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CN111057606B - Viscosity index improver and preparation method and application thereof - Google Patents

Viscosity index improver and preparation method and application thereof Download PDF

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Publication number
CN111057606B
CN111057606B CN201811201081.6A CN201811201081A CN111057606B CN 111057606 B CN111057606 B CN 111057606B CN 201811201081 A CN201811201081 A CN 201811201081A CN 111057606 B CN111057606 B CN 111057606B
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linear
independently selected
radical
hydrogen
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CN111057606A (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

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):

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～C16Alkyl radicalThe ester copolymer has excellent shear 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 units2Can be the same or different and are each independently selectedFrom 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 a group represented by the general formula (II), and 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 one or more of hexyl methacrylate, octyl methacrylate, decyl methacrylate, isodecyl methacrylate (wherein the isodecyl group is 2-ethyl-octyl), dodecyl methacrylate, tetradecyl methacrylate, dodecyl/tetradecyl mixed alkyl methacrylate, hexadecyl methacrylate and octadecyl methacrylate, and more preferably one or more of decyl methacrylate, dodecyl methacrylate, tetradecyl methacrylate, dodecyl/tetradecyl mixed alkyl methacrylate and hexadecyl 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' 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 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、R7Wherein one group is general formulaAnd the other of the groups of formula (II) 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)1-30A linear or branched alkyl group or a polyolefin group having a number average molecular weight Mn of 300-3000), a group represented by the general formula (Y), wherein at least one group is selected from the group represented by the general formula (Y);
Figure 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 chain orBranched 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"equal to or different from each other, each independently selected from hydrogen, 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 single bondsAnd 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 (25)

1. A viscosity index improver has a structure shown in a general formula (I):
Figure FDA0003385336130000011
wherein x sub-repeat units of the n repeat units are the same or different from each other, y sub-repeat units of the n repeat units are the same or different from each other, and z sub-repeat units of the n repeat units are the same or different from each other; r in x sub-repeating units1Are the same or different from each other and are each independently selected from H and C1～C4Alkyl, R in x sub-repeat units2Are the same or different from each other and are each independently selected from H and C1～C6An alkyl group; r in z sub-repeat units1Are the same or different from each other and are each independently selected from H and C1～C4Alkyl, R in z sub-repeat units3Are the same or different from each other and are each independently selected from H and C7～C24An alkyl group; r in y sub-repeat units1Are the same or different from each other and are each independently selected from H and C1～C4Alkyl, each radical 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 C1-300A linear or branched hydrocarbon radical, a radical of the formula (II), with the proviso that each radical R4、R5、R6、R7、R8At least one group in (a) is a group represented by the general formula (II);
Figure FDA0003385336130000012
in the general formula (II), the group R1' is selected from a single bond, C1-20A linear or branched alkylene group; radical R in m repeating units2' same or different from each other, each independently selected from the group consisting of a single bond, C1-20A linear or branched alkylene group; radicals in m repeating unitsGroup R3' same or different from each other, each independently selected from the group consisting of a single bond, C1-20A linear or branched alkylene group; radical R4' selected from hydrogen, C1-20Radical R in m repeating units of a linear or branched alkyl radical5' same or different from each other, each independently selected from hydrogen, C1-20A linear or branched alkyl group; radical R in m repeating units6' same or different from each other, each independently selected from hydrogen, C1-20A linear or branched alkyl group; m is a positive integer; x in the n repeating units are the same or different from each other and are respectively and independently selected from integers of 0-3000, y in the n repeating units are the same or different from each other and are respectively and independently selected from integers of 0-10000, at least one y is a positive integer, z in the n repeating units are the same or different from each other and are respectively and independently selected from integers of 0-5000; n is a positive integer from 2 to 5000; in each of the n repeating units, the sum of x, y, z is a positive integer.
2. The viscosity index improver of claim 1 wherein R in x of the sub-repeat units1Each independently selected from H and methyl, R in x sub-repeat units2Each independently selected from H and C1～C6A linear alkyl group; r in z sub-repeat units1Each independently selected from H and methyl, R in z sub-repeat units3Each independently selected from H and C8～C18A linear alkyl group; r in y sub-repeat units1Each independently selected from H and methyl, each group R present in y sub-repeat units4、R5、R6、R7、R8Each independently selected from hydrogen and C1-30A 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);
in the general formula (II), the group R1' is selected from the group consisting of a single bond and C1-4A linear or branched alkylene group; radical R in m repeating units2' each is independently selected from the group consisting of a single bond, C1-4A linear or branched alkylene group; radical R in m repeating units3' each is independently selected from the group consisting of a single bond, C1-4A linear or branched alkylene group; radical R4' selected from hydrogen, C1-4A linear or branched alkyl group; radical R in m repeating units5' each is independently selected from hydrogen, C1-4A linear or branched alkyl group; radical R in m repeating units6' each is independently selected from hydrogen, C1-4A linear or branched alkyl group; m is 1-10; x in the n repeating units is independently selected from an integer of 10-1000, y in the n repeating units is independently selected from an integer of 10-5000, and z in the n repeating units is independently selected from an integer of 10-2000; n is an integer of 10 to 3000.
3. The viscosity index improver of claim 1 wherein R is in each of the y sub-repeat units5、R6、R7One of the radicals of (A) is a radical of the formula (II), R4、R8The radical is H.
4. The viscosity index improver of claim 1 wherein R is in each of the y sub-repeat units4、R6、R8Is hydrogen, R5、R7One of the groups of (a) is a group represented by the general formula (II), and the other is hydrogen.
5. The viscosity index improver according to claim 1, wherein the viscosity index improver has a weight average molecular weight of 10000 to 1000000.
6. The viscosity index improver according to claim 1, wherein the viscosity index improver has a weight average molecular weight of 50000 to 800000.
7. The viscosity index improver according to claim 1, wherein the viscosity index improver has a weight average molecular weight of 200000 to 700000.
8. A method for preparing a viscosity index improver, comprising: 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 FDA0003385336130000031
wherein R is1Selected from H and C1～C4Alkyl radical, R2Selected from H and C1～C6An alkyl group;
the structure of the b-type monomer is as follows:
Figure FDA0003385336130000032
wherein R is1Selected from H and C1～C4Alkyl radical, R3Selected from H and C7～C24An alkyl group;
the structure of the c-type monomer is as follows:
Figure FDA0003385336130000033
wherein R is4、R5、R6、R7、R8Are the same or different from each other and are each independently selected from hydrogen and C1-300A linear or branched hydrocarbon group, 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 FDA0003385336130000034
in the general formula (II), the group R1' is selected from a single bond, C1-20A linear or branched alkylene group; radical R in m repeating units2' itThe same or different, each independently selected from the group consisting of a single bond, C1-20A linear or branched alkylene group; radical R in m repeating units3' same or different from each other, each independently selected from the group consisting of a single bond, C1-20A linear or branched alkylene group; radical R4' selected from hydrogen, C1-20A linear or branched alkyl group; radical R in m repeating units5' same or different from each other, each independently selected from hydrogen, C1-20A linear or branched alkyl group; radical R in m repeating units6' same or different from each other, each independently selected from hydrogen, C1-20A linear or branched alkyl group; m is a positive integer.
9. The process according to claim 8, wherein R is1Selected from H and methyl; r2Selected from H and C1～C6A linear alkyl group; r3Selected from H and C8～C18A linear alkyl group; r4、R5、R6、R7、R8Each independently selected from hydrogen and C1-30A 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);
in the general formula (II), the group R1' is selected from the group consisting of a single bond and C1-4A linear or branched alkylene group; radical R in m repeating units2' each is independently selected from the group consisting of a single bond, C1-4A linear or branched alkylene group; radical R in m repeating units3' each is independently selected from the group consisting of a single bond, C1-4A linear or branched alkylene group; radical R4' selected from hydrogen, C1-4A linear or branched alkyl group; radical R in m repeating units5' each is independently selected from hydrogen, C1-4A linear or branched alkyl group; radical R in m repeating units6' each is independently selected from hydrogen, C1-4A linear or branched alkyl group; m is a positive integer between 1 and 10.
10. The process according to claim 8, wherein in said c-type monomer, R is5、R6、R7WhereinOne group being a group of the formula (II), R4、R8The radical is H.
11. The process according to claim 8, wherein in said c-type monomer, R is4、R6、R8Is hydrogen, R5、R7One of the groups of (a) is a group represented by the general formula (II), and the other is hydrogen.
12. The method according to claim 8, wherein the a-type monomer is selected from one or more of methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate; the b-type monomer is selected from one or more of hexyl methacrylate, octyl methacrylate, decyl methacrylate, isodecyl methacrylate, dodecyl methacrylate, tetradecyl methacrylate, dodecyl/tetradecyl methacrylate, hexadecyl methacrylate and octadecyl methacrylate; the c-type monomer is selected from one or more of 3-epoxy tetradecyl phenyl methacrylate, 3-epoxy tetradecyl phenyl acrylate, 3-epoxy pentadecyl phenyl methacrylate, 3-epoxy pentadecyl phenyl acrylate, 3-epoxy hexadecyl phenyl methacrylate and 3-epoxy hexadecyl phenyl acrylate.
13. The process according to claim 8, wherein the monomer of group a is selected from methyl methacrylate and/or butyl methacrylate; the b type monomer is selected from one or more of decyl methacrylate, dodecyl methacrylate, tetradecyl methacrylate, dodecyl/tetradecyl mixed alkyl methacrylate and hexadecyl methacrylate; the c-type monomer is selected from 3-epoxy pentadecyl phenyl methacrylate and/or 3-epoxy pentadecyl phenyl acrylate.
14. The process according to claim 8, wherein the mass of the group a monomer is 0 to 50% of the total mass, the mass of the group b monomer is 0 to 80% of the total mass, and the mass of the group c monomer is 10 to 60% of the total mass, based on the total mass of the group a monomer, the group b monomer and the group c monomer.
15. The process according to claim 8, wherein the mass of the group a monomer is 5 to 30% of the total mass, the mass of the group b monomer is 20 to 70% of the total mass, and the mass of the group c monomer is 20 to 50% of the total mass, based on the total mass of the group a monomer, the group b monomer and the group c monomer.
16. The process according to claim 8, wherein an initiator is added to the polymerization reaction; adding chain transfer agent into the polymerization reaction.
17. The process according to claim 16, wherein the initiator is selected from one or more of cumene hydroperoxide, 2 '-azobis (2, 4-dimethylbutyronitrile) and 2, 2' -azobis (2, 4-dimethylvaleronitrile) (ADVN); the chain transfer agent is selected from alkyl mercaptans.
18. The process according to claim 8, wherein the polymerization reaction temperature is 60 ℃ to 140 ℃; the time of the polymerization reaction is 1-5 h; and introducing inert gas in the polymerization reaction process.
19. The process according to claim 8, wherein the polymerization reaction is carried out at a temperature of 80 ℃ to 100 ℃; the time of the polymerization reaction is 2 to 4 hours; nitrogen was passed during the polymerization.
20. The process according to claim 8, wherein the c-type monomer is prepared by a process comprising the steps of subjecting the phenol compound represented by the general formula (X) to epoxidation reaction and esterification reaction,
Figure FDA0003385336130000051
in the general formula (X), each group R4”、R5”、R6”、R7”、R8"equal to or different from each other, each independently selected from hydrogen, C1-300A linear or branched hydrocarbon group, a group represented by the general formula (Y), wherein at least one group is selected from the group represented by the general formula (Y);
Figure FDA0003385336130000052
wherein the radical R1' is selected from a single bond, C1-20A linear or branched alkylene group; radical R in m repeating units3' same or different from each other, each independently selected from the group consisting of a single bond, C1-20A linear or branched alkylene group; radical R4' selected from hydrogen, C1-20A linear or branched alkyl group; radical R in m repeating units5' same or different from each other, each independently selected from hydrogen, C1-20A linear or branched alkyl group; radical R in m repeating units6' same or different from each other, each independently selected from hydrogen, C1-20A linear or branched alkyl group; m is a positive integer.
21. The process according to claim 20, wherein in the formula (X), each group R4”、R5”、R6”、R7”、R8Each independently selected from hydrogen, C1-30A 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); radical R1' is selected from the group consisting of a single bond and C1-4A linear or branched alkylene group; radical R in m repeating units3' each is independently selected from the group consisting of a single bond, C1-4A linear or branched alkylene group; radical R4' selected from hydrogen, C1-4A linear or branched alkyl group; radical R in m repeating units5' each is independently selected from hydrogen,C1-4A linear or branched alkyl group; radical R in m repeating units6' each is independently selected from hydrogen, C1-4A linear or branched alkyl group; m is a positive integer between 1 and 10.
22. The process according to claim 20, wherein 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 esterification reaction comprises a step of subjecting an epoxide of the phenol compound represented by the general formula (X) to esterification reaction with a compound of the structure of the formula (Z);
Figure FDA0003385336130000061
wherein R is1Selected from H and C1～C4Alkyl, X is selected from F, Cl, Br, I and OH.
23. The process according to claim 22, wherein R is1Selected from H and methyl, and X is selected from Cl and Br.
24. The method according to claim 20, wherein the phenol compound represented by the general formula (X) is derived from a natural plant cashew nut.
25. The viscosity index improver according to any one of claims 1 to 7 and the viscosity index improver obtained by the method according to any one of claims 8 to 24 are used as a viscosity index improver for lubricating oil.
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