WO2021027210A1 - 含有星型sep共聚物润滑油粘度指数改性剂及其制备方法 - Google Patents

含有星型sep共聚物润滑油粘度指数改性剂及其制备方法 Download PDF

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WO2021027210A1
WO2021027210A1 PCT/CN2019/125752 CN2019125752W WO2021027210A1 WO 2021027210 A1 WO2021027210 A1 WO 2021027210A1 CN 2019125752 W CN2019125752 W CN 2019125752W WO 2021027210 A1 WO2021027210 A1 WO 2021027210A1
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viscosity index
star
shaped
terpolymer
lubricating oil
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PCT/CN2019/125752
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English (en)
French (fr)
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马道林
马浚轩
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深圳昆油石化技术有限公司
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Publication of WO2021027210A1 publication Critical patent/WO2021027210A1/zh

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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
    • C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
    • 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
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/06—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing conjugated dienes
    • 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

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.
  • Hydrogenated styrene diene copolymer (HSD) type VII is a product developed in the 1960s and 1970s.
  • HSD type VII has good shear stability, good viscosity, viscosity-temperature performance, and thermal stability, but the preparation process is more complicated And the low temperature performance is poor.
  • the preparation process of HSD has been improved, but the viscosity is small under high temperature and high shear, and the low temperature performance has not been improved (the current shear stability index of HSD is below 25 (30 cycles of diesel nozzles).
  • the higher temperature oxidation detergency is 4.0 Below (level 4.0 is the heat pipe oxidation rating, the smaller the oil detergency, the better)).
  • the low temperature performance of VII is related to the molecular weight and distribution.
  • the molecular weight should be appropriately reduced and the molecular weight distribution width should be increased. However, this will reduce the viscosity-increasing performance of VII.
  • the patent application 201910075144.6 relates to an improver for lubricating oil and its preparation process.
  • the improver for lubricating oil includes the following components: a star-shaped hydrogenated styrene diene copolymer with a mass fraction of 0.4-1% and a mass fraction of 10-60 % Of polyisobutylene, the rest is base oil; among them, the molecular weight of the star-shaped hydrogenated styrene diolefin copolymer is 80,000 to 400,000; the molecular weight of polyisobutylene is 200 to 5,000.
  • the lubricating oil improver of the present invention is used in lubricating oil, so that the lubricating oil has good shear resistance, good low-temperature fluidity, excellent anti-oxidation performance, and the viscosity index improver with improved cleanness and dispersibility, and the price is relatively traditional star type Hydrogenated styrene diolefin copolymer has obvious advantages, saving about 25% of cost.
  • the above methods still have problems that cannot be balanced, such as viscosity increasing performance, shear stability, oil detergency, and low temperature resistance.
  • the primary purpose of the present invention is to provide a star-shaped SEP copolymer lubricant viscosity index modification that improves the shear stability or low temperature performance without reducing the detergency of the oil (HSD class VII). Sex agent and its preparation method.
  • the purpose of the present invention is to provide a viscosity index modifier containing star-shaped SEP copolymer lubricating oil and its preparation method which takes into account viscosity increasing (thickening ability), shear stability, oil detergency and low temperature performance, and its preparation method.
  • the occurrence of irreversible crosslinking improves the production efficiency and reliability of the product.
  • a viscosity index modifier for lubricating oil containing star-shaped SEP copolymer which is characterized in that it is mainly composed of terpolymer (I), catalyst (II), modified monomer (III), auxiliary monomer (IV)
  • terpolymer (I) terpolymer
  • catalyst (II) catalyst
  • modified monomer (III) auxiliary monomer
  • IV A star-shaped polymer solid prepared by a melt polymerization method, or a star-shaped polymer composition solution prepared by a solution polymerization method.
  • the solid is a paste or a block.
  • the terpolymer (I) is not less than 94 parts, the catalyst (II) is not more than 0.5 parts, the modified monomer (III) is not more than 3.5 parts, and the auxiliary monomer (IV) is not less than More than 2 servings.
  • the terpolymer (I) is a linear copolymer composed of units ( ⁇ ), unit ( ⁇ ), and unit ( ⁇ ) with minimal crystallinity, and its number average molecular weight is 20,000 to 500,000; among them, the unit
  • the molecular formulas of ( ⁇ ), unit ( ⁇ ), and unit ( ⁇ ) are as follows:
  • the catalyst (II) is a compound containing a structural unit of formula ( ⁇ ), wherein R1 and R2 are hydrogen, C1-12 alkyl, cycloalkyl, aryl, ketone, ester, and carbonate groups, respectively Any one or any combination of acyl groups.
  • R1 and R2 are hydrogen, C1-12 alkyl, cycloalkyl, aryl, ketone, ester, and carbonate groups, respectively Any one or any combination of acyl groups.
  • the alkyl group, cycloalkyl group, aryl group, acyl group, ester group, carbonate group, and ketone group may be further substituted by 1 to 6 substituents independently selected from alkyl, cycloalkyl, and aryl groups. Substitution; wherein, the molecular formula of the structural unit of formula ( ⁇ ) is as follows:
  • the catalyst (II) can be selected from hydrogen peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, dicumyl peroxide, di-tert-butyl peroxide, dibenzoyl peroxide , Lauryl peroxide, t-butyl peroxybenzoate, t-butyl peroxy-t-valerate, diisopropyl peroxydicarbonate, and dicyclohexyl peroxydicarbonate.
  • the modified monomer (III) is a compound containing two or less ( ⁇ ) or ( ⁇ ) structural units, and the molecular formula of the ( ⁇ ) or ( ⁇ ) structural unit is:
  • the modified monomer (III) can be trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, 3 (propoxy) glycerol triacrylate, tris (2-hydroxyethyl) isocyanuric acid triacrylate, di (trimethylolpropane) tetraacrylate, pentaerythritol tetraacrylate, 4 (ethoxy (Base) any one or any combination of pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate.
  • the auxiliary monomer (IV) 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 , Aryl, benzyl, isobutyl, piperidinyl; wherein, the molecular formula of formula ( ⁇ ) is as follows:
  • the thiuram derivative may be tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabenzylthiuram disulfide, disulfide Methyl diphenylthiuram, diisobutylthiuram disulfide, dicyclopentamethylene disulfide tetraalkylthiuram, dipentamethylenethiuram tetrasulfide, dipentamethyl hexasulfide Support any of the thiuram.
  • 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 structural unit ( ⁇ ) on the SEP terpolymer is degraded, the ratio of the ( ⁇ ) unit on the molecular chain is reduced, and the molecular weight distribution of the molecular chain becomes wider.
  • the formed star-shaped SEP terpolymer shrinks its molecular chains at low temperatures, but does not cause serious entanglement, and has little effect on viscosity; at high temperatures, molecular chains stretch, It has a significant viscosity-increasing effect on lubricating oil, so that the dosage of lubricating oil can be reduced, and the main carbon chain and ( ⁇ ) unit are reduced, which helps to improve the shear stability and high temperature and high shear viscosity.
  • the preparation method of the modified copolymer overcomes the crosslinking problem in the polymerization reaction process.
  • the thickening ability, shear stability, low temperature performance, high temperature oxidation detergency of lubricating oil VII prepared with the modified SEP terpolymer Can be greatly improved.
  • the viscosity index modifier of lubricating oil containing star SEP copolymer realized by the present invention is mainly composed of terpolymer (I), catalyst (II), modified monomer (III), auxiliary monomer (IV) Star-shaped polymer paste prepared by melt polymerization method, or star-shaped polymer composition solution prepared by solution polymerization method. In the modifier and the preparation process, it is not excluded that other auxiliary agents can be added.
  • the terpolymer (I) is not less than 94 parts, the catalyst (II) is not more than 0.5 parts, the modified monomer (III) is not more than 3.5 parts, and the auxiliary monomer (IV) is not less than More than 2 servings.
  • the terpolymer (I) is a linear copolymer composed of units ( ⁇ ), unit ( ⁇ ), and unit ( ⁇ ) with minimal crystallinity, and its number average molecular weight is 20,000 to 500,000; among them, the unit
  • the molecular formulas of ( ⁇ ), unit ( ⁇ ), and unit ( ⁇ ) are as follows:
  • the catalyst (II) 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, keto, ester, carbonate, and acyl.
  • the alkyl group, cycloalkyl group, aryl group, acyl group, ester group, carbonate group, and ketone group may be further substituted by 1 to 6 substituents independently selected from alkyl, cycloalkyl, and aryl groups. Substitution; wherein, the molecular formula of the structural unit of formula ( ⁇ ) is as follows:
  • the catalyst (II) can be selected from hydrogen peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, dicumyl peroxide, di-tert-butyl peroxide, dibenzoyl peroxide, peroxy Any one of lauryl oxide, tert-butyl peroxybenzoate, tert-butyl peroxy-t-valerate, diisopropyl peroxydicarbonate, and dicyclohexyl peroxydicarbonate.
  • the modified monomer (III) is a compound containing two or less ( ⁇ ) or ( ⁇ ) structural units, and the molecular formula of the ( ⁇ ) or ( ⁇ ) structural unit is:
  • the modified monomer (III) can be trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, 3 (propoxy) glycerol triacrylate, tris (2-hydroxyethyl) isocyanuric acid triacrylate, di (trimethylolpropane) tetraacrylate, pentaerythritol tetraacrylate, 4 (ethoxy (Base) any one or any combination of pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate.
  • the auxiliary monomer (IV) 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 , Aryl, benzyl, isobutyl, piperidinyl; wherein, the molecular formula of formula ( ⁇ ) is as follows:
  • the thiuram derivative may be tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabenzylthiuram disulfide, disulfide Methyl diphenylthiuram, diisobutylthiuram disulfide, dicyclopentamethylene disulfide tetraalkylthiuram, dipentamethylenethiuram tetrasulfide, dipentamethyl hexasulfide Support any of the thiuram.
  • 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.
  • each component is identified as follows: based on parts by mass, 95.8 parts of terpolymer (I), 0.2 part of catalyst (II), 3.0 parts of modified monomer (III), auxiliary monomer ( IV) 2.0 parts.
  • the viscosity index modifier composition thus obtained has a kinematic viscosity of 1411 mm 2 /s, a shear stability index of 15 (30 cycles SSI for diesel nozzles), and a thickening capacity of 7.2 mm 2 / at 100°C for a 10% concentration liquid glue.
  • the low temperature apparent viscosity index CCSI can reach 50 (measured at -20°C)
  • the high temperature oxidation detergency can reach at least 3.5 grades (heat pipe oxidation).
  • the terpolymer (I) (one of hydrogenated styrene-isoprene block copolymers and hydrogenated styrene-isoprene random copolymers) was cut into pellets and sent to the reactor containing the base oil Add the terpolymer (I) pellets in batches, control the temperature not to exceed 130°C, start the stirrer to dissolve the terpolymer, and the mass ratio of the terpolymer in the base oil does not exceed 30%.
  • the amount of each component is identified as follows: based on parts by mass, terpolymer (I) not less than 94.9 parts, catalyst (II) 0.1 part, modified monomer (III) 3.0 parts, auxiliary Monomer (IV) 2.0 parts.
  • the viscosity index modifier concentrate (10% liquid glue) thus obtained has a kinematic viscosity of 1355mm 2 /s at 100°C, a shear stability index of 18 (30 cycle SSI for diesel nozzles), and a thickening capacity of 7.3mm 2 /s, low temperature apparent viscosity index CCSI can reach 35 (measured at -20°C), high temperature oxidation detergency 3.5 (heat pipe oxidation).
  • the modified monomer (III) trimethylolpropane triacrylate was replaced with trimethylolpropane trimethacrylate; the rest of the operation steps and quantity identification refer to the first embodiment.
  • the viscosity index modifier mixture (melt polymerization method) thus obtained has a kinematic viscosity of 1267mm 2 /s at 100°C, a shear stability index of 14 (30 cycles of diesel nozzle SSI), and a thickening capacity of 6.5mm 2 / s, the low temperature apparent viscosity index CCSI can reach 55 (measured at -20°C), and the high temperature oxidation detergency can reach 3.5 (heat pipe oxidation).
  • the obtained viscosity index modifier concentrate (solution polymerization product, 10% liquid glue) has a kinematic viscosity of 1288mm 2 /s at 100°C, a shear stability index of 15 (30 cycles of diesel nozzle SSI), and thickening ability 6.6mm 2 /s, low temperature apparent viscosity index CCSI up to 70 (measured at -20 °C), high temperature oxidation detergency 3.5 (heat pipe oxidation).
  • the modifying monomer (III) can be trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, 3(propoxy )Glycerol triacrylate, tris(2-hydroxyethyl)isocyanuric acid triacrylate, di(trimethylolpropane) tetraacrylate, pentaerythritol tetraacrylate, 4(ethoxy) pentaerythritol tetraacrylate Any one or any combination of esters and dipentaerythritol hexaacrylate.
  • the auxiliary monomer is replaced with acrylamide, and the rest of the operation steps and the quantity identification refer to the first embodiment.
  • the viscosity index modifier mixture (melt polymerization method) thus obtained has a kinematic viscosity of 1250 mm 2 /s and a shear stability index of 14 (30 cycles SSI for diesel nozzles) at 100°C with a 10% concentration liquid glue, which is thickened
  • the capacity is 5.8mm 2 /s
  • the low temperature apparent viscosity index CCSI can reach 65 (measured at -20°C)
  • the high temperature oxidation detergency is 3.5 (heat pipe oxidation).
  • the obtained viscosity index modifier concentrate (solution polymerization product, 10% liquid glue) has a kinematic viscosity of 1262 mm 2 /s at 100°C, a shear stability index of 14 (30 cycles SSI for diesel nozzles), and thickening ability 5.7mm 2 /s, low temperature apparent viscosity index CCSI can reach 68 (measured at -20°C), high temperature oxidation detergency can reach 3.5 (heat pipe oxidation).
  • the auxiliary monomer may be any one of styrene, acrylamide, and thiuram derivative containing the structure of formula ( ⁇ ), wherein the thiuram derivative containing the structure of formula ( ⁇ ) is , R3 and R4 are any one or more of C1-7 alkyl, cycloalkyl, aryl, benzyl, isobutyl, and piperidinyl.
  • thiuram derivatives are tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabenzylthiuram disulfide, dimethyldiphenyl disulfide Kethiuram, diisobutylthiuram disulfide, tetraalkylthiuram dicyclopentamethylene disulfide, dipentamethylenethiuram tetrasulfide, dipentamethylenethiuram hexasulfide Any one or any combination of.
  • the hydroperoxide catalyst (II) such as one of dicumyl peroxide and di-tert-butyl peroxide
  • solution (A) combine the terpolymer ( I) (one of hydrogenated styrene-isoprene block copolymer and hydrogenated styrene-isoprene random copolymer) pellets to obtain terpolymer pellets (B); the solution ( A) Spray evenly into the terpolymer pellets (B) and stir, and let stand for a period of time until the solvent is completely volatilized to obtain the mixed material (C); extrude the mixed modified material (C) on the extruder, Control the extrusion temperature to 300°C, and add the modified monomer (III) trimethylolpropane triacrylate and the auxiliary monomer (IV) styrene (D) in the middle or end of the heating section of the extruder.
  • the amount of each component is identified as: based on parts by mass, 96.4 parts of terpolymer (I), 0.1 part of catalyst (II), 2.0 parts of modified monomer (III), auxiliary monomer ( IV) 1.5 parts.
  • the obtained viscosity index modifier composition 10% concentration liquid glue has a kinematic viscosity of 1360mm 2 /s at 100°C, a shear stability index of 10 (30 cycles SSI for diesel nozzles), and a thickening capacity of 6.6mm 2 / s, low temperature apparent viscosity index CCSI can reach 54 (measured at -20°C), high temperature oxidation detergency level 3 (heat pipe oxidation).
  • the terpolymer (I) (one of hydrogenated styrene-isoprene block copolymers and hydrogenated styrene-isoprene random copolymers) was cut into pellets and sent to the reactor containing the base oil Add the terpolymer (I) pellets in batches, control the temperature not to exceed 130°C, start the stirrer to dissolve the terpolymer, and the mass ratio of the terpolymer in the base oil does not exceed 30%.
  • the amount of each component is identified as: based on parts by mass, 96.4 parts of terpolymer (I), 0.1 part of catalyst (II), 2.0 parts of modified monomer (III), auxiliary monomer ( IV) 1.5 parts.
  • the viscosity index modifier concentrate (solution polymerization product, 10% liquid glue) has a kinematic viscosity of 1387mm 2 /s at 100°C, a shear stability index of 9 (30 cycles of diesel nozzle SSI), and a thickening capacity of 6.8 mm 2 /s, low temperature apparent viscosity index CCSI can reach 45 (measured at -20°C), high temperature oxidation detergency level 3 (heat pipe oxidation).
  • the modified monomer trimethylolpropane triacrylate was changed to trimethylolpropane trimethacrylate; the remaining operation steps and dosage standards refer to the fourth embodiment.
  • the viscosity index modifier composition (product of melt polymerization method) thus obtained has a kinematic viscosity of 1412mm 2 /s at 100°C and a shear stability index of 11 (30 cycles SSI for diesel nozzles).
  • the chemical capacity is 6.8mm 2 /s
  • the low temperature apparent viscosity index CCSI can reach 47 (measured at -20°C)
  • the high temperature oxidation detergency level 3 heat pipe oxidation
  • the obtained viscosity index modifier concentrate (solution polymerization product, 10% liquid glue) at 100°C has a kinematic viscosity of 1420 mm 2 /s, a shear stability index of 12 (30 cycles of diesel nozzle SSI), and a thickening capacity of 6.7 mm 2 /s, low temperature apparent viscosity index CCSI45 (measured at -20°C), high temperature oxidation detergency 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 more of pentaerythritol hexaacrylate.
  • Embodiment 6 is a diagrammatic representation of Embodiment 6
  • the auxiliary monomer is replaced with acrylamide, and the remaining operation steps and dosage standards refer to the fourth embodiment.
  • the viscosity index modifier composition (product of the melt polymerization method) thus obtained has a kinematic viscosity of 1435 mm 2 /s at 100°C and a shear stability index of 15 (30 cycles SSI for diesel nozzles).
  • the chemical capacity is 7.1mm 2 /s
  • the low temperature apparent viscosity index CCSI can reach 55 (measured at -20°C)
  • the high temperature oxidation detergency level 3 heat pipe oxidation
  • the obtained viscosity index modifier concentrate (solution polymerization product, 10% liquid glue) has a kinematic viscosity of 1367mm 2 /s at 100°C, a shear stability index of 12 (30 cycle SSI for diesel nozzles), and thickening ability 6.9mm 2 /s, low temperature apparent viscosity index CCSI up to 48 (measured at -20°C), high temperature oxidation detergency level 3 (heat pipe oxidation).
  • the auxiliary monomer may be any one of styrene, acrylamide, and thiuram derivative containing the structure of formula ( ⁇ ), wherein the thiuram derivative containing the structure of formula ( ⁇ ) is , R3 and R4 are any one or more of C1-7 alkyl, cycloalkyl, aryl, benzyl, isobutyl, and piperidinyl.
  • the thiuram derivative can be tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabenzylthiuram disulfide, dimethylthiuram disulfide Phenylthiuram, diisobutylthiuram disulfide, tetraalkylthiuram dicyclopentamethylene disulfide, dipentamethylenethiuram tetrasulfide, dipentamethylenethiuram hexasulfide Any one or any combination of
  • the amount of each component is identified as follows: based on parts by mass, 94 parts of terpolymer (I), 0.5 part of catalyst (II), 3.5 parts of modified monomer (III), auxiliary monomer ( IV) 2.0 parts.
  • the viscosity index modifier composition (product of melt polymerization) thus obtained has a kinematic viscosity of 1430 mm 2 /s and a shear stability index of 15 (30 cycle SSI for diesel nozzles) at 100°C at a concentration of 10%.
  • the chemical capacity is 7.0mm 2 /s
  • the low temperature apparent viscosity index CCSI can reach 56 (measured at -20°C)
  • the high temperature oxidation detergency is level 3 (heat pipe oxidation).
  • the terpolymer (I) (one of hydrogenated styrene-isoprene block copolymers and hydrogenated styrene-isoprene random copolymers) was cut into pellets and sent to the reactor containing the base oil Add the terpolymer (I) pellets in batches, control the temperature not to exceed 130°C, start the stirrer to dissolve the terpolymer, and the mass ratio of the terpolymer in the base oil does not exceed 30%.
  • the obtained viscosity index modifier concentrate (solution polymerization product, 10% liquid glue) at 100°C has a kinematic viscosity of 1389 mm 2 /s, a shear stability index of 14 (30 cycles of diesel nozzle SSI), and a thickening capacity of 7.1 mm 2 /s, low temperature apparent viscosity index CCSI up to 41 (measured at -20°C), high temperature oxidation detergency level 3 (heat pipe oxidation).
  • Embodiment 8 is a diagrammatic representation of Embodiment 8
  • Example 7 Based on Example 7, the modified monomer was replaced with trimethylolpropane trimethacrylate, and the remaining operation steps and dosage standards refer to Example 7.
  • the viscosity index modifier composition (product of melt polymerization) thus obtained has a kinematic viscosity of 1389mm 2 /s at 100°C and a shear stability index of 13 (30 cycles SSI for diesel nozzles).
  • the chemical capacity is 6.6mm 2 /s
  • the low temperature apparent viscosity index CCSI can reach 52 (measured at -20°C)
  • the high temperature oxidation detergency is 3.5 (heat pipe oxidation).
  • the obtained viscosity index modifier concentrate (solution polymerization product, 10% liquid glue) has a kinematic viscosity of 1411mm 2 /s at 100°C, a shear stability index of 14 (30 cycles SSI for diesel nozzles), and a thickening capacity of 6.7 mm 2 /s, low temperature apparent viscosity index CCSI up to 50 (measured at -20 °C), high temperature oxidation detergency 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 more of pentaerythritol hexaacrylate.
  • the auxiliary monomer is replaced with acrylamide, and the remaining operation steps and dosage standards refer to the seventh embodiment.
  • the viscosity index modifier composition (product of melt polymerization method) thus obtained has a kinematic viscosity of 1435 mm 2 /s and a shear stability index of 17 (30 cycle SSI for diesel nozzles) at 100° C., and thickening Capability 7.5mm 2 /s, low temperature apparent viscosity index CCSI45 (measured at -20°C), high temperature oxidation detergency 3.5 (heat pipe oxidation).
  • the viscosity index modifier concentrate (product of solution polymerization, 10% liquid glue) at 100°C has a kinematic viscosity of 1337mm 2 /s, a shear stability index of 13 (30 cycles of diesel nozzle SSI), and thickening ability 6.7mm 2 /s, low temperature apparent viscosity index CCSI 51 (measured at -20°C), high temperature oxidation detergency level 3 (heat pipe oxidation).
  • the auxiliary monomer may be any one of styrene, acrylamide, and thiuram derivative containing the structure of formula ( ⁇ ), wherein the thiuram derivative containing the structure of formula ( ⁇ ) is , R3 and R4 are any one or more of C1-7 alkyl, cycloalkyl, aryl, benzyl, isobutyl, and piperidinyl.
  • the thiuram derivative can be tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabenzylthiuram disulfide, dimethylthiuram disulfide Phenylthiuram, diisobutylthiuram disulfide, tetraalkylthiuram dicyclopentamethylene disulfide, dipentamethylenethiuram tetrasulfide, dipentamethylenethiuram hexasulfide Any one or any combination of
  • the amount of each component is identified as: based on parts by mass, 94.4 parts of terpolymer (I), 0.3 parts of catalyst (II), 3.5 parts of modified monomer (III), auxiliary monomer ( IV) 1.8 parts.
  • the viscosity index modifier composition (product of melt polymerization method) thus obtained has a kinematic viscosity of 1431 mm 2 /s at 100°C and a shear stability index of 16 (30 cycles SSI for diesel nozzles), and thickened. Capacity 7.3mm 2 /s, low temperature apparent viscosity index CCSI 40 (measured at -20°C), high temperature oxidation detergency 3.5 (heat pipe oxidation).
  • the terpolymer (I) (one of hydrogenated styrene-isoprene block copolymers and hydrogenated styrene-isoprene random copolymers) was cut into pellets and sent to the reactor containing the base oil Add the terpolymer (I) pellets in batches, control the temperature not to exceed 130°C, start the stirrer to dissolve the terpolymer, and the mass ratio of the terpolymer in the base oil does not exceed 30%.
  • the amount of each component is identified as: based on parts by mass, 94.4 parts of terpolymer (I), 0.3 parts of catalyst (II), 3.5 parts of modified monomer (III), auxiliary monomer ( IV) 1.8 parts.
  • the obtained viscosity index modifier concentrate (product of solution polymerization, 10% liquid glue) at 100°C has a kinematic viscosity of 1427 mm 2 /s, a shear stability index of 14 (30 cycles of diesel nozzle SSI), and thickening
  • the capacity is 6.9mm 2 /s
  • the low temperature apparent viscosity index CCSI can reach 46 (measured at -20°C)
  • the high temperature oxidation detergency can reach at least 3.5 grades (heat pipe oxidation).
  • the catalyst (II) in the present invention by adding the catalyst (II) in the present invention, the structural unit ( ⁇ ) on the SEP terpolymer is degraded, the ratio of the ( ⁇ ) unit on the molecular chain is reduced, and the molecular weight distribution of the molecular chain becomes wider.
  • control the amount and order of addition of the catalyst (II) and the modified monomer (III) to make the macromolecular free radicals react with the modified monomer (III) to form a long-chain branched star copolymer, and the auxiliary monomer ( The use of IV) reduces the occurrence of irreversible cross-linking.
  • the formed star-shaped SEP terpolymer shrinks its molecular chains at low temperatures, but does not cause serious entanglement, and has little effect on viscosity; at high temperatures, molecular chains stretch, It has a significant viscosity-increasing effect on lubricating oil, so that the dosage of lubricating oil can be reduced, and the main carbon chain and ( ⁇ ) unit are reduced, which helps to improve the shear stability and high temperature and high shear viscosity.
  • the preparation method of the modified copolymer overcomes the crosslinking problem in the polymerization reaction process.
  • the thickening ability, shear stability, low temperature performance, high temperature oxidation detergency of lubricating oil VII prepared with the modified SEP terpolymer Can be greatly improved.

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Abstract

一种含有星型SEP共聚物润滑油粘度指数改性剂及其制备方法，所述改性剂是由三元共聚物(I)、催化剂(II)、改性单体(III)、辅助单体(IV)经过熔融聚合方法制备的星型固体，或经溶液聚合方法制备而成的星型聚合物组合物溶液。该粘度指数改性剂在不降低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SEP共聚物润滑油粘度指数改性剂及其制备方法 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。
氢化苯乙烯双烯共聚物(HSD)类VII是60-70年代开发的产品，HSD类VII的剪切稳定性很佳，增粘性、粘温性能、热稳定性尚可，但制备工艺较为复杂且低温性能差。随着工业技术的不断更新，HSD的制备工艺得到了提升，但是在高温高剪切下粘度较小，且低温性能未得到改善(目前HSD的剪切稳定性指数为25以下(柴油喷嘴30循环SSI，剪切稳定性指数越小则剪切稳定性越好)，低温表观粘度指数CCSI为80以下(-20℃下测量，越小则低温性能越好)，高温氧化清净性为4.0级以下(4.0级是热管氧化评级，越小则油品清净性越好))。
VII的低温性能与分子量大小及分布有关，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，长链和短链分子比例越少，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。为了提高VII的低温性能，则应适当降低分子量，增大分子量分布宽度。但如此，会降低VII的增粘性能。
如专利申请201910075144.6涉及一种润滑油用改进剂及其制备工艺，其中润滑油用改进剂，包括以下成分：质量分数0.4-1％的星型氢化苯乙烯双烯烃共聚物以及质量分数10-60％的聚异丁烯，其余为基础油；其中，星型氢化苯乙烯双烯烃共聚物的分子量为8-40万；聚异丁烯的分子量为200-5000。本发明的润滑油用改进剂用于润滑油，使得润滑油抗剪切性能好，低温流动性好，抗氧化性能优异，清净分散性得到提高的粘度指数改进剂，并且价格相对传统的星型氢化苯乙烯双烯烃共聚物具有明显优势，约节省成本25％。然而上述办法仍然存在着增粘性能、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
经研究发现，VII的增粘性能与分子链的结构有关，星型VII的分子链在低温下收缩，但未发生严重缠结，对粘度的影响较小；高温下，分子链伸展，起到增粘作用。因此，制备星型SEP类VII润滑油粘度指数改性剂是获得兼具增粘性、剪切稳定性、热氧化安定性、油品清净性、低温性能的最有效办法。
基于此，因此本发明的首要目地是在不降低油品清净性(HSD类VII的)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SEP共聚物润滑油粘度指数改性剂及其制备方法。
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SEP共聚物润滑油粘度指数改性剂及其制备方法，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SEP共聚物润滑油粘度指数改性剂，其特征在于它主要是由三元共聚物(I)、催化剂(II)、改性单体(III)、辅助单体(IV)经过熔融聚合 方法制备的星型聚合物固体，或经溶液聚合方法制备而成的星型聚合物组合物溶液。
所述固体为膏状物或块状物。
依据质量份数计，所述的三元共聚物(I)不低于94份，催化剂(II)不超过0.5份、改性单体(III)不超过3.5份、辅助单体(IV)不超过2份。
所述的三元共聚物(I)是由单元(α)、单元(β)、单元(χ)组成的结晶性最小化的线性共聚物，其数均分子量为2～50万；其中，单元(α)、单元(β)、单元(χ)的分子式如下：
Figure PCTCN2019125752-appb-000001
所述的催化剂(II)是含式(γ)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、酮基、酯基、碳酸酯基、酰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，可以进一步被1～6个独立选自烷基、环烷基、芳基的取代基所取代；其中，式(γ)结构单元的分子式如下：
Figure PCTCN2019125752-appb-000002
进一步，所述的催化剂(II)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任意一种。
所述的改性单体(III)是含有两个或两个以下(ε)或(ζ)结构单元的化合物，所述(ε)或(ζ)结构单元的分子式为：
Figure PCTCN2019125752-appb-000003
所述的改性单体(III)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或任意组合。
所述的辅助单体(IV)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；其中，式(δ)的分子式如下：
Figure PCTCN2019125752-appb-000004
进一步，所述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中任意一种。
一种含有星型SEP共聚物润滑油粘度指数改性剂的熔融聚合方法，其特征在于该方法包括以下步骤：
(1)准确称取催化剂(II)，并溶于溶剂中，得到溶液(A)。将溶液(A)均匀地喷入三元共聚物粒料(B)中搅拌，静置，待溶剂完全挥发后，得到混合料(C)；
(2)将混合改性料(C)经挤出机上挤出，控制挤出温度为120-300℃之间，在挤出机加热段的中或末端滴加改性单体(III)和辅助单体(IV)的组合物(D)，挤出后即得到所述的星型SEP共聚物润滑油粘度指数改性剂组合物。
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。
一种含有星型SEP共聚物润滑油粘度指数改性剂的溶液聚合方法，其特征在于该方法包括以下步骤：
(1)将三元共聚物(I)切粒，向盛有基础油的反应器中分批次加入三元共聚物(I)粒料，控制温度不超过130℃，开动搅拌器，使三元共聚物溶解，三元共聚物在基础油中的质量比不超过30％；
(2)升温至130℃～300℃，再向反应釜中注入催化剂(II)，等待1～30min，再注入改性单体(III)、辅助单体(IV)的组合物，持续搅拌5-30min，冷却出料，即得到含有所述的星型聚合物的混合浓缩液。
本发明的通过加入催化剂(II)，使得SEP三元共聚物的上的结构单元(β)发生降解，分子链上(β)单元比例减少，分子链的分子量分布会变宽。同时控制催化剂(II)和改性单体(III)的用量和加入顺序，使大分子自由基与改性单体(III)发生反应，形成长支链的星型共聚物，辅助单体(IV)的使用，减少了不可逆交联的发生，所形成的星型SEP三元共聚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，对润滑油起到显著增粘效果，使得润滑油加剂量得以减少，加之主碳链和(β)单元减少，有助于提高剪切稳定性和高温高剪切粘度。
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VII的低温性能显著。该改性共聚物的制备方法克服了聚合反应过程中的交联问题，以该改性SEP三元共聚物制备的润滑油VII的稠化能力、剪切稳定性、低温性能、高温氧化清净性的都能够得以大大提高。
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，以下结合附图及实施例，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SEP共聚物润滑油粘度指数改性剂，它主要是由三元共聚物(I)、催化剂(II)、改性单体(III)、辅助单体(IV)经过熔融聚合方法制备的星型聚合物膏状物，或经溶液聚合方法制备而成的星型聚合物组合物溶液。在改性剂及制备过程中，不排除可以添加其他的辅助制剂。
依据质量份数计，所述的三元共聚物(I)不低于94份，催化剂(II)不超过0.5份、改性单体(III)不超过3.5份、辅助单体(IV)不超过2份。
所述的三元共聚物(I)是由单元(α)、单元(β)、单元(χ)组成的结晶性最小化的线性共聚物，其数均分子量为2～50万；其中，单元(α)、单元(β)、单元(χ)的分子式如下：
Figure PCTCN2019125752-appb-000005
所述的催化剂(II)是含式(γ)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、酮基、酯基、碳酸酯基、酰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，可以进一步被1～6个独立选自烷基、环烷基、芳基的取代基所取代；其中，式(γ)结构单元的分子式如下：
Figure PCTCN2019125752-appb-000006
所述的催化剂(II)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任意一种。
所述的改性单体(III)是含有两个或两个以下(ε)或(ζ)结构单元的化合物，所述(ε)或(ζ)结构单元的分子式为：
Figure PCTCN2019125752-appb-000007
所述的改性单体(III)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或任意组合。
所述的辅助单体(IV)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；其中，式(δ)的分子式如下：
Figure PCTCN2019125752-appb-000008
进一步，所述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中任意一种。
一种含有星型SEP共聚物润滑油粘度指数改性剂的熔融聚合方法，其特征在于该方法包括以下步骤：
(1)准确称取催化剂(II)，并溶于溶剂中，得到溶液(A)。将溶液(A)均匀地喷入三元共聚物粒料(B)中搅拌，静置，待溶剂完全挥发后，得到混合料(C)；
(2)将混合改性料(C)经挤出机上挤出，控制挤出温度为120-300℃之 间，挤出机中，在加热段的中间或末端滴加改性单体(III)和辅助单体(IV)的组合物(D)，挤出后即得到所述的星型SEP共聚物润滑油粘度指数改性剂组合物。
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。
一种含有星型SEP共聚物润滑油粘度指数改性剂的溶液聚合方法，其特征在于该方法包括以下步骤：
(1)将三元共聚物(I)切粒，向盛有基础油的反应器中分批次加入三元共聚物(I)粒料，控制温度不超过130℃，开动搅拌器，使三元共聚物溶解，三元共聚物在基础油中的质量比不超过30％；
(2)升温至130℃～300℃，再向反应釜中注入催化剂(II)，等待1～30min，再注入改性单体(III)、辅助单体(IV)的组合物，持续搅拌5-30min，冷却出料，即得到含有所述的星型聚合物的混合浓缩液。
具体实施方式如下：
实施例一：
熔融聚合法：
准确称量氢过氧化物催化剂(II)(过氧化氢、异丙苯过氧化氢、叔丁基过氧化氢中的一种)，并溶于溶剂中，得到溶液(A)；将三元共聚物(I)(氢化苯乙烯-异戊二烯嵌段共聚物、氢化苯乙烯-异戊二烯无规共聚物中的一种)切粒，得到三元共聚物粒料(B)；将溶液(A)均匀地喷入三元共聚物粒料(B)中搅拌，静置一段时间待溶剂完全挥发后，得到混合料(C)；将混合改性料(C)经挤出机上挤出，控制挤出温度为140℃，在挤出机加热段的中或末端滴加改性单体(III)三羟甲基丙烷三丙烯酸酯和辅助单体(IV)苯乙烯的组合物(D)，挤出后即得到所述的星型SEP共聚物润滑油粘度指数改性剂组合物。
在该方法中，各组份的用量标识为：依据质量份数计，三元共聚物(I)95.8份，催化剂(II)0.2份、改性单体(III)3.0份、辅助单体(IV)2.0份。
由此获得的粘度指数改性剂组合物在10％浓度液胶100℃时其运动粘度在1411mm 2/s，剪切稳定性指数15(柴油喷嘴30循环SSI)，稠化能力7.2mm 2/s，低温表观粘度指数CCSI可达50(-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：
将三元共聚物(I)(氢化苯乙烯-异戊二烯嵌段共聚物、氢化苯乙烯-异戊二烯无规共聚物中的一种)切粒，向盛有基础油的反应器中分批次加入三元共聚物(I)粒料，控制温度不超过130℃，开动搅拌器，使三元共聚物溶解，三元共聚物在基础油中的质量比不超过30％。升温至160℃，再向反应釜中注入氢过氧化物催化剂(II)(过氧化氢、异丙苯过氧化氢、叔丁基过氧化氢中的一种)，等待10min，再注入改性单体(III)三羟甲基丙烷三丙烯酸酯、辅助单体(IV)苯乙烯的组合物，持续搅拌30min，冷却出料，即得到含有所述的星型聚合物的混合浓缩液。
在该方法中，各组份的用量标识为：依据质量份数计，三元共聚物(I)不低于94.9份，催化剂(II)0.1份、改性单体(III)3.0份、辅助单体(IV)2.0份。
由此获得的粘度指数改性剂浓缩液(10％液胶)在100℃时其运动粘度在1355mm 2/s，剪切稳定性指数18(柴油喷嘴30循环SSI)，稠化能力7.3mm 2/s，低温表观粘度指数CCSI可达35(-20℃下测量)，高温氧化清净性3.5级(热管氧化)。
实施例二：
基于实施例一，将改性单体(III)三羟甲基丙烷三丙烯酸酯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识参照实施例一。
由此获得的粘度指数改性剂混合料(熔融聚合法)在100℃时其运动粘度在1267mm 2/s，剪切稳定性指数14(柴油喷嘴30循环SSI)，稠化能力6.5mm 2/s，低温表观粘度指数CCSI可达55(-20℃下测量)，高温氧化清净性达3.5级(热 管氧化)。获得的粘度指数改性剂浓缩液(溶液聚合法产物，10％液胶)在100℃时其运动粘度在1288mm 2/s，剪切稳定性指数15(柴油喷嘴30循环SSI)，稠化能力6.6mm 2/s，低温表观粘度指数CCSI可达70(-20℃下测量)，高温氧化清净性3.5级(热管氧化)。
在其它的实施方式中，改性单体(III)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。
实施例三：
基于实施例一，辅助单体更换为丙烯酰胺，其余操作步骤及用量标识参照实施例一。
由此获得的粘度指数改性剂混合料(熔融聚合法)10％浓度液胶在100℃时其运动粘度在1250mm 2/s，剪切稳定性指数14(柴油喷嘴30循环SSI)，稠化能力5.8mm 2/s，低温表观粘度指数CCSI可达65(-20℃下测量)，高温氧化清净性3.5级(热管氧化)。获得的粘度指数改性剂浓缩液(溶液聚合法产物，10％液胶)在100℃时其运动粘度在1262mm 2/s，剪切稳定性指数14(柴油喷嘴30循环SSI)，稠化能力5.7mm 2/s，低温表观粘度指数CCSI可达68(-20℃下测量)，高温氧化清净性可达到3.5级(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，其中含式(δ)结构的秋兰姆衍生物中，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多种。其中秋兰姆衍生物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的任意一种或任意组合。
实施例四：
熔融聚合法：
准确称量氢过氧化物催化剂(II)(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)；将三元共聚物(I)(氢化苯乙烯-异戊二烯嵌段共聚物、氢化苯乙烯-异戊二烯无规共聚物中的一种)切粒，得到三元共聚物粒料(B)；将溶液(A)均匀地喷入三元共聚物粒料(B)中搅拌，静置一段时间待溶剂完全挥发后，得到混合料(C)；将混合改性料(C)经挤出机上挤出，控制挤出温度为300℃，在挤出机加热段的中或末端滴加改性单体(III)三羟甲基丙烷三丙烯酸酯和辅助单体(IV)苯乙烯的组合物(D)，挤出后即得到所述的星型SEP共聚物润滑油粘度指数改性剂组合物。
在该方法中，各组份的用量标识为：依据质量份数计，三元共聚物(I)96.4份，催化剂(II)0.1份、改性单体(III)2.0份、辅助单体(IV)1.5份。
由此获得的粘度指数改性剂组合物10％浓度液胶在100℃时其运动粘度在1360mm 2/s，剪切稳定性指数10(柴油喷嘴30循环SSI)，稠化能力6.6mm 2/s，低温表观粘度指数CCSI可达54(-20℃下测量)，高温氧化清净性3级(热管氧化)。
溶液聚合法：
将三元共聚物(I)(氢化苯乙烯-异戊二烯嵌段共聚物、氢化苯乙烯-异戊二烯无规共聚物中的一种)切粒，向盛有基础油的反应器中分批次加入三元共聚物(I)粒料，控制温度不超过130℃，开动搅拌器，使三元共聚物溶解，三元共聚物在基础油中的质量比不超过30％。升温至300℃，再向反应釜中注入过氧化二烷基催化剂(II)(如过氧化二异丙苯、过氧化二叔丁基中的一种)，等待20min，再注入改性单体(III)三羟甲基丙烷三丙烯酸酯、辅助单体(IV)苯乙烯的组合物，持续搅拌30min，冷却出料，即得到含有所述的星型聚合物的混合浓缩液。
在该方法中，各组份的用量标识为：依据质量份数计，三元共聚物(I)96.4 份，催化剂(II)0.1份、改性单体(III)2.0份、辅助单体(IV)1.5份。
该粘度指数改性剂浓缩液(溶液聚合法产物，10％液胶)在100℃时其运动粘度在1387mm 2/s，剪切稳定性指数9(柴油喷嘴30循环SSI)，稠化能力6.8mm 2/s，低温表观粘度指数CCSI可达45(-20℃下测量)，高温氧化清净性3级(热管氧化)。
实施例五：
基于实施例四，将改性单体三羟甲基丙烷三丙烯酸酯改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四。
由此获得的粘度指数改性剂组合物(熔融聚合法产物)10％浓度液胶在100℃时其运动粘度在1412mm 2/s，剪切稳定性指数11(柴油喷嘴30循环SSI)，稠化能力6.8mm 2/s，低温表观粘度指数CCSI可达47(-20℃下测量)，高温氧化清净性3级(热管氧化)。
得到的粘度指数改性剂浓缩液(溶液聚合法产物，10％液胶)在100℃时其运动粘度1420mm 2/s，剪切稳定性指数12(柴油喷嘴30循环SSI)，稠化能力6.7mm 2/s，低温表观粘度指数CCSI45(-20℃下测量)，高温氧化清净性3级(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多种。
实施例六：
基于实施例四，辅助单体更换为丙烯酰胺，其余操作步骤及用量标准参考实施例四。
由此获得的粘度指数改性剂组合物(熔融聚合法产物)10％浓度液胶在100℃时其运动粘度在1435mm 2/s，剪切稳定性指数15(柴油喷嘴30循环SSI)， 稠化能力7.1mm 2/s，低温表观粘度指数CCSI可达55(-20℃下测量)，高温氧化清净性3级(热管氧化)。得到的粘度指数改性剂浓缩液(溶液聚合法产物，10％液胶)在100℃时其运动粘度在1367mm 2/s，剪切稳定性指数12(柴油喷嘴30循环SSI)，稠化能力6.9mm 2/s，低温表观粘度指数CCSI可达48(-20℃下测量)，高温氧化清净性3级(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，其中含式(δ)结构的秋兰姆衍生物中，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多种。其中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的任意一种或任意组合。
实施例七：
熔融聚合法：
准确称量氢过氧化物催化剂(II)(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)；将三元共聚物(I)(氢化苯乙烯-异戊二烯嵌段共聚物、氢化苯乙烯-异戊二烯无规共聚物中的一种)切粒，得到三元共聚物粒料(B)；将溶液(A)均匀地喷入三元共聚物粒料(B)中搅拌，静置一段时间待溶剂完全挥发后，得到混合料(C)；将混合改性料(C)经挤出机上挤出，控制挤出温度为250℃，在挤出机加热段的中或末端滴加改性单体(III)三羟甲基丙烷三丙烯酸酯和辅助单体(IV)苯乙烯的组合物(D)，挤出后即得到所述的星型SEP共聚物润滑油粘度指数改性剂组合物。
在该方法中，各组份的用量标识为：依据质量份数计，三元共聚物(I)94份，催化剂(II)0.5份、改性单体(III)3.5份、辅助单体(IV)2.0份。
由此获得的粘度指数改性剂组合物(熔融聚合法产物)10％浓度液胶在100℃时其运动粘度在1430mm 2/s，剪切稳定性指数15(柴油喷嘴30循环SSI)， 稠化能力7.0mm 2/s，低温表观粘度指数CCSI可达56(-20℃下测量)，高温氧化清净性3级(热管氧化)。
溶液聚合法：
将三元共聚物(I)(氢化苯乙烯-异戊二烯嵌段共聚物、氢化苯乙烯-异戊二烯无规共聚物中的一种)切粒，向盛有基础油的反应器中分批次加入三元共聚物(I)粒料，控制温度不超过130℃，开动搅拌器，使三元共聚物溶解，三元共聚物在基础油中的质量比不超过30％。升温至150℃，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)，再注入改性单体(III)三羟甲基丙烷三丙烯酸酯、辅助单体(IV)苯乙烯的组合物，持续搅拌10min，冷却出料，即得到含有所述的星型聚合物的混合浓缩液。
得到的粘度指数改性剂浓缩液(溶液聚合法产物，10％液胶)在100℃时其运动粘度1389mm 2/s，剪切稳定性指数14(柴油喷嘴30循环SSI)，稠化能力7.1mm 2/s，低温表观粘度指数CCSI可达41(-20℃下测量)，高温氧化清净性3级(热管氧化)。
实施例八：
基于实施例七，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七。
由此得到的粘度指数改性剂组合物(熔融聚合法产物)10％浓度液胶在100℃时其运动粘度在1389mm 2/s，剪切稳定性指数13(柴油喷嘴30循环SSI)，稠化能力6.6mm 2/s，低温表观粘度指数CCSI可达52(-20℃下测量)，高温氧化清净性3.5级(热管氧化)。
获得的粘度指数改性剂浓缩液(溶液聚合法产物，10％液胶)在100℃时其运动粘度1411mm 2/s，剪切稳定性指数14(柴油喷嘴30循环SSI)，稠化能力6.7mm 2/s，低温表观粘度指数CCSI可达50(-20℃下测量)，高温氧化清净 性3级(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多种。
实施例九：
基于实施例七，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七。
由此获得的粘度指数改性剂组合物(熔融聚合法产物)10％浓度液胶在100℃时其运动粘度1435mm 2/s，剪切稳定性指数17(柴油喷嘴30循环SSI)，稠化能力7.5mm 2/s，低温表观粘度指数CCSI45(-20℃下测量)，高温氧化清净性3.5级(热管氧化)。所述的粘度指数改性剂浓缩液(溶液聚合法产物，10％液胶)在100℃时其运动粘度1337mm 2/s，剪切稳定性指数13(柴油喷嘴30循环SSI)，稠化能力6.7mm 2/s，低温表观粘度指数CCSI 51(-20℃下测量)，高温氧化清净性3级(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，其中含式(δ)结构的秋兰姆衍生物中，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多种。其中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的任意一种或任意组合。
实施例十：
熔融聚合法：
准确称量氢过氧化物催化剂(II)(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)；将三元共聚物(I)(氢化苯乙烯-异戊二烯嵌段共聚物、氢化苯乙烯-异戊二烯无规共聚物中的一种或两种)切粒，得到三元共聚物粒料(B)；将溶液(A)均匀地喷入三元共聚物粒料(B)中搅拌，静置一段时间待溶剂完全挥发后，得到混合料(C)；将混合改性料(C)经挤出机上挤出，控制挤出温度为120℃，在挤出机加热段的中或末端滴加改性单体(III)三羟甲基丙烷三丙烯酸酯和辅助单体(IV)苯乙烯的组合物(D)，挤出后即得到所述的星型SEP共聚物润滑油粘度指数改性剂组合物。
在该方法中，各组份的用量标识为：依据质量份数计，三元共聚物(I)94.4份，催化剂(II)0.3份、改性单体(III)3.5份、辅助单体(IV)1.8份。
由此获得的粘度指数改性剂组合物(熔融聚合法产物)10％浓度液胶在100℃时其运动粘度1431mm 2/s，剪切稳定性指数16(柴油喷嘴30循环SSI)，稠化能力7.3mm 2/s，低温表观粘度指数CCSI 40(-20℃下测量)，高温氧化清净性3.5级(热管氧化)。
溶液聚合法：
将三元共聚物(I)(氢化苯乙烯-异戊二烯嵌段共聚物、氢化苯乙烯-异戊二烯无规共聚物中的一种)切粒，向盛有基础油的反应器中分批次加入三元共聚物(I)粒料，控制温度不超过130℃，开动搅拌器，使三元共聚物溶解，三元共聚物在基础油中的质量比不超过30％。升温至130℃，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)，再注入改性单体(III)三羟甲基丙烷三丙烯酸酯、辅助单体(IV)苯乙烯的组合物，持续搅拌10min，冷却出料，即得到含有所述的星型聚合物的混合浓缩液。
在该方法中，各组份的用量标识为：依据质量份数计，三元共聚物(I)94.4份，催化剂(II)0.3份、改性单体(III)3.5份、辅助单体(IV)1.8份。
所获得的粘度指数改性剂浓缩液(溶液聚合法产物，10％液胶)在100℃时其运动粘度在1427mm 2/s，剪切稳定性指数14(柴油喷嘴30循环SSI)，稠化能力6.9mm 2/s，低温表观粘度指数CCSI可达46(-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)。
由此，本发明的通过加入催化剂(II)，使得SEP三元共聚物的上的结构单元(β)发生降解，分子链上(β)单元比例减少，分子链的分子量分布会变宽。同时控制催化剂(II)和改性单体(III)的用量和加入顺序，使大分子自由基与改性单体(III)发生反应，形成长支链的星型共聚物，辅助单体(IV)的使用，减少了不可逆交联的发生，所形成的星型SEP三元共聚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，对润滑油起到显著增粘效果，使得润滑油加剂量得以减少，加之主碳链和(β)单元减少，有助于提高剪切稳定性和高温高剪切粘度。
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VII的低温性能显著。该改性共聚物的制备方法克服了聚合反应过程中的交联问题，以该改性SEP三元共聚物制备的润滑油VII的稠化能力、剪切稳定性、低温性能、高温氧化清净性的都能够得以大大提高。
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SEP共聚物润滑油粘度指数改性剂，其特征在于所述改性剂主要是由三元共聚物(I)、催化剂(II)、改性单体(III)、辅助单体(IV)经过熔融聚合方法制备的星型聚合物固体，或经溶液聚合方法制备而成的星型聚合物组合物溶液。
  2. 如权利要求1所述的含有星型SEP共聚物润滑油粘度指数改性剂，其特征在于所述依据质量份数计，所述的三元共聚物(I)不低于94份，催化剂(II)不超过0.5份、改性单体(III)不超过3.5份、辅助单体(IV)不超过2份。
  3. 如权利要求1所述的含有星型SEP共聚物润滑油粘度指数改性剂，其特征在于所述的三元共聚物(I)是由单元(α)、单元(β)、单元(χ)组成的结晶性最小化的线性共聚物，其数均分子量为2～50万；其中，单元(α)、单元(β)、单元(χ)的分子式如下：
    Figure PCTCN2019125752-appb-100001
  4. 如权利要求1所述的含有星型SEP共聚物润滑油粘度指数改性剂，其特征在于所述的催化剂(II)是含式(γ)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、酮基、酯基、碳酸酯基、酰基中的任意一种或任意组合；其中，式(γ)结构单元的分子式如下：
    Figure PCTCN2019125752-appb-100002
  5. 如权利要求1所述的含有星型SEP共聚物润滑油粘度指数改性剂，其特征在于所述的改性单体(III)是含有两个或两个以上(ε)或(ζ)结构单元的化合物，所述(ε)或(ζ)结构单元的分子式为：
    Figure PCTCN2019125752-appb-100003
  6. 如权利要求5所述的含有星型SEP共聚物润滑油粘度指数改性剂，其特征在于所述的改性单体(III)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或任意组合。
  7. 如权利要求1所述的含有星型SEP共聚物润滑油粘度指数改性剂，其特征在于所述的辅助单体(IV)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，式(δ)的分子式如下，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：
    Figure PCTCN2019125752-appb-100004
  8. 一种含有星型SEP共聚物润滑油粘度指数改性剂的熔融聚合方法，其特征在于该方法包括以下步骤：
    (1)准确称取催化剂(II)，并溶于溶剂中，得到溶液(A)；将溶液(A)均匀地喷入三元共聚物粒料(B)中搅拌，静置，待溶剂完全挥发后，得到混合料(C)；
    (2)将混合改性料(C)经挤出机上挤出，控制挤出温度为120-300℃之间，挤出机中，在加热段的中间或加热段的末端滴加改性单体(III)和辅助单 体(IV)的组合物(D)，挤出后即得到所述的星型SEP共聚物润滑油粘度指数改性剂组合物。
  9. 如权利要求10所述的含有星型SEP共聚物润滑油粘度指数改性剂的熔融聚合方法，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。
  10. 一种含有星型SEP共聚物润滑油粘度指数改性剂的溶液聚合方法，其特征在于该方法包括以下步骤：
    (1)将三元共聚物(I)切粒，向盛有基础油的反应器中分批次加入三元共聚物(I)粒料，控制温度不超过130℃，开动搅拌器，使三元共聚物溶解，三元共聚物在基础油中的质量比不超过30％；
    (2)升温至130℃～300℃，再向反应釜中注入催化剂(II)，等待1～30min，再注入改性单体(III)、辅助单体(IV)的组合物，持续搅拌5-30min，冷却出料，即得到含有所述的含有星型SEP共聚物润滑油粘度指数改性剂的混合浓缩液。
PCT/CN2019/125752 2019-08-14 2019-12-16 含有星型sep共聚物润滑油粘度指数改性剂及其制备方法 WO2021027210A1 (zh)

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