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CN111057606A - A kind of viscosity index improver and preparation method and use thereof - Google Patents

A kind of viscosity index improver and preparation method and use thereof Download PDF

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Publication number
CN111057606A
CN111057606A CN201811201081.6A CN201811201081A CN111057606A CN 111057606 A CN111057606 A CN 111057606A CN 201811201081 A CN201811201081 A CN 201811201081A CN 111057606 A CN111057606 A CN 111057606A
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group
independently selected
alkyl
hydrogen
repeating units
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CN111057606B (en
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陈晓伟
刘辉
韩天昊
梁宇翔
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • 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
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
    • C10M145/12—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate monocarboxylic
    • C10M145/14—Acrylate; Methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Lubricants (AREA)

Abstract

本发明提出了一种黏度指数改进剂及其制备方法、用途。本发明的黏度指数改进剂，其结构如通式(I)所示：

Figure DDA0001830004900000011
其中各基团的定义见说明书。本发明的黏度指数改进剂可以用作润滑油的粘度指数改进剂。本发明的黏度指数改进剂具有优异的增稠性能、剪切稳定性和抗氧化性能。The invention provides a viscosity index improver, a preparation method and an application thereof. Viscosity index improver of the present invention, its structure is shown in general formula (I):
Figure DDA0001830004900000011
The definition of each group is shown in the specification. The viscosity index improver of the present invention can be used as a viscosity index improver for lubricating oils. The viscosity index improver of the present invention has excellent thickening properties, shear stability and antioxidant properties.

Description

Viscosity index improver and preparation method and application thereof
Technical Field
The invention relates to a viscosity index improver, in particular to a viscosity index improver for lubricating oil.
Background
In recent years, with the increasing demand for environmental protection, there is a further demand for energy saving of mechanical equipment. The low viscosity of the lubricating oil can effectively save energy, but the problems of liquid leakage and poor lubrication exist, the method for improving the viscosity index of the lubricating oil is considered to be a method for better solving the contradiction, and various polymers (such as polyisobutylene, ethylene propylene olefin polymers and the like) are widely applied to automobile engine lubricating oil as viscosity index improvers to improve the viscosity characteristics of the lubricating oil related to high and low temperatures. As the viscosity index improver which is used at the earliest, Polymethacrylate (PMA) has excellent viscosity-temperature performance, oxidation stability and low-temperature performance, is widely applied to lubricating oil, but has poor shear stability and thickening capability.
CN 104178253A discloses methacrylic acid C2～C5Alkyl esters, methacrylic acid C7～C10Alkyl esters, methacrylic acid C11～C12Alkyl esters and methacrylic acid C13～C16The copolymer of alkyl ester has excellent shearing stability, low temperature performance, viscosity increasing performance and hydrolysis stability. CN 103965394B discloses the use of methacrylic acid C8～C12The PMA-type viscosity index improver is obtained by copolymerizing alkyl ester serving as a monomer, and has the characteristics of average molecular weight, low acid value, low condensation point, low-temperature viscosity, good shear stability, good viscosity-temperature performance and the like. CN 102295973A discloses the use of 20-80 mass% of methacrylic acid C1～C25Alkyl ester, 10-70 mass% of methacrylic acid C1～C20The copolymer is prepared by copolymerizing alkyl ester and 1-10 mass% of nitrogen-containing compound with carbon-carbon double bonds, and has good anti-wear performance and dispersing performance while keeping good pour point depression effect and shear stability. The viscosity index improver does not have oxidation resistance.
The cardanol is a main component of cashew nut shell oil, is a natural phenolic compound, is an important agricultural and sideline product for cashew nut production, and is wide in source and huge in storage amount. Therefore, the natural compound with rich sources and low cost is adopted as the raw material to synthesize the viscosity index improver, and the green chemistry definition and the strategic requirements of national sustainable development are met.
Disclosure of Invention
The invention provides a viscosity index improver, a preparation method and application thereof.
The viscosity index improver has a structure shown in a general formula (I):
Figure BDA0001830004890000021
wherein x sub-repeat units of the n repeat units may be the same or different, y sub-repeat units of the n repeat units may be the same or different, and z sub-repeat units of the n repeat units may be the same or different; r in x sub-repeating units1May be the same or different and are each independently selected from H and C1～C4Alkyl (preferably H and methyl), R in x sub-repeat units2May be the same or different and are each independently selected from H and C1～C6Alkyl (preferably C)1～C6Straight chain alkyl); r in z sub-repeat units1May be the same or different and are each independently selected from H and C1～C4Alkyl (preferably selected from H and methyl), R in z sub-repeat units3May be the same or different and are each independently selected from H and C7～C24Alkyl (preferably selected from H and C)8～C18Straight chain alkyl); r in y sub-repeat units1May be the same or different and are each independently selected from H and C1～C4Alkyl (preferably H and methyl), each group R present in y sub-repeat units4、R5、R6、R7、R8Are 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 each4、R5、R6、R7、R8At least one group in (a) is a group represented by the general formula (II);
Figure BDA0001830004890000022
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); radical R in m repeating units2' 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 single bond, C)1-4Linear or branched alkylene); radical R in m repeating units3' 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 single bond, C)1-4Linear or branched alkylene); radical R4' selected from hydrogen, C1-20Straight or branched alkyl (preferably selected from hydrogen, C)1-4Straight or branched chain alkyl); radical R in m repeating units5' 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 R in m repeating units6' 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); m is a positive integer (preferably a positive integer between 1 and 10, more preferably a positive integer between 1 and 3); x in the n repeating units can be the same or different and is respectively and independently selected from an integer of 0-3000 (preferably an integer of 10-1000), y in the n repeating units can be the same or different and is respectively and independently selected from an integer of 0-10000 (preferably an integer of 10-5000), at least one y is a positive integer, and z in the n repeating units can be the same or different and is respectively and independently selected from an integer of 0-5000 (preferably an integer of 10-2000); n is a positive integer of 2 to 5000 (preferably an integer of 10 to 3000); in each of the n repeating units, the sum of x, y, z is a positive integer.
According to the viscosity index improver of the present invention, preferably, R is in each of y sub-repeating units5、R6、R7One of the groups of (A) is represented by the general formula (II)The other two groups are H; more preferably, in each of the y sub-repeating units, R4、R6、R8Is hydrogen, R5、R7One of the groups of (a) is a group represented by the general formula (II), and the other is hydrogen.
According to the viscosity index improver, the weight average molecular weight of the viscosity index improver is preferably 10000-1000000, more preferably 50000-800000, and even more preferably 200000-700000.
The preparation method of the viscosity index improver comprises the following steps: carrying out polymerization reaction on optional a type monomers, optional b type monomers and c type monomers, and collecting a polymerization product;
the structure of the a-type monomer is as follows:
Figure BDA0001830004890000031
wherein R is1Selected from H and C1～C4Alkyl (preferably H and methyl), R2Selected from H and C1～C6Alkyl (preferably C)1～C6Straight chain alkyl); the a-type monomer is preferably one or more of methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate, and is more preferably methyl methacrylate and/or butyl methacrylate;
the structure of the b-type monomer is as follows:
Figure BDA0001830004890000041
wherein R is1Selected from H and C1～C4Alkyl (preferably H and methyl), R3Selected from H and C7～C24Alkyl (preferably selected from H and C)8～C18Straight chain alkyl); the b-type monomer is preferably hexyl methacrylate, octyl methacrylate, decyl methacrylate, isodecyl methacrylate (wherein the isodecyl group is 2-ethyl-octyl), dodecyl methacrylate, tetradecyl methacrylate, or dodecyl methacrylateOne or more of ditetradecyl methacrylate, cetyl methacrylate and stearyl methacrylate, more preferably one or more of decyl methacrylate, dodecyl methacrylate, tetradecyl methacrylate, dodecyl/tetradecyl methacrylate and cetyl methacrylate;
the structure of the c-type monomer is as follows:
Figure BDA0001830004890000042
wherein R is4、R5、R6、R7、R8Are 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 of the formula (II), with the proviso that R4、R5、R6、R7、R8At least one group in (a) is a group represented by the general formula (II);
Figure BDA0001830004890000043
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); radical R in m repeating units2' 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 single bond, C)1-4Linear or branched alkylene); radical R in m repeating units3' 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 single bond, C)1-4Linear or branched alkylene); radical R4' selected from hydrogen, C1-20Straight or branched alkyl (preferably selected from hydrogen, C)1-4Straight or branched chain alkyl); radical R in m repeating units5' the same or different from each other, each independentlySelected from hydrogen, C1-20Straight or branched chain alkyl (preferably each independently selected from hydrogen, C1-4Straight or branched chain alkyl); radical R in m repeating units6' 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); m is a positive integer (preferably a positive integer between 1 and 10, more preferably a positive integer between 1 and 3).
According to the preparation method of the present invention, in the c-type monomer, preferably, R5、R6、R7One of the groups of (a) is a group represented by the general formula (II), and the other two groups are H; more preferably, R4、R6、R8Is hydrogen, R5、R7One of the groups of (a) is a group represented by the general formula (II), and the other is hydrogen.
The c-type monomer is preferably one or more of 3-epoxytetradecylphenyl methacrylate, 3-epoxytetradecylphenyl acrylate, 3-epoxypentadecylphenyl methacrylate, 3-epoxypentadecylphenyl acrylate, 3-epoxyhexadecylphenyl methacrylate and 3-epoxyhexadecylphenyl acrylate, and is preferably 3-epoxypentadecylphenyl methacrylate and/or 3-epoxypentadecylphenyl acrylate.
The above-mentioned a-type monomer, b-type monomer and c-type monomer may be compounds of a single structure, or may be a mixture comprising compounds of different structures.
According to the preparation method of the present invention, preferably, the mass of the a-type monomer is 0 to 50% (preferably 5 to 30%) of the total mass, the mass of the b-type monomer is 0 to 80% (preferably 20 to 70%) of the total mass, and the mass of the c-type monomer is 10 to 60% (preferably 20 to 50%) of the total mass, based on the total mass of the a-type monomer, the b-type monomer and the c-type monomer.
According to the preparation method of the present invention, preferably, an initiator, preferably one or more of cumene hydroperoxide, 2 '-azobis (2, 4-dimethylbutyronitrile) and 2, 2' -azobis (2, 4-dimethylvaleronitrile) (ADVN), may be added to the polymerization reaction. The addition amount of the initiator is preferably 0.2-0.5% of the total mass of the a-type monomer, the b-type monomer and the c-type monomer.
According to the preparation method of the present invention, a chain transfer agent, preferably an alkyl mercaptan, such as Dodecyl Mercaptan (DM) and/or hexadecyl mercaptan, may be preferably added to the polymerization reaction. The addition amount of the chain transfer agent is preferably 0.1-0.25% of the total mass of the a-type monomer, the b-type monomer and the c-type monomer.
According to the preparation method of the present invention, preferably, a diluent, which may be mineral oil, ester oil and polyolefin, may be added in the polymerization reaction. The amount of the diluent added is preferably 10 to 200%, more preferably 20 to 100% of the total mass of the a-type monomer, the b-type monomer and the c-type monomer.
According to the preparation method of the invention, the temperature of the polymerization reaction is preferably 60-140 ℃, preferably 80-100 ℃; the polymerization time is 1 to 5 hours, preferably 2 to 4 hours. During the polymerization, an inert gas is preferably introduced, and for example, nitrogen gas may be introduced.
According to the preparation method of the invention, preferably, after the polymerization reaction is finished, the reaction product can be distilled under normal pressure or reduced pressure to remove volatile monomers and unreacted monomers, and the viscosity index improver can be obtained by collection.
According to the preparation method of the present invention, preferably, the preparation method of the c-type monomer comprises the steps of subjecting the phenol compound represented by the general formula (X) to epoxidation reaction, esterification reaction,
Figure BDA0001830004890000061
in the general formula (X), each group R4”、R5”、R6”、R7”、R8"equal to or different from each other, each independently selected from hydrogen, C1-300Straight or branched chain hydrocarbon radical (preferably C)1-30Linear or branched alkyl or polyolefin group having a number average molecular weight Mn of 300-3000), a salt thereof, a polymerA group represented by the formula (Y), wherein at least one group is selected from the group represented by the general formula (Y);
Figure BDA0001830004890000062
wherein the radical R1' is selected from a single bond, C1-20Straight or branched alkylene (preferably selected from single bond and C)1-4Linear or branched alkylene); radical R in m repeating units3' 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 single bond, C)1-4Linear or branched alkylene); radical R4' selected from hydrogen, C1-20Straight or branched alkyl (preferably selected from hydrogen, C)1-4Straight or branched chain alkyl); radical R in m repeating units5' 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 R in m repeating units6' 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); m is a positive integer (preferably a positive integer between 1 and 10, more preferably a positive integer between 1 and 3).
According to the process for preparing the monomer of class c of the present invention, in the general formula (X), preferably, the group R4”、R6”、R8"equal to or different from each other, each independently selected from hydrogen, C1-4A linear or branched alkyl group; radical R5”、R7"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).
According to the process for preparing a monomer of class c of the present invention, in the general formula (X), further preferably, the group R4”、R6”、R8"are identical or different from each otherAnd each is independently selected from hydrogen and C1-4A linear or branched alkyl group; radical R5”、R7One 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 preparing the c-type monomer of the present invention, the epoxidation reaction is a reaction of the phenol compound represented by the general formula (X) with an epoxidizing agent to obtain an epoxide of the phenol compound represented by the general formula (X). The epoxidizing agent is preferably a peroxide, and for example, one or more of hydrogen peroxide, formic acid peroxide, peracetic acid, peroxosulfonic acid, m-chloroperoxybenzoic acid, t-butyl hydroperoxide, t-butyl peroxyacetate, methyl ethyl ketone peroxide, dibenzoyl peroxide and cyclohexanone peroxide can be used. The molar ratio of the phenol compound represented by the general formula (X) to the epoxidizing agent is preferably 1: 1 to 10, more preferably 1: 2 to 5. The temperature of the epoxidation reaction is 0-100 ℃, preferably 10-80 ℃; 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 preparation method of the c-type monomer, a catalyst can be added or not added in the epoxidation reaction, and the catalyst is preferably 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).
According to the preparation method of the c-type monomer, a solvent can be added or not added in the epoxidation reaction, and the solvent is preferably added. The solvent is preferably a non-polar or weakly polar organic solvent, and for example, one or more of acetone, hexane, cyclohexane, petroleum ether, benzene, toluene, and xylene may be used. The mass of the solvent is 20 to 300%, preferably 80 to 200%, of the mass of the phenol compound represented by the general formula (X).
According to the preparation method of the c-type monomer, after the epoxidation reaction is finished, the reaction product can be purified, and the purification treatment method includes one or more of water washing, distillation, filtration, drying and recrystallization methods, and is not particularly limited; 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 method for preparing the c-type monomer of the present invention, preferably, the esterification reaction includes a step of subjecting the epoxide of the phenol compound represented by the general formula (X) to esterification reaction with the compound of the structure of the formula (Z);
Figure BDA0001830004890000071
wherein R is1Selected from H and C1～C4Alkyl (preferably H and methyl), X is selected from F, Cl, Br, I and OH (preferably Cl, Br).
According to the method for preparing the c-type monomer of the present invention, preferably, the molar ratio between the compound of the structure of formula (Z) and the phenol compound represented by the general formula (X) is 1: 1-10, preferably 1: 1 to 5.
According to the preparation method of the c-type monomer, the esterification reaction temperature is preferably 0-150 ℃, preferably 30-80 ℃: generally, the reaction time is preferably as long as possible, and may be 2 to 10 hours, preferably 4 to 8 hours. According to the preparation method of the c-type monomer, preferably, in the esterification reaction, a catalyst can be added or not be added, and the catalyst is preferably added. The catalyst is preferably C1～C10The organic amine and/or ammonia may be selected from one or more of methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine and ammonia. The amount of the catalyst to be added is preferably 0.1 to 20% by mass, more preferably 1 to 15% by mass, based on the mass of the phenol compound represented by the general formula (X).
According to the preparation method of the c-type monomer, a polymerization inhibitor can be added or not added in the esterification reaction, and the polymerization inhibitor is preferably added. The polymerization inhibitor is preferably selected from the group consisting of metal chlorides, phenolic polymerization inhibitors, quinoid polymerization inhibitors and metal powders, and for example, one or more of cuprous chloride, ferric trichloride, hydroquinone, benzoquinone and copper powder may be used. The amount of the polymerization inhibitor added is preferably 0.01 to 1% by mass, more preferably 0.05 to 0.5% by mass, based on the phenol compound represented by the general formula (X).
According to the preparation method of the c-type monomer, a solvent can be added or not added in the esterification reaction, and the solvent is preferably added. The solvent is preferably one or more of methanol, toluene, ethanol, acetone, chloroform and petroleum ether; the amount of the solvent to be added is preferably 10 to 120% by mass, more preferably 50 to 100% by mass, based on the phenol compound represented by the general formula (X).
According to the preparation method of the c-type monomer of the present invention, after the esterification reaction is finished, the reaction product may be subjected to a purification treatment, and the purification treatment may include one or more of water washing, distillation, filtration, drying and recrystallization methods, and is 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 BDA0001830004890000081
wherein R is C15H(31+x)And x is 0, -2, -4 or-6.
The viscosity index improver can be used as a viscosity index improver of lubricating oil.
The viscosity index improver disclosed by the invention has excellent thickening performance, shear stability and oxidation resistance.
Detailed Description
The present invention will be described in more detail with reference to examples. The invention is not so limited. All proportions and parts are by mass unless otherwise indicated.
In the context of the present invention, the straight-chain or branched-chain alkyl group may be a straight-chain or branched-chain alkyl group, may also be a straight-chain or branched-chain alkenyl group containing one or more (e.g., 1 to 5, 1 to 4, 1 to 3, 1 to 2) carbon-carbon double bonds, may also be a straight-chain or branched-chain alkynyl group containing one or more (e.g., 1 to 5, 1 to 4, 1 to 3, 1 to 2) carbon-carbon triple bonds, and may also be a straight-chain or branched-chain alkyl group containing one or more (e.g., 1 to 5, 1 to 4, 1 to 3, 1 to 2) carbon-carbon double bonds and carbon-carbon triple bonds.
In the present specification, the term "single bond" is sometimes used in the definition of a group. By "single bond", it is meant that the group is absent. For example, assume the formula-CH2-A-CH3Wherein the group a is defined as being selected from the group consisting of a single bond and a methyl group. In this respect, if A is a single bond, this means that the group A is absent, in which case the formula is correspondingly simplified to-CH2-CH3。
The main raw materials used are as follows:
cardanol, Shanghai Bingshi Binghe chemical science & technology Limited, Industrial products
The structure of the cardanol is shown as the following formula:
Figure BDA0001830004890000091
wherein R is C15H(31-X)And X is 0, 2,4 or 6. The cardanol is a compound with a single structure or a mixture containing a plurality of compounds with different structures.
Concentrated sulfuric acid, national drug group chemical reagent limited, analytically pure; hydrogen peroxide (30%), national drug group chemical reagent limited company, analytically pure; formic acid, national pharmaceutical group chemical reagents ltd, analytically pure;
methacryloyl chloride, national pharmaceutical group chemical reagents ltd, analytically pure; acryloyl chloride, national drug group chemical reagent limited, analytically pure; triethylamine, chemical reagent of national drug group, ltd, analytically pure;
alkyl methacrylate, national pharmaceutical group chemical reagents ltd, analytical purity; cuprous chloride, national drug group chemical reagents limited, chemically pure; 2, 2' -azobis (2, 4-dimethylvaleronitrile), lark waffle chemicals, analytically pure.
Example 1 preparation of epoxidized cardanol
100g of cardanol, 8g of formic acid, 0.3g of concentrated sulfuric acid and 200g of hydrogen peroxide are added into a three-neck flask with mechanical stirring, a reflux condenser and temperature control, and stirring and heating are 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, washing with 5% KOH solution by 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 red transparent liquid, namely the epoxidized cardanol. The conversion rate of the product is 96.2%, and the purity of the epoxidized cardanol is more than 98%.
Example 2 preparation of epoxidized cardanol
Adding 100g of cardanol into a three-neck flask with mechanical stirring, a reflux condenser and temperature control, starting stirring and heating. While maintaining the reaction temperature at 12 ℃, 150g of m-chloroperoxybenzoic acid was slowly added and reacted for 5 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 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 red transparent liquid, namely the epoxidized cardanol. The conversion rate of the product is 97.6%, and the purity of the epoxidized cardanol is more than 98%.
Example 3 preparation of 3-Oxopentadecylphenyl acrylate (PODPPA)
30g of the epoxidized cardanol obtained in example 1 was dissolved in 100ml of methanol, and after dissolving, the mixture was placed in a 250ml three-neck reaction flask, 0.5g of cuprous chloride was added, and stirring and heating were started. Maintaining the reaction temperature at 50 ℃, slowly dropping 9g of acryloyl chloride into the reaction flask, dropping 5g of triethylamine again after the dropping is finished, and then heating to 60 ℃ to continue the reaction for 5 hours. And after the reaction is finished, cooling to obtain a dark yellow transparent liquid. Filtering the reaction product, evaporating the solvent and the raw materials to obtain brownish red viscous liquid, namely the acrylic acid 3-epoxy pentadecyl phenyl ester. The product conversion was 62.2%.
Example 4 preparation of 3-Oxpentadecylphenyl Methacrylate (MODPA)
30g of the epoxidized cardanol obtained in example 2 was dissolved in 100ml of methanol, and after dissolving, the mixture was placed in a 250ml three-neck reaction flask, 0.5g of cuprous chloride was added, and stirring and heating were started. Maintaining the reaction temperature at 50 ℃, slowly dropping 10g of methacryloyl chloride into the reaction flask, dropping 5g of triethylamine again after the dropping is finished, and then heating to 60 ℃ to continue the reaction for 5 hours. And after the reaction is finished, cooling to obtain a dark yellow transparent liquid. And filtering the reaction product, and evaporating the solvent and the raw materials to obtain brownish red viscous liquid, namely the 3-epoxy pentadecyl phenyl methacrylate. The product conversion was 61.2%.
Examples 5 to 9 of viscosity index improvers and comparative example 1
The monomers of class a used in the polymerization reaction include: MMA, methyl methacrylate; BMA, butyl methacrylate; the b-type monomers used in the polymerization reaction include: DMA, decyl methacrylate; nTM, tetradecyl methacrylate; nDM, dodecyl methacrylate; nHM, cetyl methacrylate; the c-type monomers used in the polymerization reaction include: PODPA, 3-epoxypentadecylphenyl acrylate; MODPA, 3-epoxypentadecylphenyl methacrylate.
75 parts of Shanghai Gaoqiao No. 6 hydrogenated oil (diluent) was charged into a reactor equipped with a stirring, heating and cooling device, a dropping funnel, a thermometer, and a nitrogen line. In another reaction flask, 100 parts in total of the monomers shown in Table 1, and the amounts of the initiator and the chain transfer agent shown in Table 1 were charged, and the mixture was stirred at room temperature and charged into a dropping funnel. Starting a reactor to stir, heating the reactor to 90 ℃, opening a dropping funnel under the protection of nitrogen, slowly dropping the solution, finishing dropping within 5 hours, continuing to react for 2 hours at 90 ℃ after dropping, then carrying out reduced pressure distillation on the reaction product at the vacuum degree of 100Pa and the distillation temperature of 120 ℃, removing volatile monomers, obtaining a uniform solution containing 57% of viscosity index improver and 43% of diluent, and respectively naming the viscosity index improver therein as S-1-S-5 and B-1.
TABLE 1
Figure BDA0001830004890000111
Example 10 viscosity measurement and shear stability test
When PAO2 was used as a base fluid, the viscosity index improver solutions obtained in examples 5 to 9 and comparative example 1 were added to the base fluid to obtain lubricating oil compositions, which contained the base fluid, a diluent and a viscosity index improver in the viscosity index improver solutions, wherein the mass fractions of the viscosity index improvers S-1 to S-5 and B-1 in the lubricating oil compositions are shown in table 2. The lubricating oil composition obtained above was subjected to viscosity measurement and shear stability test. Measuring the change of the viscosity of the lubricating oil composition along with the temperature according to GB/T265 'petroleum product kinematic viscosity determination method and dynamic viscometer algorithm', and measuring the kinematic viscosity at 100 ℃; the shear stability test is carried out by adopting SH/T0505 'method for measuring shear stability of polymer-containing oil', the lubricating oil composition is respectively radiated and treated for 15 minutes in an ultrasonic oscillator, the liquid viscosity before and after ultrasonic shearing is measured, and the shear stability index (SSI value) is determined, generally, the lower the SSI value is, the better the shear stability of the measured polymer solution is. The SSI values and viscosity measurements of the respective lubricating oil compositions are shown in Table 2. As can be seen from Table 2, the viscosity index improver provided by the invention has strong thickening capability at low dosage, good low-temperature fluidity and better shear stability.
TABLE 2
Figure BDA0001830004890000121
Example 11 Oxidation resistance test
The viscosity index improver solutions of examples 5 to 9 and comparative example 1 were dissolved in shanghai gaoqiao 6# hydrogenated oil to prepare solutions with a viscosity index improver mass fraction of 10%, and the solutions were subjected to oxidation resistance tests respectively, wherein the test apparatus was a TA5000 model DSC apparatus manufactured by TA corporation, and the test conditions were as follows: 180 ℃, the oxygen pressure is 0.5MPa, the temperature rising speed is 10 ℃/min, and the test results are shown in table 3.
TABLE 3
Figure BDA0001830004890000131
As can be seen from Table 3, the viscosity index improver of the present invention has a significant antioxidant property as compared with the conventional viscosity index improver.

Claims (13)

1.一种黏度指数改进剂，其结构如通式(I)所示：1. a viscosity index improver, its structure is shown in general formula (I):
Figure FDA0001830004880000011
Figure FDA0001830004880000011
 其中，n个重复单元的x个子重复单元可以相同或不同，n个重复单元的y个子重复单元可以相同或不同，n个重复单元的z个子重复单元可以相同或不同；x个子重复单元中的R1可以相同或不同，各自独立地选自H和C1～C4烷基(优选H和甲基)，x个子重复单元中的R2可以相同或不同，各自独立地选自H和C1～C6烷基(优选C1～C6直链烷基)；z个子重复单元中的R1可以相同或不同，各自独立地选自H和C1～C4烷基(优选选自H和甲基)，z个子重复单元中的R3可以相同或不同，各自独立地选自H和C7～C24烷基(优选选自H和C8～C18直链烷基)；y个子重复单元中的R1可以相同或不同，各自独立地选自H和C1～C4烷基(优选H和甲基)，y个子重复单元中存在的各基团R4、R5、R6、R7、R8彼此相同或不同，各自独立地选自氢、C1-300直链或支链烃基(优选C1-30直链或支链烷基或者数均分子量Mn为300-3000的聚烯烃基)、通式(II)所示的基团，前提是各基团R4、R5、R6、R7、R8中的至少一个基团是通式(II)所示的基团；Wherein, the x sub-repeating units of the n repeating units may be the same or different, the y sub-repeating units of the n repeating units may be the same or different, and the z sub-repeating units of the n repeating units may be the same or different; R 1 may be the same or different, each independently selected from H and C 1 -C 4 alkyl (preferably H and methyl), and R 2 in the x sub-repeating units may be the same or different, each independently selected from H and C 1 -C 6 alkyl group (preferably C 1 -C 6 straight-chain alkyl group); R 1 in the z sub-repeating units may be the same or different, each independently selected from H and C 1 -C 4 alkyl group (preferably selected from H and methyl), R 3 in the z sub-repeating units may be the same or different, each independently selected from H and C 7 -C 24 alkyl (preferably selected from H and C 8 -C 18 straight-chain alkyl); R 1 in the y sub-repeating units may be the same or different, and each is independently selected from H and C 1 -C 4 alkyl (preferably H and methyl), and each group R 4 , R 5 present in the y sub-repeating units , R 6 , R 7 , R 8 are the same or different from each other, each independently selected from hydrogen, C 1-300 straight or branched chain hydrocarbon group (preferably C 1-30 straight or branched chain alkyl or number average molecular weight Mn is 300-3000 polyolefin group), the group represented by the general formula (II), provided that at least one group in each group R 4 , R 5 , R 6 , R 7 , R 8 is the general formula (II) ) shown in the group;
Figure FDA0001830004880000012
Figure FDA0001830004880000012
 在通式(II)中，基团R1'选自单键、C1-20直链或支链的亚烷基(优选选自单键和C1-4直链或支链的亚烷基)；m个重复单元中的基团R2'彼此相同或不同，各自独立地选自单键、C1-20直链或支链的亚烷基(优选各自独立地选自单键、C1-4直链或支链的亚烷基)；m个重复单元中的基团R3'彼此相同或不同，各自独立地选自单键、C1-20直链或支链的亚烷基(优选各自独立地选自单键、C1-4直链或支链的亚烷基)；基团R4'选自氢、C1-20直链或支链烷基(优选选自氢、C1-4直链或支链烷基)；m个重复单元中的基团R5'彼此相同或不同，各自独立地选自氢、C1-20直链或支链烷基(优选各自独立地选自氢、C1-4直链或支链烷基)；m个重复单元中的基团R6'彼此相同或不同，各自独立地选自氢、C1-20直链或支链烷基(优选各自独立地选自氢、C1-4直链或支链烷基)；m为正整数(优选1～10之间的正整数，更优选1～3之间的正整数)；n个重复单元中的x可以相同或不同，各自独立地选自0～3000的整数(优选10～1000的整数)，n个重复单元中的y可以相同或不同，各自独立地选自0～10000的整数(优选10～5000的整数)，且至少一个y为正整数，n个重复单元中的z可以相同或不同，各自独立地选自0～5000的整数(优选10～2000的整数)；n为2到5000的正整数(优选10～3000的整数)；在n个重复单元的每个重复单元中，x、y、z之和为正整数。In the general formula (II), the group R 1 ' is selected from a single bond, a C 1-20 linear or branched alkylene (preferably selected from a single bond and a C 1-4 linear or branched alkylene) group); the groups R 2 ' in the m repeating units are the same or different from each other, each independently selected from a single bond, a C 1-20 linear or branched alkylene group (preferably each independently selected from a single bond, C 1-4 straight-chain or branched alkylene); groups R 3 ' in m repeating units are the same or different from each other, each independently selected from single bond, C 1-20 straight-chain or branched alkylene Alkyl (preferably each independently selected from single bond, C 1-4 linear or branched alkylene); group R 4 ' is selected from hydrogen, C 1-20 linear or branched alkyl (preferably selected from hydrogen, C 1-4 linear or branched alkyl); the groups R 5 ' in m repeating units are the same or different from each other, each independently selected from hydrogen, C 1-20 linear or branched alkyl (preferably each independently selected from hydrogen, C 1-4 straight or branched chain alkyl); the groups R 6 ' in m repeating units are the same or different from each other, each independently selected from hydrogen, C 1-20 straight chain Chain or branched alkyl (preferably each independently selected from hydrogen, C 1-4 linear or branched alkyl); m is a positive integer (preferably a positive integer between 1-10, more preferably between 1-3 positive integers); x in the n repeating units may be the same or different, each independently selected from an integer of 0-3000 (preferably an integer of 10-1000), and y in the n repeating units may be the same or different, each independently is independently selected from an integer from 0 to 10000 (preferably an integer from 10 to 5000), and at least one y is a positive integer, and z in the n repeating units may be the same or different, and each is independently selected from an integer from 0 to 5000 (preferably 10 ～2000 integer); n is a positive integer from 2 to 5000 (preferably an integer from 10 to 3000); in each repeating unit of n repeating units, the sum of x, y, z is a positive integer. 2.按照权利要求1所述的黏度指数改进剂，其特征在于，在y个子重复单元的每个子重复单元中，R5、R6、R7的其中一个基团为通式(II)所示的基团，其它两个基团为H(优选地，在y个子重复单元的每个子重复单元中，R4、R6、R8为氢，R5、R7的其中一个基团为通式(II)所示的基团，另外一个为氢)。2. The viscosity index improver according to claim 1, characterized in that, in each sub-repeat unit of the y sub-repeat units, one of the groups of R 5 , R 6 and R 7 is represented by the general formula (II) The group shown, the other two groups are H (preferably, in each sub-repeating unit of the y sub-repeating units, R 4 , R 6 , R 8 are hydrogen, and one of the groups of R 5 , R 7 is The group represented by the general formula (II), the other one is hydrogen). 3.按照权利要求1所述的黏度指数改进剂，其特征在于，所述黏度指数改进剂的重均分子量为10000～1000000(优选50000～800000，更优选200000～700000)。3. The viscosity index improver according to claim 1, wherein the weight average molecular weight of the viscosity index improver is 10,000-1,000,000 (preferably 50,000-800,000, more preferably 200,000-700,000). 4.一种黏度指数改进剂的制备方法，包括：将任选的a类单体、任选的b类单体与c类单体进行聚合反应，收集聚合产物；4. A preparation method of a viscosity index improver, comprising: carrying out a polymerization reaction with optional a-type monomers, optional b-type monomers and c-type monomers, and collecting a polymerization product; 所述a类单体的结构为：The structure of the a-type monomer is:
Figure FDA0001830004880000021
Figure FDA0001830004880000021
 其中R1选自H和C1～C4烷基(优选H和甲基)，R2选自H和C1～C6烷基(优选C1～C6直链烷基)；wherein R 1 is selected from H and C 1 -C 4 alkyl (preferably H and methyl), and R 2 is selected from H and C 1 -C 6 alkyl (preferably C 1 -C 6 straight-chain alkyl); 所述b类单体的结构为：The structure of the b-type monomer is:
Figure FDA0001830004880000031
Figure FDA0001830004880000031
 其中R1选自H和C1～C4烷基(优选H和甲基)，R3选自H和C7～C24烷基(优选选自H和C8～C18直链烷基)；wherein R 1 is selected from H and C 1 -C 4 alkyl (preferably H and methyl), R 3 is selected from H and C 7 -C 24 alkyl (preferably selected from H and C 8 -C 18 straight chain alkyl ); 所述c类单体的结构为：The structure of the class c monomer is:
Figure FDA0001830004880000032
Figure FDA0001830004880000032
 其中的R4、R5、R6、R7、R8彼此相同或不同，各自独立地选自氢、C1-300直链或支链烃基(优选C1-30直链或支链烷基或者数均分子量Mn为300-3000的聚烯烃基)、通式(II)所示的基团，前提是R4、R5、R6、R7、R8中的至少一个基团是通式(II)所示的基团；wherein R 4 , R 5 , R 6 , R 7 , R 8 are the same or different from each other, and are each independently selected from hydrogen, C 1-300 straight or branched chain hydrocarbon groups (preferably C 1-30 straight or branched chain alkanes) base or polyolefin base with a number average molecular weight Mn of 300-3000), a group represented by the general formula (II), provided that at least one group in R 4 , R 5 , R 6 , R 7 , R 8 is A group represented by general formula (II);
Figure FDA0001830004880000033
Figure FDA0001830004880000033
 在通式(II)中，基团R1'选自单键、C1-20直链或支链的亚烷基(优选选自单键和C1-4直链或支链的亚烷基)；m个重复单元中的基团R2'彼此相同或不同，各自独立地选自单键、C1-20直链或支链的亚烷基(优选各自独立地选自单键、C1-4直链或支链的亚烷基)；m个重复单元中的基团R3'彼此相同或不同，各自独立地选自单键、C1-20直链或支链的亚烷基(优选各自独立地选自单键、C1-4直链或支链的亚烷基)；基团R4'选自氢、C1-20直链或支链烷基(优选选自氢、C1-4直链或支链烷基)；m个重复单元中的基团R5'彼此相同或不同，各自独立地选自氢、C1-20直链或支链烷基(优选各自独立地选自氢、C1-4直链或支链烷基)；m个重复单元中的基团R6'彼此相同或不同，各自独立地选自氢、C1-20直链或支链烷基(优选各自独立地选自氢、C1-4直链或支链烷基)；m为正整数(优选1～10之间的正整数，更优选1～3之间的正整数)。In the general formula (II), the group R 1 ' is selected from a single bond, a C 1-20 linear or branched alkylene (preferably selected from a single bond and a C 1-4 linear or branched alkylene) group); the groups R 2 ' in the m repeating units are the same or different from each other, each independently selected from a single bond, a C 1-20 linear or branched alkylene group (preferably each independently selected from a single bond, C 1-4 straight-chain or branched alkylene); groups R 3 ' in m repeating units are the same or different from each other, each independently selected from single bond, C 1-20 straight-chain or branched alkylene Alkyl (preferably each independently selected from single bond, C 1-4 linear or branched alkylene); group R 4 ' is selected from hydrogen, C 1-20 linear or branched alkyl (preferably selected from hydrogen, C 1-4 linear or branched alkyl); the groups R 5 ' in m repeating units are the same or different from each other, each independently selected from hydrogen, C 1-20 linear or branched alkyl (preferably each independently selected from hydrogen, C 1-4 straight or branched chain alkyl); the groups R 6 ' in m repeating units are the same or different from each other, each independently selected from hydrogen, C 1-20 straight chain Chain or branched alkyl (preferably each independently selected from hydrogen, C 1-4 linear or branched alkyl); m is a positive integer (preferably a positive integer between 1-10, more preferably between 1-3 positive integer). 5.按照权利要求4所述的制备方法，其特征在于，在所述c类单体中，R5、R6、R7的其中一个基团为通式(II)所示的基团，其它两个基团为H(优选地，R4、R6、R8为氢，R5、R7的其中一个基团为通式(II)所示的基团，另外一个为氢)。5. The preparation method according to claim 4, characterized in that, in the c-type monomer, one of the groups of R 5 , R 6 , and R 7 is a group represented by the general formula (II), The other two groups are H (preferably, R 4 , R 6 , R 8 are hydrogen, one of R 5 , R 7 is a group represented by general formula (II), and the other is hydrogen). 6.按照权利要求4所述的制备方法，其特征在于，所述a类单体选自甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯和甲基丙烯酸丁酯中的一种或多种(优选甲基丙烯酸甲酯和/或甲基丙烯酸丁酯)；所述b类单体选自甲基丙烯酸己酯、甲基丙烯酸辛酯、甲基丙烯酸癸酯、甲基丙烯酸异癸酯(其中的异癸基为2-乙基-辛基)、甲基丙烯酸十二烷基酯、甲基丙烯酸十四烷基酯、甲基丙烯酸十二/十四混合烷基酯、甲基丙烯酸十六烷基酯和甲基丙烯酸十八烷基酯中的一种或多种(优选甲基丙烯酸癸酯、甲基丙烯酸十二烷基酯、甲基丙烯酸十四烷基酯、甲基丙烯酸十二/十四混合烷基酯和甲基丙烯酸十六烷基酯中的一种或多种)；所述c类单体选自甲基丙烯酸3-环氧十四烷基苯基酯、丙烯酸3-环氧十四烷基苯基酯、甲基丙烯酸3-环氧十五烷基苯基酯、丙烯酸3-环氧十五烷基苯基酯、甲基丙烯酸3-环氧十六烷基苯基酯和丙烯酸3-环氧十六烷基苯基酯中的一种或多种(优选甲基丙烯酸3-环氧十五烷基苯基酯和/或丙烯酸3-环氧十五烷基苯基酯)。6. according to the described preparation method of claim 4, it is characterized in that, described a type monomer is selected from methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate. One or more (preferably methyl methacrylate and/or butyl methacrylate); the b-type monomer is selected from hexyl methacrylate, octyl methacrylate, decyl methacrylate, methacrylic acid Isodecyl ester (wherein the isodecyl group is 2-ethyl-octyl), dodecyl methacrylate, tetradecyl methacrylate, mixed dodecyl methacrylate/tetradecyl methacrylate, One or more of cetyl methacrylate and octadecyl methacrylate (preferably decyl methacrylate, dodecyl methacrylate, tetradecyl methacrylate, one or more of dodecyl/tetradecyl methacrylate and cetyl methacrylate); the c-type monomer is selected from 3-epoxytetradecylbenzene methacrylate base ester, 3-epoxytetradecylphenyl acrylate, 3-epoxypentadecylphenyl methacrylate, 3-epoxypentadecylphenyl acrylate, 3-ring methacrylate One or more of oxyhexadecyl phenyl ester and 3-epoxy hexadecyl phenyl acrylate (preferably 3-epoxy pentadecyl phenyl methacrylate and/or 3-epoxy pentadecyl phenyl acrylate) epoxy pentadecyl phenyl ester). 7.按照权利要求4所述的制备方法，其特征在于，按照a类单体、b类单体与c类单体的总质量计，所述a类单体的质量为总质量的0～50％(优选5％～30％)，所述b类单体的质量为总质量的0～80％(优选20％～70％)，所述c类单体的质量为总质量的10％～60％(优选20％～50％)。7 . The preparation method according to claim 4 , wherein, according to the total mass of the a-type monomer, the b-type monomer and the c-type monomer, the mass of the a-type monomer is 0~ 50% (preferably 5%-30%), the mass of the b-type monomer is 0-80% (preferably 20-70%) of the total mass, and the mass of the c-type monomer is 10% of the total mass ~60% (preferably 20% to 50%). 8.按照权利要求4所述的制备方法，其特征在于，在所述的聚合反应中加入引发剂(优选氢过氧化异丙苯、2,2’-偶氮双(2,4-二甲基丁腈)和2,2’-偶氮双(2,4-二甲基戊腈)(ADVN)中的一种或多种)；在所述的聚合反应中加入链转移剂(所述链转移剂优选烷基硫醇)。8. according to the described preparation method of claim 4, it is characterized in that, in described polymerization reaction, add initiator (preferably cumene hydroperoxide, 2,2'-azobis (2,4-dimethyl benzene) One or more of 2,2'-azobis(2,4-dimethylvaleronitrile) (ADVN); adding a chain transfer agent (the described polymerization reaction) The chain transfer agent is preferably an alkylthiol). 9.按照权利要求4所述的制备方法，其特征在于，所述聚合反应的温度为60℃～140℃(优选80℃～100℃)；聚合反应的时间为1h～5h(优选2h～4h)；在所述聚合反应过程中通入惰性气体(优选)通入氮气。9. The preparation method according to claim 4, characterized in that, the temperature of the polymerization reaction is 60°C to 140°C (preferably 80°C to 100°C); the time of the polymerization reaction is 1h to 5h (preferably 2h to 4h). ); inert gas (preferably) nitrogen is passed through during the polymerization reaction. 10.按照权利要求4所述的制备方法，其特征在于，所述c类单体的制备方法包括使通式(X)所示的酚化合物发生环氧化反应、酯化反应的步骤，10. The preparation method according to claim 4, wherein the preparation method of the c-type monomer comprises the steps of epoxidizing and esterifying the phenolic compound represented by the general formula (X),
Figure FDA0001830004880000051
Figure FDA0001830004880000051
 通式(X)中，各基团R4”、R5”、R6”、R7”、R8”彼此相同或不同，各自独立地选自氢、C1-300直链或支链烃基(优选C1-30直链或支链烷基或者数均分子量Mn为300-3000的聚烯烃基)、通式(Y)所示的基团，其中至少一个基团选自通式(Y)所示的基团；In the general formula (X), each group R 4 ", R 5 ", R 6 ", R 7 ", R 8 " is the same or different from each other, and each is independently selected from hydrogen, C 1-300 straight chain or branched chain Hydrocarbyl group (preferably C 1-30 straight or branched chain alkyl group or polyolefin group with number average molecular weight Mn of 300-3000), group represented by general formula (Y), wherein at least one group is selected from general formula ( Y) the group shown;
Figure FDA0001830004880000052
Figure FDA0001830004880000052
 其中基团R1'选自单键、C1-20直链或支链的亚烷基(优选选自单键和C1-4直链或支链的亚烷基)；m个重复单元中的基团R3'彼此相同或不同，各自独立地选自单键、C1-20直链或支链的亚烷基(优选各自独立地选自单键、C1-4直链或支链的亚烷基)；基团R4'选自氢、C1-20直链或支链烷基(优选选自氢、C1-4直链或支链烷基)；m个重复单元中的基团R5'彼此相同或不同，各自独立地选自氢、C1-20直链或支链烷基(优选各自独立地选自氢、C1-4直链或支链烷基)；m个重复单元中的基团R6'彼此相同或不同，各自独立地选自氢、C1-20直链或支链烷基(优选各自独立地选自氢、C1-4直链或支链烷基)；m为正整数(优选1～10之间的正整数，更优选1～3之间的正整数)。wherein the group R 1 ' is selected from a single bond, a C 1-20 linear or branched alkylene group (preferably selected from a single bond and a C 1-4 linear or branched alkylene group); m repeating units The groups R 3 ' in are the same or different from each other, each independently selected from a single bond, a C 1-20 straight or branched alkylene group (preferably each independently selected from a single bond, a C 1-4 straight chain or branched alkylene); group R 4 ' is selected from hydrogen, C 1-20 linear or branched alkyl (preferably selected from hydrogen, C 1-4 linear or branched alkyl); m repeats The groups R 5 ' in the unit are the same or different from each other, each independently selected from hydrogen, C 1-20 linear or branched alkyl (preferably each independently selected from hydrogen, C 1-4 linear or branched alkane) group); the groups R 6 ' in the m repeating units are the same or different from each other, each independently selected from hydrogen, C 1-20 straight or branched chain alkyl (preferably each independently selected from hydrogen, C 1-4 straight or branched chain alkyl); m is a positive integer (preferably a positive integer between 1-10, more preferably a positive integer between 1-3). 11.按照权利要求4所述的制备方法，其特征在于，所述环氧化反应是将通式(X)所示的酚化合物与环氧化剂发生反应，得到通式(X)所示酚化合物的环氧化物；所述酯化反应包括使所述通式(X)所示酚化合物的环氧化物与式(Z)结构的化合物发生酯化反应的步骤；11. preparation method according to claim 4 is characterized in that, described epoxidation reaction is to react the phenolic compound shown in general formula (X) and epoxidizing agent, obtain phenolic compound shown in general formula (X) The epoxide; the esterification reaction includes the step of esterification reaction between the epoxide of the phenolic compound represented by the general formula (X) and the compound of the formula (Z) structure;
Figure FDA0001830004880000053
Figure FDA0001830004880000053
 其中R1选自H和C1～C4烷基(优选H和甲基)，X选自F、Cl、Br、I和OH(优选Cl、Br)。wherein R 1 is selected from H and C 1 -C 4 alkyl (preferably H and methyl), and X is selected from F, Cl, Br, I and OH (preferably Cl, Br). 12.按照权利要求4所述的制备方法，其特征在于，通式(X)所示的酚化合物来源于天然植物腰果。12. The preparation method according to claim 4, wherein the phenolic compound represented by the general formula (X) is derived from a natural plant cashew. 13.权利要求1～3之一的黏度指数改进剂和由权利要求4～12之一方法制得的黏度指数改进剂用作润滑油的黏度指数改进剂。13. The viscosity index improver of one of claims 1 to 3 and the viscosity index improver obtained by the method of one of claims 4 to 12 are used as a viscosity index improver for lubricating oils.
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