, chemical reagent of national drug group, analytical purity
Sodium bicarbonate, national pharmaceutical group chemical reagents, Inc., analytical purity
Hydrogen peroxide (30%), national chemical reagent limited, analytical pure
Potassium hydroxide, national chemical group chemical reagent Limited, analytical pure
Hydrochloric acid (36%), national chemical group chemical reagent limited, analytical grade
Octanoic acid, national chemical group chemical reagent, Inc., analytical grade
Acetic anhydride, chemical reagent of carbofuran, chemical purity
Valeric acid, national drug group chemical reagent, Inc., analytical pure
Oleic acid, national chemical group chemical reagent, Ltd, analytical purity
150BS base oil, Shinpu, institute of petrochemical institute, Ltd
120BS base oil, Shinpu, institute of petrochemical institute, Ltd
Soybean oil, Shanghai Binghi chemical science and technology Limited, Industrial products
EXAMPLE 1 preparation of m-pentadecenylphenol acetate
100g of cashew nut shell oil, 40.5g of acetic anhydride and 7.5g of potassium carbonate are placed in a three-neck flask with a reflux condenser and an electric stirrer, the temperature is controlled at 70 ℃, and the reaction lasts for 4.5 hours. After the reaction is finished, cooling to 60 ℃, taking out a reaction mixture, adding 100g of KOH solution with the mass fraction of 1% for alkali washing, then washing with distilled water until the discharged water is neutral, then distilling the organic phase under the reduced pressure at 100Pa and 120 ℃ for 1h, and cooling to obtain a light yellow clear liquid, wherein the reaction conversion rate is 93.6%, and the purity of the m-pentadecenylphenol acetate in the product is more than 95%.
Example 2 preparation of an epoxide of m-pentadecenylphenol acetate
120g of m-pentadecenylphenol acetate prepared in example 1, 8g of formic acid, 0.3g of sulfuric acid and 160g of hydrogen peroxide were added to a three-neck flask equipped with a mechanical stirrer, a reflux condenser and a temperature controller, and stirring and heating were started. The reaction temperature was maintained at 70 ℃ and the reaction was carried out for 3 hours. And cooling after the reaction is finished to obtain a brownish red transparent liquid. Filtering the reaction product, washing with 5% KOH solution by using alkali, washing with distilled water to neutrality, distilling the organic phase under reduced pressure at 100Pa and 150 ℃ for 1h, removing water and unreacted raw materials to obtain orange transparent liquid, namely the epoxide of the m-pentadecenyl phenol acetate. The product conversion rate is 98.1%, and the purity is more than 98%.
Example 3 preparation of high viscosity Biomass base oil
50g of the m-pentadecenylphenol acetate epoxide prepared in example 2, 100g of octanoic acid and 0.5g of sulfuric acid were charged in a four-necked flask equipped with a mechanical stirrer, a reflux condenser, a nitrogen gas tube and a temperature controller, and nitrogen gas was bubbled, and the mixture was stirred and heated. The reaction temperature was maintained at 180 ℃ for 15 hours. And cooling after the reaction is finished to obtain a brownish red transparent liquid. Filtering the reaction product, then washing with 1% hydrochloric acid solution by mass fraction, then washing with distilled water to neutrality, distilling the organic phase under reduced pressure at 1000Pa and 120 ℃ for 1h, removing water, and cooling to obtain brownish red viscous liquid, namely the phenolic ester compound. The product conversion was 88.1%.
Example 4 high viscosity Biomass base oil preparation
50g of the m-pentadecenylphenol acetate epoxide prepared in example 2, 40g of valeric acid and 0.25g of sulfuric acid were charged into a four-necked flask equipped with a mechanical stirrer, a reflux condenser, a nitrogen gas tube and a temperature controller, and nitrogen gas was bubbled through the mixture, followed by stirring and heating. The reaction temperature was maintained at 140 ℃ for 8 hours. And cooling after the reaction is finished to obtain a brownish red transparent liquid. Filtering the reaction product, then washing with 1% hydrochloric acid solution by mass fraction, then washing with distilled water to neutrality, distilling the organic phase under reduced pressure at 1000Pa and 120 ℃ for 1h, removing water, and cooling to obtain brownish red viscous liquid, namely the phenolic ester compound. The product conversion was 91.3%.
Example 5 high viscosity Biomass base oil preparation
50g of the m-pentadecenylphenol acetate epoxide prepared in example 2, 186g of lauric acid and 1g of sulfuric acid were charged in a four-necked flask equipped with a mechanical stirrer, a reflux condenser, a nitrogen gas tube and a temperature control, and nitrogen gas was blown thereinto, followed by stirring and heating. The reaction temperature was maintained at 210 ℃ and the reaction was carried out for 18 hours. And cooling after the reaction is finished to obtain a brownish red transparent liquid. Filtering the reaction product, then washing with 1% hydrochloric acid solution by mass fraction, then washing with distilled water to neutrality, distilling the organic phase under reduced pressure at 1000Pa and 120 ℃ for 1h, removing water, and cooling to obtain brownish red viscous liquid, namely the phenolic ester compound. The product conversion was 87.6%.
Example 6
The performance analysis and evaluation of the phenolic ester compound prepared by the invention, the conventional mineral oil type high-viscosity base oil 150BS, 120BS and soybean oil in the market are respectively carried out, wherein the test conditions of the PDSC oxidation resistance test are as follows: the testing instrument is a TA5000 DSC instrument of TA company of America, 190 ℃, the oxygen pressure is 0.5MPa, and the temperature rise speed is 10 ℃/min; the standard method of the four-ball machine test is SH/T0189, and the test conditions are as follows: 1200r/min, load 392N, time 30 min. The results of the performance analysis and evaluation are shown in table 1.
As can be seen by comparison, compared with the conventional mineral oil type high-viscosity base oil 150BS and 120BS, the phenolic ester compound has obvious advantages in the aspects of viscosity-temperature performance (viscosity index), low-temperature performance (pour point), lubricating performance and the like; compared with soybean oil which is also used as the biomass base oil, the soybean oil has obvious advantages in oxidation stability, low-temperature performance (pour point), lubricating performance and the like, and is lubricating oil base oil with excellent comprehensive performance.
TABLE 1
Figure BDA0001830002850000101
Example 7
The product prepared in example 3 was subjected to nuclear magnetic spectrum analysis, see fig. 1, and the analysis results are shown in table 2.
TABLE 2 NMR analysis results of the product of example 3
Figure BDA0001830002850000102

Claims (17)

1. Phenolic ester compound selected from the group consisting of compounds wherein R is 0Is ethyl, R2Is independently selected from C4~C11Alkyl of R3Is independently selected from C4~C11The alkyl group (b) of (a),
Figure 815167DEST_PATH_IMAGE002
2. a process for producing a phenol ester compound, which comprises subjecting a phenol compound represented by the general formula (X) to a first esterification reaction, an epoxidation reaction and a second esterification reaction,
Figure DEST_PATH_IMAGE003
(X)
in the general formula (X), the group R1''、R3''、R4''、R5'' is selected from hydrogen, the radical R2'' is selected from the group represented by the general formula (Y);
Figure 919258DEST_PATH_IMAGE004
(Y)
in the group (Y) of the formula R1' selected from C1-20A linear or branched alkylene group; radicals R in n repeating units4' same or different from each other, each independently selected from the group consisting of a single bond, C1-20A linear or branched alkylene group; each radical R of n repeating units5'、R6' same or different from each other, each independently selected from hydrogen, C1-20A linear or branched alkyl group; radical R7' selected from hydrogen, C1-20A straight or branched chain hydrocarbon group; n is a positive integer between 1 and 30;
the first esterification reaction is an esterification reaction of a phenol compound represented by the general formula (X) with a first esterifying agent to obtain a phenol ester compound represented by the general formula (Z),
Figure DEST_PATH_IMAGE005
(Z)
in the general formula (Z), the group R0Is selected from ethyl; radical R1''、R3''、R4''、R5'' is selected from hydrogen, the radical R2'' is selected from the group represented by the general formula (Y);
Figure 121831DEST_PATH_IMAGE006
(Y)
in the group (Y) of the formula R1' selected from C1-20A linear or branched alkylene group; radicals R in n repeating units 4' the same or different from each other, each independently selected from the group consisting of a single bond, C1-20A linear or branched alkylene group; each radical R in n repeating units5'、R6' same or different from each other, each independently selected from hydrogen, C1-20A linear or branched alkyl group; radical R7' is selected from hydrogen, C1-20A straight or branched chain hydrocarbon group; n is a positive integer between 1 and 30;
the first esterifying agent comprises one or more of alkyl acid anhydride, alkyl halide and alkyl acid, wherein the alkyl is selected from ethyl;
the epoxidation reaction is to react the phenolic ester compound shown in the general formula (Z) with an epoxidizing agent to obtain an epoxide of the phenolic ester compound shown in the general formula (Z);
the second esterification reaction is to react an epoxide of the phenolic ester compound shown by the general formula (Z) with a second esterifying agent to obtain the phenolic ester compound;
the second esterifying agent comprises one or more of fatty acid, fatty acid anhydride and alkyl halide, wherein the alkyl is C4~C11Linear or branched alkyl.
3. A process according to claim 2, wherein in the group (Y) of the formula, R1' is selected from the group consisting of a single bond and C1-4A linear or branched alkylene group; radicals R in n repeating units4' each is independently selected from the group consisting of a single bond, C1-4A linear or branched alkylene group; each radical R of n repeating units 5'、R6' Each is independently selected from hydrogen, C1-4A linear or branched alkyl group; radical R7' is selected from hydrogen, C1-10A linear or branched alkyl group; n is a positive integer between 1 and 5.
4. The process according to claim 2, wherein the reaction conditions of the first esterification reaction are: the molar ratio between the phenol compound represented by the general formula (X) and the first esterifying agent is 1: 1-10; the reaction temperature is 20-120 ℃.
5. The process of claim 2, wherein the reaction conditions of the first esterification reaction are: the molar ratio between the phenol compound represented by the general formula (X) and the first esterifying agent is 1: 1-5; the reaction temperature is 40-80 ℃.
6. The process of claim 2, wherein a catalyst is added to said first esterification reaction, said catalyst being an inorganic base or a weak acid salt of an inorganic base.
7. The process of claim 2, wherein a catalyst is added to the first esterification reaction, the catalyst being selected from one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate and potassium carbonate.
8. The method of claim 2, wherein the epoxidizing agent is selected from the group consisting of peroxides; the molar ratio of the phenolic ester compound represented by the general formula (Z) to the epoxidizing agent is 1: 1-10; the temperature of the epoxidation reaction is 20-100 ℃.
9. The process of claim 2, wherein the epoxidizing agent is selected from the group consisting of one or more of hydrogen peroxide, m-chloroperoxybenzoic acid, t-butyl hydroperoxide, di-t-butyl peroxide, peracetic acid, and benzoyl peroxide; the molar ratio of the phenolic ester compound represented by the general formula (Z) to the epoxidizing agent is 1: 2-5; the temperature of the epoxidation reaction is 50-80 ℃.
10. The process of claim 2, wherein a catalyst is added to the epoxidation reaction; the catalyst is inorganic acid.
11. The process of claim 2, wherein a catalyst is added to the epoxidation reaction; the catalyst is selected from one or more of sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, heteropolyacid and solid acid.
12. The method of claim 2, wherein the second esterification reaction is carried out under the following reaction conditions: the molar ratio of the epoxide to the second esterifying agent of the phenolic ester compound represented by the general formula (Z) is 1: 1-10; the reaction temperature is 80-260 ℃.
13. The method of claim 2, wherein the second esterification reaction is carried out under reaction conditions of: the molar ratio between the epoxide and the second esterifying agent of the phenolic ester compound shown by the general formula (Z) is 1: 2-8; the reaction temperature is 120-210 ℃.
14. The process of claim 2 wherein a catalyst is added to said second esterification reaction; the catalyst is inorganic acid.
15. The process of claim 2 wherein a catalyst is added to said second esterification reaction; the catalyst is selected from one or more of sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid.
16. The method according to claim 2, wherein the phenol compound represented by the general formula (X) is derived from a natural plant cashew nut.
17. Use of the phenolic ester compound of claim 1 or the phenolic ester compound prepared by the method of any one of claims 2 to 16 as a high viscosity base oil in lubricating oils and greases.
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