CN113249158B - Pour point depressant, preparation method and application thereof - Google Patents
Pour point depressant, preparation method and application thereof Download PDFInfo
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- CN113249158B CN113249158B CN202010090408.8A CN202010090408A CN113249158B CN 113249158 B CN113249158 B CN 113249158B CN 202010090408 A CN202010090408 A CN 202010090408A CN 113249158 B CN113249158 B CN 113249158B
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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
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- 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
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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
- 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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Abstract
The invention provides a pour point depressant, a preparation method and application thereof. The structure of the pour point depressant is shown as a general formula (I):
Description
Technical Field
The invention relates to the field of lubricating oil additives, in particular to a pour point depressant for lubricating oil.
Background
The lubricating oil is used as a liquid lubricant for various machines, and has the functions of lubrication, cooling, rust prevention, cleaning, sealing, buffering and the like, so that the friction is reduced, and the machines are protected. At present, crude oil produced in China has high wax content, and particularly, along with continuous depletion of petroleum resources, the wax content of the produced crude oil is increased year by year, so that lubricating oil prepared from the high-wax crude oil has the defects of high condensation point, poor low-temperature flow property and the like, and the service performance of the lubricating oil is seriously influenced. In order to improve the service performance and meet the development requirements of modern society, new additives are needed to improve the low-temperature fluidity of oil products and reduce the freezing point of the oil products, so that the application range of lubricating oil is expanded.
Pour point depressants are compounds that are chemically polymerized to lower the freezing point or cold filter plugging point of the oil. To improve the low temperature properties of base oils, it is common to treat the oils in a dewaxing process to improve their low temperature flow properties. However, in the dewaxing process, in order to obtain a lower freezing point of the oil product, the temperature of the dewaxing process is usually continuously reduced, which increases energy consumption and increases cost, and in order to solve the above problems and achieve deep pour point reduction, the deep pour point reduction is generally achieved by adding a pour point reducer to the oil product. The pour point depressant sold in the market has more types, wherein the poly (methyl) acrylate has strong adaptability in structure, composition and preparation process, has excellent pour point depressing performance in base oil, and is an important component of the pour point depressant market at home and abroad. A variety of poly (meth) acrylate pour point depressants have been developed.
CN105524209A and CN107540783A disclose preparation methods of polyacrylate pour point depressants, which contain polymers obtained by copolymerization of a plurality of alkyl acrylate monomers and have better pour point depressing effect. CN104530306A discloses the use of methacrylic acid C 16 The PMA pour point depressant obtained by copolymerizing alkyl ester, styrene and maleic anhydride has the characteristics of high purity, high yield, good pour point depression effect and the like. CN102101900A discloses the use of methacrylic acid C 8 ～C 16 The copolymer pour point depressant obtained by copolymerizing alkyl ester and vinyl acetate has stable performance and better pour point depression effect. However, none of the above pour point depressants have antioxidant properties.
Disclosure of Invention
The invention provides a pour point depressant, a preparation method and application thereof.
The structure of the pour point depressant is shown as the general formula (I):
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 units 1 Are the same or different from each other and are each independently selected from H and C 1 ～C 4 Alkyl (preferably H and methyl), R in x sub-repeating units 2 Are the same or different from each other, and are each independentlySelected from H and C 1 ～C 10 Alkyl (preferably C) 6 ～C 10 Straight chain alkyl);
r in z sub-repeat units 1 Are the same or different from each other and are each independently selected from H and C 1 ～C 4 Alkyl (preferably selected from H and methyl), R in z sub-repeat units 3 Are the same or different from each other and are each independently selected from H and C 10 ～C 24 Alkyl (preferably selected from H and C) 12 ～C 20 Straight chain alkyl);
r in y sub-repeating units 4 Are the same or different from each other and are each independently selected from H, C 1 ～C 10 Alkyl and a group of formula (II) (preferably selected from H and C) 1 ～C 8 Alkyl groups); r in y sub-repeat units 5 Are the same or different from each other and are each independently selected from C 1 ～C 10 And a group of formula (III) (preferably selected from C) 1 ～C 8 Alkylene groups of (a);
in formula (II), the radical R 1 ' is selected from a single bond, C 1-20 Straight or branched alkylene (preferably selected from single bond and C) 1-4 Linear or branched alkylene); radical R in m repeating units 2 ' same or different from each other, each independently selected from the group consisting of a single bond, C 1-20 Straight or branched alkylene (preferably each independently selected from the group consisting of a single bond, C 1-4 Linear or branched alkylene); radical R 3 ' is selected from hydrogen, C 1-20 Straight or branched alkyl (preferably selected from hydrogen, C) 1-4 Straight or branched chain alkyl); radical R in m repeating units 4 ' 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); radical R in m repeating units 5 ' 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 chainOr a branched alkyl group); m is a positive integer (preferably a positive integer between 1 and 10, more preferably a positive integer between 1 and 3);
in formula (III), the radical R 1 "is selected from a single bond, C 1-20 Straight or branched alkylene (preferably selected from single bond and C) 1-4 Linear or branched alkylene); radical R in m' repeating units 2 "the same or different from each other, each independently selected from the group consisting of a single bond, C 1-20 Straight or branched alkylene (preferably each independently selected from the group consisting of a single bond, C 1-4 Straight or branched chain alkylene); radical R 3 "is selected from C 1-20 Straight or branched alkylene (preferably selected from C) 1-4 Linear or branched alkylene); radical R in m' repeating units 4 "identical to 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); radical R in m' repeating units 5 "equal to 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 and 10, more preferably a positive integer between 1 and 3);
r in y sub-repeat units 6 、R 7 、R 8 、R 9 、R 10 Are the same or different from each other and are each independently selected from H, OH, C 1 ～C 20 Straight or branched chain alkyl, a group of formula (II) (preferably selected from H, OH, C) 1 ～C 10 Straight or branched chain alkyl);
at least one OH exists on each benzene ring molecule in the y sub-repeating units;
x in the n repeating units are the same or different from each other and are each independently selected from an integer of 0 to 3000 (preferably an integer of 10 to 1000), y in the n repeating units are the same or different from each other and are each independently selected from an integer of 0 to 10000 (preferably an integer of 10 to 5000), and at least one y is a positive integer, and z in the n repeating units are the same or different from each other and are each independently selected from an integer of 0 to 5000 (preferably an integer of 10 to 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.
The pour point depressant according to the present invention is preferably such that R is present on each benzene ring molecule of y sub-repeating units 6 、R 8 、R 10 Are the same or different from each other and are each independently selected from H, C 1 ～C 4 A linear or branched alkyl group; r 7 、R 9 Are the same or different from each other and are each independently selected from H, OH, C 1 ～C 10 A linear or branched alkyl group, and R 7 、R 9 At least one group in (a) is OH.
More preferably, R is present in each benzene ring molecule of y repeating subunits 6 、R 8 、R 10 Are the same or different from each other and are each independently selected from H, C 1 ～C 4 A linear or branched alkyl group, and R 8 Is tert-butyl; r 7 、R 9 One group is OH and the other group is H.
According to the pour point depressant of the present invention, the weight average molecular weight of the pour point depressant is preferably 3000 to 1000000, more preferably 5000 to 300000, and still more preferably 10000 to 100000.
The preparation method of the pour point depressant comprises the following steps: carrying out polymerization reaction on optional a-type monomers, b-type monomers and c-type monomers, and collecting a polymerization product;
the structure of the a-type monomer is as follows:
wherein R is 1 Is selected from H and C 1 ～C 4 Alkyl (preferably H and methyl), R 2 Selected from H and C 1 ～C 10 Alkyl (preferably C) 6 ～C 10 Straight chain alkyl). The monomer a is preferably hexyl methacrylate or heptyl methacrylateOne or more of an ester, octyl methacrylate, decyl methacrylate, isodecyl methacrylate (wherein the isodecyl group is 2-ethyl-octyl), more preferably octyl methacrylate and/or decyl methacrylate.
The structure of the b-type monomer is as follows:
wherein R is 1 Is selected from H and C 1 ～C 4 Alkyl (preferably H and methyl), R 3 Selected from H and C 10 ～C 24 Alkyl (preferably selected from H and C) 12 ～C 20 Straight chain alkyl). The b-type monomer is preferably one or more of lauryl methacrylate, tetradecyl methacrylate, dodecyl/tetradecyl mixed methacrylate, hexadecyl methacrylate, octadecyl methacrylate and eicosyl methacrylate, and more preferably one or more of lauryl methacrylate, tetradecyl methacrylate, hexadecyl methacrylate, octadecyl methacrylate and eicosyl methacrylate.
The structure of the c-type monomer is as follows:
wherein R is 4 Selected from H, C 1 ～C 10 Alkyl and a group of formula (II) (preferably selected from H and C) 1 ～C 8 Alkyl); r 5 Is selected from C 1 ～C 10 And a group of formula (III) (preferably selected from C) 1 ～C 8 Alkylene groups of (a); r 6 、R 7 、R 8 、R 9 、R 10 Are the same or different from each other and are independently selected from H, OH, C 1 ～C 20 Straight or branched chain alkyl, a group of formula (II) (preferably selected from H, OH, C) 1 ～C 10 Straight or branched chain alkyl); r 6 、R 7 、R 8 、R 9 、R 10 At least one group of (a) is OH; for reasons of space, the radicals of the formula (II) and of the formula (III) are as defined above.
The c-type monomer is preferably one or more of cardanol, o-methyl cardanol (methyl is preferably positioned at the ortho position of phenolic hydroxyl group) and o-tert-butyl cardanol (tert-butyl is preferably positioned at the ortho position of phenolic hydroxyl group), and more preferably o-tert-butyl cardanol.
According to the invention, R in the c-type monomer molecule 7 、R 9 One group in (1) is OH, R 8 In the case of H, the polymerization may be carried out after the alkylation reaction (preferably, the tertiary butylation reaction) of the c-type monomer. The alkylation reaction (preferably tertiary butylation) is carried out by reacting the c-type monomer with an alkylating agent (tertiary butylation agent). The alkylating agent is selected from halogenated hydrocarbons, fatty alcohols and olefins, preferably from C 1-4 Alkyl halide and C 2-4 For example, one or more of tert-butyl chloride, tert-butyl bromide, isopropene and isobutylene can be used (the tert-butyl alkylating agent is preferably one or more of tert-butyl chloride, tert-butyl bromide and isobutylene). The molar ratio between said c-type monomer and said alkylating agent is preferably 1: 1 to 5, more preferably 1: 1 to 2.5; the temperature of the alkylation reaction is preferably 20-100 ℃, and more preferably 40-80 ℃; generally, the longer the reaction time, the higher the conversion, and the time for the alkylation reaction is preferably 0.5 to 10 hours, more preferably 3 to 5 hours, in view of the conversion of the reaction and the economy of the reaction. A catalyst can be added or not added in the alkylation reaction, and preferably the catalyst is added; the catalyst comprises one or more of metal chloride, inorganic acid, organic acid and Lewis acid, preferably metal chloride and inorganic acid, for example, one or more of zinc chloride, aluminum chloride, stannic chloride, concentrated sulfuric acid, concentrated hydrochloric acid, concentrated nitric acid, boron trifluoride and heteropoly acid. The mass of the catalyst is preferably 0.1% to 10%, more preferably 1% to 6%, of the mass of the c-type monomer. A solvent can be added or not added in the alkylation reaction, and the solvent is preferably added; the solution isThe solvent is preferably one or more of hydrocarbon solvents, alcohol solvents, ether solvents and ketone solvents, and for example, one or more of hexane, cyclohexane, benzene, toluene, xylene, methanol, ethanol, propanol, butanol, methyl ether, ethyl ether, propyl ether, butyl ether, acetone and methyl ethyl ketone may be used, and preferably, hydrocarbon solvents and/or alcohol solvents are used. The mass of the solvent is preferably 10 to 1000%, more preferably 50 to 500%, of the mass of the c-type monomer. The c-type monomer is preferably selected from cardanol (derived from natural plant cashew), the main component of which is meta-phenol, and the structure of the c-type monomer is as follows:
wherein R is C 15 H 31+x And x is 0, -2, -4 or-6.
According to the present invention, after the alkylation reaction is completed, the alkylation product may be subjected to a purification treatment by one or more methods selected from water washing, water washing after acid washing, water washing after alkali washing, distillation, filtration, drying and recrystallization, without particular limitation.
According to the preparation method of the present invention, preferably, R 4 、R 8 Is H, R 5 、R 6 、R 7 Wherein one group is C 1 ～C 20 Straight or branched alkyl (preferably C) 1 ～C 20 Straight chain alkyl), the other two groups are H; more preferably, R 4 、R 6 、R 8 Is H, R 5 、R 7 Wherein one group is C 1 ～C 20 Straight or branched chain alkyl (preferably C) 1 ～C 20 Straight chain alkyl) and the other is H.
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 20% (preferably 2 to 15%) of the total mass, the mass of the b-type monomer is 50 to 90% (preferably 60 to 80%) of the total mass, and the mass of the c-type monomer is 1 to 30% (preferably 5 to 25%) 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 may be added to the polymerization reaction, and the diluent may be mineral oil, ester oil and polyolefin. 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 pour point depressant of the invention is collected.
The pour point depressant of the present invention can be used as a pour point depressant for lubricating oils.
The pour point depressant has an outstanding pour point depression effect, good adaptability and strong 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.
The main raw materials used are as follows:
cardanol, Shanghai Bingshi Binghe chemical science & technology Limited, Industrial products
Zinc chloride, chemical reagents of national drug group, Ltd, analytical purity
Sodium bicarbonate, national pharmaceutical group chemical reagents, Inc., analytical purity
Sodium hydroxide, national pharmaceutical group chemical reagents, Inc., analytical purity
Tert-butyl chloride, national pharmaceutical group chemical reagents, Inc., analytical purity
Alkyl methacrylate, national pharmaceutical group chemical reagents, Ltd, analytical purity
2, 2' -azobis (2, 4-dimethylvaleronitrile), lark waffle Chemicals, Inc., analytical purity
Dodecyl mercaptan, national pharmaceutical group chemical reagents, chemical purity
Example 12 preparation of tert-butyl Cardanol
30g of cardanol is dissolved in 100ml of cyclohexane, the mixture is placed into a 250ml three-neck reaction flask after being dissolved, 1.5g of zinc chloride catalyst is added, stirring is started, and heating is carried out. While maintaining the reaction temperature at 50 ℃, 9.5g of t-butyl chloride was slowly added dropwise to the reaction flask, and the reaction was continued for 5 hours after the completion of the dropwise addition. And cooling after the reaction is finished to obtain a brownish red transparent liquid. Filtering the reaction product, washing with 5% KOH solution, washing with distilled water to neutrality, distilling at 1000Pa and 120 deg.C under reduced pressure for 1h, removing solvent, water and unreacted raw materials, and cooling to obtain brown yellow liquid. The product conversion was 81.3%.
The following raw materials are monomers used in the polymerization reaction of the present invention:
the monomers of a type are as follows:
SMA: octyl methacrylate;
DMA: decyl methacrylate;
the b type monomers are as follows:
nDM: dodecyl methacrylate;
nFM: tetradecyl methacrylate;
nHM: cetyl methacrylate;
nEM: octadecyl methacrylate;
nTM: eicosyl methacrylate;
the c-type monomer was 2-tert-butyl cardanol prepared in example 1.
Examples 2 to 4 and comparative example 1
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, stirring, 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 conditions of vacuum degree of 100Pa and distillation temperature of 120 ℃ to remove volatile monomers, obtaining uniform solution containing 57% of pour point depressant and 43% of diluent, respectively naming the pour point depressant as S-1-S-3 and B-1, wherein the weight average molecular weight (liquid chromatography) results are shown in Table 1.
TABLE 1
Example 5 pour Point testing
The pour point depressant solutions obtained in examples 2 to 4 and comparative example 1 were added to different base oils to prepare lubricating oil compositions, and the formulation compositions thereof are shown in table 2. These compositions were tested for pour point. The pour points of the lubricating oil compositions were measured according to GB/T3535 "Petroleum products pour Point test" and are shown in Table 2.
TABLE 2 composition of lubricating oil compositions and pour point test results
As can be seen from Table 2, the pour point depressant of the present invention has a prominent pour point depressing effect and good adaptability.
Example 6 Oxidation resistance test
The pour point depressant solutions obtained in the embodiments 2 to 4 and the comparative example 1 are respectively dissolved in Shanghai Gaoqiao No. 6 hydrogenated oil to prepare a solution with 10% (m/m) of pour point depressant, and the oxidation resistance test is performed, the test results are shown in Table 3, the test instrument is a TA5000 DSC instrument of the American TA company, and the test conditions are as follows: 180 ℃, oxygen pressure of 0.5MPa and heating speed of 10 ℃/min.
As can be seen from Table 3, the pour point depressant of the present invention has more excellent antioxidant properties than conventional pour point depressants.
TABLE 3 evaluation of antioxidant Properties
Claims (26)
1. The structure of the pour point depressant is shown as the general formula (I):
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 units 1 Are the same or different from each other and are each independently selected from H and C 1 ～C 4 Alkyl, R in x sub-repeat units 2 Are the same or different from each other and are each independently selected from H and C 1 ～C 10 An alkyl group;
r in z sub-repeat units 1 Are the same or different from each other and are each independently selected from H and C 1 ～C 4 Alkyl, R in z sub-repeat units 3 Are the same or different from each other and are each independently selected from H and C 10 ～C 24 An alkyl group;
r in y sub-repeat units 4 Are the same or different from each other and are each independently selected from H, C 1 ～C 10 Alkyl and a group of formula (II); r in y sub-repeat units 5 Are the same or different from each other and are each independently selected from C 1 ～C 10 Alkylene groups of formula (III);
in formula (II), the radical R 1 ' is selected from the group consisting of a single bond, C 1-20 A linear or branched alkylene group; radical R in m repeating units 2 ' the same or different from each other, each independently selected from the group consisting of a single bond, C 1-20 A linear or branched alkylene group; radical R 3 ' selected from hydrogen, C 1-20 A linear or branched alkyl group; radical R in m repeating units 4 ' same or different from each other, each independently selected from hydrogen, C 1-20 A linear or branched alkyl group; radical R in m repeating units 5 ' same or different from each other, each independently selected from hydrogen, C 1-20 A linear or branched alkyl group; m is a positive integer between 1 and 10;
in formula (III), the radical R 1 '' is selected from the group consisting of a single bond, C 1-20 A linear or branched alkylene group; radical R in m' repeating units 2 '' are the same or different from each other and are each independently selected from the group consisting of a single bond, C 1-20 A linear or branched alkylene group; radical R 3 '' is selected from C 1-20 A linear or branched alkylene group; m' number ofRadical R in the repeating unit 4 '' are the same or different from each other and are each independently selected from hydrogen, C 1-20 A linear or branched alkyl group; radical R in m' repeating units 5 '' are the same or different from each other and are each independently selected from hydrogen, C 1-20 A linear or branched alkyl group; m' is a positive integer between 1 and 10;
r in y sub-repeat units 6 、R 7 、R 8 、R 9 、R 10 Are the same or different from each other and are each independently selected from H, OH, C 1 ～C 20 A linear or branched alkyl group, a group of formula (II);
at least one OH exists on each benzene ring molecule in y sub-repeating units;
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 pour point depressant of claim 1, wherein R in x number of sub-repeating units 1 Each independently selected from H and methyl, R in x sub-repeat units 2 Each independently selected from H and C 6 ～C 10 A linear alkyl group;
r in z sub-repeat units 1 Each independently selected from H and methyl, R in z sub-repeat units 3 Each independently selected from H and C 12 ～C 20 A linear alkyl group; r in y sub-repeat units 4 Each independently selected from H and C 1 ～C 8 An alkyl group; r in y sub-repeating units 5 Each independently selected from C 1 ～C 8 An alkylene group of (a);
in formula (II), the radical R 1 ' is selected from the group consisting of a single bond and C 1-4 A linear or branched alkylene group; radicals R in m repeating units 2 ' each is independently selected fromKey, C 1-4 A linear or branched alkylene group; radical R 3 ' selected from hydrogen, C 1-4 A linear or branched alkyl group; radical R in m repeating units 4 ' each is independently selected from hydrogen, C 1-4 A linear or branched alkyl group; radical R in m repeating units 5 ' each is independently selected from hydrogen, C 1-4 A linear or branched alkyl group; m is a positive integer between 1 and 3;
in formula (III), the radical R 1 '' is selected from the group consisting of a single bond and C 1-4 A linear or branched alkylene group; radical R in m' repeating units 2 '' are each independently selected from the group consisting of a single bond, C 1-4 A linear or branched alkylene group; radical R 3 '' is selected from C 1-4 A linear or branched alkylene group; radical R in m' repeating units 4 '' are each independently selected from hydrogen, C 1-4 A linear or branched alkyl group; radical R in m' repeating units 5 '' are each independently selected from hydrogen, C 1-4 A linear or branched alkyl group; m' is a positive integer between 1 and 3;
r in y sub-repeat units 6 、R 7 、R 8 、R 9 、R 10 Each independently selected from H, OH, C 1 ～C 10 A linear or branched alkyl group;
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 pour point depressant of claim 1, wherein R is on each benzene ring molecule of the y sub-repeating units 6 、R 8 、R 10 Are the same or different from each other and are each independently selected from H, C 1 ～C 4 A linear or branched alkyl group; r 7 、R 9 Are the same or different from each other and are each independently selected from H, OH, C 1 ～C 10 A linear or branched alkyl group, and R 7 、R 9 At least one group in (a) is OH.
4. Push buttonThe pour point depressant of claim 1, wherein R is on each benzene ring molecule of the y sub-repeat units 6 、R 8 、R 10 Are the same or different from each other and are each independently selected from H, C 1 ～C 4 A linear or branched alkyl group, and R 8 Is tert-butyl; r 7 、R 9 One group is OH and the other group is H.
5. The pour point depressant according to claim 1, wherein the weight average molecular weight of the pour point depressant is 3000 to 1000000.
6. The pour point depressant according to claim 1, wherein the weight average molecular weight of the pour point depressant is 5000 to 300000.
7. A method of preparing a pour point depressant, comprising: carrying out polymerization reaction on optional a-type monomers, b-type monomers and c-type monomers, and collecting a polymerization product;
the structure of the a-type monomer is as follows:
wherein R is 1 Selected from H and C 1 ～C 4 Alkyl radical, R 2 Selected from H and C 1 ～C 10 An alkyl group;
the structure of the b-type monomer is as follows:
wherein R is 1 Selected from H and C 1 ～C 4 Alkyl radical, R 3 Selected from H and C 10 ～C 24 An alkyl group;
the structure of the c-type monomer is as follows:
wherein R is 4 Selected from H, C 1 ～C 10 Alkyl and a group of formula (II); r 5 Is selected from C 1 ～C 10 Alkylene groups of formula (III); r 6 、R 7 、R 8 、R 9 、R 10 Are the same or different from each other and are each independently selected from H, OH, C 1 ～C 20 A linear or branched alkyl group, a group of formula (II); r 6 、R 7 、R 8 、R 9 、R 10 At least one group of (a) is OH;
in formula (II), the radical R 1 ' is selected from a single bond, C 1-20 A linear or branched alkylene group; radical R in m repeating units 2 ' the same or different from each other, each independently selected from the group consisting of a single bond, C 1-20 A linear or branched alkylene group; radical R 3 ' selected from hydrogen, C 1-20 A linear or branched alkyl group; radical R in m repeating units 4 ' same or different from each other, each independently selected from hydrogen, C 1-20 A linear or branched alkyl group; radical R in m repeating units 5 ' same or different from each other, each independently selected from hydrogen, C 1-20 A linear or branched alkyl group; m is a positive integer between 1 and 10;
in formula (III), the radical R 1 '' is selected from single bond, C 1-20 A linear or branched alkylene group; radical R in m' repeating units 2 '' are the same or different from each other and are each independently selected from the group consisting of a single bond, C 1-20 A linear or branched alkylene group; radical R 3 '' is selected from C 1-20 A linear or branched alkylene group; radical R in m' repeating units 4 '' are identical to each otherOr different, each independently selected from hydrogen, C 1-20 A linear or branched alkyl group; radical R in m' repeating units 5 '' are the same or different from each other and are each independently selected from hydrogen, C 1-20 A linear or branched alkyl group; m' is a positive integer between 1 and 10.
8. The method according to claim 7,
in the monomers of type a, R 1 Selected from H and methyl, R 2 Selected from H and C 6 ～C 10 Linear alkyl;
in monomers of type b, R 1 Selected from H and methyl, R 3 Selected from H and C 12 ～C 20 Linear alkyl;
in the monomers of type c, R 4 Selected from H and C 1 ～C 8 An alkyl group; r 5 Is selected from C 1 ～C 8 An alkylene group of (a); r 6 、R 7 、R 8 、R 9 、R 10 Each independently selected from H, OH, C 1 ～C 10 A linear or branched alkyl group;
in formula (II), the radical R 1 ' is selected from the group consisting of a single bond and C 1-4 A linear or branched alkylene group; radicals R in m repeating units 2 ' Each is independently selected from the group consisting of a single bond, C 1-4 A linear or branched alkylene group; radical R 3 ' selected from hydrogen, C 1-4 A linear or branched alkyl group; radicals R in m repeating units 4 ' Each is independently selected from hydrogen, C 1-4 A linear or branched alkyl group; radicals R in m repeating units 5 ' each is independently selected from hydrogen, C 1-4 A linear or branched alkyl group; m is a positive integer between 1 and 3;
in formula (III), the radical R 1 '' is selected from the group consisting of a single bond and C 1-4 A linear or branched alkylene group; radical R in m' repeating units 2 '' are each independently selected from the group consisting of a single bond, C 1-4 A linear or branched alkylene group; radical R 3 '' is selected from C 1-4 A linear or branched alkylene group; radical R in m' repeating units 4 '' are each independently selected from hydrogen, C 1-4 A linear or branched alkyl group; m' repeatsRadical R in the unit 5 '' are each independently selected from hydrogen, C 1-4 A linear or branched alkyl group; m' is a positive integer between 1 and 3.
9. The method of claim 7, wherein,
the a-type monomer is one or more of hexyl methacrylate, heptyl methacrylate, octyl methacrylate, decyl methacrylate and isodecyl methacrylate; the b-type monomer is one or more of dodecyl methacrylate, tetradecyl methacrylate, dodecyl/tetradecyl mixed methacrylate, hexadecyl methacrylate, octadecyl methacrylate and eicosyl methacrylate; the c-type monomer is one or more of cardanol, o-methyl cardanol and o-tert-butyl cardanol.
10. The method according to claim 7, wherein R in said c-type monomer molecule is 7 、R 9 One group in (1) is OH, R 8 And in the case of H, performing the polymerization reaction after the alkylation reaction of the c type monomer.
11. The method according to claim 7, wherein R in said c-type monomer molecule is 7 、R 9 One group in (1) is OH, R 8 And in the case of H, carrying out the polymerization reaction after carrying out the tertiary butylation reaction on the c type monomer.
12. The process of claim 10 wherein said alkylation reaction is carried out by reacting said c-type monomer with an alkylating agent; the alkylating agent is selected from the group consisting of halogenated hydrocarbons, fatty alcohols and olefins.
13. The process according to claim 11, wherein said tertiary butylation reaction is carried out by reacting said c-type monomer with a tertiary butylation agent; the tert-butyl alkylating agent is selected from one or more of tert-butyl chloride, tert-butyl bromide and isobutene.
14. The process according to claim 10, wherein the molar ratio between said c-type monomer and said alkylating agent is 1: 1-5; the temperature of the alkylation reaction is 20-100 ℃.
15. The process according to claim 10, wherein a catalyst is added to the alkylation reaction; the catalyst comprises one or more of a metal chloride, an inorganic acid, an organic acid, and a lewis acid.
16. The process according to claim 10, wherein a catalyst is added to the alkylation reaction; the catalyst is selected from one or more of zinc chloride, aluminum chloride, stannic chloride, concentrated sulfuric acid, concentrated hydrochloric acid, concentrated nitric acid, boron trifluoride and heteropoly acid.
17. The method according to claim 10, wherein the c-type monomer is cardanol.
18. The method according to claim 7, wherein R is 4 、R 8 Is H, R 5 、R 6 、R 7 Wherein one group is C 1 ～C 20 Straight or branched chain alkyl, the other two groups being H.
19. The process according to claim 7, wherein R is 4 、R 6 、R 8 Is H, R 5 、R 7 Wherein one group is C 1 ～C 20 Straight or branched chain alkyl, the other group being H.
20. The process according to claim 7, wherein the mass of the group a monomer is 0 to 20% of the total mass, the mass of the group b monomer is 50 to 90% of the total mass, and the mass of the group c monomer is 1 to 30% of the total mass, based on the total mass of the group a monomer, the group b monomer and the group c monomer.
21. The process according to claim 7, wherein the mass of the group a monomer is 2 to 15%, the mass of the group b monomer is 60 to 80%, and the mass of the group c monomer is 5 to 25% of the total mass, based on the total mass of the group a monomer, the group b monomer and the group c monomer.
22. The process of claim 7 wherein one or more of an initiator, a chain transfer agent and a diluent is added to the polymerization reaction.
23. The process according to claim 7, wherein the polymerization reaction temperature is 60 ℃ to 140 ℃; the time of the polymerization reaction is 1-5 h.
24. The process according to claim 7, 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.
25. The process according to claim 7, wherein an inert gas is introduced during the polymerization.
26. Use of a pour point depressant according to any one of claims 1 to 6 or prepared by the process of claims 7 to 25 in a lubricating oil.
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