CN111057180B - Viscosity index improver and preparation method and application thereof - Google Patents
Viscosity index improver and preparation method and application thereof Download PDFInfo
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- CN111057180B CN111057180B CN201811201083.5A CN201811201083A CN111057180B CN 111057180 B CN111057180 B CN 111057180B CN 201811201083 A CN201811201083 A CN 201811201083A CN 111057180 B CN111057180 B CN 111057180B
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- 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
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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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- 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
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
Technical Field
The invention relates to a viscosity index improver, in particular to a viscosity index improver for lubricating oil.
Background
In recent years, with the increasing demand for environmental protection, there is a further demand for energy saving of mechanical equipment. The low viscosity of the lubricating oil can effectively save energy, but the problems of liquid leakage and poor lubrication exist, the method for improving the viscosity index of the lubricating oil is considered to be a method for better solving the contradiction, and various polymers (such as polyisobutylene, ethylene propylene olefin polymers and the like) are widely applied to automobile engine lubricating oil as viscosity index improvers to improve the viscosity characteristics of the lubricating oil related to high and low temperatures. As the viscosity index improver which is used at the earliest, Polymethacrylate (PMA) has excellent viscosity-temperature performance, oxidation stability and low-temperature performance, is widely applied to lubricating oil, but has poor shear stability and thickening capability.
CN 104178253A discloses methacrylic acid C2～C5Alkyl esters, methacrylic acid C7～C10Alkyl esters, methacrylic acid C11～C12Alkyl esters and methacrylic acid C13～C16The copolymer of alkyl ester has excellent shearing stability, low temperature performance, viscosity increasing performance and hydrolysis stability. CN 103965394B discloses the use of methacrylic acid C8～C12The alkyl ester as monomer is copolymerized to obtain a PMA-type viscosityThe index improver 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):
wherein x sub-repeat units of the n repeat units may be the same or different, y sub-repeat units of the n repeat units may be the same or different, and z sub-repeat units of the n repeat units may be the same or different; r in x sub-repeating units1May be the same or different and are each independently selected from H and C1～C4Alkyl (preferably H and methyl), R in x sub-repeat units2May be the same or different and are each independently selected from H and C1～C6Alkyl (preferably C)1～C6Straight chain alkyl); r in y sub-repeat units1May be the same or different and are each independently selected from H and C1～C4Alkyl (preferably H and A)Base), R in y sub-repeat units4May be the same or different and are each independently selected from H and C1～C4Alkyl (preferably H), R in y sub-repeat units5May be the same or different and are each independently selected from H and C1～C20Straight or branched alkyl (preferably selected from H and C)1～C20Straight chain alkyl), R in y repeating subunits6May be the same or different and are each independently selected from H and C1～C20Straight or branched alkyl (preferably selected from H and C)1～C20Straight chain alkyl), R in y repeating subunits7May be the same or different and are each independently selected from H and C1～C20Straight or branched alkyl (preferably selected from H and C)1～C20Straight chain alkyl), R in y repeating subunits8May 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 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); 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、R7Wherein one group is C1～C20Straight or branched alkyl (preferably C)1～C20Straight chain alkyl) ofIt has two groups of H; more preferably, in each of the y sub-repeating units, R5、R7Wherein one group is C1～C20Straight or branched alkyl (preferably C)1～C20Straight chain alkyl) and the other is H, R6The radical is H.
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:
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 monomer of the a type is preferably one or more of methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate, and more preferably methyl methacrylate and/or butyl methacrylate.
The structure of the b-type monomer is as follows:
wherein R is1Selected from H and C1～C4Alkyl (preferably H and methyl), R3Selected from H and C7～C24Alkyl (preferably selected from H and C)8～C18Straight chain alkyl). The b-type monomer is preferably hexyl methacrylate, octyl methacrylate, decyl methacrylate, isodecyl methacrylate (wherein the isodecyl group is 2-ethyl-octyl), methyl propylOne or more of dodecyl alkenoic acid, 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:
wherein R is1Selected from H and C1～C4Alkyl (preferably H and methyl), R4Selected from H and C1～C4Alkyl (preferably H), R5Selected from H and C1～C20Straight or branched alkyl (preferably selected from H and C)1～C20Straight chain alkyl), R6Selected from H and C1～C20Straight or branched alkyl (preferably selected from H and C)1～C20Straight chain alkyl), R7Selected from H and C1～C20Straight or branched alkyl (preferably selected from H and C)1～C20Straight chain alkyl), R8Selected from H and C1～C4Alkyl (preferably selected from H and methyl). The c-type monomer is preferably one or more of tetradecylphenyl methacrylate, tetradecylphenyl acrylate, pentadecylphenyl methacrylate, pentadecylphenyl acrylate, hexadecylphenyl methacrylate and hexadecylphenyl acrylate (more preferably 3-pentadecylphenyl methacrylate and/or 3-pentadecylphenyl 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, R4、R8Is H, R5、R6、R7Wherein one group is C1～C20Straight or branched alkyl (preferably C)1～C20Straight chain alkyl), the other two groups are H; more preferably, R4、R6、R8Is H, R5、R7Wherein one group is C1～C20Straight or branched alkyl (preferably C)1～C20Straight chain alkyl) and the other is H.
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 invention, the c-type monomer is preferably prepared by the following steps:
a step of carrying out esterification reaction on the compound with the structure of formula (II) and the compound with the structure of formula (III);
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); r4Selected from H and C1～C4Alkyl (preferably H), R5Selected from H and C1～C20Straight or branched alkyl (preferably selected from H and C)1～C20Straight chain alkyl), R6Selected from H and C1～C20Straight or branched alkyl (preferably selected from H and C)1～C20Straight chain alkyl), R7Selected from H and C1～C20Straight or branched alkyl (preferably selected from H and C)1～C20Straight chain alkyl), R8Selected from H and C1～C4Alkyl (preferably selected from H and methyl).
According to the preparation method of the c-type monomer, preferably, R4、R8Is H, R5、R6、R7Wherein one group is C1～C20Straight or branched alkyl (preferably C)1～C20Straight chain alkyl), the other two groups are H; more preferably, R4、R6、R8Is H, R5、R7Wherein one group is C1～C20Straight or branched alkyl (preferably C)1～C20Straight chain alkyl) and the other is H.
According to the preparation method of the c-type monomer, the molar ratio of the compound with the structure of the formula (II) to the compound with the structure of the formula (III) is preferably 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 added is preferably 0.1 to 20%, more preferably 1 to 15% of the amount of the compound having the structure of formula (III).
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 addition amount of the polymerization inhibitor is preferably 0.01-1%, more preferably 0.05-0.5% of the mass of the compound with the structure shown in the formula (III).
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 added is preferably 10% to 120%, more preferably 50% to 100%, of the amount of the compound of formula (III) in mass.
According to the preparation method of the c-type monomer, preferably, the compound with the structure of the formula (III) is obtained by hydrogenation reaction of the compound with the structure of the formula (IV);
wherein R is4' selected from H and C1～C4Alkyl, alkenyl or alkynyl, R5' selected from H and C1～C20Straight-chain or branched alkyl, alkenyl or alkynyl, R6' selected from H and C1～C20Straight-chain or branched alkyl, alkenyl or alkynyl, R7' selected from H and C1～C20Straight-chain or branched alkyl, alkenyl or alkynyl, R8' selected from H and C1～C4Alkyl, alkenyl or alkynyl, wherein at least one group is selected from alkenyl or alkynyl.
According to the preparation method of the c-type monomer, the hydrogenation reaction conditions are preferably as follows: hydrogen pressure is 1.0-6.0 MPa (preferably 3.0-4.0 MPa), temperature is 60-260 deg.C (preferably 180-220 deg.C), and time is 0.5-10 h (preferably 3-5 h).
The phenol compound represented by formula (IV) of the present invention is preferably derived from a natural plant cashew nut, contains a large amount of cashew nut shell oil in the cashew nut shell, contains meta-phenol as a main component, is generally called cardanol, and has the following structure:
wherein R is C15H31+xAnd x is 0, -2, -4 or-6. The 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.
The main raw materials used are as follows:
cardanol, Shanghai Bingshi Binghe chemical science & technology Limited, Industrial products
Methacryloyl chloride, national pharmaceutical group chemical reagents, analytical purity
Acryloyl chloride, chemical reagents of national drug group, Ltd, analytical purity
Triethylamine, chemical reagent of national drug group, analytical purity
Alkyl methacrylate, national pharmaceutical group chemical reagents, Ltd, analytical purity
Cuprous chloride, chemical reagents of national drug group, chemical purity
2, 2' -azobis (2, 4-dimethylvaleronitrile), lark waffle Chemicals, Inc., analytical purity
Palladium-carbon catalyst (active carbon loaded with 10% of metal palladium), Xian Kaili chemical Co., Ltd., industrial products
Methanol, chemical reagents of national drug group, Ltd, analytical purity
The aforementioned c-type monomer can be selected
Wherein R is1Selected from H and C1～C4Alkyl (preferably H and methyl), R5Is C15Linear alkyl group of (1). The compound can be obtained by hydrogenation of cardanol.
The structure of the cardanol is shown as the following formula:
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.
EXAMPLE 1 preparation of m-pentadecylphenol
100g of cardanol and 1.5g of palladium-carbon catalyst are put into a 200ml high-pressure reaction kettle, the high-pressure kettle is sealed, hydrogen is introduced to 3.5MPa, and stirring and heating are started. The temperature was 200 ℃ and the reaction was carried out for 4.5 hours. And after the reaction is finished, cooling to 60 ℃, taking out the viscous reaction mixture, carrying out reduced pressure distillation for 1h at the temperature of 100Pa and 160 ℃, cooling to obtain a milky white solid, dissolving the milky white solid with petroleum ether, and then crystallizing and purifying to obtain the m-pentadecylphenol with the purity of more than 98%, wherein the reaction conversion rate is 83.6%.
Example 2 preparation of 3-pentadecylphenyl acrylate (PDPA)
30g of m-pentadecylphenol is dissolved in 100ml of methanol, the solution is placed into a 250ml three-neck reaction flask, 0.05g of cuprous chloride is added, and stirring and heating are started. Maintaining the reaction temperature at 50 ℃, slowly dropping 9g of acryloyl chloride into the reaction flask, dropping 4g 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 yellow transparent liquid. The reaction product was filtered and recrystallized to give a pale yellow solid with a product conversion of 60.1%.
Example 3 preparation of 3-pentadecylphenyl Methacrylate (MDPA)
30g of m-pentadecylphenol is dissolved in 100ml of methanol, the solution is placed into a 250ml three-neck reaction flask, 0.025g of cuprous chloride is added, stirring is started, and heating is carried out. Maintaining the reaction temperature at 60 ℃, slowly dropping 10g of methacryloyl chloride into the reaction flask, dropping 2g of triethylamine again after the dropping is finished, and then heating to 60 ℃ to continue the reaction for 7 hours. And after the reaction is finished, cooling to obtain yellow transparent liquid. The reaction product was filtered and recrystallized to give a pale yellow solid with a product conversion of 58.2%.
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.
Examples 4 to 8 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 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 and unreacted monomers, obtaining 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
Example 9 viscosity measurement and shear stability test
In examples 9 to 13 and comparative examples 2 and 3, in which the lubricating oil compositions were obtained by adding the viscosity index improver solutions obtained in examples 4 to 8 and comparative example 1 to a base liquid using PAO2 as a base liquid, respectively, these lubricating oil compositions contained the base liquid, a diluent and a viscosity index improver in the viscosity index improver solution, 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 resulting lubricating oil compositions were subjected to viscosity measurement and shear stability tests. 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', and the measuring method comprises the following steps: respectively carrying out radiation treatment on the lubricating oil composition in an ultrasonic oscillator for 15 minutes, measuring the liquid viscosity before and after ultrasonic shearing, and determining the shearing stability index (SSI value), wherein generally, the lower the SSI value is, the better the shearing 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 of the present invention has strong thickening ability at low dosage, good low temperature fluidity, and good shear stability.
TABLE 2
Example 10 Oxidation resistance test
Respectively dissolving the viscosity index improver obtained in the embodiments 4 to 8 and the viscosity index improver obtained in the comparative example 1 in Shanghai Gaoqiao No. 6 hydrogenated oil to prepare solutions with the viscosity index improver content of 10% (mass fraction), and carrying out an antioxidant performance test on the solutions, wherein the test instrument is a TA5000 DSC instrument of the American TA company, and the test conditions are as follows: 180 ℃, the oxygen pressure of 0.5MPa and the heating speed of 10 ℃/min. The test results are shown in Table 3.
TABLE 3
As can be seen from Table 3, the viscosity index improver of the present invention has better antioxidant properties.
Claims (30)
1. A viscosity index improver has a structure shown in a 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 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 C1～C6An alkyl group; r in y sub-repeat units1Are mutually connectedIs the same or different and is each independently selected from H and C1～C4Alkyl, R in y sub-repeat units4Are the same or different from each other and are each independently selected from H and C1～C4Alkyl, R in y sub-repeat units5Are the same or different from each other and are each independently selected from H and C1～C20Straight or branched alkyl, R in y sub-repeating units6Are the same or different from each other and are each independently selected from H and C1～C20Straight or branched alkyl, R in y sub-repeating units7Are the same or different from each other and are each independently selected from H and C1～C20Straight or branched alkyl, R in y sub-repeating units8Are the same or different from each other and are each independently selected from H and C1～C4An 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 C7～C24An alkyl group; x in the n repeating units are the same or different from each other and are respectively and independently selected from integers of 10-1000, y in the n repeating units are the same or different from each other and are respectively and independently selected from integers of 10-5000, 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 10-2000; 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 C1～C6A linear alkyl group; r in y sub-repeat units1Each independently selected from H and methyl, R in y sub-repeat units4R selected from H, y sub-repeat units5Each independently selected from H and C1～C20Straight chain alkyl, R in y sub-repeat units6Each independently selected from H and C1～C20Straight chain alkyl, R in y sub-repeat units7Each independently selected from H and C1～C20Straight chain alkyl, R in y sub-repeat units8Each independently selected from H and methyl; r in z sub-repeat units1Each independently selected from H and methyl, R in z sub-repeat units3Each independently selected from C8～C18A linear alkyl group.
3. The viscosity index improver of claim 1 wherein R is in each of the y sub-repeat units5、R6、R7Wherein one group is C1～C20Straight or branched chain alkyl, the other two groups being H.
4. The viscosity index improver of claim 3 wherein R is in each of the y sub-repeat units5、R6、R7Wherein one group is C1～C20Straight chain alkyl, the other two groups are H.
5. The viscosity index improver of claim 3 wherein R is in each of the y sub-repeat units5、R7Wherein one group is C1～C20Straight or branched chain alkyl, the other being H, R6The radical is H.
6. The viscosity index improver according to claim 1, wherein the viscosity index improver has a weight average molecular weight of 10000 to 1000000.
7. The viscosity index improver according to claim 1, wherein the viscosity index improver has a weight average molecular weight of 50000 to 800000.
8. The viscosity index improver according to claim 1, wherein the viscosity index improver has a weight average molecular weight of 200000 to 700000.
9. A method for preparing a viscosity index improver, comprising: carrying out polymerization reaction on a type monomer, a type monomer and a type c monomer, and collecting a polymerization product;
the structure of the a-type monomer is as follows:
wherein R is1Selected from H and C1～C4Alkyl radical, R2Is selected from C1～C6An alkyl group;
the structure of the b-type monomer is as follows:
wherein R is1Selected from H and C1～C4Alkyl radical, R3Is selected from C7～C24An alkyl group;
the structure of the c-type monomer is as follows:
wherein R is1Selected from H and C1～C4Alkyl radical, R4Selected from H and C1～C4Alkyl radical, R5Selected from H and C1～C20Straight or branched alkyl, R6Selected from H and C1～C20Straight or branched alkyl, R7Selected from H and C1～C20Straight or branched alkyl, R8Selected from H and C1～C4An alkyl group; the mass of the a-type monomer is 5-30% of the total mass, the mass of the b-type monomer is 20-70% of the total mass, and the mass of the c-type monomer is calculated according to the total mass of the a-type monomer, the b-type monomer and the c-type monomerThe mass of (A) is 20-50% of the total mass.
10. The process of claim 9 wherein in said class a monomers, wherein R is1Selected from H and methyl, R2Is selected from C1～C6A linear alkyl group;
in the b-type monomer, wherein R1Selected from H and methyl, R3Is selected from C8～C18A linear alkyl group;
in the c-type monomer, wherein R1Selected from H and methyl, R4Selected from H, R5Selected from H and C1～C20Straight chain alkyl radical, R6Selected from H and C1～C20Straight chain alkyl radical, R7Selected from H and C1～C20Straight chain alkyl radical, R8Selected from H and methyl.
11. The method of claim 9, 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 tetradecylphenyl methacrylate, tetradecylphenyl acrylate, pentadecylphenyl methacrylate, pentadecylphenyl acrylate, hexadecylphenyl methacrylate and hexadecylphenyl acrylate.
12. The process according to claim 9, 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-pentadecylphenyl methacrylate and/or 3-pentadecylphenyl acrylate.
13. The method of claim 9, wherein R is4、R8Is H, R5、R6、R7Wherein one group is C1～C20Straight or branched chain alkyl, the other two groups being H.
14. The method of claim 9, wherein R is4、R8Is H, R5、R6、R7Wherein one group is C1～C20Straight chain alkyl, the other two groups are H.
15. The method of claim 9, wherein R is4、R6、R8Is H, R5、R7Wherein one group is C1～C20Straight or branched chain alkyl, the other group being H.
16. The process of claim 9 wherein an initiator is added to said 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 9, wherein the polymerization 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 9, wherein the polymerization reaction temperature is 80 ℃ to 100 ℃; the time of the polymerization reaction is 2 to 4 hours; nitrogen was passed during the polymerization.
20. The method of claim 9, wherein the c-type monomer is prepared by: a step of carrying out esterification reaction on the compound with the structure of formula (II) and the compound with the structure of formula (III);
wherein R is1Selected from H and C1～C4Alkyl, X is selected from F, Cl, Br, I and OH; r4Selected from H and C1～C4Alkyl radical, R5Selected from H and C1～C20Straight or branched alkyl, R6Selected from H and C1～C20Straight or branched alkyl, R7Selected from H and C1～C20Straight or branched alkyl, R8Selected from H and C1～C4An alkyl group.
21. The method of claim 20, wherein R1Selected from H and methyl, X is selected from Cl and Br; r4Selected from H, R5Selected from H and C1～C20Straight chain alkyl radical, R6Selected from H and C1～C20Straight chain alkyl radical, R7Selected from H and C1～C20Straight chain alkyl radical, R8Selected from H and methyl.
22. The method of claim 20, wherein R is4、R8Is H, R5、R6、R7WhereinOne group being C1～C20Straight or branched chain alkyl, the other two groups being H.
23. The method of claim 20, wherein R is4、R8Is H, R5、R6、R7Wherein one group is C1～C20Straight chain alkyl, the other two groups are H.
24. The method of claim 20, wherein R is4、R6、R8Is H, R5、R7Wherein one group is C1～C20Straight or branched chain alkyl, the other group being H.
25. The process of claim 20, wherein a catalyst is added to said esterification reaction; and adding a polymerization inhibitor in the esterification reaction.
26. The process of claim 25 wherein said catalyst is selected from the group consisting of C1～C10Organic amine and/or ammonia; the polymerization inhibitor is selected from metal chloride, phenolic polymerization inhibitor, quinoid polymerization inhibitor and metal powder.
27. The method of claim 25, wherein the catalyst is selected from one or more of methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, and ammonia; the polymerization inhibitor is selected from one or more of cuprous chloride, ferric trichloride, hydroquinone, benzoquinone and copper powder.
28. The method according to claim 20, wherein the compound having the structure of formula (III) is obtained by subjecting a compound having the structure of formula (IV) to hydrogenation reaction;
wherein R is4' selected from H and C1～C4Alkyl, alkenyl or alkynyl, R5' selected from H and C1～C20Straight-chain or branched alkyl, alkenyl or alkynyl, R6' selected from H and C1～C20Straight-chain or branched alkyl, alkenyl or alkynyl, R7' selected from H and C1～C20Straight-chain or branched alkyl, alkenyl or alkynyl, R8' selected from H and C1～C4Alkyl, alkenyl or alkynyl, wherein at least one group is selected from alkenyl or alkynyl.
29. The method according to claim 28, wherein the phenol compound represented by formula (IV) is derived from a natural plant cashew nut.
30. The viscosity index improver of claims 1 to 8 and the viscosity index improver prepared by the method of claims 9 to 29 are used as a viscosity index improver for lubricating oil.
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| CN103459569A (en) * | 2011-03-25 | 2013-12-18 | 巴斯夫欧洲公司 | Lubricant composition having improved non-Newtonian viscometrics |
| CN103897101A (en) * | 2014-04-23 | 2014-07-02 | 郑州大学 | Acrylic polyester-type hyperdispersant and preparation method and application thereof |
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| CN103459569A (en) * | 2011-03-25 | 2013-12-18 | 巴斯夫欧洲公司 | Lubricant composition having improved non-Newtonian viscometrics |
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