CN113249157B - 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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- CN113249157B CN113249157B CN202010090407.3A CN202010090407A CN113249157B CN 113249157 B CN113249157 B CN 113249157B CN 202010090407 A CN202010090407 A CN 202010090407A CN 113249157 B CN113249157 B CN 113249157B
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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
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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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
- 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
Abstract
The invention provides a viscosity index improver and a preparation method and application thereof. The structure of the viscosity index improver is shown as a general formula (I):
Description
Technical Field
The invention relates to the field of lubricating oil additives, 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 C 2 ～C 5 Alkyl esters, methacrylic acid C 7 ～C 10 Alkyl esters, methacrylic acid C 11 ～C 12 Alkyl esters and methacrylic acid C 13 ～C 16 The 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 C 8 ～C 12 Alkyl esters as monomers by copolymerizationThe PMA type viscosity index improver is obtained by polymerization, and has the characteristics of average molecular weight, low acid value, low condensation point, small low-temperature viscosity, good shear stability, good viscosity-temperature performance and the like. CN 102295973A discloses the use of 20-80 mass% methacrylic acid C 1 ～C 25 Alkyl ester, 10 to 70 mass% of methacrylic acid C 1 ～C 20 The copolymer is prepared by copolymerizing alkyl ester and 1-10 mass percent of nitrogen-containing compound with carbon-carbon double bonds, and has better anti-wear performance and dispersion performance while keeping better 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 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-repeat units 2 Are the same or different from each other and are each independently selected from H and C 1 ～C 6 Alkyl (preferably C) 1 ～C 6 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 7 ～C 24 Alkyl (preferably selected from H and C) 8 ～C 18 Straight chain alkyl);
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) (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); radicals 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 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 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);
in formula (III), the radical R 1 "is selected from a single bond, C 1-20 Straight or branched alkylene (preferably selected from the group consisting of 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 single bond, C) 1-4 Linear or branched 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 "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); 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 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 viscosity index improver according to the present invention preferably has R in each benzene ring molecule of y 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 is 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.
The viscosity index improver according to the present invention, more preferably, R is 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, and R 8 Is tert-butyl; r 7 、R 9 One group is OH and the other group is H.
The viscosity index improver according to the present invention preferably has a weight average molecular weight of 10000 to 1000000, more preferably 50000 to 800000, and still more preferably 100000 to 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 is 1 Selected from H and C 1 ～C 4 Alkyl (preferably H and methyl), R 2 Selected from H and C 1 ～C 6 Alkyl (preferably C) 1 ～C 6 Straight chain alkyl). The a-type monomer is preferably one or more of methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate, and more preferably methyl propyl methacrylateMethyl enoate and/or butyl methacrylate.
The structure of the b-type monomer is as follows:
wherein R is 1 Selected from H and C 1 ～C 4 Alkyl (preferably H and methyl), R 3 Selected from H and C 7 ～C 24 Alkyl (preferably selected from H and C) 8 ～C 18 Straight 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:
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 groups); 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 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); 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 located in the ortho position of phenolic hydroxyl group) and o-tert-butyl cardanol (tert-butyl is preferably located in the ortho position of phenolic hydroxyl group), and more preferably o-tert-butyl cardanol.
According to the invention, R in the class c 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 halides and C 2-4 For example, one or more of tert-butyl chloride, tert-butyl bromide, isopropene and isobutene can be used (the tert-butyl alkylating agent is preferably one or more of tert-butyl chloride, tert-butyl bromide and isobutene). 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 speaking, 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. The catalyst can be added or not added in the alkylation reaction, and the catalyst is preferably 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 solvent is preferably a hydrocarbon solvent, an alcohol solvent, an ether solvent andone or more ketone solvents may be selected, for example, from hexane, cyclohexane, benzene, toluene, xylene, methanol, ethanol, propanol, butanol, methyl ether, ethyl ether, propyl ether, butyl ether, acetone and methyl ethyl ketone, and preferably from hydrocarbon solvents and/or alcohol solvents. 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 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 production method of the present invention, preferably, the mass of the a-type monomer is 1 to 50% (preferably 5 to 40%) of the total mass, the mass of the b-type monomer is 20 to 90% (preferably 40 to 80%) of the total mass, and the mass of the c-type monomer is 1 to 30% (preferably 5 to 20%) 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 invention, preferably, an initiator can be added in the polymerization reaction, and the initiator is preferably one or more of cumene hydroperoxide, 2,2 '-azo bis (2,4-dimethylbutyronitrile) and 2,2' -azo bis (2,4-dimethylvaleronitrile) (ADVN). 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.
The viscosity index improver can be used as a viscosity index improver of lubricating oil.
The viscosity index improver has the advantages of strong thickening capability under low dosage, high shear stability and good low-temperature fluidity, and simultaneously has stronger 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), bailingwei Chemicals, inc., analytical purity
Dodecyl mercaptan, national pharmaceutical group chemical reagents, chemical purity
Example 1 preparation of 2-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 1 hr, 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:
MMA: methyl methacrylate;
BMA: methacrylic acid butyl ester
The b type monomers are as follows:
DMA: decyl methacrylate;
nTM: tetradecyl methacrylate;
nDM: dodecyl methacrylate;
nHM: cetyl 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 viscosity index improver and 43% of diluent, respectively naming the viscosity index improver therein 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 viscosity measurement and shear stability test
The viscosity index improver solutions obtained in examples 2 to 4 and comparative example 1 were added to a base fluid using PAO 2 as the base fluid to obtain lubricating oil compositions containing the base fluid, a diluent in the viscosity index improver solution, and a viscosity index improver, wherein the mass fractions of the viscosity index improvers S-1 to S-3 and B-1 to the lubricating oil compositions are shown in table 2. These 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', 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.
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.
Example 6 Oxidation resistance test
The viscosity index improver solutions obtained in examples 2 to 4 and comparative example 1 were dissolved in shanghai high bridge 6# hydrogenated oil to prepare a solution with a viscosity index improver content of 10% (m/m), and the oxidation resistance test was performed, the test results are shown in table 3, the test apparatus is a TA5000 DSC instrument from TA corporation, and the test conditions are as follows: 180 ℃, oxygen pressure of 0.5MPa and heating speed of 10 ℃/min.
TABLE 3
As can be seen from Table 3, the viscosity index improver of the present invention has excellent antioxidant properties.
Claims (22)
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 units 1 Identical to or different from each other, each independently selected from H and methyl, R in x sub-repeating units 2 Are the same or different from each other and are each independently selected from C 1 ～C 6 A linear alkyl group;
r in z sub-repeat units 1 Equal to or different from each other, each independently selected from H and methyl, R in z sub-repeating units 3 Are the same or different from each other and are each independently selected from H and C 8 ～C 18 A linear 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 8 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 8 Alkylene groups of formula (III);
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; 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 1-4 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 ' same or different from each other, each independently selected from hydrogen, C 1-4 A linear or branched alkyl group; radical R in m repeating units 5 ' same or different from each otherEach independently selected from hydrogen, C 1-4 A linear or branched alkyl group; m is a positive integer between 1~3;
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 the same or different from each other and 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 the same or different from each other, and are each independently selected from hydrogen, C 1-4 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 1-4 A linear or branched alkyl group; m' is a positive integer between 1~3;
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 10 A linear or branched alkyl group;
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 each independently selected from 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 10 to 5000, and z in the n repeating units are the same or different from each other and are each independently selected from an integer of 10 to 2000; n is an integer of 10 to 3000.
2. The viscosity index improver of claim 1 wherein R is present 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.
3. The viscosity index improver according to claim 1, wherein R is represented by R in 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, and R 8 Is tert-butyl; r 7 、R 9 One group is OH and the other group is H.
4. The viscosity index improver according to claim 1, wherein the viscosity index improver has a weight average molecular weight of 10000 to 1000000.
5. The viscosity index improver according to claim 1, wherein the viscosity index improver has a weight average molecular weight of 50000 to 800000.
6. A method of preparing a viscosity index improver comprising: carrying out polymerization reaction on a type monomer, a type monomer and collecting a polymerization product;
the structure of the a-type monomer is as follows:
wherein R is 1 Selected from H and methyl, R 2 Is selected from C 1 ～C 6 A linear alkyl group;
the structure of the b-type monomer is as follows:
wherein R is 1 Selected from H and methyl, R 3 Selected from H and C 8 ～C 18 A linear alkyl group;
the structure of the c-type monomer is as follows:
wherein R is 4 Selected from H, C 1 ～C 8 Alkyl and a group of formula (II); r 5 Is selected from C 1 ～C 8 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 10 A linear or branched alkyl group; 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 the group consisting of a single bond and C 1-4 A linear or branched alkylene group; 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 1-4 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 ' same or different from each other, each independently selected from hydrogen, C 1-4 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 1-4 A linear or branched alkyl group; m is a positive integer between 1~3;
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 mutually oppositeAre the same or different and 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 the same or different from each other and are each independently selected from hydrogen, C 1-4 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 1-4 A linear or branched alkyl group; m' is a positive integer between 1~3.
7. The method according to claim 6, wherein the a-type monomer is one or more of methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate; the b type monomer is one or more of octyl methacrylate, decyl methacrylate, dodecyl methacrylate, tetradecyl methacrylate, dodecyl/tetradecyl methacrylate, hexadecyl methacrylate and octadecyl methacrylate, and the c type monomer is one or more of cardanol, o-methyl cardanol and o-tert-butyl cardanol.
8. The method according to claim 6, 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.
9. The method according to claim 6, 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.
10. The process of claim 8 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.
11. The process according to claim 9, wherein the tertiary butylation reaction is carried out by reacting the c-type monomer with a tertiary butylating agent; the tertiary butyl agent is selected from one or more of tertiary butyl chloride, tertiary butyl bromide, isopropene and isobutene.
12. 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 ℃.
13. The process according to claim 8, 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.
14. The process according to claim 8, wherein a catalyst is added to the alkylation reaction; the catalyst is selected from metal chlorides and inorganic acids.
15. The method according to claim 8, wherein the c-type monomer is cardanol.
16. The process according to claim 6, wherein the mass of the group a monomer is 1 to 50% of the total mass, the mass of the group b monomer is 20 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.
17. The process according to claim 6, wherein the mass of the group a monomer is 5 to 40% of the total mass, the mass of the group b monomer is 40 to 80% of the total mass, and the mass of the group c monomer is 5 to 20% of the total mass, based on the total mass of the group a monomer, the group b monomer and the group c monomer.
18. The process according to claim 6, wherein one or more of an initiator, a chain transfer agent and a diluent are added to the polymerization reaction.
19. The process according to claim 6, wherein the polymerization reaction temperature is 60 ℃ to 140 ℃; the time of the polymerization reaction is 1-5 h.
20. The process according to claim 6, 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.
21. The process according to claim 6, wherein an inert gas is introduced during the polymerization.
22. Use of a viscosity index improver according to any one of claims 1~5 or a viscosity index improver prepared by a process according to any one of claims 6 to 21 in a lubricating oil.
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| TW413701B (en) * | 1997-05-09 | 2000-12-01 | Guo Bing Lin | Copolymers used as lubricant additives |
| US20030171223A1 (en) * | 2002-01-31 | 2003-09-11 | Winemiller Mark D. | Lubricating oil compositions with improved friction properties |
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