CN111056944A - Phenolic ester compound and preparation method and application thereof - Google Patents
Phenolic ester compound and preparation method and application thereof Download PDFInfo
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- CN111056944A CN111056944A CN201811201072.7A CN201811201072A CN111056944A CN 111056944 A CN111056944 A CN 111056944A CN 201811201072 A CN201811201072 A CN 201811201072A CN 111056944 A CN111056944 A CN 111056944A
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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
- C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
- C07C69/22—Esters 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
- C07C69/33—Esters 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
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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
- 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 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):
wherein the definition of each group is shown in the specification. The phenolic ester compound of the invention hasExcellent viscosity-temperature performance, oxidation resistance, low-temperature performance and lubricating performance, and can replace BS bright stock.
Description
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 development of the lubricant. Conventional mineral-based lubricating oils have been difficult to meet these demanding requirements. Furthermore, mineral-based lubricating oils face a dual 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 utilized, does not 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, and the vegetable oil becomes a main resource of high-quality bio-based lubricating oil base oil, and of course, the vegetable oil also has the problems of poor oxidation stability and poor low-temperature flow 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 a lubricating oil. For this reason, many methods have been used to improve the properties of vegetable oils. For example, modern biotechnology is used to cultivate vegetable oils with high oleic acid content, such as canola oil and high oleic acid sunflower oil, which have oleic acid content of over 90% but are more costly than conventional vegetable oils. In addition, the vegetable oil can be subjected to chemical modification such as 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 be mixed to obtain lubricating oil base oil with oxidation resistance meeting the requirement. CN 101892111A discloses a method for modifying a catalyst by hydrogenationA method for obtaining biodegradable and nontoxic lubricating oil base oil with good lubricating property and oxidation resistance from the soybean oil. CN 106118804A discloses a method for obtaining lubricating oil 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 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 vegetable oil carbonyl removal. However, the methods can only obtain the lubricant base oil with lower kinematic viscosity, and cannot obtain the kinematic viscosity of more than 20mm at 100 DEG C2A high viscosity lubricant base oil per second. CN105175698A discloses a lubricating oil base oil which is obtained by polymerizing and modifying castor oil by dicarboxylic acid and dihydric polyol, has high viscosity, degradability and good lubricating property, but the base oil obtained by the method has high acid value and pour point, is extremely easy to emulsify, and cannot be used in other types of lubricating oil such as engine lubricating oil, gear oil, hydraulic oil, compressor oil and the like except for being used as metal processing 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 almost not 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):
in the general formula (I), the radical R0Is selected from C1-300Straight or branched alkyl (preferably C)1-30Linear or branched alkyl or polyolefin group having a number average molecular weight Mn of 300-3000); each radical R1、R2、R3、R4、R5Are identical or different from each other and are each independently selected from hydrogen、C1-300Straight or branched chain hydrocarbon radical (preferably C)1-30Linear or branched alkyl radicals or polyolefin radicals having a number average molecular weight Mn of 300-3000), radicals of the general formula (II), with the proviso that the radicals R are each1、R2、R3、R4、R5At least one group in (a) is a group represented by the general formula (II);
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
Hydrogen (preferably each independently selected from
) 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
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, C1-4Straight or branched chain alkyl); radical R7' selected from hydrogen, C1-20Straight or branched chain hydrocarbon radical (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 of 1 to 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 is selected from the group consisting of0Is ethyl, R2Independently selected from C2～C18Alkyl of R3Independently selected from C2～C18Alkyl group of (1).
The process 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,
in the general formula (X), each group R1”、R2”、R3”、R4”、R5"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);
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, C1-4Straight or branched chain alkyl); radical R7' selected from hydrogen, C1-20Straight or branched chain hydrocarbon radical (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"equal 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)The groups shown.
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);
in the general formula (Z), the groups are 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 alkyl (more preferably C)1-30Linear or branched alkyl groups or polyolefin groups having 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 a 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 used.
According to the method for producing a phenol ester compound of the present invention, the molar ratio of the phenol 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 phenol ester compound of the present invention, after the epoxidation reaction is completed, the epoxide of the phenol 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 particular limitation; when the inorganic acid catalyst is added in 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 preparation method of the phenolic ester compound, the second esterification reaction is to react the epoxide of the phenolic ester compound shown in 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 C1～C30Straight or branched alkyl (more preferably C)1～C20Linear or branched alkyl groups of (ii). 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:
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 limited by the following examples.
The raw materials used were as follows:
cashew nut shell oil, Shanghai Bingsheng chemical science and technology Co., Ltd, Industrial products
Potassium carbonate, chemical reagents of national drug group, Ltd, analytical purity
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 pharmaceutical group chemical reagents, analytical purity
Hydrochloric acid (36%), national drug group chemical reagent limited, analytical pure
Octanoic acid, chemical reagents of national drug group, Ltd, analytical purity
Acetic anhydride, chemical purity of carbofuran chemical reagent
Valeric acid, national drug group chemical reagents, analytical purity
Oleic acid, national drug group chemical reagents, analytical purity
150BS base oil, Kyop, institute of petrochemical institute, Industrial products
120BS base oil, Kyop, institute of petrochemical institute, Industrial products
Soybean oil, Shanghai Bingzhang 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 put into a three-neck flask with a reflux condenser and an electric stirrer, the temperature is controlled at 70 ℃, and the reaction is carried out 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 charged into a three-necked 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 ℃ for 3 hours. And cooling after the reaction is finished to obtain a brownish red transparent liquid. Filtering the reaction product, performing alkali washing by using a KOH solution with the mass fraction of 5%, then washing by using distilled water to be neutral, performing reduced pressure distillation on an organic phase for 1h at the temperature of 100Pa and 150 ℃, removing water and unreacted raw materials, and obtaining orange yellow transparent liquid, namely the epoxide of the m-pentadecenylphenol 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, reflux condenser, nitrogen line and temperature control, and nitrogen gas was blown, 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 in a four-necked flask equipped with a mechanical stirrer, a reflux condenser, a nitrogen line, and a temperature controller, and nitrogen gas was blown thereinto, 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 phenolic ester compound prepared by the invention, the conventional mineral oil type high-viscosity base oil 150BS and 120BS in the market and the soybean oil are respectively subjected to performance analysis and evaluation, 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 rising 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.
The comparison shows that 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 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
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
Claims (18)
1. A phenolic ester compound has a structure shown in a general formula (I):
in the general formula (I), the radical R0Is selected from C1-300Straight or branched alkyl (preferably C)1-30Linear or branched alkyl or 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 and C1-300Straight or branched chain hydrocarbon radical (preferably C)1-30Linear or branched alkyl radicals or polyolefin radicals having a number average molecular weight Mn of 300-3000), radicals of the general formula (II), with the proviso that the radicals R are each1、R2、R3、R4、R5At least one group in (a) is a group represented by the general formula (II);
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
Hydrogen (preferably each independently selected from
) 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
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, C1-4Straight or branched chain alkyl); radical R7' selected from hydrogen, C1-20Straight or branched chain hydrocarbon radical (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).
2. A phenolic ester compound according to claim 1, characterized in that in formula (I) the group R1、R3、R5Each independently selected from hydrogen and C1-4A linear or branched alkyl group; radical R2、R4Each 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).
3. A phenolic ester compound according to claim 1, characterized in that in formula (I) the group R1、R3、R5Each 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.
4. The phenolic ester compound of claim 1, wherein the phenolic ester compound is selected from the group consisting of compounds wherein R is0Is ethyl, R2Independently selectFrom C2～C18Alkyl of R3Independently selected from C2～C18The alkyl group of (a) is,
5. a process for producing a phenol ester compound, comprising 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,
in the general formula (X), each group R1”、R2”、R3”、R4”、R5"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);
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, C1-4Straight or branched chain alkyl); radical R7' selected from hydrogen, C1-20Straight or branched chain hydrocarbon radical (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).
6. A process according to claim 5, wherein, in the formula (X), the radical R1”、R3”、R5Each independently selected from hydrogen, C1-4A linear or branched alkyl group; radical R2”、R4Each 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).
7. A process according to claim 5, wherein, in the formula (X), the radical 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.
8. The method according to claim 5, wherein the first esterification reaction is an esterification reaction of the 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),
in the general formula (Z), the group R0Is selected from C1-300Straight or branched alkyl (preferably C)1-30Linear or branched alkyl or polyolefin group having a number average molecular weight Mn of 300-3000); each radical R1”、R2”、R3”、R4”、R5"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 of the formula (Y) up toAt least one group is selected from the group represented by the general formula (Y);
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, C1-4Straight or branched chain alkyl); radical R7' selected from hydrogen, C1-20Straight or branched chain hydrocarbon radical (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).
9. The method of claim 8, wherein the first esterification agent comprises one or more of an alkyl anhydride, alkyl halide and alkyl acid, wherein the alkyl group is preferably selected from the group consisting of C1-300Straight or branched alkyl (more preferably C)1-30Linear or branched alkyl or polyolefin group having a number average molecular weight Mn of 300-3000); 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 ℃ to 120 ℃ (preferably 40 ℃ to 80 ℃).
10. A process according to claim 8, wherein a catalyst is added to the first esterification reaction, preferably an inorganic base or a weak acid salt of an inorganic base (e.g. one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate and potassium carbonate may be used).
11. The method according to claim 8, wherein the epoxidation reaction is a reaction of the 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).
12. The method of claim 11, wherein the epoxidizing agent is selected from peroxides (e.g., one or more of hydrogen peroxide, m-chloroperoxybenzoic acid, t-butyl hydroperoxide, di-t-butyl peroxide, peracetic acid, and benzoyl peroxide may be used); the molar ratio of the phenol ester compound represented by the general formula (Z) to the epoxidizing agent is preferably 1: 1 to 10, more preferably 1: 2-5; the temperature of the epoxidation reaction is 20 ℃ to 100 ℃, preferably 50 ℃ to 80 ℃.
13. The process of claim 11 wherein a catalyst is added to said epoxidation reaction; the catalyst is preferably an inorganic acid (for example, one or more of sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, heteropolyacid and solid acid may be used).
14. The method of claim 11, wherein the second esterification reaction comprises reacting an epoxide of the phenolic ester compound of formula (Z) with a second esterifying agent to provide the phenolic ester compound.
15. The method of claim 11, wherein the second esterification agent comprises one or more of a fatty acid, a fatty acid anhydride, and an alkyl halide, wherein the alkyl group is C1～C30Straight or branched alkyl (more preferably C)1～C20Linear or branched alkyl groups of (a); 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 deg.c (preferably 120-210 deg.c).
16. The process of claim 15 wherein a catalyst is added to said second esterification reaction; the catalyst is preferably an inorganic acid (for example, one or more of sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid may be used).
17. The method according to claim 5, wherein the phenol compound represented by the general formula (X) is derived from a natural plant cashew nut.
18. The phenolic ester compound of any one of claims 1 to 4 and the phenolic ester compound prepared by the method of any one of claims 5 to 17 as a high viscosity base oil for use in lubricating oils and greases.
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