WO2021027211A1 - 含有星型的马来酸酐接枝三元乙丙共聚物润滑油粘度指数改进剂及其制备方法 - Google Patents

含有星型的马来酸酐接枝三元乙丙共聚物润滑油粘度指数改进剂及其制备方法 Download PDF

Info

Publication number
WO2021027211A1
WO2021027211A1 PCT/CN2019/125756 CN2019125756W WO2021027211A1 WO 2021027211 A1 WO2021027211 A1 WO 2021027211A1 CN 2019125756 W CN2019125756 W CN 2019125756W WO 2021027211 A1 WO2021027211 A1 WO 2021027211A1
Authority
WO
WIPO (PCT)
Prior art keywords
maleic anhydride
viscosity index
anhydride grafted
star
index improver
Prior art date
Application number
PCT/CN2019/125756
Other languages
English (en)
French (fr)
Inventor
马道林
马浚轩
Original Assignee
深圳昆油石化技术有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 深圳昆油石化技术有限公司 filed Critical 深圳昆油石化技术有限公司
Publication of WO2021027211A1 publication Critical patent/WO2021027211A1/zh

Links

Classifications

    • 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
    • C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/50—Partial depolymerisation
    • 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
    • C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/022—Ethene
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/024—Propene
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
    • 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
    • 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
    • C10M2209/086—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 polycarboxylic, e.g. maleic acid

Definitions

  • the invention belongs to the technical field of lubricating oil modification, and in particular relates to a lubricating oil viscosity index improver composition and a preparation method thereof.
  • Viscosity index improver is an oil-soluble polymer compound that is rubbery or solid at room temperature. It is usually diluted with a 150SN or 100SN neutral oil to a 5-10% concentrate for use (Li Zhongming. A kind of Viscosity index improver of lubricating oil composition. CN 108048167A). Adding VII to the lubricating oil can obtain a multi-grade oil with good low-temperature startability, suitable high-temperature viscosity, universal use in all seasons and long service life. The polymer chain of VII in the lubricating oil is fully extended at high temperature to increase viscosity; at low temperature, it will shrink and curl, which has little effect on viscosity. Therefore, compared with the single-grade lubricating oil with the same viscosity, the multi-grade oil containing VII has a higher viscosity index and a smooth viscosity-temperature curve.
  • the viscosity index improver of ethylene-propylene copolymer has better viscosity, shear stability and viscosity-temperature performance, and the raw materials are easily available and the process is simple (Xiang Wencheng. Dispersed ethylene-propylene copolymer viscosity index improver. Lubrication) Oil. 1994, 5: 36-42.), but the low temperature resistance is also slightly worse, often need to add lipid pour point depressant.
  • PMA VII has excellent low temperature properties and oxidation stability, but poor viscosity increasing performance and oil detergency. If the advantages of the two are combined together, a certain overall performance improvement can be obtained.
  • maleic anhydride grafted EPDM rubber is a product obtained by grafting EPDM rubber with maleic anhydride.
  • the molecular backbone contains acid anhydride groups, which is beneficial to improve low temperature performance. It is used to prepare VII It is a good choice.
  • patent application 99108204.4 discloses a lubricating oil tackifier and its production method.
  • the lubricating oil tackifier is composed of the following components: A. There are 3.98% to 9.96% of two yuan ethylene propylene rubber or three yuan ethylene propylene rubber Or a mixture of them; B. Dicyclopentadienyl iron of 0.02% to 0.04%; C. The balance is motor oil; or it is composed of the following components: A. There are 3.96% to 9.92% of two yuan ethylene propylene rubber or three Ethylene propylene rubber or their mixtures: B. Dicyclopentadienyl iron from 0.02% to 0.04%; C.
  • Succinimide from 0.02% to 0.04%; D.
  • the balance is motor oil.
  • the lubricating oil tackifier cannot improve the shear stability under low temperature conditions, and there are problems that cannot be balanced, such as tackifying performance, shear stability, oil detergency, and low temperature resistance.
  • the primary purpose of the present invention is to provide a star-shaped maleic anhydride grafted terylene propylene copolymer with improved shear stability or low temperature performance without reducing the detergency of OCP VII oils.
  • Lubricating oil viscosity index improver and preparation method thereof are provided.
  • the purpose of the present invention is to provide a star-shaped maleic anhydride grafted ethylene-propylene copolymer lubricant containing star-shaped maleic anhydride grafted ethylene propylene diene copolymer with improved viscosity index (thickening ability), shear stability, oil detergency and low temperature performance.
  • the preparation method thereof reduces the occurrence of irreversible crosslinking, and improves the preparation efficiency and reliability of the product.
  • a star-shaped maleic anhydride grafted EPDM copolymer lubricant viscosity index improver which is characterized in that it is an EPDM rubber grafted with maleic anhydride, a catalyst (I), a modified monomer Body (II), auxiliary monomer (III), a solid star polymer prepared by a specific melt polymerization method, or a liquid composition of a star polymer prepared by a solution polymerization method.
  • the solid is a paste or a block.
  • the dosage range of the four raw material components is: maleic anhydride grafted EPDM rubber is not less than 98 parts, catalyst (I) is not more than 0.1 part, and modified monomer ( II) does not exceed 1.2 parts, and auxiliary monomer (III) does not exceed 0.7 parts.
  • the preferred dosage ranges of the four raw material components are: 98-99.5 parts of maleic anhydride grafted EPDM rubber, 0.05-0.1 parts of catalyst (I), and modified monomer (II) It is 0.3 to 1.2 parts, and the auxiliary monomer (III) is 0.15 to 0.7 parts.
  • the number average molecular weight of the maleic anhydride grafted EPDM rubber is 20,000 to 150,000.
  • the catalyst (I) is a compound containing a structural unit of formula ( ⁇ ).
  • R1 and R2 are respectively any one or any combination of hydrogen, C1-12 alkyl, cycloalkyl, aryl, acyl, ester, carbonate, and ketone.
  • the alkyl group, cycloalkyl group, aryl group, acyl group, ester group, carbonate group, and ketone group may be further substituted with 1 to 6 substituents independently selected from the group consisting of alkyl, cycloalkyl, and aryl.
  • the molecular formula of the ( ⁇ ) structural unit is as follows:
  • the catalyst (I) can be selected from hydrogen peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, dicumyl peroxide, di-tert-butyl peroxide, dibenzoyl peroxide , Lauryl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy-t-valerate, diisopropyl peroxydicarbonate, and dicyclohexyl peroxydicarbonate.
  • the modified monomer (II) is a compound containing two of the following ( ⁇ ) or ( ⁇ ) structural units.
  • the molecular formulas of the ( ⁇ ) and ( ⁇ ) structural units are as follows:
  • the modified monomer (II) can be trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate Esters, 3 (propoxy) glycerol triacrylate, tris (2-hydroxyethyl) isocyanuric acid triacrylate, di (trimethylolpropane) tetraacrylate, pentaerythritol tetraacrylate, 4 ( Ethoxy) any one of pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate.
  • the auxiliary monomer (III) is any one of styrene, acrylamide, and thiuram derivatives containing the structure of formula ( ⁇ ), wherein R3 and R4 can be C1-7 alkyl or cycloalkyl Any one or any combination of, aryl, benzyl, isobutyl, piperidinyl; wherein the molecular formula of formula ( ⁇ ) is:
  • the thiuram derivative can be tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabenzylthiuram disulfide, dimethylthiuram disulfide Diphenylthiuram, diisobutylthiuram disulfide, dicyclopentamethylene disulfide tetraalkylthiuram, dipentamethylenethiuram tetrasulfide, dipentamethylene hexasulfide Thiuram waited.
  • a melt polymerization method containing star-shaped maleic anhydride grafted EPDM copolymer lubricant viscosity index improver characterized in that the method comprises the following steps:
  • the solvent used is a solvent that can dissolve the catalyst but cannot dissolve the terpolymer (I), and can be acetone, ethyl acetate, methanol, ethanol, and other solvents that are easy to volatilize.
  • a solution polymerization method containing star-shaped maleic anhydride grafted EPDM copolymer lubricating oil viscosity index improver characterized in that the method comprises the following steps:
  • the base oil is any one of mineral base oil, synthetic base oil, and vegetable base oil, and the kinematic viscosity of the base oil at 40°C is 5.0-160.0mm 2 /s and/or the kinematic viscosity at 100°C is 1.50-34.0mm 2 /s.
  • the main components of the mineral base oil include alkanes, cycloalkanes, aromatic hydrocarbons, cycloalkyl aromatic hydrocarbons and organic compounds containing oxygen, nitrogen, and sulfur;
  • the synthetic oil may be polyalphaolefin, synthetic ester, polyether, silicone oil, fluorine-containing oil , Any one or any combination of phosphate esters;
  • vegetable base oils are natural animal and vegetable oils containing ester bonds in the molecular structure.
  • the propyl structural unit on the maleic anhydride grafted ethylene-propylene copolymer is degraded, the proportion of propyl unit is reduced, and the molecular weight distribution of the molecular chain is broadened; combined with the control catalyst ( I) and the adding order and amount of the modified monomer (II) to make the macromolecular free radicals react with the modified monomer (II) to form a long-chain branched star copolymer; use of auxiliary monomer (III) , Reducing the occurrence of irreversible cross-linking, the formed star polymer shrinks the molecular chain at low temperature, but does not cause serious entanglement, and has little effect on viscosity; at high temperature, the molecular chain stretches, which has a significant effect on lubricating oil viscosity. .
  • Lubricant VII More importantly, the proportion of structural units ( ⁇ ) is reduced and the molecular weight distribution of the molecular chain is broadened, and the low temperature performance of the obtained Lubricant VII is remarkable.
  • the improver and its preparation method overcome the crosslinking problem in the polymerization reaction process, so that the prepared lubricating oil VII has the characteristics of strong thickening ability, good shear stability, low temperature performance and excellent high temperature oxidation detergency.
  • the viscosity index improver for lubricating oil containing star-shaped maleic anhydride grafted EPDM copolymer realized by the present invention is EPDM rubber grafted with maleic anhydride, catalyst (I), and modified monomer (II)
  • Auxiliary monomer (III) is a solid of a star polymer prepared by a specific melt polymerization method, such as a paste or block, or a liquid composition prepared by a solution polymerization method.
  • the dosage range of the four raw material components is: maleic anhydride grafted EPDM rubber is not less than 98 parts, catalyst (I) is not more than 0.1 part, and modified monomer ( II) does not exceed 1.2 parts, and auxiliary monomer (III) does not exceed 0.7 parts.
  • the preferred dosage range of the above-mentioned four raw material components is: 98-99.5 parts of maleic anhydride grafted EPDM, 0.05-0.1 parts of catalyst (I), and 0.3-1.2 parts of modified monomer (II) Parts, auxiliary monomer (III) is 0.15-0.7 parts.
  • the number average molecular weight of the maleic anhydride grafted EPDM rubber is 20,000 to 150,000.
  • the catalyst (I) is a compound containing a structural unit of formula ( ⁇ ).
  • R1 and R2 are respectively any one or any combination of hydrogen, C1-12 alkyl, cycloalkyl, aryl, acyl, ester, carbonate, and ketone.
  • the alkyl group, cycloalkyl group, aryl group, acyl group, ester group, carbonate group, and ketone group may be further substituted with 1 to 6 substituents independently selected from the group consisting of alkyl, cycloalkyl, and aryl.
  • the molecular formula of the ( ⁇ ) structural unit is as follows:
  • the catalyst (I) can be selected from hydrogen peroxide, cumene hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, di-tert-butyl peroxide, dibenzoyl peroxide , Lauryl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy-t-valerate, diisopropyl peroxydicarbonate, and dicyclohexyl peroxydicarbonate.
  • the modified monomer (II) is a compound containing two of the following ( ⁇ ) or ( ⁇ ) structural units.
  • the molecular formulas of the ( ⁇ ) and ( ⁇ ) structural units are as follows:
  • the modified monomer (II) can be trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate Esters, 3 (propoxy) glycerol triacrylate, tris (2-hydroxyethyl) isocyanuric acid triacrylate, di (trimethylolpropane) tetraacrylate, pentaerythritol tetraacrylate, 4 ( Ethoxy) any one of pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate.
  • the auxiliary monomer (III) is any one of styrene, acrylamide, and thiuram derivatives containing the structure of formula ( ⁇ ), wherein R3 and R4 can be C1-7 alkyl or cycloalkyl Any one or any combination of, aryl, benzyl, isobutyl, piperidinyl; wherein the molecular formula of formula ( ⁇ ) is:
  • the thiuram derivative can be tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabenzylthiuram disulfide, dimethylthiuram disulfide Diphenylthiuram, diisobutylthiuram disulfide, dicyclopentamethylene disulfide tetraalkylthiuram, dipentamethylenethiuram tetrasulfide, dipentamethylene hexasulfide Thiuram waited.
  • the melt polymerization method of star-shaped maleic anhydride grafted EPDM copolymer lubricating oil viscosity index improver realized by the present invention includes the following steps:
  • the solvent used is a solvent that can dissolve the catalyst but cannot dissolve the terpolymer (I), and can be acetone, ethyl acetate, methanol, ethanol, and other solvents that are easy to volatilize.
  • the solution polymerization method of star-shaped maleic anhydride grafted EPDM copolymer lubricant viscosity index improver realized by the present invention includes the following steps:
  • the base oil is any one of mineral base oil, synthetic base oil, and vegetable base oil, and the kinematic viscosity of the base oil at 40°C is 5.0-160.0mm 2 /s and/or the kinematic viscosity at 100°C is 1.50-34.0mm 2 /s.
  • the main components of the mineral base oil include alkanes, cycloalkanes, aromatic hydrocarbons, cycloalkyl aromatic hydrocarbons and organic compounds containing oxygen, nitrogen, and sulfur;
  • the synthetic oil may be polyalphaolefin, synthetic ester, polyether, silicone oil, fluorine-containing oil , Any one or any combination of phosphate esters;
  • vegetable base oils are natural animal and vegetable oils containing ester bonds in the molecular structure.
  • the hydroperoxide catalyst (I) any one of hydrogen peroxide, cumene hydroperoxide, and tert-butyl hydroperoxide
  • a solution (A) Spray the solution (A) evenly into the maleic anhydride grafted terpolymer pellets (B) and stir, and let it stand for a period of time until the solvent is completely volatilized to obtain the composition (C); mix the modified material ( C) Extrude on the extruder, control the extrusion temperature to 150°C, add the modified monomer trimethylolpropane triacrylate (II) and the auxiliary monomer styrene in the middle or the end of the heating section of the extruder.
  • the modified material ( C) Extrude on the extruder, control the extrusion temperature to 150°C, add the modified monomer trimethylolpropane triacrylate (II) and the auxiliary monomer styrene in the middle or the end of the heating section of the extruder.
  • the mixture (D) of (III) is extruded to obtain the star-shaped maleic anhydride grafted EPDM copolymer lubricant viscosity index improver.
  • the solvent used is a solvent that can dissolve the catalyst but cannot dissolve the terpolymer (I), and can be acetone, ethyl acetate, methanol, ethanol, and other solvents that are easy to volatilize.
  • the dosage range of the above-mentioned four raw material components is: maleic anhydride grafted terpolymer rubber (maleic anhydride grafted terpolymer pellets) not less than 98 parts , Catalyst (I) does not exceed 0.1 parts, modified monomer (II) does not exceed 1.2 parts, auxiliary monomer (III) does not exceed 0.7 parts.
  • the obtained viscosity index improver composition (that is, the star-shaped maleic anhydride grafted EPDM copolymer lubricating oil viscosity index improver, the same below) is dissolved at a concentration of 10% at 100°C and has a kinematic viscosity of 5.1 mm 2
  • the 100°C kinematic viscosity tested in the base oil /s (the same below) is within the range of 300-1200mm 2 /s, the shear stability index does not exceed 14 (diesel nozzle SSI), and the thickening capacity is not less than 3mm 2 /s ,
  • the low temperature apparent viscosity index is below CCSI90 (measured at -20°C), and the high temperature oxidation detergency can reach at least 3.5 grades (heat pipe oxidation).
  • the base oil is mineral oil.
  • the main components of the mineral base oil include alkanes, cycloalkanes, aromatics, cycloalkyl aromatics, and organic compounds containing oxygen, nitrogen, and sulfur.
  • the base oil may have a kinematic viscosity of 5.0-160.0 mm 2 /s at 40°C and/or a kinematic viscosity of 1.50-34.0 mm 2 /s at 100°C.
  • the hydroperoxide catalyst (I) hydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide
  • a star-shaped structure that is, star-shaped maleic anhydride graf
  • the dosage range of the above four raw material components is: 99.5 parts of maleic anhydride grafted EPDM, 0.05 parts of catalyst (I), and 0.3 parts of modified monomer (II) , Auxiliary monomer (III) is 0.15 parts.
  • the obtained viscosity index improver concentrate (10% liquid glue) (that is, the star-shaped maleic anhydride grafted EPDM copolymer lubricating oil viscosity index improver composition, the same below) moves at 100°C
  • the viscosity is within the range of 300-1200mm 2 /s
  • the shear stability index is no more than 12 (diesel nozzle SSI)
  • the thickening capacity is no less than 3mm 2 /s
  • the low temperature apparent viscosity index is below CCSI90 (measured at -20°C)
  • the high temperature oxidation detergency can reach at least 3.5 grades (heat pipe oxidation).
  • dialkyl peroxide catalyst (I) such as one of dicumyl peroxide and di-tert-butyl peroxide
  • a solution (A) Spray the solution (A) evenly into the maleic anhydride grafted terpolymer pellets (B) and stir, and let it stand for a period of time until the solvent is completely volatilized to obtain the composition (C); mix the modified material ( C) Extrude on the extruder, control the extrusion temperature to 230°C, add the modified monomer trimethylolpropane triacrylate (II) and auxiliary monomer styrene in the middle or end of the heating section of the extruder.
  • II modified monomer trimethylolpropane triacrylate
  • the composition (D) of (III) is extruded to obtain the star-shaped maleic anhydride grafted EPDM copolymer lubricating oil viscosity index improver composition.
  • the solvent used is a solvent that can dissolve the catalyst but cannot dissolve the terpolymer (I), and can be acetone, ethyl acetate, methanol, ethanol, and other solvents that are easy to volatilize.
  • the dosage range of the four raw material components is: maleic anhydride grafted ethylene propylene diene rubber (maleic anhydride grafted terpolymer pellets) 98.5 parts, catalyst (I ) Is 0.07 parts, the modified monomer (II) is 0.8 parts, and the auxiliary monomer (III) is 0.45 parts.
  • the obtained viscosity index improver composition has a kinematic viscosity in the range of 300-1200mm 2 /s at 100°C, a shear stability index of no more than 15 (diesel nozzle SSI), and a thickening capacity of no less than 3mm 2 /s ,
  • the low temperature apparent viscosity index is below 100 CCSI (measured at -20°C), and the high temperature oxidation detergency can reach at least level 3 (heat pipe oxidation).
  • the base oil is a synthetic base oil
  • the synthetic oil can be any one or any combination of polyalphaolefin, synthetic ester, polyether, silicone oil, fluorine-containing oil, and phosphate ester.
  • the base oil may have a kinematic viscosity of 5.0-160.0 mm 2 /s at 40°C and/or a kinematic viscosity of 1.50-34.0 mm 2 /s at 100°C.
  • the catalyst (II) dialkyl peroxide such as dicumyl peroxide, di-tert-butyl peroxide
  • the reaction is carried out for 20 minutes to make the two
  • the meta-copolymer is degraded to form macromolecular free radicals; then the modified monomer (II) trimethylolpropane triacrylate and the auxiliary monomer styrene (III) composition (D) are injected into the reactor, and continue Stir for 30 minutes to cause the macromolecular free radicals to initiate the reaction of the multifunctional modified monomer to form a lubricant viscosity index improver composition concentrate with a star-shaped structure.
  • the dosage range of the above-mentioned four raw material components is: maleic anhydride grafted EPDM rubber is not less than 98 parts, catalyst (I) is not more than 0.1 part, and modified monomer (II) does not exceed 1.2 parts, and auxiliary monomer (III) does not exceed 0.7 parts.
  • the obtained viscosity index improver concentrate (10% liquid glue) has a kinematic viscosity in the range of 300-1200mm2/s at 100°C, a shear stability index not exceeding 14 (diesel nozzle SSI), and thickening ability is not low At 4mm2/s, the low-temperature apparent viscosity index is below CCSI80 (measured at -20°C), and the high-temperature oxidation detergency can reach at least level 3 or less (heat pipe oxidation).
  • the peroxyester catalyst (I) for example, one of tert-butyl peroxybenzoate and tert-butyl peroxyvalerate
  • a solution (A) Spray the solution (A) evenly into the maleic anhydride grafted terpolymer pellets (B) and stir, and let it stand for a period of time until the solvent is completely volatilized to obtain the composition (C); mix the modified material ( C) Extrude on the extruder, control the extrusion temperature to 160°C, add the modified monomer trimethylolpropane triacrylate (II) and the auxiliary monomer styrene in the middle or the end of the heating section of the extruder.
  • the peroxyester catalyst (I) for example, one of tert-butyl peroxybenzoate and tert-butyl peroxyvalerate
  • the composition (D) of (III) is extruded to obtain the star-shaped maleic anhydride grafted EPDM copolymer lubricating oil viscosity index improver composition.
  • the solvent used is a solvent that can dissolve the catalyst but cannot dissolve the terpolymer (I), and can be acetone, ethyl acetate, methanol, ethanol, and other solvents that are easy to volatilize.
  • the dosage range of the above-mentioned four raw material components is: maleic anhydride grafted terpolymer rubber (maleic anhydride grafted terpolymer pellets) not less than 98 parts , Catalyst (I) does not exceed 0.1 parts, modified monomer (II) does not exceed 1.2 parts, auxiliary monomer (III) does not exceed 0.7 parts.
  • the obtained viscosity index improver composition has a kinematic viscosity in the range of 300-1200mm 2 /s at 100°C, a shear stability index no more than 14 (diesel nozzle SSI), and a thickening capacity no less than 5mm 2 /s ,
  • the low-temperature apparent viscosity index is below CCSI90 (measured at -20°C), and the high-temperature oxidation detergency can reach at least level 3 (heat pipe oxidation).
  • the base oil is a vegetable base oil, which is a natural animal and vegetable oil with an ester bond in the molecular structure.
  • the base oil may have a kinematic viscosity of 5.0-160.0 mm 2 /s at 40°C and/or a kinematic viscosity of 1.50-34.0 mm 2 /s at 100°C.
  • the dosage range of the four raw material components is: 99 parts of maleic anhydride grafted EPDM, 0.08 parts of catalyst (I), and 0.5 parts of modified monomer (II) Parts, auxiliary monomer (III) is 0.42 parts.
  • the obtained viscosity index improver concentrate (10% liquid glue) has a kinematic viscosity in the range of 300-1200mm2/s at 100°C, a shear stability index not exceeding 13 (diesel nozzle SSI), and thickening ability is not low At 5mm2/s, the low-temperature apparent viscosity index is below CCSI90 (measured at -20°C), and the high-temperature oxidation detergency can reach at least level 3 (heat pipe oxidation).
  • Example 4 Based on Example 1, the modified monomer was replaced with trimethylolpropane trimethacrylate, and the remaining operation steps and dosage standards refer to Example 1.
  • the obtained viscosity index improver composition (melt polymerized product) has a kinematic viscosity in the range of 300-1200mm 2 /s at 100°C, a shear stability index of no more than 14 (diesel nozzle SSI), and a high thickening ability At 3mm 2 /s, the low-temperature apparent viscosity index is below CCSI80 (measured at -20°C), and the high-temperature oxidation detergency can reach at least class 3.5 (heat pipe oxidation).
  • the obtained viscosity index improver concentrate (solution polymerization product, 10% liquid glue) has a kinematic viscosity in the range of 300-1200mm 2 /s at 100°C, and a shear stability index of no more than 15 (diesel nozzle SSI), The thickening ability is not less than 3mm 2 /s, the low temperature apparent viscosity index is below CCSI90 (measured at -20°C), and the high temperature oxidation detergency can reach at least class 3.5 (heat pipe oxidation).
  • the modifying monomer can be trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, 3 (propoxy) propylene triacrylate, Alcohol triacrylate, tris(2-hydroxyethyl) isocyanuric acid triacrylate, di(trimethylolpropane) tetraacrylate, pentaerythritol tetraacrylate, 4(ethoxy) pentaerythritol tetraacrylate, double Any one or any combination of pentaerythritol hexaacrylate.
  • Example 5 Based on Example 1, the auxiliary monomer was replaced with acrylamide, and the remaining operation steps and dosage standards refer to Example 1.
  • the obtained viscosity index improver composition (melt polymerized product) has a kinematic viscosity in the range of 300-1200mm 2 /s at 100°C, a shear stability index no more than 15 (diesel nozzle SSI), and thickening ability is not low At 3mm 2 /s, the low temperature apparent viscosity index is below CCSI90 (measured at -20°C), and the high temperature oxidation detergency can reach at least class 3.5 (heat pipe oxidation).
  • the obtained viscosity index improver concentrate (solution polymerization product, 10% liquid glue) has a kinematic viscosity in the range of 300-1200mm 2 /s at 100°C, and a shear stability index of no more than 16 (diesel nozzle SSI), The thickening ability is not less than 3mm 2 /s, the low temperature apparent viscosity index is below CCSI90 (measured at -20°C), and the high temperature oxidation detergency can reach at least class 3.5 (heat pipe oxidation).
  • the auxiliary monomer may be any one of styrene, acrylamide, and a thiuram derivative containing a structure of formula ( ⁇ ).
  • Embodiment 6 is a diagrammatic representation of Embodiment 6
  • Example 6 Based on Example 2, the modified monomer was replaced with trimethylolpropane trimethacrylate, and the remaining operation steps and dosage standards refer to Example 2.
  • the obtained viscosity index improver composition (melt polymerized product) has a kinematic viscosity in the range of 300-1200mm 2 /s at 100°C, a shear stability index of no more than 14 (diesel nozzle SSI), and a high thickening ability At 4mm 2 /s, the low-temperature apparent viscosity index is below CCSI90 (measured at -20°C), and the high-temperature oxidation detergency can reach at least level 3 (heat pipe oxidation).
  • the obtained viscosity index improver concentrate (solution polymerization product, 10% liquid glue) has a kinematic viscosity in the range of 300-1200mm 2 /s at 100°C, and a shear stability index of no more than 12 (diesel nozzle SSI),
  • the thickening capacity is not less than 4mm 2 /s, the low temperature apparent viscosity index is below CCSI80 (measured at -20°C), and the high temperature oxidation detergency can reach at least level 3 (heat pipe oxidation).
  • the modifying monomer can be trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, 3 (propoxy) propylene triacrylate, Alcohol triacrylate, tris(2-hydroxyethyl) isocyanuric acid triacrylate, di(trimethylolpropane) tetraacrylate, pentaerythritol tetraacrylate, 4(ethoxy) pentaerythritol tetraacrylate, double Any one or any combination of pentaerythritol hexaacrylate.
  • Example 7 Based on Example 2, the auxiliary monomer was replaced with acrylamide, and the rest of the operation steps and dosage standards refer to Example 2.
  • the obtained viscosity index improver composition (melt polymerization product) has a kinematic viscosity in the range of 300-1200mm 2 /s at 100°C, a shear stability index of no more than 13 (diesel nozzle SSI), and a high thickening ability At 4mm 2 /s, the low-temperature apparent viscosity index is below CCSI90 (measured at -20°C), and the high-temperature oxidation detergency can reach at least level 3 (heat pipe oxidation).
  • the obtained viscosity index improver concentrate (solution polymerization product, 10% liquid glue) has a kinematic viscosity in the range of 300-1200mm 2 /s at 100°C, and a shear stability index of no more than 11 (diesel nozzle SSI),
  • the thickening capacity is not less than 4mm 2 /s, the low temperature apparent viscosity index CCSI100 is below (measured at -20°C), and the high temperature oxidation detergency can reach at least level 3 (heat pipe oxidation).
  • the auxiliary monomer may be any one of styrene, acrylamide, and a thiuram derivative containing a structure of formula ( ⁇ ).
  • Embodiment 8 is a diagrammatic representation of Embodiment 8
  • Example 8 Based on Example 3, the modified monomer was replaced with trimethylolpropane trimethacrylate, and the rest of the operation steps and dosage standards refer to Example 3.
  • the obtained viscosity index improver composition (melt polymerization product) has a kinematic viscosity in the range of 300-1200mm2/s at 100°C, a shear stability index not exceeding 15 (diesel nozzle SSI), and a thickening ability not lower than 5mm2/s, low temperature apparent viscosity index CCSI95 below (measured at -20°C), high temperature oxidation detergency can reach at least 3 levels (heat pipe oxidation).
  • the obtained viscosity index improver concentrate (solution polymerization product, 10% liquid glue) has a kinematic viscosity in the range of 300-1200mm2/s at 100°C, a shear stability index not exceeding 14 (diesel nozzle SSI), and thick
  • the chemical ability is not less than 5mm2/s, the low temperature apparent viscosity index is below CCSI80 (measured at -20°C), and the high temperature oxidation detergency can reach at least level 3 (heat pipe oxidation).
  • the modifying monomer can be trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, 3 (propoxy) propylene triacrylate, Alcohol triacrylate, tris(2-hydroxyethyl) isocyanuric acid triacrylate, di(trimethylolpropane) tetraacrylate, pentaerythritol tetraacrylate, 4(ethoxy) pentaerythritol tetraacrylate, double Any one or any combination of pentaerythritol hexaacrylate.
  • the ninth embodiment is based on the third embodiment, the auxiliary monomer is replaced with acrylamide, and the remaining operation steps and dosage standards are in the third embodiment.
  • the obtained viscosity index improver composition (melt polymerization product) has a kinematic viscosity in the range of 300-1200mm2/s at 100°C, a shear stability index not exceeding 15 (diesel nozzle SSI), and a thickening ability not lower than 4mm2/s, low temperature apparent viscosity index below CCSI80 (measured at -20°C), high temperature oxidation detergency can reach at least level 3 or less (heat pipe oxidation).
  • the obtained viscosity index improver concentrate (solution polymerization product, 10% liquid glue) has a kinematic viscosity in the range of 300-1200mm2/s at 100°C, a shear stability index not exceeding 14 (diesel nozzle SSI), and thick
  • the chemical ability is not less than 5mm2/s, the low temperature apparent viscosity index is below CCSI85 (measured at -20°C), and the high temperature oxidation detergency can reach at least level 3 (heat pipe oxidation).
  • the auxiliary monomer may be any one of styrene, acrylamide, and a thiuram derivative containing a structure of formula ( ⁇ ).
  • the catalyst (II) in the present invention by adding the catalyst (II) in the present invention, the propyl structural unit on the maleic anhydride grafted EPDM copolymer is degraded, the proportion of the propyl unit is reduced, and the molecular weight distribution of the molecular chain is broadened. ; Combining the control of the order and amount of addition of the catalyst (I) and the modified monomer (II) to make the macromolecular free radicals react with the modified monomer (II) to form a long-chain branched star copolymer; auxiliary monomer The use of (III) reduces the occurrence of irreversible cross-linking.
  • the molecular chain of the formed star polymer shrinks at low temperature, but does not cause serious entanglement, which has a small effect on viscosity; at high temperature, the molecular chain stretches, which is very lubricating. Oil has a significant effect of increasing viscosity.
  • Lubricant VII More importantly, the proportion of structural units ( ⁇ ) is reduced and the molecular weight distribution of the molecular chain is broadened, and the low temperature performance of the obtained Lubricant VII is remarkable.
  • the improver and its preparation method overcome the crosslinking problem in the polymerization reaction process, so that the prepared lubricating oil VII has the characteristics of strong thickening ability, good shear stability, low temperature performance and excellent high temperature oxidation detergency.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Lubricants (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

本发明公开了一种含有星型的马来酸酐接枝三元乙丙共聚物润滑油粘度指数改进剂及其制备方法，它是将马来酸酐接枝的三元乙丙橡胶、催化剂(I)、改性单体(II)、辅助单体(III)，经过特定的熔融聚合方法制备而成的的星型聚合物的固体，或溶液聚合方法制备而成的星型聚合物的液体组合物。本发明的在不降低OCP类VII的油品清净性的前提下，能够改善剪切稳定性或低温性能。

Description

含有星型的马来酸酐接枝三元乙丙共聚物润滑油粘度指数改进剂及其制备方法 技术领域
本发明属于润滑油改性技术领域，尤其涉及一种润滑油粘度指数改进剂组合物及其制备方法。
背景技术
粘度指数改进剂(VII)是一种常温下呈橡胶状或固体状的油溶性高分子化合物，通常用150SN或100SN的中性油稀释成5-10％的浓缩物来使用(李仲明.一种润滑油组合物粘度指数改进剂.CN 108048167A)。向润滑油中添加VII，可得到低温起动性好、高温粘度适宜、四季通用的多级油，使用寿命长。润滑油中VII的高分子链在高温下充分伸展，起到增加粘度作用；低温下会收缩卷曲，对粘度的影响小。因而，与粘度相同的单级润滑油相比，含有VII的多级油具有较高的粘度指数和平滑的粘温曲线。
乙丙共聚物粘度指数改进剂(OCP)的增粘性、剪切稳定性、粘温性能均较佳，而且原料易得、工艺简单(向文成.分散型乙丙共聚物粘度指数改进剂.润滑油.1994,5:36-42.)，但耐低温性能也稍差，常需要加入脂类降凝剂。PMA类VII的低温性和氧化稳定性优异，但是增粘性能和油品清净性差。若将两者的优势结合在一起，可获得一定的综合性能提升，例如MA类单体对OCP进行接枝或共聚，但效果仍不够显著(陈德宏,宋庆武,刘建新.分散抗氧型乙丙共聚物粘度指数改进剂DAOCP的研制.石油炼制与化工.2001,1:34-36.)。马来酸酐接枝三元乙丙橡胶是一种由三元乙丙橡胶经过马来酸酐接枝后的产物，分子主链上含有酸酐基团，对提高低温性能有利的，以其来制备VII是一个不错选择。
一般来说，OCP类VII分子量越大，低温下分子链缠结越显著，在一定剪切速率作用下，流动阻力越大。分子量分布越窄，长、短链分子比例越少，在一定剪切力作用下，发生断链可能性越小，粘度保持性较强。因此，分子量越小且分子量分布越宽，对提高低温性能优异，但对增粘性能不利(王国金，朱和菊，叶元凯，陈月珠.OCP粘度指数改进剂分子结构对低温性能的影响.润滑与密封.1999,6:26-29.)因此，为了获得兼具增粘性、剪切稳定性、热氧化安定性、油品清净性、低温性能的OCP，可以进一步从马来酸酐接枝三元乙丙橡胶的分子结构、分子量、分子量分布上着手。
如专利申请99108204.4公开了一种润滑油增粘剂及其生产方法，其润滑油增粘剂由以下成份组成的：A.有3.98％至9.96％的二元乙丙橡胶或三元乙丙橡胶或它们的混合物；B.有0.02％至0.04％的双环戊二烯基铁；C.余量为机油；或者由以下成份组成：A.有3.96％至9.92％的二元乙丙橡胶或三元乙丙橡胶或它们的混合物：B.有0.02％至0.04％的双环戊二烯基铁；C.有0.02％至0.04％的丁二酰亚胺；D.余量为机油。然而，该润滑油增粘剂并不能在低温条件下改善剪切稳定性，存在着增粘性能、剪切稳定性、油品清净性、耐低温性能等不能兼顾的问题。
发明内容
基于此，本发明的首要目的在于不降低OCP类VII的油品清净性的前提下，提供一种改善剪切稳定性或低温性能的含有星型的马来酸酐接枝三元乙丙共聚物润滑油粘度指数改进剂及其制备方法。
本发明的目的在于提供一种兼顾增粘性(稠化能力)、剪切稳定性、油品清净性和低温性能的含有星型的马来酸酐接枝三元乙丙共聚物润滑油粘度指数改进剂及其制备方法，且减少了不可逆交联的发生，提高了产品的制备效率和可靠性。
为实现上述目的，本发明的技术方案为：
一种含有星型的马来酸酐接枝三元乙丙共聚物润滑油粘度指数改进剂，其特征在于它是将马来酸酐接枝的三元乙丙橡胶、催化剂(I)、改性单体(II)、辅助单体(III)，经过特定的熔融聚合方法制备而成的的星型聚合物的固体，或溶液聚合方法制备而成的星型聚合物的液体组合物。
所述固体，为膏状物或块状物。
按照质量份数计，所述的四种原料组分的用量范围为：马来酸酐接枝的三元乙丙橡胶不低于98份，催化剂(I)不超过0.1份、改性单体(II)不超过1.2份、辅助单体(III)不超过0.7份。
进一步地，所述的四种原料组分的优选用量范围为：马来酸酐接枝的三元乙丙橡胶98～99.5份，催化剂(I)为0.05～0.1份、改性单体(II)为0.3～1.2份、辅助单体(III)为0.15～0.7份。
所述的马来酸酐接枝的三元乙丙橡胶数均分子量为2～15万。
所述的催化剂(I)是含式(α)结构单元的化合物。其中，R1和R2分别为氢、C1～12的烷基、环烷基、芳基、酰基、酯基、碳酸酯基、酮基中的任意一种或任意组合。其中，所述的烷基、环烷基、芳基、酰基、酯基、碳酸酯基、酮基，可以进一步1～6个独立选自烷基、环烷基、芳基的取代基所取代；所述(α)结构单元的的分子式如下：
Figure PCTCN2019125756-appb-000001
进一步，所述的催化剂(I)可以选自过氧化氢、异丙苯过氧化氢、叔丁基过氧化氢、过氧化二异丙苯、过氧化二叔丁基、过氧化二苯甲酰、过氧化十二酰、过氧化苯甲酸叔丁酯、过氧化叔戊酸叔丁酯、过氧化二碳酸二异丙酯、过氧化二碳酸二环己酯中的任意一种。
所述的改性单体(II)是含有两个以下(β)或(γ)结构单元的化合物，(β)和(γ)结构单元的分子式如下：
Figure PCTCN2019125756-appb-000002
进一步，所述改性单体(II)是可以是三羟甲基丙烷三丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、乙氧基化三羟甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、3(丙氧基)丙三醇三丙烯酸酯、三(2-羟乙基)异氰脲酸三丙烯酸酯、二(三羟甲基丙烷)四丙烯酸酯、季戊四醇四丙烯酸酯、4(乙氧基)季戊四醇四丙烯酸酯、双季戊四醇六丙烯酸酯中的任意一种。
所述的辅助单体(III)为苯乙烯、丙烯酰胺、含式(δ)结构的秋兰姆衍生物中的任意一种，其中R3和R4可以是C1～7的烷基、环烷基、芳基、苄基、异丁基、哌啶基中的任意一种或任意组合；其中，式(δ)的分子式为：
Figure PCTCN2019125756-appb-000003
所述的秋兰姆衍生物可以是一硫化四甲基秋兰姆、二硫化四甲基秋兰姆、二硫化四乙基秋兰姆、二硫化四苄基秋兰姆、二硫化二甲基二苯基秋兰姆、二硫化二异丁基秋兰姆、二环戊亚甲基二硫化四烷基秋兰姆、四硫化双五亚甲基秋兰姆、六硫化双五甲撑秋兰姆等。
一种含有星型的马来酸酐接枝三元乙丙共聚物润滑油粘度指数改进剂的熔融聚合方法，其特征在于该方法包括以下步骤：
(11)准确称取催化剂(I)，并溶于溶剂中，得到溶液(A)；将溶液(A)均匀地喷入马来酸酐接枝的三元共聚物粒料(B)中搅拌，静置，待溶剂完全挥发后，得到组合物(C)；
(12)将混合改性料(C)经挤出机上挤出，控制挤出温度为150-300℃之间，在挤出机加热段的中或末端滴加改性单体(II)和辅助单体(III)的混合 物(D)，挤出后即得到所述星型的马来酸酐接枝三元乙丙共聚物润滑油粘度指数改进剂。
所述的熔融聚合法中，所用的溶剂是能溶解催化剂但不能溶解三元共聚物(I)的溶剂，可以是丙酮、乙酸乙酯、甲醇、乙醇以及其他易于挥发的溶剂。
一种含有星型的马来酸酐接枝三元乙丙共聚物润滑油粘度指数改进剂的溶液聚合方法，其特征在于所述方法包括以下步骤：
(21)向盛有基础油的反应器中分批次加入马来酸酐接枝的三元乙丙橡胶，控制温度不超过100℃，开动搅拌器，使三元共聚物溶解，控制质量浓度在不超过30％。
(22)升温至120℃～300℃，再向反应釜中注入催化剂(I)，经过1～30min反应，使得共聚物发生降解，形成大分子自由基；
(23)再注入改性单体(II)辅助单体(III)的混合物(D)，持续搅拌10-30min，冷却出料，即得到所述星型的马来酸酐接枝三元乙丙共聚物润滑油粘度指数改进剂的组合物。
所述基础油为矿物基础油、合成基础油、植物性基础油的任意一种，基础油的40℃运动粘度为5.0～160.0mm 2/s和/或100℃运动粘度为1.50～34.0mm 2/s。
进一步，所述矿物基础油主要成分包含烷烃、环烷烃、芳烃、环烷基芳烃以及含氧、氮、硫有机化合物；合成油可以是聚α烯烃、合成酯、聚醚、硅油、含氟油、磷酸酯中的任意一种或任意组合；植物性基础油是分子结构中含有酯键的天然动植物油脂。
本发明通过加入催化剂(II)，使得马来酸酐接枝三元乙丙共聚物的上的丙基结构单元发生降解，丙基单元比例减少，而且分子链的分子量分布变宽；结合控制催化剂(I)和改性单体(II)的加入顺序和用量，使大分子自由基与改性单体(II)发生反应，形成长支链的星型共聚物；辅助单体(III)的使用，减少了不可逆交联的发生，所形成的星型聚合物低温下分子链收缩，但未发生严重缠结，对粘度的影响较小；高温下，分子链舒展，对润滑油增黏作用显著。
更重要的是结构单元(β)比例减少且分子链的分子量分布变宽，所得润滑油VII的低温性能显著。该改进剂及其制备方法克服了聚合反应过程中的交联问题，从而使制备的润滑油VII具有增稠能力强、剪切安定性好、低温性能和高温氧化清净性优异的特点。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
本发明所实现的含有星型的马来酸酐接枝三元乙丙共聚物润滑油粘度指数改进剂，是将马来酸酐接枝的三元乙丙橡胶、催化剂(I)、改性单体(II)、辅助单体(III)，经过特定的熔融聚合方法制备而成的星型聚合物的固体，例如膏状物或块状物，或溶液聚合方法制备而成的液体组合物。
按照质量份数计，所述的四种原料组分的用量范围为：马来酸酐接枝的三元乙丙橡胶不低于98份，催化剂(I)不超过0.1份、改性单体(II)不超过1.2份、辅助单体(III)不超过0.7份。上述的四种原料组分的优选用量范围为：马来酸酐接枝的三元乙丙橡胶98～99.5份，催化剂(I)为0.05～0.1份、改性单体(II)为0.3～1.2份、辅助单体(III)为0.15～0.7份。
所述的马来酸酐接枝的三元乙丙橡胶数均分子量为2～15万。
所述的催化剂(I)是含式(α)结构单元的化合物。其中，R1和R2分别为氢、C1～12的烷基、环烷基、芳基、酰基、酯基、碳酸酯基、酮基中的任意一种或任意组合。其中，所述的烷基、环烷基、芳基、酰基、酯基、碳酸酯基、酮基，可以进一步1～6个独立选自烷基、环烷基、芳基的取代基所取代；所述(α)结构单元的的分子式如下：
Figure PCTCN2019125756-appb-000004
其中，所述的催化剂(I)可以选自过氧化氢、异丙苯过氧化氢、叔丁基过氧化氢、过氧化二异丙苯、过氧化二叔丁基、过氧化二苯甲酰、过氧化十二酰、过氧化苯甲酸叔丁酯、过氧化叔戊酸叔丁酯、过氧化二碳酸二异丙酯、过氧化二碳酸二环己酯中的任意一种。
所述的改性单体(II)是含有两个以下(β)或(γ)结构单元的化合物，(β)和(γ)结构单元的分子式如下：
Figure PCTCN2019125756-appb-000005
其中，所述改性单体(II)是可以是三羟甲基丙烷三丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、乙氧基化三羟甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、3(丙氧基)丙三醇三丙烯酸酯、三(2-羟乙基)异氰脲酸三丙烯酸酯、二(三羟甲基丙烷)四丙烯酸酯、季戊四醇四丙烯酸酯、4(乙氧基)季戊四醇四丙烯酸酯、双季戊四醇六丙烯酸酯中的任意一种。
所述的辅助单体(III)为苯乙烯、丙烯酰胺、含式(δ)结构的秋兰姆衍生物中的任意一种，其中R3和R4可以是C1～7的烷基、环烷基、芳基、苄基、异丁基、哌啶基中的任意一种或任意组合；其中，式(δ)的分子式为：
Figure PCTCN2019125756-appb-000006
所述的秋兰姆衍生物可以是一硫化四甲基秋兰姆、二硫化四甲基秋兰姆、二硫化四乙基秋兰姆、二硫化四苄基秋兰姆、二硫化二甲基二苯基秋兰姆、二硫化二异丁基秋兰姆、二环戊亚甲基二硫化四烷基秋兰姆、四硫化双五亚甲基秋兰姆、六硫化双五甲撑秋兰姆等。
本发明所实现星型的马来酸酐接枝三元乙丙共聚物润滑油粘度指数改进剂 的熔融聚合方法，包括以下步骤：
(11)准确称取催化剂(I)，并溶于溶剂中，得到溶液(A)；将溶液(A)均匀地喷入马来酸酐接枝的三元共聚物粒料(B)中搅拌，静置，待溶剂完全挥发后，得到组合物(C)；
(12)将混合改性料(C)经挤出机上挤出，控制挤出温度为150-300℃之间，在挤出机加热段的中或末端滴加改性单体(II)和辅助单体(III)的混合物(D)，挤出后即得到所述的星型的马来酸酐接枝三元乙丙共聚物润滑油粘度指数改进剂。
所述的熔融聚合法中，所用的溶剂是能溶解催化剂但不能溶解三元共聚物(I)的溶剂，可以是丙酮、乙酸乙酯、甲醇、乙醇以及其他易于挥发的溶剂。
本发明所实现星型的马来酸酐接枝三元乙丙共聚物润滑油粘度指数改进剂的溶液聚合方法，包括以下步骤：
(21)向盛有基础油的反应器中分批次加入马来酸酐接枝的三元乙丙橡胶，控制温度不超过100℃，开动搅拌器，使三元共聚物溶解，控制质量浓度在不超过30％。
(22)升温至120℃～300℃，再向反应釜中注入催化剂(I)，经过1～30min反应，使得共聚物发生降解，形成大分子自由基；
(23)再注入改性单体(II)辅助单体(III)的混合物(D)，持续搅拌10-30min，冷却出料，即得到所述的星型的马来酸酐接枝三元乙丙共聚物润滑油粘度指数改进剂的组合物。
所述基础油为矿物基础油、合成基础油、植物性基础油的任意一种，基础油的40℃运动粘度为5.0～160.0mm 2/s和/或100℃运动粘度为1.50～34.0mm 2/s。
其中，所述矿物基础油主要成分包含烷烃、环烷烃、芳烃、环烷基芳烃以及含氧、氮、硫有机化合物；合成油可以是聚α烯烃、合成酯、聚醚、硅油、含氟油、磷酸酯中的任意一种或任意组合；植物性基础油是分子结构中含有酯键的天然动植物油脂。
具体实现方式如下：
实施例一：
熔融聚合法：
准确称取氢过氧化物催化剂(I)(过氧化氢、异丙苯过氧化氢、叔丁基过氧化氢中的任意一种)，并溶于溶剂中，得到溶液(A)。将溶液(A)均匀地喷入马来酸酐接枝的三元共聚物粒料(B)中搅拌，静置一段时间待溶剂完全挥发后，得到组合物(C)；将混合改性料(C)经挤出机上挤出，控制挤出温度为150℃，在挤出机加热段的中间或末端滴加改性单体三羟甲基丙烷三丙烯酸酯(II)和辅助单体苯乙烯(III)的混合物(D)，挤出后即得到所述的星型的马来酸酐接枝三元乙丙共聚物润滑油粘度指数改进剂。所述的熔融聚合法中，所用的溶剂是能溶解催化剂但不能溶解三元共聚物(I)的溶剂，可以是丙酮、乙酸乙酯、甲醇、乙醇以及其他易于挥发的溶剂。
其中，按照质量份数计，上述的四种原料组分的用量范围为：马来酸酐接枝的三元乙丙橡胶(马来酸酐接枝的三元共聚物粒料)不低于98份，催化剂(I)不超过0.1份、改性单体(II)不超过1.2份、辅助单体(III)不超过0.7份。
所得到的粘度指数改进剂组合物(即星型的马来酸酐接枝三元乙丙共聚物润滑油粘度指数改进剂，以下相同)在以10m％浓度溶解在100℃运动粘度为5.1mm 2/s的基础油中测试(下同)的100℃运动粘度在300-1200mm 2/s范围内，剪切稳定性指数不超过14(柴油喷嘴SSI)，稠化能力不低于3mm 2/s，低温表观粘度指数CCSI90以下(-20℃下测量)，高温氧化清净性可达到至少3.5级以下(热管氧化)。
溶液聚合法：
向盛有基础油(V)的反应器中分批次加入马来酸酐接枝的三元乙丙橡胶，控制温度不超过100℃，开动搅拌器，使二元共聚物(马来酸酐接枝的三元乙丙橡胶)溶解，二元共聚物在基础油中的质量分数在不超过30％。其中基础油选用矿物油，矿物基础油主要成分包含烷烃、环烷烃、芳烃、环烷基芳烃以及 含氧、氮、硫有机化合物。基础油可以是40℃运动粘度为5.0～160.0mm 2/s和/或100℃运动粘度为1.50～34.0mm 2/s。升温至300℃，并使得反应温度稳定后，再向反应釜中注入氢过氧化物催化剂(I)(过氧化氢、异丙苯过氧化氢、叔丁基过氧化氢)，经过30min反应，使得二元共聚物发生降解，形成大分子自由基；再向反应釜中注入改性单体(II)三羟甲基丙烷三丙烯酸酯和辅助单体苯乙烯(III)的组合物(D)，持续搅拌10min，使大分子自由基引发多官能度改性单体发生反应，形成具有星型结构的润滑油粘度指数改进剂组合物浓缩液(即星型的马来酸酐接枝三元乙丙共聚物润滑油粘度指数改进剂的组合物，以下相同)。
按照质量份数计，上述的四种原料组分的用量范围为：马来酸酐接枝的三元乙丙橡胶99.5份，催化剂(I)为0.05份、改性单体(II)为0.3份、辅助单体(III)为0.15份。
所得到的粘度指数改进剂浓缩液(10％液胶)(即星型的马来酸酐接枝三元乙丙共聚物润滑油粘度指数改进剂的组合物，以下相同)在100℃时其运动粘度在300-1200mm 2/s范围内，剪切稳定性指数不超过12(柴油喷嘴SSI)，稠化能力不低于3mm 2/s，低温表观粘度指数CCSI90以下(-20℃下测量)，高温氧化清净性可达到至少3.5级以下(热管氧化)。
实施例二：
熔融聚合法：
准确称取过氧化二烷基类催化剂(I)(如过氧化二异丙苯、过氧化二叔丁基中的一种)，并溶于溶剂中，得到溶液(A)。将溶液(A)均匀地喷入马来酸酐接枝的三元共聚物粒料(B)中搅拌，静置一段时间待溶剂完全挥发后，得到组合物(C)；将混合改性料(C)经挤出机上挤出，控制挤出温度为230℃，在挤出机加热段的中或末端滴加改性单体三羟甲基丙烷三丙烯酸酯(II)和辅助单体苯乙烯(III)的组合物(D)，挤出后即得到所述的星型马来酸酐接枝三元乙丙共聚物润滑油粘度指数改进剂组合物。所述的熔融聚合法中，所用的 溶剂是能溶解催化剂但不能溶解三元共聚物(I)的溶剂，可以是丙酮、乙酸乙酯、甲醇、乙醇以及其他易于挥发的溶剂。
按照质量份数计，所述的四种原料组分的用量范围为：马来酸酐接枝的三元乙丙橡胶(马来酸酐接枝的三元共聚物粒料)98.5份，催化剂(I)为0.07份、改性单体(II)为0.8份、辅助单体(III)为0.45份。
所得到的粘度指数改进剂组合物在100℃时其运动粘度在300-1200mm 2/s范围内，剪切稳定性指数不超过15(柴油喷嘴SSI)，稠化能力不低于3mm 2/s，低温表观粘度指数CCSI100以下(-20℃下测量)，高温氧化清净性可达到至少3级以下(热管氧化)。
溶液聚合法：
向盛有基础油(V)的反应器中分批次加入马来酸酐接枝的三元乙丙橡胶，控制温度不超过100℃，开动搅拌器，使二元共聚物(马来酸酐接枝的三元乙丙橡胶)溶解，二元共聚物在基础油中的质量分数在不超过30％。其中基础油选用合成基础油，合成油可以是聚α烯烃、合成酯、聚醚、硅油、含氟油、磷酸酯中的任意一种或任意组合。基础油可以是40℃运动粘度为5.0～160.0mm 2/s和/或100℃运动粘度为1.50～34.0mm 2/s。升温至130℃，并使得反应温度稳定后，再向反应釜中注入催化剂(II)过氧化二烷基(如过氧化二异丙苯、过氧化二叔丁基)，经过20min反应，使得二元共聚物发生降解，形成大分子自由基；再向反应釜中注入改性单体(II)三羟甲基丙烷三丙烯酸酯和辅助单体苯乙烯(III)的组合物(D)，持续搅拌30min，使大分子自由基引发多官能度改性单体发生反应，形成具有星型结构的润滑油粘度指数改进剂组合物浓缩液。
其中，按照质量份数计，上述的四种原料组分的用量范围为：马来酸酐接枝的三元乙丙橡胶不低于98份，催化剂(I)不超过0.1份、改性单体(II)不超过1.2份、辅助单体(III)不超过0.7份。
所得到的粘度指数改进剂浓缩液(10％液胶)在100℃时其运动粘度在300-1200mm2/s范围内，剪切稳定性指数不超过14(柴油喷嘴SSI)，稠化能 力不低于4mm2/s，低温表观粘度指数CCSI80以下(-20℃下测量)，高温氧化清净性可达到至少3级以下(热管氧化)。
实施例三：
熔融聚合法：
准确称取过氧化酯类催化剂(I)(如过氧化苯甲酸叔丁酯、过氧化叔戊酸叔丁酯中的一种)，并溶于溶剂中，得到溶液(A)。将溶液(A)均匀地喷入马来酸酐接枝的三元共聚物粒料(B)中搅拌，静置一段时间待溶剂完全挥发后，得到组合物(C)；将混合改性料(C)经挤出机上挤出，控制挤出温度为160℃，在挤出机加热段的中间或末端滴加改性单体三羟甲基丙烷三丙烯酸酯(II)和辅助单体苯乙烯(III)的组合物(D)，挤出后即得到所述的星型马来酸酐接枝三元乙丙共聚物润滑油粘度指数改进剂组合物。所述的熔融聚合法中，所用的溶剂是能溶解催化剂但不能溶解三元共聚物(I)的溶剂，可以是丙酮、乙酸乙酯、甲醇、乙醇以及其他易于挥发的溶剂。
其中，按照质量份数计，上述的四种原料组分的用量范围为：马来酸酐接枝的三元乙丙橡胶(马来酸酐接枝的三元共聚物粒料)不低于98份，催化剂(I)不超过0.1份、改性单体(II)不超过1.2份、辅助单体(III)不超过0.7份。
所得到的粘度指数改进剂组合物在100℃时其运动粘度在300-1200mm 2/s范围内，剪切稳定性指数不超过14(柴油喷嘴SSI)，稠化能力不低于5mm 2/s，低温表观粘度指数CCSI90以下(-20℃下测量)，高温氧化清净性可达到至少3级以下(热管氧化)。
溶液聚合法：
向盛有基础油(V)的反应器中分批次加入马来酸酐接枝的三元乙丙橡胶，控制温度不超过100℃，开动搅拌器，使二元共聚物(马来酸酐接枝的三元乙丙橡胶)溶解，二元共聚物在基础油中的质量分数在不超过30％。其中基础油选用植物性基础油，植物性基础油是分子结构中含有酯键的天然动植物油脂。基础油可以是40℃运动粘度为5.0～160.0mm 2/s和/或100℃运动粘度为 1.50～34.0mm 2/s。升温至120℃，并使得反应温度稳定后，再向反应釜中注入催化剂(II)过氧化酯类(过氧化苯甲酸叔丁酯、过氧化叔戊酸叔丁酯)，经过30/10min反应(过氧化苯甲酸叔丁酯为引发剂时，反应时间30min；过氧化叔戊酸叔丁酯为引发剂时，反应时间10min)，使得二元共聚物发生降解，形成大分子自由基；再向反应釜中注入改性单体(II)三羟甲基丙烷三丙烯酸酯和辅助单体苯乙烯(III)的组合物(D)，持续搅拌20min，使大分子自由基引发多官能度改性单体发生反应，形成具有星型结构的润滑油粘度指数改进剂组合物浓缩液。
按照质量份数计，所述的四种原料组分的用量范围为：马来酸酐接枝的三元乙丙橡胶99份，催化剂(I)为0.08份、改性单体(II)为0.5份、辅助单体(III)为0.42份。
所得到的粘度指数改进剂浓缩液(10％液胶)在100℃时其运动粘度在300-1200mm2/s范围内，剪切稳定性指数不超过13(柴油喷嘴SSI)，稠化能力不低于5mm2/s，低温表观粘度指数CCSI90以下(-20℃下测量)，高温氧化清净性可达到至少3级以下(热管氧化)。
实施例四：
实施例四基于实施例一将改性单体更换为三羟甲基丙烷三甲基丙烯酸酯，其余操作步骤及用量标准参照实施例一。
所得到的粘度指数改进剂组合物(熔融聚合产物)在100℃时其运动粘度在300-1200mm 2/s范围内，剪切稳定性指数不超过14(柴油喷嘴SSI)，稠化能力不低于3mm 2/s，低温表观粘度指数CCSI80以下(-20℃下测量)，高温氧化清净性可达到至少3.5级以下(热管氧化)。
所得到的粘度指数改进剂浓缩液(溶液聚合产物，10％液胶)在100℃时其运动粘度在300-1200mm 2/s范围内，剪切稳定性指数不超过15(柴油喷嘴SSI)，稠化能力不低于3mm 2/s，低温表观粘度指数CCSI90以下(-20℃下测量)，高温氧化清净性可达到至少3.5级以下(热管氧化)。
在其它的实施方式中，改性单体可以为三羟甲基丙烷三甲基丙烯酸酯、乙氧基化三羟甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、3(丙氧基)丙三醇三丙烯酸酯、三(2-羟乙基)异氰脲酸三丙烯酸酯、二(三羟甲基丙烷)四丙烯酸酯、季戊四醇四丙烯酸酯、4(乙氧基)季戊四醇四丙烯酸酯、双季戊四醇六丙烯酸酯中的任意一种或任意组合。
实施例五：
实施例五基于实施例一将辅助单体更换为丙烯酰胺，其余操作步骤及用量标准参照实施例一。
所得到的粘度指数改进剂组合物(熔融聚合产物)在100℃时其运动粘度在300-1200mm 2/s范围内，剪切稳定性指数不超过15(柴油喷嘴SSI)，稠化能力不低于3mm 2/s，低温表观粘度指数CCSI90以下(-20℃下测量)，高温氧化清净性可达到至少3.5级以下(热管氧化)。
所得到的粘度指数改进剂浓缩液(溶液聚合产物，10％液胶)在100℃时其运动粘度在300-1200mm 2/s范围内，剪切稳定性指数不超过16(柴油喷嘴SSI)，稠化能力不低于3mm 2/s，低温表观粘度指数CCSI90以下(-20℃下测量)，高温氧化清净性可达到至少3.5级以下(热管氧化)。
在其它的实施方式中，辅助单体可以为苯乙烯、丙烯酰胺、含式(δ)结构的秋兰姆衍生物中的任意一种。
实施例六：
实施例六基于实施例二将改性单体更换为三羟甲基丙烷三甲基丙烯酸酯，其余操作步骤及用量标准参照实施例二。
所得到的粘度指数改进剂组合物(熔融聚合产物)在100℃时其运动粘度在300-1200mm 2/s范围内，剪切稳定性指数不超过14(柴油喷嘴SSI)，稠化能力不低于4mm 2/s，低温表观粘度指数CCSI90以下(-20℃下测量)，高温氧化清净性可达到至少3级以下(热管氧化)。
所得到的粘度指数改进剂浓缩液(溶液聚合产物，10％液胶)在100℃时其 运动粘度在300-1200mm 2/s范围内，剪切稳定性指数不超过12(柴油喷嘴SSI)，稠化能力不低于4mm 2/s，低温表观粘度指数CCSI80以下(-20℃下测量)，高温氧化清净性可达到至少3级以下(热管氧化)。
在其它的实施方式中，改性单体可以为三羟甲基丙烷三甲基丙烯酸酯、乙氧基化三羟甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、3(丙氧基)丙三醇三丙烯酸酯、三(2-羟乙基)异氰脲酸三丙烯酸酯、二(三羟甲基丙烷)四丙烯酸酯、季戊四醇四丙烯酸酯、4(乙氧基)季戊四醇四丙烯酸酯、双季戊四醇六丙烯酸酯中的任意一种或任意组合。
实施例七：
实施例七基于实施例二将辅助单体更换为丙烯酰胺，其余操作步骤及用量标准参照实施例二。
所得到的粘度指数改进剂组合物(熔融聚合产物)在100℃时其运动粘度在300-1200mm 2/s范围内，剪切稳定性指数不超过13(柴油喷嘴SSI)，稠化能力不低于4mm 2/s，低温表观粘度指数CCSI90以下(-20℃下测量)，高温氧化清净性可达到至少3级以下(热管氧化)。
所得到的粘度指数改进剂浓缩液(溶液聚合产物，10％液胶)在100℃时其运动粘度在300-1200mm 2/s范围内，剪切稳定性指数不超过11(柴油喷嘴SSI)，稠化能力不低于4mm 2/s，低温表观粘度指数CCSI100以下(-20℃下测量)，高温氧化清净性可达到至少3级以下(热管氧化)。
在其它的实施方式中，辅助单体可以为苯乙烯、丙烯酰胺、含式(δ)结构的秋兰姆衍生物中的任意一种。
实施例八：
实施例八基于实施例三将改性单体更换为三羟甲基丙烷三甲基丙烯酸酯，其余操作步骤及用量标准参照实施例三。
所得到的粘度指数改进剂组合物(熔融聚合产物)在100℃时其运动粘度在300-1200mm2/s范围内，剪切稳定性指数不超过15(柴油喷嘴SSI)，稠化能 力不低于5mm2/s，低温表观粘度指数CCSI95以下(-20℃下测量)，高温氧化清净性可达到至少3级以下(热管氧化)。
所得到的粘度指数改进剂浓缩液(溶液聚合产物，10％液胶)在100℃时其运动粘度在300-1200mm2/s范围内，剪切稳定性指数不超过14(柴油喷嘴SSI)，稠化能力不低于5mm2/s，低温表观粘度指数CCSI80以下(-20℃下测量)，高温氧化清净性可达到至少3级以下(热管氧化)。
在其它的实施方式中，改性单体可以为三羟甲基丙烷三甲基丙烯酸酯、乙氧基化三羟甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、3(丙氧基)丙三醇三丙烯酸酯、三(2-羟乙基)异氰脲酸三丙烯酸酯、二(三羟甲基丙烷)四丙烯酸酯、季戊四醇四丙烯酸酯、4(乙氧基)季戊四醇四丙烯酸酯、双季戊四醇六丙烯酸酯中的任意一种或任意组合。
实施例九：
实施例九是基于实施例三将辅助单体更换为丙烯酰胺，其余操作步骤及用量标准实施例三。
所得到的粘度指数改进剂组合物(熔融聚合产物)在100℃时其运动粘度在300-1200mm2/s范围内，剪切稳定性指数不超过15(柴油喷嘴SSI)，稠化能力不低于4mm2/s，低温表观粘度指数CCSI80以下(-20℃下测量)，高温氧化清净性可达到至少3级以下(热管氧化)。
所得到的粘度指数改进剂浓缩液(溶液聚合产物，10％液胶)在100℃时其运动粘度在300-1200mm2/s范围内，剪切稳定性指数不超过14(柴油喷嘴SSI)，稠化能力不低于5mm2/s，低温表观粘度指数CCSI85以下(-20℃下测量)，高温氧化清净性可达到至少3级以下(热管氧化)。
在其它的实施方式中，辅助单体可以为苯乙烯、丙烯酰胺、含式(δ)结构的秋兰姆衍生物中的任意一种。
综上所述，本发明通过加入催化剂(II)，使得马来酸酐接枝三元乙丙共聚物的上的丙基结构单元发生降解，丙基单元比例减少，而且分子链的分子量分 布变宽；结合控制催化剂(I)和改性单体(II)的加入顺序和用量，使大分子自由基与改性单体(II)发生反应，形成长支链的星型共聚物；辅助单体(III)的使用，减少了不可逆交联的发生，所形成的星型聚合物低温下分子链收缩，但未发生严重缠结，对粘度的影响较小；高温下，分子链舒展，对润滑油增黏作用显著。
更重要的是结构单元(β)比例减少且分子链的分子量分布变宽，所得润滑油VII的低温性能显著。该改进剂及其制备方法克服了聚合反应过程中的交联问题，从而使制备的润滑油VII具有增稠能力强、剪切安定性好、低温性能和高温氧化清净性优异的特点。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种含有星型的马来酸酐接枝三元乙丙共聚物润滑油粘度指数改进剂，其特征在于所述改进剂是将马来酸酐接枝的三元乙丙橡胶、催化剂(I)、改性单体(II)、辅助单体(III)，经过熔融聚合方法制备而成的的星型聚合物的固体，或溶液聚合方法制备而成的液体组合物。
  2. 如权利要求1所述的含有星型的马来酸酐接枝三元乙丙共聚物润滑油粘度指数改进剂，其特征在于按照质量份数计，所述的四种原料组分的用量范围为：马来酸酐接枝的三元乙丙橡胶不低于98份，催化剂(I)不超过0.1份、改性单体(II)不超过1.2份、辅助单体(III)不超过0.7份。
  3. 如权利要求1所述的含有星型的马来酸酐接枝三元乙丙共聚物润滑油粘度指数改进剂，其特征在于所述的催化剂(I)是含式(α)结构单元的化合物，其中，R1和R2分别为氢、C1～12的烷基、环烷基、芳基、酰基、酯基、碳酸酯基、酮基中的任意一种或任意组合；所述的烷基、环烷基、芳基、酰基、酯基、碳酸酯基、酮基；所述(α)结构单元的的分子式如下：
    Figure PCTCN2019125756-appb-100001
  4. 如权利要求1所述的含有星型的马来酸酐接枝三元乙丙共聚物润滑油粘度指数改进剂，其特征在于所述的改性单体(II)是含有两个以下(β)或(γ)结构单元的化合物，(β)和(γ)结构单元的分子式如下：
    Figure PCTCN2019125756-appb-100002
  5. 如权利要求1所述的含有星型的马来酸酐接枝三元乙丙共聚物润滑油粘度指数改进剂，其特征在于所述的辅助单体(III)为苯乙烯、、丙烯酰胺、含式(δ)结构的秋兰姆衍生物中的任意一种，其中R3和R4是C1～7的烷基、 环烷基、芳基、苄基、异丁基、哌啶基中的任意一种或任意组合；其中，式(δ)的分子式为：
    Figure PCTCN2019125756-appb-100003
  6. 一种含有星型的马来酸酐接枝三元乙丙共聚物润滑油粘度指数改进剂的熔融聚合方法，其特征在于该方法包括以下步骤：
    (11)准确称取催化剂(I)，并溶于溶剂中，得到溶液(A)；将溶液(A)均匀地喷入马来酸酐接枝的三元共聚物粒料(B)中搅拌，静置，待溶剂完全挥发后，得到组合物(C)；
    (12)将混合改性料(C)经挤出机上挤出，控制挤出温度为150-300℃之间，在挤出机加热段的中或末端滴加改性单体(II)和辅助单体(III)的混合物(D)，挤出后即得到所述星型的马来酸酐接枝三元乙丙共聚物润滑油粘度指数改进剂。
  7. 如权利要求6所述的含有星型的马来酸酐接枝三元乙丙共聚物润滑油粘度指数改进剂的熔融聚合方法，其特征在于所述的熔融聚合法中，所用的溶剂是能溶解催化剂但不能溶解三元共聚物(I)的溶剂，是丙酮、乙酸乙酯、甲醇、乙醇的任意一种。
  8. 一种含有星型的马来酸酐接枝三元乙丙共聚物润滑油粘度指数改进剂的溶液聚合方法，其特征在于所述方法包括以下步骤：
    (21)向盛有基础油的反应器中分批次加入马来酸酐接枝的三元乙丙橡胶，控制温度不超过100℃，开动搅拌器，使三元共聚物溶解，控制质量浓度在不超过30％。
    (22)升温至120℃～300℃，再向反应釜中注入催化剂(I)，经过1～30min反应，使得共聚物发生降解，形成大分子自由基；
    (23)再注入改性单体(II)辅助单体(III)的混合物(D)，持续搅拌10-30 min，冷却出料，即得到所述星型的马来酸酐接枝三元乙丙共聚物润滑油粘度指数改进剂的组合物。
  9. 如权利要求8所述的含有星型的马来酸酐接枝三元乙丙共聚物润滑油粘度指数改进剂的溶液聚合方法，其特征在于所述基础油为矿物基础油、合成基础油、植物性基础油的任意一种，基础油的40℃运动粘度为5.0～160.0mm 2/s和/或100℃运动粘度为1.50～34.0mm 2/s。
  10. 如权利要求9所述的含有星型的马来酸酐接枝三元乙丙共聚物润滑油粘度指数改进剂的溶液聚合方法，其特征在于所述矿物基础油主要成分包含烷烃、环烷烃、芳烃、环烷基芳烃以及含氧、氮、硫有机化合物；合成油是聚α烯烃、合成酯、聚醚、硅油、含氟油、磷酸酯中的任意一种或任意组合；植物性基础油是分子结构中含有酯键的天然动植物油脂。
PCT/CN2019/125756 2019-08-14 2019-12-16 含有星型的马来酸酐接枝三元乙丙共聚物润滑油粘度指数改进剂及其制备方法 WO2021027211A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201910749637.3 2019-08-14
CN201910749637.3A CN110511333B (zh) 2019-08-14 2019-08-14 含有星型的马来酸酐接枝三元乙丙共聚物润滑油粘度指数改进剂及其制备方法

Publications (1)

Publication Number Publication Date
WO2021027211A1 true WO2021027211A1 (zh) 2021-02-18

Family

ID=68625151

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/125756 WO2021027211A1 (zh) 2019-08-14 2019-12-16 含有星型的马来酸酐接枝三元乙丙共聚物润滑油粘度指数改进剂及其制备方法

Country Status (2)

Country Link
CN (1) CN110511333B (zh)
WO (1) WO2021027211A1 (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110511333B (zh) * 2019-08-14 2022-02-22 深圳昆油石化技术有限公司 含有星型的马来酸酐接枝三元乙丙共聚物润滑油粘度指数改进剂及其制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4358565A (en) * 1979-11-16 1982-11-09 Shell Oil Company Lube oil additive
US5030695A (en) * 1983-06-15 1991-07-09 Exxon Research & Engineering Company End-capped polymer chains, star and graft copolymers, and process of making same
US5460739A (en) * 1994-09-09 1995-10-24 Shell Oil Company Star polymer viscosity index improver for oil compositions
CN101087823A (zh) * 2004-10-25 2007-12-12 卢布里佐尔公司 星形聚合物及其组合物
WO2012055802A1 (en) * 2010-10-25 2012-05-03 Polimeri Europa S.P.A. Hydrogenated styrene-butadiene copolymers and process for their preparation
CN110511333A (zh) * 2019-08-14 2019-11-29 深圳昆油石化技术有限公司 含有星型的马来酸酐接枝三元乙丙共聚物润滑油粘度指数改进剂及其制备方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4533482A (en) * 1982-12-30 1985-08-06 Rohm And Haas Company Hydrogenated diolefin-lower alkyl acrylate or methacrylate viscosity index improving copolymers for lubricating oils
CA2110649C (en) * 1992-12-17 2004-10-26 Jacob Emert Gel-free alpha-olefin dispersant additives useful in oleaginous compositions
CN101376860B (zh) * 2007-08-27 2011-02-09 中国石油化工股份有限公司 一种润滑油粘度指数改进剂及其制备方法和润滑油

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4358565A (en) * 1979-11-16 1982-11-09 Shell Oil Company Lube oil additive
US5030695A (en) * 1983-06-15 1991-07-09 Exxon Research & Engineering Company End-capped polymer chains, star and graft copolymers, and process of making same
US5460739A (en) * 1994-09-09 1995-10-24 Shell Oil Company Star polymer viscosity index improver for oil compositions
CN101087823A (zh) * 2004-10-25 2007-12-12 卢布里佐尔公司 星形聚合物及其组合物
WO2012055802A1 (en) * 2010-10-25 2012-05-03 Polimeri Europa S.P.A. Hydrogenated styrene-butadiene copolymers and process for their preparation
CN110511333A (zh) * 2019-08-14 2019-11-29 深圳昆油石化技术有限公司 含有星型的马来酸酐接枝三元乙丙共聚物润滑油粘度指数改进剂及其制备方法

Also Published As

Publication number Publication date
CN110511333A (zh) 2019-11-29
CN110511333B (zh) 2022-02-22

Similar Documents

Publication Publication Date Title
US5726136A (en) Multifunctional additive for lubricating oils compatible with fluoroelastomers
US4611031A (en) Process for the preparation of a compatibilizer for concentrated polymer blends and compatibilizer product
MX2007001464A (es) Metodo para polimerizacion a radical libre de compuestos insaturados etilenicamente.
EP2167548A1 (en) Improved process for preparing continuously variable-composition copolymers
RU2091404C1 (ru) Способ получения сополимера
WO2021027209A1 (zh) 含有星型二元乙丙共聚物润滑油粘度指数改进剂组合物及其制备方法
WO2021027211A1 (zh) 含有星型的马来酸酐接枝三元乙丙共聚物润滑油粘度指数改进剂及其制备方法
CN110499206B (zh) 含有星型sep共聚物润滑油粘度指数改性剂及其制备方法
CN102295972B (zh) 聚甲基丙烯酸酯型粘度指数改进剂及制备方法
CN107540783B (zh) 丙烯酸酯系聚合物及其应用和润滑油降凝剂及其制备方法
CZ295195A3 (en) Copolymer, lubricating oil means containing thereof and process for preparing a polymer improving index of dispersion viscosity
CA2146604C (en) Process for making a viscosity index improving copolymer
CN112876625A (zh) 一种聚（甲基）丙烯酸酯类粘度指数改进剂及其制备方法和应用
CA2694376A1 (en) Graft modified vinyl ester and ethylene polymers, preparation method thereof and use of same as additives that improve the cold properties of liquid hydrocarbons
KR102049311B1 (ko) 저-점도 중합체의 제조
RU2793326C1 (ru) Способ получения депрессорно-диспергирующей присадки и депрессорно-диспергирующая присадка
JP2928919B2 (ja) 粘度指数向上剤
CN101392207A (zh) 润滑油粘度指数改进剂
JP2001146594A (ja) 流動性向上剤及び潤滑油組成物
CN109880671A (zh) 一种高黏度指数改进剂及其制备方法和应用
CN116003678B (zh) 一种微反应器连续合成原油降凝剂的方法与应用
CN102295973B (zh) 聚甲基丙烯酸酯型粘度指数改进剂及制备
CN115485354B (zh) 分散剂聚(甲基)丙烯酸烷基酯聚合物的制备方法
JP4485268B2 (ja) ポリオレフィンマクロモノマーおよびその製造方法
CN110016101B (zh) 烟炱分散型聚甲基丙烯酸酯类化合物的制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19941495

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19941495

Country of ref document: EP

Kind code of ref document: A1

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 03/08/2022)