EP3535357B1 - Composition de lubrifiant avec une caractéristique de viscosité améliorée à basse température d'utilisation - Google Patents

Composition de lubrifiant avec une caractéristique de viscosité améliorée à basse température d'utilisation Download PDF

Info

Publication number
EP3535357B1
EP3535357B1 EP17787940.0A EP17787940A EP3535357B1 EP 3535357 B1 EP3535357 B1 EP 3535357B1 EP 17787940 A EP17787940 A EP 17787940A EP 3535357 B1 EP3535357 B1 EP 3535357B1
Authority
EP
European Patent Office
Prior art keywords
weight
lubricant composition
base oil
kinematic viscosity
astm
Prior art date
Legal status (The legal status 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 status listed.)
Active
Application number
EP17787940.0A
Other languages
German (de)
English (en)
Other versions
EP3535357A1 (fr
Inventor
Ronny Sondjaja
Frank-Olaf Mähling
Michael Alibert
Jennifer HOLTZINGER
Stefan Maier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Evonik Operations GmbH
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 Evonik Operations GmbH filed Critical Evonik Operations GmbH
Publication of EP3535357A1 publication Critical patent/EP3535357A1/fr
Application granted granted Critical
Publication of EP3535357B1 publication Critical patent/EP3535357B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
    • 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
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
    • C10M107/22—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M107/28—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
    • 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
    • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • C10M143/10—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing aromatic monomer, 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
    • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • C10M143/12—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing conjugated diene
    • 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
    • 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
    • C10M145/24—Polyethers
    • C10M145/26—Polyoxyalkylenes
    • C10M145/32—Polyoxyalkylenes of alkylene oxides containing 4 or more carbon atoms
    • 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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • 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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/041—Mixtures of base-materials and additives the additives being macromolecular compounds only
    • 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
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • 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
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
    • 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
    • C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
    • C10M2205/043—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene used as base material
    • 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
    • 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
    • C10M2209/0845—Acrylate; Methacrylate used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/04—Molecular weight; Molecular weight distribution
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/071—Branched chain compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02—Pour-point; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/08—Resistance to extreme temperature

Definitions

  • the invention relates to lubricant compositions for use in industrial applications having improved low temperature viscosity characteristics.
  • Lubricants for use in industrial applications typically comprise a base oil, such as a mineral oil or synthetic oil, and one or more additives.
  • Additives deliver, for example, reduced friction and wear, increased viscosity, improved viscosity index, and resistance to corrosion, oxidation, aging or contamination.
  • a lubricant to reduce friction is dependent on its viscosity. Generally, the least viscous fluid, which still forces two moving surfaces apart, is desired. Many lubricant applications require good lubricant properties over a broad temperature range, for example, when the engine is cold as well as when it has reached its operating temperature. Therefore, a lubricant's viscosity should change as little as possible with temperature, to provide constant lubricant properties over a broad temperature range.
  • the temperature-dependence of a lubricant's viscosity is measured by the viscosity index (VI).
  • the viscosity index is determined from the kinematic viscosity at 40°C (KV 40 ) and the kinematic viscosity at 100°C (KV 100 ), which is a good reflection of most engines' operating conditions.
  • Additives which increase the viscosity index are referred to as viscosity index improvers (VIIs).
  • Polymers of alkyl (meth)acrylates, and especially polyalkyl(meth)acrylate based comb polymers, are known in the art to act as good viscosity index improvers in lubricant oils.
  • WO 2007/003238 A1 describes oil-soluble comb polymers based on polyolefin-based macromonomers, especially polybutadiene-based methacrylic esters, and C1-C10 alkyl methacrylates.
  • the comb polymers can be used as an additive for lubricant oils, in order to improve the viscosity index and shear stability. They show a particularly high viscosity index-improving action in lubricant oils. Low temperature properties are not disclosed therein.
  • the viscosity index does not properly reflect the lubricant's properties at temperatures lower than 40°C, for instance at a low temperature range of -20°C to +20°C.
  • a lubricant having good lubricant properties at the operating temperature of a machine or an engine therefore, does not necessarily have equally good properties during the engine's cold-start phase.
  • the cold-start properties of a lubricant are, however, an important factor contributing to an improved fuel efficiency of engines.
  • the low-temperature properties of lubricants can be measured by the R-factor, which is defined as the ratio of the kinematic viscosity at -20°C to the kinematic viscosity at +20°C. Since the kinematic viscosity at -20°C is generally higher than at +20°C, the R-factor is generally greater than 1. Thus, a narrow viscosity difference between -20°C and +20°C is reflected by a low R-factor (an R-factor close to 1).
  • the aim of the present invention is to provide a lubricant composition with good low temperature viscosity properties.
  • the difference of the kinematic viscosity of the lubricant composition at -20°C and +20°C should be small.
  • the present invention further aims at providing an additive for a lubricant composition for lowering the difference between the kinematic viscosity at -20°C and +20°C.
  • the present invention is therefore directed to a lubricant composition, comprising:
  • the lubricant composition is preferably defined by an R-factor of less than or equal to 8, wherein the R-factor is defined as the ratio of the kinematic viscosity of the lubricant composition at -20°C (KV -20 ) to the kinematic viscosity at +20°C (KV +20 ), KV -20 /KV +20 , the kinematic viscosities are measured according to ASTM D445.
  • the lubricant composition has an R-factor of 1 to 8.
  • the composition is preferably formulated to yield a certain kinematic viscosity at 40°C according to ASTM D445. This can be achieved by adjusting the relative amounts of comb polymer, base oil and optional additives.
  • the composition has a kinematic viscosity at 40°C according to ASTM D445 of 10 to 120 mm 2 /s, more preferably 40 to 100 mm 2 /s, most preferably 70 to 80 mm 2 /s.
  • the lubricant composition comprises:
  • Suitable synthetic base oils are selected from API Group IV oils. Particularly preferred are polyalphaolefins (PAOs).
  • the synthetic base oil is typically characterized by its kinematic viscosity, i.e. the kinematic viscosity of the pure base oil without any additives.
  • the synthetic base oil has a kinematic viscosity at 100°C according to ASTM D445 of 1 mm 2 /s to 20 mm 2 /s, more preferably 1 to 10 mm 2 /s, most preferably 1 to 5 mm 2 /s and especially preferred 2 to 3 mm 2 /s.
  • the synthetic base oil is a polyalphaolefin having a kinematic viscosity at 100°C according to ASTM D445 of 1 mm 2 /s to 20 mm 2 /s, more preferably 1 to 10 mm 2 /s, most preferably 1 to 5 mm 2 /s and especially preferred 2 to 3 mm 2 /s.
  • a comb polymer in the context of this invention comprises a first polymer, which is also referred to as backbone or main chain, and a multitude of further polymers which are referred to as side chains and are bonded covalently to the backbone.
  • the backbone of the comb polymer is formed by the interlinked unsaturated groups of the mentioned (meth)acrylates.
  • the ester groups of the (meth)acrylic esters, the phenyl radicals of the styrene monomers and the substituents of further free-radically polymerizable comonomers form the side chains of the comb polymer.
  • the term "main chain” does not necessarily mean that the chain length of the main chain is greater than that of the side chains.
  • the amount of styrene in the comb polymer is given in percent by weight based on the total weight of the monomer mixture.
  • total weight of the monomer mixture refers to the total weight of the monomers, excluding any additives, such as polymerization initiators, polymerization promotors, chain transfer agents and diluents, which might be added to the monomer mixture to facilitate polymerization.
  • the relative amounts of monomers in the monomer mixture correspond to the relative amounts of the corresponding monomer units in the copolymer.
  • the hydroxylated hydrogenated polybutadiene for use in accordance with the invention has a number-average molar mass M n of 4.000 to 6.000 g/mol, preferably 4.000 to 5.000 g/mol. Because of their high molar mass, the hydroxylated hydrogenated polybutadienes can also be referred to as macroalcohols in the context of this invention.
  • the number-average weight M n is determined by size exclusion chromatography using commercially available polybutadiene standards. The determination is effected to DIN 55672-1 by gel permeation chromatography with THF as eluent.
  • the hydroxylated hydrogenated polybutadiene has a hydrogenation level of at least 99%.
  • An alternative measure of the hydrogenation level which can be determined on the copolymer of the invention is the iodine number.
  • the iodine number refers to the number of grams of iodine which can be added onto 100 g of copolymer.
  • the copolymer of the invention has an iodine number of not more than 5 g of iodine per 100 g of copolymer.
  • the iodine number is determined by the Wijs method according to DIN 53241-1:1995-05.
  • Preferred hydroxylated hydrogenated polybutadienes can be obtained according to GB 2270317 .
  • hydroxylated hydrogenated polybutadienes are also commercially available.
  • a further supplier of suitable alcohols based on hydrogenated polybutadiene is Cray Valley (Paris), a daughter company of Total (Paris), or the Sartomer Company (Exton, PA, USA).
  • the hydroxylated hydrogenated polybutadiene is a hydroxyethyl- or hydroxypropyl-terminated hydrogenated polybutadiene. Particular preference is given to hydroxypropyl-terminated polybutadienes.
  • These monohydroxylated hydrogenated polybutadienes can be prepared by first converting butadiene monomers by anionic polymerization to polybutadiene. Subsequently, by reaction of the polybutadiene monomers with ethylene oxide or propylene oxide, a hydroxy-functionalized polybutadiene can be prepared. This hydroxylated polybutadiene can be hydrogenated in the presence of a suitable transition metal catalyst.
  • esters of (meth)acrylic acid for use in accordance with the invention and a hydroxylated hydrogenated polybutadiene described are also referred to as macromonomers in the context of this invention because of their high molar mass.
  • (meth)acrylic acid refers to acrylic acid and methacrylic acid and to mixtures thereof; methacrylic acid being particularly preferred.
  • (meth)acrylate refers to esters of acrylic acid and esters of methacrylic acid and to mixtures thereof; esters of methacrylic acid being particularly preferred.
  • the macromonomers for use in accordance with the invention can be prepared by transesterification of alkyl (meth)acrylates. Reaction of the alkyl (meth)acrylate with the hydroxylated hydrogenated polybutadiene forms the ester of the invention. Preference is given to using methyl (meth)acrylate or ethyl (meth)acrylate as reactant.
  • This transesterification is widely known.
  • a heterogeneous catalyst system such as lithium hydroxide/calcium oxide mixture (LiOH/CaO), pure lithium hydroxide (LiOH), lithium methoxide (LiOMe) or sodium methoxide (NaOMe) or a homogeneous catalyst system such as isopropyl titanate (Ti(OiPr)4) or dioctyltin oxide (Sn(OCt)2O).
  • the reaction is an equilibrium reaction. Therefore, the low molecular weight alcohol released is typically removed, for example by distillation.
  • the macromonomers can be obtained by a direct esterification proceeding, for example, from (meth)acrylic acid or (meth)acrylic anhydride, preferably under acidic catalysis by p-toluenesulfonic acid or methanesulfonic acid, or from free methacrylic acid by the DCC method (dicyclohexylcarbodiimide).
  • the present hydroxylated hydrogenated polybutadiene can be converted to an ester by reaction with an acid chloride such as (meth)acryloyl chloride.
  • polymerization inhibitors are used, for example the 4-hydroxy-2,2,6,6-tetramethylpiperidinooxyl radical and/or hydroquinone monomethyl ether.
  • Some of the macromonomers for use in accordance with the invention are also commercially available, for example Kraton Liquid® L-1253 which is produced from Kraton Liquid® L-1203 and is a hydrogenated polybutadiene methacrylate-functionalized to an extent of about 96% by weight, having about 50% each of 1,2 repeat units and 1,4 repeat units, from Kraton Polymers GmbH (Eschborn, Germany).
  • Kraton® L-1253 is likewise synthesized according to GB 2270317 .
  • Suitable alkyl (meth)acrylates are, for example, methyl and ethyl acrylate, propyl methacrylate, butyl methacrylate (BMA) and acrylate (BA), isobutyl methacrylate (IBMA), hexyl and cyclohexyl methacrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate (EHA), 2-ethylhexyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, isodecyl methacrylate (IDMA, based on branched (C10)alkyl isomer mixture), undecyl methacrylate, dodecyl methacrylate (also known as lauryl methacrylate), tridecyl methacrylate, tetradecyl methacrylate (also known as myristyl methacrylate), penta
  • the suitable C10-15 alkyl (meth)acrylates include, for example, decyl (meth)acrylate, undecyl (meth)acrylate, 5-methylundecyl (meth)acrylate, dodecyl (meth)acrylate, 2-methyldodecyl (meth)acrylate, tridecyl (meth)acrylate, 5-methyltridecyl (meth)acrylate, tetradecyl (meth)acrylate and/or pentadecyl (meth)acrylate.
  • Particularly preferred C10-15 alkyl (meth)acrylates are (meth)acrylic esters of a linear C12-14 alcohol mixture (C12-14 alkyl (meth)acrylate).
  • the comb polymer (B) comprises:
  • the polyalkyl(meth)acrylate based comb polymer in accordance with the invention may preferably be obtained by radical polymerization.
  • the comb polymer may also be obtained by polymer-analogous reactions and/or graft copolymerization.
  • the comb polymer may be obtained by radical polymerization involving the steps of
  • the polymerization reaction is preferably initiated by mixing the monomer mixture with a radical initiator. In some cases, it may be required to heat the reaction mixture to the reaction temperatures specified below to initiate the polymerization.
  • Radical initiators may be selected from any of the well-known free-radical-producing compounds such as peroxy, hydroperoxy and azo initiators, including, for example, acetyl peroxide, benzoyl peroxide, lauroyl peroxide, tert-butyl peroxyisobutyrate, caproyl peroxide, cumene hydroperoxide, 1, 1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, azobisisobutyronitrile and tert-butyl peroctoate (also known as tert-butylperoxy-2-ethylhexanoate).
  • peroxy hydroperoxy and azo initiators
  • Preferable radical initiators are benzoyl peroxide, lauroyl peroxide, tert-butyl peroxyisobutyrate, azobisisobutyronitrile and tert-butyl peroctoate. Tert-butyl peroctoate is particularly preferred.
  • the initiator concentration is typically between 0.025 and 1 wt-%, preferably from 0.05 to 0.75 wt-%, more preferably from 0.1 to 0.5 wt-% and most preferably from 0.2 to 0.4 wt-%, based on the total weight of the monomers.
  • the polymerization is preferably conducted at a temperature below the boiling point of the reaction mixtures.
  • the temperature is in the range of 60 to 150°C, more preferably 85 to 130°C, most preferably 90 to 110°C.
  • One or more polymerization promoters may also be added to the monomer mixture.
  • Suitable promoters include, for example, quaternary ammonium salts such as benzyl(hydrogenated-tallow)-dimethylammonium chloride and amines.
  • the promoters are soluble in hydrocarbons. When used, these promoters are present at levels from 1 to 50 wt-%, preferably from 5 to 25 wt-%, based on total weight of initiator.
  • Chain transfer agents may also be added to control the molecular weight of the copolymer.
  • the preferred chain transfer agents are alkyl mercaptans such as lauryl mercaptan (also known as dodecyl mercaptan, DDM).
  • the amount of chain transfer agent is preferably 5 wt-% or less, more preferably 2 wt-% or less, based on the total weight of monomers.
  • Diluents may also be added to the monomer mixture.
  • the first and second reaction mixture each comprise up to 60 wt-% diluent, more preferably 5 to 60 wt-%, most preferably 10 to 60 wt-%.
  • aromatic hydrocarbons such as benzene, toluene, xylene and aromatic naphthas
  • chlorinated hydrocarbons such as ethylene dichloride, chlorobenzene and dichlorobenzene
  • esters such as ethyl propionate or butyl acetate
  • C6-C20 aliphatic hydrocarbons (such as cyclohexane, heptane and octane)
  • mineral oils such as paraffinic and naphthenic oils
  • synthetic base oils such as poly([alpha]-olefin) oligomer (PAO) lubricating oils, for example, [alpha]-decene dimers, trimers and mixtures thereof).
  • PAO poly([alpha]-olefin) oligomer
  • the lubricant composition in accordance with the present invention may further comprise auxiliary additives selected from the group consisting of pour point depressants, antiwear agents, antioxidants, dispersants, detergents, friction modifiers, antifoam agents, extreme pressure additives, and corrosion inhibitors.
  • auxiliary additives selected from the group consisting of pour point depressants, antiwear agents, antioxidants, dispersants, detergents, friction modifiers, antifoam agents, extreme pressure additives, and corrosion inhibitors.
  • the auxiliary additives are preferably added in an amount of 0.1 to 25 weight-%, based on the total weight of the lubricant composition.
  • Suitable pour-point depressants include ethylene-vinyl acetate copolymers, chlorinated paraffin-naphthalene condensates, chlorinated paraffin-phenol condensates, polymethacrylates, polyalkylstyrenes, etc. Preferred are polymethacrylates having a mass-average molecular weight of from 5.000 to 50.000 g/mol.
  • the preferred antiwear and extreme pressure additives include sulfur-containing compounds such as zinc dithiophosphate, zinc di-C3-12-alkyldithiophosphates (ZnDTPs), zinc phosphate, zinc dithiocarbamate, molybdenum dithiocarbamate, molybdenum dithiophosphate, disulfides, sulfurized olefins, sulfurized oils and fats, sulfurized esters, thiocarbonates, thiocarbamates, polysulfides, etc.; phosphorus-containing compounds such as phosphites, phosphates, for example trialkyl phosphates, triaryl phosphates, e.g.
  • tricresyl phosphate amine-neutralized mono- and dialkyl phosphates, ethoxylated mono-and dialkyl phosphates,phosphonates, phosphines, amine salts or metal salts of those compounds, etc.; sulfur and phosphorus-containing anti-wear agents such as thiophosphites, thiophosphates, thiophosphonates, amine salts or metal salts of those compounds, etc.
  • the suitable antioxidants include, for example, phenol-based antioxidants and amine-based antioxidants.
  • Phenol-based antioxidants include, for example, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; 4,4' -methylenebis(2,6-di-tert-butylphenol); 4,4' -bis(2,6-di-t-butylphenol); 4,4' -b is(2-methyl-6-t-butylphenol); 2,2' -methylenebis(4-ethyl-6-t-butylphenol); 2,2' -methylenebis(4-methyl-6-t-butyl phenol); 4,4' -butyl idenebis(3-methyl-6-t-butylphenol); 4,4'-isopropylidenebis(2,6-di-t-butylphenol); 2,2'-methylenebis(4-methyl-6-nonylphenol); 2,2
  • the amine-based antioxidants include, for example, monoalkyldiphenylamines such as monooctyldiphenylamine, monononyldiphenylamine, etc.; dialkyldiphenylamines such as 4,4' -dibutyldiphenylamine, 4,4'-dipentyldiphe nylamine, 4,4'- dihexyldiphenylamine, 4,4'-diheptyldiphenylamine, 4,4'-dioctyldiphenylamine, 4,4'-dinonyldiphenylamine, etc.; polyalkyldiphenylamines such as tetrabutyldiphenylamine, tetrahexyldiphenylamine, tetraoctyldiphenylamine, tetranonyldiphenylamine, etc.; nap
  • Appropriate dispersants include poly(isobutylene) derivatives, for example poly(isobutylene)succinimides (PIBSIs), including borated PIBSIs; and ethylenepropylene oligomers having N/O functionalities.
  • PIBSIs poly(isobutylene)succinimides
  • the preferred detergents include metal-containing compounds, for example phenoxides; salicylates; thiophosphonates, especially thiopyrophosphonates, thiophosphonates and phosphonates; sulfonates and carbonates.
  • metal these compounds may contain especially calcium, magnesium and barium. These compounds may preferably be used in neutral or overbased form.
  • Friction modifiers used may include mechanically active compounds, for example molybdenum disulfide, graphite (including fluorinated graphite), poly(trifluoroethylene), polyamide, polyimide; compounds that form adsorption layers, for example long-chain carboxylic acids, fatty acid esters, ethers, alcohols, amines, amides, imides; compounds which form layers through tribochemical reactions, for example saturated fatty acids, phosphoric acid and thiophosphoric esters, xanthogenates, sulfurized fatty acids; compounds that form polymer-like layers, for example ethoxylated dicarboxylic partial esters, dialkyl phthalates, methacrylates, unsaturated fatty acids, sulfurized olefins or organometallic compounds, for example molybdenum compounds (molybdenum dithiophosphates and molybdenum dithiocarbamates MoDTCs) and combinations thereof with ZnDTPs, copper-containing organic compounds.
  • Suitable antifoam agents are silicone oils, fluorosilicone oils, fluoroalkyl ethers, etc..
  • the lubricant composition according to the invention can be useful for various applications including industrial gear oil, lubricant for wind turbine, compressor oil, hydraulic fluid, paper machine lubricant, engine or motor oil, transmission and/or drive-trains fluid, machine tools lubricant, metalworking fluids, and transformer oils to name a few.
  • the invention also relates to the use of a comb polymer as described above as an additive for a base oil to produce a lubricant composition, characterized in that the lubricant composition preferably has an R-factor of less than or equal to 8, wherein the R-factor is defined as the ratio of the kinematic viscosity of the lubricant composition at -20°C to the kinematic viscosity at +20°C measured according to ASTM D445.
  • the lubricant composition has an R-factor of 1 to 8.
  • the lubricant composition comprises a synthetic base oil.
  • the base oil is preferably selected form the group consisting of polyalphaolefins, naphthenic base oils and mixtures thereof.
  • the lubricant composition comprises a polyalphaolefin base oil having a kinematic viscosity at 100°C according to ASTM D445 of 1 mm 2 /s to 20 mm 2 /s, more preferably 1 to 10 mm 2 /s, most preferably 1 to 5 mm 2 /s and especially preferred 2 to 3 mm 2 /s.
  • the lubricant composition preferably has a kinematic viscosity at 40°C according to ASTM D445 of 10 to 120 mm 2 /s, more preferably 40 to 100 mm 2 /s, most preferably 70 to 80 mm 2 /s.
  • the invention relates to a method of producing a lubricant composition having an R-factor of less than or equal to 8, preferably 1 to 8, wherein the R-factor is defined as the ratio of the kinematic viscosity of the lubricant composition at -20°C to the kinematic viscosity at +20°C measured according to ASTM D445, the method comprising the step of adding a comb polymer according to the present invention to a synthetic base oil, the synthetic base oil being preferably a polyalphaolefin base oil having a kinematic viscosity at 100°C according to ASTM D445 of 1 mm 2 /s to 20 mm 2 /s, more preferably 1 to 10 mm 2 /s, most preferably 1 to 5 mm 2 /s and especially preferred 2 to 3 mm 2 /s.
  • the method is preferably characterized by adding the comb polymer in an amount to get a lubricant composition with a kinematic viscosity at 40°C according to ASTM D445 of 10 to 120 mm 2 /s, more preferably 40 to 100 mm 2 /s, most preferably 70 to 80 mm 2 /s.
  • the macroalcohol was synthesized by an anionic polymerization of 1,3-butadiene with butyllithium at 20-45°C. On attainment of the desired degree of polymerization, the reaction was stopped by adding propylene oxide and lithium was removed by precipitation with methanol. Subsequently, the polymer was hydrogenated under a hydrogen atmosphere in the presence of a noble metal catalyst at up to 140°C and pressure 200 bar. After the hydrogenation had ended, the noble metal catalyst was removed and organic solvent was drawn off under reduced pressure. Finally, the base oil NB 3020 was used for dilution to a polymer content of 70% by weight.
  • the vinyl content of the macroalcohol was 61%, the hydrogenation level > 99% and the OH functionality > 98%. These values were determined by H-NMR (nuclear resonance spectroscopy).
  • Comb polymers according to the invention were prepared according to the following free radical polymerization procedure.
  • a mixture of 100 g of all the monomers e.g. as detailed in Table 1
  • ester oil e.g. diisononyl adipate
  • 35% of this diluted mixture is charged into a continuously stirred glass reactor, followed by addition of 0.105 g of initiator t -butylperoxy 2-ethylhexanoate.
  • the rest of the monomer mixture is gradually added into the glass reactor at constant flow rate for 3 h, in parallel with the addition of another 0.195 g of initiator t -butylperoxy 2-ethylhexanoate, also being introduced at constant flow rate for 3 h.
  • Reaction temperature is held constant at 90°C.
  • additional 2x0.2 g of initiator t -butylperoxy 2-ethylhexanoate is added to ensure the completion of the polymerization, 2 and 5 hours after the end of the monomer feeding, while the reaction is kept at 90°C.
  • additional dilution ester oil can be added.
  • Lauryl methacrylate is a mixture of linear C 12 and C 14 alkyl methacrylates with a ratio of C 12 to C 14 alkyl methacrylate of around 73/27.
  • compositions of the monomer mixtures used to prepare exemplary copolymers according to the invention are given in the following Table 1.
  • the amounts of monomers are given as weight-% based on the total weight of the comb polymer.
  • Comb polymers A and B are inventive examples and have a styrene content claimed by the present invention.
  • Comb polymer C is a comparative example and comprises a higher amount of styrene. It was prepared to show that a higher amount of styrene leads to a higher R-factor.
  • polyalkylmethacrylates are known viscosity index improvers and were used in comparative lubricant compositions. They were prepared to show that an R-factor within the claimed range of 1-8 can only be reached by using comb polymers which comprise a certain amount of an ester of (meth)acrylic acid and a hydroxylated hydrogenated polybutadiene.
  • Comparative copolymer D is a polyalkylmethacrylate prepared through similar aforementioned free radical polymerization procedure from 89.97% by weight of dodecyl pentadecyl methacrylate and 10.03% by weight of methyl methacrylate.
  • Dodecyl pentadecyl methacrylate is a mixture of branched and linear C 12 to C 15 alkyl methacrylates with an average composition of 16 to 26% by weight of C 12 alkyl methacrylate, 24 to 34% by weight of C 13 alkyl methacrylate, 24 to 34% by weight of C 14 alkyl methacrylate, and 16 to 26% by weight of C 15 alkyl methacrylate, and approximately 80% linear alkyl methacrylates.
  • Comparative copolymer E is a polyalkylmethacrylate prepared through similar aforementioned free radical polymerization procedure from 99.80% by weight of C 12 to C 15 alkyl methacrylate (comprising 20% C 12 alkyl methacrylate, 34% C 13 alkyl methacrylate, 29% C 14 alkyl methacrylate, and 17% C 15 alkyl methacrylate, with approximately 40% linear alkyl methacrylates) and 0.20% by weight of methyl methacrylate.
  • Lubricant compositions were obtained by mixing a poly-alpha-olefin base oil (PAO2) having a kinematic viscosity at 100°C of 2 mm 2 /s according to ASTM D445 and the indicated amount of copolymers as viscosity index improvers according to the following table targeting a KV 40 of 76 mm 2 /s.
  • PAO2 poly-alpha-olefin base oil
  • Table 2 lubricant compositions comprising comb polymers and base oil No Base oil Copolymer Amount of styrene [% by weight]* ) Amount of copolymer [% by weight]** ) 1 PAO2 A 0.2 25.2 2 PAO2 B 11.0 63.9 3 PAO2 C 39.8 40.8 CE 4 PAO2 D -- 41.1 CE 5 PAO2 E -- 48.5 CE * ) based on the total weight of the comb polymer ** ) based on the total weight of the lubricant composition CE: comparative example
  • the lubricant compositions were tested by determining the kinematic viscosity at different temperatures, the viscosity index and the R-factor.
  • the kinematic viscosity was determined according to ASTM D445, the viscosity index was determined according to ASTM D2270, and the R-factor was calculated as the ratio of the kinematic viscosity at -20°C to the kinematic viscosity at +20°C.
  • Table 3 viscosity data of lubricant compositions No.
  • compositions 1 and 2 comprising the comb polymers A and B, respectively
  • compositions according to the invention therefore guarantee a good viscosity characteristic at low operating temperature, defined as an R-factor lower than 8.
  • the comparative lubricant compositions compositions 3, 4 and 5, comprising comb polymers with a higher amount of styrene or conventional polyalkylmethacrylates D and E
  • Example 1 By using the inventive polymers (Examples 1 and 2) the viscosity increase is much lower compared to the use of standard polymers (Examples 4 and 5) or a polymer with higher styrene content (Example 3).
  • the lubricant compositions comprising the comb polymers according to the present invention show a KV 20 in the range of 130 to 140 and a KV -20 in the range of 640 to 870.
  • VI is not appropriate to extrapolate viscosities down to temperatures below 40°C, e.g. to -20°C.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Lubricants (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Graft Or Block Polymers (AREA)

Claims (16)

  1. Composition de lubrifiant, comprenant :
    (A) 20 à 90 % en poids d'une huile de base synthétique ; et
    (B) 10 à 80 % en poids d'un polymère en peigne, comprenant les monomères suivants :
    (a) 20 à 35 % en poids d'esters d'acide (méth)acrylique et d'un polybutadiène hydrogéné hydroxylé ; et
    (b) 0,2 % en poids à 15 % en poids de styrène,
    (c) 0,2 à 20 % en poids de méthacrylates d'alkyle ayant 12 à 15 atomes de carbone dans la chaîne alkyle,
    (d) 50 à 70 % en poids de (méth)acrylates d'alkyle ayant 1 à 4 atomes de carbone dans la chaîne alkyle,
    par rapport au poids total du polymère en peigne, dans laquelle les quantités des composants (A) et (B) sont par rapport au poids total de la composition de lubrifiant.
  2. Composition de lubrifiant selon la revendication 1, dans laquelle la composition de lubrifiant est caractérisée par un rapport de la viscosité cinématique de la composition de lubrifiant à -20 °C (KV-20) à la viscosité cinématique à +20 °C (KV+20), KV-20/KV+20, inférieur ou égal à 8, dans laquelle les viscosités cinématiques sont mesurées selon la norme ASTM D445.
  3. Composition de lubrifiant selon la revendication 1 ou 2, dans laquelle l'huile de base synthétique (A) est une poly-alpha-oléfine ayant une viscosité cinématique à 100 °C selon la norme ASTM D445 de 1 à 20 mm2/s.
  4. Composition de lubrifiant selon la revendication 1 ou 2, dans laquelle l'huile de base synthétique (A) est une poly-alpha-oléfine ayant une viscosité cinématique à 100 °C selon la norme ASTM D445 de 1 à 10 mm2/s.
  5. Composition de lubrifiant selon la revendication 1 ou 2, dans laquelle l'huile de base synthétique (A) est une poly-alpha-oléfine ayant une viscosité cinématique à 100 °C selon la norme ASTM D445 de 1 à 5 mm2/s.
  6. Composition de lubrifiant selon la revendication 1 ou 2, dans laquelle l'huile de base synthétique (A) est une poly-alpha-oléfine ayant une viscosité cinématique à 100 °C selon la norme ASTM D445 de 2 à 3 mm2/s.
  7. Composition de lubrifiant selon l'une quelconque des revendications précédentes, caractérisée en ce qu'elle comprend 30 à 80 % en poids de l'huile de base synthétique (A) et 20 à 70 % en poids du polymère en peigne (B), par rapport au poids total de la composition de lubrifiant.
  8. Composition de lubrifiant selon l'une quelconque des revendications précédentes, dans laquelle le polybutadiène hydrogéné hydroxylé du composant (a) a une masse moléculaire moyenne en nombre Mn selon la norme DIN 55672-1 de 4 000 à 5 000 g/mol.
  9. Composition de lubrifiant selon l'une quelconque des revendications précédentes, dans laquelle le polymère en peigne (B) comprend :
    (a) 25 à 30 % en poids d'esters d'acide (méth)acrylique et d'un polybutadiène hydrogéné hydroxylé,
    (b) 0,2 à 15 % en poids de styrène,
    (c) 0,2 à 15 % en poids de méthacrylates d'alkyle ayant 12 à 14 atomes de carbone dans la chaîne alkyle,
    (d) 50 à 65 % en poids de méthacrylate de butyle et
    (e) 0,1 à 0,2 % en poids de méthacrylate de méthyle, par rapport au poids total du polymère en peigne.
  10. Utilisation d'un polymère en peigne, comprenant :
    (a) 20 à 35 % en poids d'esters d'acide (méth)acrylique et d'un polybutadiène hydrogéné hydroxylé,
    (b) 0,2 à 15 % en poids de styrène,
    (c) 0,2 à 20 % en poids de méthacrylates d'alkyle ayant 12 à 15 atomes de carbone dans la chaîne alkyle,
    (d) 50 à 65 % en poids de (méth)acrylates d'alkyle ayant 1 à 4 atomes de carbone dans la chaîne alkyle,
    par rapport au poids total du polymère en peigne,
    en tant qu'additif pour une huile de base pour produire une composition de lubrifiant ayant un facteur R inférieur ou égal à 8, dans laquelle le facteur R est défini comme le rapport de la viscosité cinématique de la composition de lubrifiant à -20 °C à la viscosité cinématique à +20 °C mesurées selon la norme ASTM D445.
  11. Utilisation selon la revendication 10, dans laquelle l'huile de base est une huile de base poly-alpha-oléfine ayant une viscosité cinématique à 100 °C selon la norme ASTM D445 de 1 mm2/s à 20 mm2/s.
  12. Utilisation selon la revendication 10, dans laquelle l'huile de base est une huile de base poly-alpha-oléfine ayant une viscosité cinématique à 100 °C selon la norme ASTM D445 de 1 à 10 mm2/s.
  13. Utilisation selon la revendication 10, dans laquelle l'huile de base est une huile de base poly-alpha-oléfine ayant une viscosité cinématique à 100 °C selon la norme ASTM D445 de 1 à 5 mm2/s.
  14. Utilisation selon la revendication 10, dans laquelle l'huile de base est une huile de base poly-alpha-oléfine ayant une viscosité cinématique à 100 °C selon la norme ASTM D445 de 2 à 3 mm2/s.
  15. Utilisation selon les revendications 10 à 14, caractérisée en ce que la composition de lubrifiant a un facteur R de 1 à 8.
  16. Utilisation selon les revendications 10 à 15, caractérisée en ce que le polymère en peigne (B) comprend :
    (a) 25 à 30 % en poids d'esters d'acide (méth)acrylique et d'un polybutadiène hydrogéné hydroxylé,
    (b) 0,2 à 15 % en poids de styrène,
    (c) 0,2 à 15 % en poids de méthacrylates d'alkyle ayant 12 à 14 atomes de carbone dans la chaîne alkyle,
    (d) 50 à 65 % en poids de méthacrylate de butyle et
    (e) 0,1 à 0,2 % en poids de méthacrylate de méthyle, par rapport au poids total du polymère en peigne.
EP17787940.0A 2016-11-02 2017-10-27 Composition de lubrifiant avec une caractéristique de viscosité améliorée à basse température d'utilisation Active EP3535357B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP16196796 2016-11-02
PCT/EP2017/077605 WO2018083027A1 (fr) 2016-11-02 2017-10-27 Composition lubrifiante d'une caractéristique de viscosité améliorée à basse température de fonctionnement

Publications (2)

Publication Number Publication Date
EP3535357A1 EP3535357A1 (fr) 2019-09-11
EP3535357B1 true EP3535357B1 (fr) 2020-12-16

Family

ID=57218823

Family Applications (1)

Application Number Title Priority Date Filing Date
EP17787940.0A Active EP3535357B1 (fr) 2016-11-02 2017-10-27 Composition de lubrifiant avec une caractéristique de viscosité améliorée à basse température d'utilisation

Country Status (10)

Country Link
US (1) US20190300808A1 (fr)
EP (1) EP3535357B1 (fr)
JP (1) JP6890658B2 (fr)
KR (1) KR102455761B1 (fr)
CN (1) CN109923195B (fr)
CA (1) CA3042119A1 (fr)
ES (1) ES2854939T3 (fr)
RU (1) RU2747727C2 (fr)
SG (1) SG11201903781QA (fr)
WO (1) WO2018083027A1 (fr)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MX2019007208A (es) * 2016-12-19 2019-08-16 Evonik Oil Additives Gmbh Composicion de aceites lubricantes que comprende polimeros peine dispersantes.
EP3652284B1 (fr) * 2017-07-14 2021-06-02 Evonik Operations GmbH Polymères en peigne à fonctionnalité imide
EP3498808B1 (fr) 2017-12-13 2020-05-13 Evonik Operations GmbH Agent améliorant l'indice de viscosité présentant une meilleure résistance au cisaillement et une meilleure solubilité après cisaillement
MX2021011416A (es) * 2019-03-20 2021-10-13 Evonik Operations Gmbh Nuevos (met)acrilatos de polialquilo para mejorar la economia de combustible, la dispersion y el rendimiento de los depositos.
AU2019477845A1 (en) * 2019-12-12 2022-07-28 Evonik Operations Gmbh High viscosity polyacrylate base fluids
US20210179965A1 (en) * 2019-12-16 2021-06-17 Infineum International Limited High Viscosity Index Comb Copolymer Viscosity Modifiers and Methods of Modifying Lubricant Viscosity Using Same
US11384311B2 (en) * 2019-12-16 2022-07-12 Infineum International Limited High viscosity index comb polymer viscosity modifiers and methods of modifying lubricant viscosity using same
US20210179960A1 (en) * 2019-12-16 2021-06-17 Infineum International Limited High Viscosity Index Comb Copolymer Viscosity Modifiers and Methods of Modify Lubricant Viscosity Using Same
CN114846125B (zh) * 2019-12-27 2024-01-16 出光兴产株式会社 润滑油组合物
US20230312797A1 (en) * 2020-09-14 2023-10-05 Sanyo Chemical Industries, Ltd. Viscosity index improving agent and lubricating oil composition
KR20230037047A (ko) * 2020-09-14 2023-03-15 산요가세이고교 가부시키가이샤 점도 지수 향상제 및 윤활유 조성물
EP4060009B1 (fr) * 2021-03-19 2023-05-03 Evonik Operations GmbH Un agent améliorant l'indice de viscosité et composition lubrifiante

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2047266B (en) * 1979-04-09 1984-02-08 Exxon Research Engineering Co Viscosity index lubricating oils
US4611031A (en) * 1985-01-28 1986-09-09 Rohm And Haas Company Process for the preparation of a compatibilizer for concentrated polymer blends and compatibilizer product
US5393843A (en) 1992-08-31 1995-02-28 Shell Oil Company Butadiene polymers having terminal functional groups
DE4312715A1 (de) * 1993-04-20 1994-10-27 Roehm Gmbh Kammpolymere
DE4431302A1 (de) 1994-09-02 1996-03-07 Roehm Gmbh Kammpolymere
KR100397715B1 (ko) * 1998-03-05 2003-09-17 이 아이 듀폰 디 네모아 앤드 캄파니 온도 및 전단에 대한 점도 반응이 제어된 중합체 필름
DE102005031244A1 (de) 2005-07-01 2007-02-15 Rohmax Additives Gmbh Öllösliche Kammpolymere
EP2164885B1 (fr) * 2007-07-09 2014-03-12 Evonik Oil Additives GmbH Utilisation de polymères en peigne pour réduire la consommation de carburant
DE102007032120A1 (de) * 2007-07-09 2009-01-15 Evonik Rohmax Additives Gmbh Verwendung von Kammpolymeren zur Verringerung des Kraftstoffverbrauchs
DE102007046223A1 (de) * 2007-09-26 2009-04-02 Evonik Rohmax Additives Gmbh Verwendung von Kammpolymeren zur Verringerung des Kraftstoffverbrauchs
DE102009001447A1 (de) * 2009-03-10 2010-09-16 Evonik Rohmax Additives Gmbh Verwendung von Kammpolymeren zur Verbesserung des Lasttragevermögens
BRPI1010725A2 (pt) * 2009-06-12 2016-03-15 Evonik Rohmax Additives Gmbh fluido tendo índice de viscosidade melhorado.
JP6014540B2 (ja) * 2013-04-17 2016-10-25 コスモ石油ルブリカンツ株式会社 内燃機関用潤滑油組成物
JP6218924B2 (ja) * 2013-04-18 2017-10-25 エボニック オイル アディティヴス ゲゼルシャフト ミット ベシュレンクテル ハフツングＥｖｏｎｉｋ Ｏｉｌ Ａｄｄｉｔｉｖｅｓ ＧｍｂＨ 燃料消費量を減少させるためのギヤーオイル配合物
RU2678102C2 (ru) * 2013-12-24 2019-01-23 Шелл Интернэшнл Рисерч Маатсхаппий Б.В. Смазочная композиция
US10584302B2 (en) * 2014-09-19 2020-03-10 Idemitsu Kosan Co., Ltd. Lubricating oil composition and method for manufacturing said lubricating oil composition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
EP3535357A1 (fr) 2019-09-11
CA3042119A1 (fr) 2018-05-11
ES2854939T3 (es) 2021-09-23
JP2019535858A (ja) 2019-12-12
RU2747727C2 (ru) 2021-05-13
SG11201903781QA (en) 2019-05-30
WO2018083027A1 (fr) 2018-05-11
RU2019116232A3 (fr) 2020-12-03
KR102455761B1 (ko) 2022-10-19
KR20190080918A (ko) 2019-07-08
CN109923195B (zh) 2022-10-11
JP6890658B2 (ja) 2021-06-18
RU2019116232A (ru) 2020-12-03
US20190300808A1 (en) 2019-10-03
CN109923195A (zh) 2019-06-21

Similar Documents

Publication Publication Date Title
EP3535357B1 (fr) Composition de lubrifiant avec une caractéristique de viscosité améliorée à basse température d'utilisation
EP3507350B1 (fr) Polymères en peigne pour améliorer la perte d'évaporation noack de formulations d'huile moteur
CN109912756B (zh) 具有改进的抗剪切性和剪切后溶解性的粘度指数改进剂
EP3555245B1 (fr) Composition d'huile lubrifiante contenant des polymères dispersants en peigne
JP6456468B1 (ja) 改善された低温粘度および剪断抵抗を有する粘度指数向上剤
CN113597463B (zh) 用于改进燃料经济性、分散性和沉积物性能的聚(甲基)丙烯酸烷基酯
EP3880773B1 (fr) Copolymères aléatoires destinés à être utilisés comme additifs d'huiles de base ou de lubrifiant
EP4119640B1 (fr) Composition d'additif lubrifiant contenant des polyalkyl méthacrylates
EP4060009B1 (fr) Un agent améliorant l'indice de viscosité et composition lubrifiante
US20240043768A1 (en) Process for preparing homo- and copolymers of alkyl (meth)acrylates with low residual monomer content
RU2814337C2 (ru) Новые присадки, улучшающие индекс вязкости
WO2023110529A1 (fr) Formulations de lubrifiant hydraulique ayant un point d'éclair élevé et une stabilité améliorée au cisaillement
JP2023013746A (ja) 潤滑剤添加剤組成物
WO2024033156A1 (fr) Polymères à base de polyalkyle (méth)acrylate présentant des propriétés à basse température améliorées
CN112390914A (zh) 具有改进的抗剪切性的粘度指数改进剂

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20190418

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: EVONIK DEGUSSA GMBH

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: EVONIK OPERATIONS GMBH

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

RIC1 Information provided on ipc code assigned before grant

Ipc: C10N 30/02 20060101ALI20200520BHEP

Ipc: C10N 30/08 20060101ALI20200520BHEP

Ipc: C10M 107/28 20060101ALI20200520BHEP

Ipc: C10N 20/00 20060101ALI20200520BHEP

Ipc: C10M 145/14 20060101AFI20200520BHEP

Ipc: C10M 169/04 20060101ALI20200520BHEP

INTG Intention to grant announced

Effective date: 20200624

GRAJ Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTC Intention to grant announced (deleted)
INTG Intention to grant announced

Effective date: 20201009

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602017029727

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1345602

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210115

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210316

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210317

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201216

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201216

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1345602

Country of ref document: AT

Kind code of ref document: T

Effective date: 20201216

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210316

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201216

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201216

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201216

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210416

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201216

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201216

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201216

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201216

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201216

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201216

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201216

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201216

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602017029727

Country of ref document: DE

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2854939

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20210923

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210416

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201216

26N No opposition filed

Effective date: 20210917

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201216

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201216

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210416

REG Reference to a national code

Ref country code: NL

Ref legal event code: MM

Effective date: 20211101

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20211031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201216

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20211101

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20211027

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20211031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20211031

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20211031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20211027

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20230202

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20211028

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230524

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20211031

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201216

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20171027

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20231020

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20231026

Year of fee payment: 7

Ref country code: DE

Payment date: 20231020

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201216