EP4143279B1 - Procédé pour la préparation de polymères poly(méth)acrylates d'alkyle dispersants - Google Patents

Procédé pour la préparation de polymères poly(méth)acrylates d'alkyle dispersants Download PDF

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Publication number
EP4143279B1
EP4143279B1 EP21720541.8A EP21720541A EP4143279B1 EP 4143279 B1 EP4143279 B1 EP 4143279B1 EP 21720541 A EP21720541 A EP 21720541A EP 4143279 B1 EP4143279 B1 EP 4143279B1
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weight
monomers
mixture
oil
total amount
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EP4143279A1 (fr
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Katrin Schöller
Fabian ZIEGLER
Wolfgang Tschepat
Sarah LIPPERT
Mara DOERFEL
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Evonik Operations GmbH
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Evonik Operations GmbH
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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
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions 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
    • 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
    • C10M2209/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical
    • 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
    • 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

Definitions

  • the present invention is directed to a novel process for the preparation of polyalkyl (meth)acrylate polymers with improved compositional distribution leading to better producibility, solubility and improved performance of the products in lubricant compositions, especially in engine oil formulations.
  • Lubricants are playing an important role in reducing a vehicle's fuel consumption and there is a continuing need for improvements in fuel economy performance.
  • SAE Society of Automotive Engineers
  • Viscosity index (VI) improvers are generally added to a lubricant to improve its thickening efficiency and to protect the engine.
  • Polyalkyl (meth)acrylate-based polymers and especially polyalkyl (meth)acrylates comprising macromonomers, are commonly used as additives, especially as viscosity index improvers. They show good viscometric properties like low KV 40 , HTHS 80 and HTHS 100 values in engine oil formulations leading to good fuel economy.
  • Polyalkyl (meth)acrylate polymers usually comprise short-chain alkyl (meth)acrylates and long-chain alkyl (meth)acrylates. Short-chain alkyl (meth)acrylates are more polar and contribute to the viscometric properties of the resulting polymer, whereas long-chain alkyl (meth)acrylates are less polar and provide the oil solubility of the resulting polymer.
  • composition of a polyalkyl (meth)acrylate has to be well balanced between polar and apolar monomers as a raise in polarity usually comes along with poor solubility and an undesired change in the viscometric performance of the polymer.
  • polar monomers like methyl (meth)acrylate (MMA), butyl (meth)acrylate (BMA), styrene or functional monomers like dimethylaminoethyl methacrylate (DMAEMA)
  • DMAEMA dimethylaminoethyl methacrylate
  • One typical approach to counteract this polarity increase is to balance the polymer polarity by increasing the amount of less polar comonomers like for example long-chain alkyl (meth)acrylates or macromonomers.
  • the solubility of the polymer in oil can be improved this way, the drawback of this approach is that the viscometric performance measured as KV 40 , HTHS 80 , or HTHS 100 values in oil is compromised. This means that increasing for example the amount of long-chain alkyl (meth)acrylates leads to an increased KV 40 , HTHS 80 and HTHS 100 and therefore reduced fuel efficiency effect.
  • the viscometric performance of a polyalkyl (meth)acylate based comb polymer can e.g. be improved by introducing novel monomers. It is already known in the art that a certain amount of macromonomers has a positive impact on fuel efficiency ( US 2010/0190671 ), that the presence of alkyl acrylates improves the NOACK volatility ( WO 2018/041755 ) and a certain amount of imide functionality has a positive impact on friction reduction ( WO 2019/012031 ).
  • the changed process conditions additionally allow the synthesis of new polymer compositions with improved viscometric properties towards fuel efficiency that were not producible before and showed an unfavorable solubility in oil.
  • US 2008/0194443 and US 2010/0190671 disclose a synthesis of comb polymers wherein a mixture of all monomers is added to an apparatus and diluted with base oil. Subsequently, the reaction mixture is heated to a desired temperature and reacted while several shots of initiator are added after certain time intervals. A split of the monomers into different feeds with different compositions and concentrations of monomers is not mentioned.
  • US 2011/0306533 and US 2011/0319305 disclose a method for the preparation of comb polymers wherein an initial reaction mixture is prepared comprising all of the monomers and solvent oil. This initial reaction mixture is then split into a heel (about one fifth of the initial reaction mixture) and a feed (about four fifth of the initial reaction mixture).
  • the compositions of the monomers in both, heel and feed are the same as well as are the concentrations of the monomers. After reaching the reaction temperature, several shots of initiator are added after certain time intervals. A split of the monomers into different feeds with different compositions and concentrations of monomers is not mentioned.
  • WO 2014/170169 discloses a method for the preparation of comb polymers wherein an initial reaction mixture is prepared comprising all the monomers and solvent oil. This initial reaction mixture is then split into a heel (about one third of the initial reaction mixture) and a feed (about two thirds of the initial reaction mixture).
  • the compositions of the monomers in both, heel and feed are the same as well as are the concentrations of the monomers. After reaching the reaction temperature, several shots of initiator are added after certain time intervals. A split of the monomers into different feeds with different compositions and concentrations is not mentioned.
  • WO 2019/012031 is directed to comb polymers and describes a base polymer synthesis wherein an apparatus is initially charged with a mixture of 300 g of monomers and 200 g of solvent oil. This mixture is heated, and initiator added. Subsequently, another mixture of 300 g of monomers and 200 g of solvent oil, having the same composition and concentration as the initial mixture, is added as a feed as well as further initiator shot. A split of the monomers into different feeds with different compositions and concentrations of monomers is not mentioned.
  • WO 2018/114673 discloses a method for the preparation of comb polymers wherein an initial reaction mixture of different monomers and solvent oil is prepared. 50% of said mixture are charged into a beaker and the other 50% of the initial mixture fed during a time interval. Monomer composition and concentration are the same. Several shots of initiator are added after certain time intervals. A split of the monomers into different feeds having different compositions and concentrations is not mentioned.
  • WO 2018/041755 discloses a method for the preparation of comb polymers wherein a heel is charged with an initial mixture of monomers and solvent oil and a feed of monomers in solvent is added.
  • the composition of the monomers in heel and feed are the same, but the concentrations of heel and feed are different.
  • Copolymerization parameters need to be defined for each comonomer couple individually and temperature, medium and initiator need to be considered as well because the copolymerization parameters are parameters for the relative reactivity only.
  • the copolymerization parameters of such a monomer A-monomer B couple differ significantly, the first synthesized polymer molecules show a different composition than the later polymerized ones. Partial demixing is therefore a known phenomenon occurring for such polymer mixtures. Copolymers with constant composition over time can then be obtained by adding the faster polymerizing monomer according to its conversion or working at azeotrope conditions. In technical copolymerizations and products where many comonomers are applied this becomes challenging.
  • the described new process can be applied to all free radical polymerizations run in a feed process wherein at least one comonomer exhibits a copolymerization kinetics that varies significantly from the kinetics of the other comonomers.
  • polyalkyl (meth)acrylates comprising monomers that show differences in polarity, reactivity and oil solubility can be prepared by the process according to the present invention.
  • a first object of the present invention is therefore directed to a method for the preparation of polyalkyl (meth)acrylate polymers consisting of:
  • a further first object of the present invention is directed to the method for the preparation of polyalkyl (meth)acrylate polymers as described further above, wherein the monomer mixture 2 can be further split into monomer mixture 2a and monomer mixture 2b , wherein
  • a further first object is directed to the method as described further above, wherein the polyalkyl (meth)acrylate polymer consists of:
  • each component (a), (b1), (b2), (b3) and (b4) is based on the total composition of the polyalkyl (meth)acrylate polymer.
  • the proportions of components (a), (b1), (b2), (b3) and (b4) add up to 100% by weight.
  • the weight-average molecular weight of the polyalkyl(meth)acrylate polymers according to the present invention is preferably in the range of 100,000 to 1,000,000 g/mol, more preferably in the range of 400,000 to 700,000 g/mol.
  • the number-average molecular weight of the polyalkyl(meth)acrylate polymers according to the present invention is preferably in the range of 60,000 to 300,000 g/mol, more preferably in the range of 100,000 to 200,000 g/mol.
  • the polyalkyl(meth)acrylate polymers according to the present invention have a polydispersity index (PDI) M w /M n in the range of 2 to 10, more preferably in the range of 2 to 6.
  • M w and M n are determined by size exclusion chromatography (SEC) using commercially available polymethylmethacrylate standards. The determination is affected by gel permeation chromatography with THF as eluent.
  • a polyalkyl(meth)acrylate 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 polyalkyl(meth)acrylate 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 the further free-radically polymerizable comonomers form the side chains of the comb polymer.
  • (meth)acrylate refers to both, esters of acrylic acid and esters of methacrylic acid. Methacrylates are preferred over acrylates.
  • Polyolefin-based macromonomers comprise at least one group which is derived from polyolefins.
  • Polyolefins are known in the technical field and can be obtained by polymerizing alkenes and/or alkadienes which consist of the elements carbon and hydrogen, for example C2-C10-alkenes such as ethylene, propylene, n-butene, isobutene, norbornene, and/or C4-C10-alkadienes such as butadiene, isoprene, norbornadiene.
  • the repeating units derived from polyolefin-based macromonomers comprise preferably at least 70% by weight and more preferably at least 80% by weight and most preferably at least 90% by weight of groups which are derived from alkenes and/or alkadienes, based on the weight of the repeating units derived from polyolefin-based macromonomers.
  • the polyolefinic groups may in particular also be present in hydrogenated form.
  • the repeating units derived from polyolefin-based macromonomers may comprise further groups. These include small proportions of copolymerizable monomers.
  • These monomers are known per se and include, among other monomers, alkyl (meth)acrylates, styrene monomers, fumarates, maleates, vinyl esters and/or vinyl ethers.
  • the proportion of these groups based on copolymerizable monomers is preferably at most 30% by weight, more preferably at most 15% by weight, based on the weight of the repeat units derived from polyolefin-based macromonomers.
  • the repeating units derived from polyolefin-based macromonomers may comprise starting groups and/or end groups which serve for functionalization or are caused by the preparation of the repeat units derived from polyolefin-based macromonomers.
  • the proportion of these starting groups and/or end groups is preferably at most 30% by weight, more preferably at most 15% by weight, based on the weight of the repeat units derived from polyolefin-based macromonomers.
  • Preferred polyolefin-based macromonomers are esters of (meth)acrylic acid and a hydroxylated hydrogenated polybutadiene.
  • 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 4,500 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 molar mass M n is determined by size exclusion chromatography using commercially available polybutadiene standards. The determination is affected 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 .
  • 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.
  • 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) 2 O).
  • 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.
  • the C 1-4 -alkyl (meth)acrylates for use in accordance with the invention are esters of (meth)acrylic acid and straight chained or branched alcohols having 1 to 4 carbon atoms.
  • the term "C 1-4 -alkyl (meth)acrylates” encompasses individual (meth)acrylic esters with an alcohol of a particular length, and likewise mixtures of (meth)acrylic esters with alcohols of different lengths.
  • Suitable C 1-4 -alkyl (meth)acrylates include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n -propyl (meth)acrylate), iso -propyl (meth)acrylate, n -butyl (meth)acrylate, iso -butyl (meth)acrylate and tert -butyl (meth)acrylate.
  • Particularly preferred C 1-4 -alkyl (meth)acrylates are methyl (meth)acrylate and n-butyl (meth)acrylate; methyl methacrylate and n -butyl methacrylate are especially preferred.
  • C 10-15 alkyl methacrylates for use in accordance with the invention are esters of methacrylic acid and alcohols having 10 to 15 carbon atoms.
  • the term "C 10-15 alkyl methacrylates” encompasses individual methacrylic esters with an alcohol of a particular length, and likewise mixtures of methacrylic esters with alcohols of different lengths.
  • Suitable C 10-15 alkyl methacrylates include, for example, decyl methacrylate, undecyl methacrylate, 5-methylundecyl methacrylate, dodecyl methacrylate, 2-methyldodecyl methacrylate, tridecyl methacrylate, 5-methyltridecyl methacrylate, tetradecyl methacrylate and/or pentadecyl methacrylate.
  • Particularly preferred C 10-15 alkyl methacrylates are methacrylic esters of a linear C 12-14 alcohol mixture (C 12-14 alkyl methacrylate).
  • the method according to the present invention is a free-radical polymerization.
  • Customary free-radical polymerization is explained, inter alia, in Ullmanns's Encylopedia of Industrial Chemistry, Sixth Editi on.
  • a polymerization initiator and a chain transfer agent are used for this purpose.
  • the use of chain transfer agents is not necessary.
  • an initiator is added to monomer mixtures 1 , 2 , 2a and 2b in amounts of 0.1% to 0.5% by weight, preferably 0.1% to 0.3% by weight, based on the total amount of monomers used in the reaction.
  • a further amount of 0.05% to 0.25% by weight, based on the total amount of monomers, of an initiator can optionally be added at the end of the reaction.
  • the initiator may be selected from the group consisting of azo initiators, such as azobisisobutyronitrile (AIBN), 2,2'-azobis(2-methylbutyronitrile) (AMBN) and 1,1-azobiscyclohexanecarbonitrile, and peroxy compounds such as methyl ethyl ketone peroxide, acetylacetone peroxide, dilauryl peroxide, tert-butyl per-2-ethylhexanoate, ketone peroxide, tert-butyl peroctoate, methyl isobutyl ketone peroxide, cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropylcarbonate, 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane, tert-butyl peroxy-2-eth
  • Preferred initiators are selected from the group consisting of 2,2'-azobis(2-methylbutyronitrile), tert-butylperoxy-2-ethylhexanoate, 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexan, tert-butylperoxybenzoate and tert-butylperoxy-3,5,5-trimethylhexanoat.
  • tert-butylperoxy-2-ethylhexanoate is especially preferred.
  • the polymerization may be carried out at standard pressure, reduced pressure or elevated pressure.
  • the polymerization temperature is generally in the range of 20° to 200°C, preferably 90° to 100°C.
  • the polymerization is carried out with a solvent.
  • solvent is to be understood here in a broad sense.
  • the solvent is selected according to the polarity of the monomers used, preference being given to using API group III oil, relatively light gas oil and/or aromatic hydrocarbons, for example toluene or xylene.
  • the polymerization is carried out in a suitable reaction vessel that is equipped with a stirrer and a temperature control system under nitrogen atmosphere.
  • the base oil to be used in the present invention comprises an oil of lubricating viscosity.
  • oils include natural and synthetic oils, oil derived from hydrocracking, hydrogenation, and hydro-finishing, unrefined, refined, re-refined oils or mixtures thereof.
  • the base oil may also be defined as specified by the American Petroleum Institute (API) (see April 2008 version of “Appendix E-API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils", section 1.3 Sub-heading 1.3. "Base Stock Categories”).
  • API American Petroleum Institute
  • API 1509 Annex E - API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils, September 2011.
  • Groups I, II and III are mineral oils which are classified by the amount of saturates and sulphur they contain and by their viscosity indices;
  • Group IV are polyalphaolefins;
  • Group V are all others, including e.g. ester oils.
  • the table below illustrates these API classifications.
  • the kinematic viscosity at 100°C (KV 100 ) of appropriate apolar base oils used to prepare an additive composition or lubricating composition in accordance with the present invention is preferably in the range of 3 mm 2 /s to 10 mm 2 /s, more preferably in the range of 4 mm 2 /s to 8 mm 2 /s, according to ASTM D445.
  • Fischer-Tropsch derived base oils are known in the art.
  • Fischer-Tropsch derived is meant that a base oil is, or is derived from, a synthesis product of a Fischer-Tropsch process.
  • a Fischer-Tropsch derived base oil may also be referred to as a GTL (Gas-To-Liquids) base oil.
  • Suitable Fischer-Tropsch derived base oils that may be conveniently used as the base oil in the lubricating composition of the present invention are those as for example disclosed in EP 0 776 959 , EP 0 668 342 , WO 97/21788 , WO 00/15736 , WO 00/14188 , WO 00/14187 , WO 00/14183 , WO 00/14179 , WO 00/08115 , WO 99/41332 , EP 1 029 029 , WO 01/18156 , WO 01/57166 and WO 2013/189951 .
  • base oils of API Group III, API Group V and mixtures thereof are used base oils of API Group III, API Group V and mixtures thereof; preferred are mixtures of API Group III and API Group V base oils.
  • Group V base oils are preferably be used dioctylsebacate (DIOS) or Berylane.
  • a further object of the present invention is therefore directed to a method for preparing the polyalkyl (meth)acrylates as outlined further above, wherein
  • a further object of the present invention is directed to a method for the preparation of polyalkyl (meth)acrylate polymers, wherein the polyalkyl (meth)acrylate polymer consists of:
  • a further first object is directed to the method as described further above, wherein the polyalkyl (meth)acrylate polymer consists of:
  • each component (a), (b1), (b2), (b3) and (b4) is based on the total composition of the polyalkyl (meth)acrylate polymer.
  • the proportions of components (a), (b1), (b2), (b3) and (b4) add up to 100% by weight.
  • the polymers prepared according to the method of the present invention are characterized by their contribution to low KV 40 , HTHS 80 and HTHS 100 values (e.g. at a given HTHS 150 of 2.6 mPas or 2.9 mPas) of lubricating oil compositions comprising them.
  • the polyalkyl(meth)acrylate polymers prepared according to the method of the present invention can therefore be used in all common grades of motor oils having the viscosity characteristics defined in the document SAE J300.
  • the base oil to be used in the additive composition comprises an oil of lubricating viscosity as described further above.
  • an additive composition comprising at least one polyalkyl(meth)acrylate polymer prepared according to the method of the present invention and a base oil to improve the kinematic viscosity and HTHS performance of lubricating oil compositions, especially of engine oil formulations.
  • the polyalkyl (meth)acrylate polymers according to the present invention and the comparative examples were characterized with respect to their molecular weight and PDI.
  • the additive compositions including the polyalkyl (meth)acrylate polymers according to the present invention and comparative examples were characterized with respect to their viscosity index (VI) to ASTM D 2270, kinematic viscosity at 40°C (KV 40 ) and 100°C (KV 100 ) to ASTM D445 and with respect to their solubility.
  • VI viscosity index
  • KV 40 kinematic viscosity at 40°C
  • KV 100 100°C
  • the lubricating oil compositions including the comb polymers according to the present invention and comparative examples were characterized with respect to kinematic viscosity at 40°C (KV 40 ) and 100°C (KV 100 ) to ASTM D445, the viscosity index (VI) to ASTM D 2270, high-temperature high-shear viscosity at 80°C, 100°C and 150°C to CEC L-036 and with respect to their solubility.
  • the PSSI Permanent Shear Stability Index
  • ASTM D 6022-01 Standard Practice for Calculation of Permanent Shear Stability Index
  • the solubility of the additive compositions was tested in solutions of 25% polymer in Group III oil; the solubility of the lubricating oil compositions was tested in solutions of 3.75% polymer in PAO4.
  • the solutions were analyzed photometrically after cooling down to room temperature for at least 1 day and the haze value was obtained using a Hunter LAB XE device and software. When measuring haze, the percentage of light diffusely scattered compared to the total light transmitted is reported.
  • the Haze level is below 5 the sample appears completely clear by eye and are considered to show very good solubility in lubricant formulations. At Haze levels between 5-10, the sample appears slightly hazy and the products are considered to show only medium solubility in lubricant formulations. At HAZE levels above 10, the sample appears obviously hazy and the products are considered to have a poor solubility in lubricant formulations.
  • 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 of 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).
  • Table 1 Net compositions (after reaction) of the comb polymers prepared according to the present invention.
  • An oil mixture of NB3043 and Group V oil was added to achieve a concentration of monomers in oil of 55%.
  • the resulting reaction mixture contained 45% of an oil mixture comprising 9.6% by weight of NB3020, 61.6% by weight of NB3043 and 28.8% by weight of Group V oil, based on the total amount of the oil composition.
  • the monomer concentration of mixture 2 was 55% and the base oil was a mixture of 9.6% by weight of NB3020, 61.6% by weight of NB3043 and 28.8% of Group V oil, based on the total amount of the oil composition.
  • An oil mixture of NB3043 and Group V oil was added to achieve a concentration of monomers in oil of 55.8%.
  • the resulting reaction mixture contained 44.2% of an oil mixture comprising 11.3% by weight of NB3020, 61% by weight of NB3043 and 27.7% by weight of Group V oil, based on the total amount of the oil composition.
  • Monomer mixture 2 contained 55% of monomers and 45% of an oil mixture comprising 7.9% by weight of NB3020, 63.3% by weight of NB3043 and 28.8% by weight of Group V oil, based on the total amount of the oil composition.
  • Monomer mixture 3 contained 53% of monomers and 47% of an oil mixture comprising 68.8% by weight of NB3043 and 31.2% by weight of Group V oil, based on the total amount of the oil composition. After that, the reaction was maintained at 95°C for another hour.
  • reaction mixture was diluted to 40% solids with NB3043 and 0.2%, based on the total amount of monomers, of tert-butylperoxy-2-ethyl-hexanoate within 3 hours. Then the reaction was again maintained at 95°C for another 2 h and after this another 0.1%, based on the total amount of monomers, of tert-butylperoxy-2-ethyl-hexanoate was added and the mixture was stirred at 95°C overnight. The next day, the mixture was diluted to 25% solids with NB3043. Table 1.2: Composition of monomer mixtures used for the preparation of Polymer 1.2.
  • An oil mixture of NB3043 and Group V oil was added to achieve a concentration of monomers in oil of 52.6%.
  • the resulting reaction mixture contained 47.4% of an oil mixture comprising 10% by weight of NB3020, 53.5% by weight of NB3043 and 36.5% by weight of Group V oil, based on the total amount of the oil composition.
  • Monomer mixture 2 contained 58% of monomers and 42% of an oil mixture comprising 4.8% by weight of NB3020, 77.6% by weight of NB3043 and 17.6% by weight of Group V oil, based on the total amount of the oil composition. The resulting reaction mixture was then maintained at 95°C for another hour.
  • reaction mixture was diluted to 40% solids with NB3043 and 0.2%, based on the total amount of monomers, of tert-butylperoxy-2-ethyl-hexanoate within one hour. Then the reaction was again maintained at 95°C for another hour and after this, another 0.1%, based on the total amount of monomers, of tert-butylperoxy-2-ethyl-hexanoate was added and the mixture was stirred at 95°C overnight. The next day, the mixture was diluted to 25% solids with NB3043. Table 1.3: Composition of monomer mixtures used for the preparation of Polymer 1.3.
  • An oil mixture of NB3043 and Group V oil was added to achieve a concentration of monomers in oil of 55%.
  • the resulting reaction mixture contained an oil mixture comprising 10.4% by weight of NB3020, 60.8% by weight of NB3043 and 28.8% by weight of Group V oil, based on the total amount of the base oil composition.
  • Monomer mixture 2 contained 55% of monomers and 45% of an oil mixture comprising 4.5% by weight of NB3020, 76.1% by weight of NB3043 and 19.4% by weight of Group V oil, based on the total amount of the oil composition. The resulting reaction mixture was then maintained at 95°C for another hour.
  • reaction mixture was diluted to 40% solids with NB3043 and 0.2%, based on the total amount of monomers, of tert-butylperoxy-2-ethyl-hexanoate within 3 hours. Then the reaction was again maintained at 95°C for another 2 hours and after this another 0.1%, based on the total amount of monomers, of tert-butylperoxy-2-ethyl-hexanoate was added and the mixture was stirred at 95°C overnight. The next day, the mixture was diluted to 25% solids with NB3043.
  • Table 1.4 Composition of monomer mixtures used for the preparation of Polymer 1.4.
  • Table 1.5 shows the molecular weights, polydispersity and HAZE values of Polymers 1.
  • CE comparative example
  • the haze values of all products from the 4 runs were well below 5.
  • the haze value of the polymer of the 4 th batch was reduced from 14 (comparative example 1.1) to 4.1. That ensures the applicability of the polymers in engine oil formulations.
  • a kettle needs to be cleaned as soon as the product haze raises to 10. That means that for the split-feed processes 1.2, 1.3 and 1.4 at least four batches can be produced in a row before cleaning the kettle. This is not possible for the process 1.1, where the kettle would have to be cleaned latest after the third batch.
  • the method according to the present invention allows the upscaled production of Polymers 1 in a plant.
  • Table 1.6 the HAZE values and viscosities of 3.75% Polymers 1 in oil are disclosed.
  • An oil mixture of NB3043 and Group V oil was added to achieve a concentration of monomers in oil of 55%.
  • the resulting reaction mixture contained 45% of an oil mixture comprising 7.9% by weight of NB3020, 63.3% by weight of NB3043 and 28.8% by weight of Group V oil, based on the total amount of the oil composition.
  • Monomer mixture 2 contained 55% of monomers and 45% of an oil mixture comprising 7.9% by weight of NB3020, 63.3% by weight of NB3043 and 28.8% by weight of Group V oil, based on the total amount of the oil composition.
  • process 1.1 was not repeated four times using the same equipment. From process 1.1 it can be seen that the haze values raised from 2.3 (process 1.1, run 1) to 3.1 (process 1.1, run 2) and 9.8 (process 1.1, run 3). This raise was observed for 6.1% of the polar monomer DMAEMA (corresponds to component (b4)). It can be expected that the raise between the runs would be similar for process 2.1 as well.
  • An oil mixture of NB3043 and Group V oil was added to achieve a concentration of monomers in oil of 55.8%.
  • the resulting reaction mixture contained 44.2% of an oil mixture comprising 11.3% by weight of NB3020, 61% by weight of NB3043 and 27.2% by weight of Group V oil, based on the total amount of the oil composition.
  • Monomer mixture 2 contained 55% of monomers and 45% of an oil mixture comprising 7.9% by weight of NB3020, 36.3% by weight of NB3043 and 28.8% by weight of Group V oil, based on the total amount of the oil composition.
  • Monomer mixture 3 contained 53% of monomers and 47% of an oil mixture comprising 68.8% by weight of NB3043 and 31.2% by weight of Group V oil, based on the total amount of the oil composition.
  • An oil mixture of NB3043 and Group V oil was added to achieve a concentration of monomers in oil of 52.6%.
  • the resulting reaction mixture contained an oil mixture comprising 10% by weight of NB3020, 53.5% by weight of NB3043 and 36.5% by weight of Group V oil, based on the total amount of the oil composition.
  • Monomer mixture 2 contained 58% of monomers and 42% of an oil mixture comprising 4.8% by weight of NB3020, 77.6% by weight of NB3043 and 17.6% by weight of Group V oil, based on the total amount of the oil composition. The resulting reaction mixture was then maintained at 95°C for another hour.
  • reaction mixture was diluted to 40% solids with NB3043 and 0.2%, based on the total amount of monomers, of tert-butylperoxy-2-ethyl-hexanoate within 3 hours. Then the reaction was again maintained at 95°C for another 2 hours and after this another 0.1%, based on the total amount of monomers, of tert-butylperoxy-2-ethyl-hexanoate was added and the mixture was stirred at 95°C overnight. The next day, the mixture was diluted to 25% solids with NB3043.
  • Table 2.3 Composition of monomer mixtures used for the preparation of Polymer 2.3.
  • An oil mixture of NB3043 and Group V oil was added to achieve a concentration of monomers in oil of 60%.
  • the resulting reaction mixture contained an oil mixture comprising 12.7% by weight of NB3020, 58.7% by weight of NB3043 and 28.6% by weight of Group V oil, based on the total amount of the oil composition.
  • Monomer mixture 2 contained 60% of monomers and 40% of an oil mixture comprising 5.6% by weight of NB3020, 75% by weight of NB3043 and 19.4% by weight of Group V oil, based on the total amount of the oil composition. The resulting reaction mixture was then maintained at 95°C for another hour.
  • reaction mixture was diluted to 40% solids with NB3043 and 0.2%, based on the total amount of monomers, of tert-butylperoxy-2-ethyl-hexanoate within 3 hours. Then the reaction was again maintained at 95°C for another 2 hours and after this another 0.1%, based on the total amount of monomers, of tert-butylperoxy-2-ethyl-hexanoate was added and the mixture was stirred at 95°C overnight. The next day, the mixture was diluted to 25% solids with NB3043.
  • Table 2.4 Composition of monomer mixtures used for the preparation of Polymer 2.4.
  • Table 2.5 shows the molecular weights, polydispersity and HAZE values of Polymers 2.
  • CE comparative example
  • Table 2.6 Viscosities of 3.75% Polymers 2 in a Group III base oil mixture (NB 3043 and NB 3080 from Neste) with KV 100 of 4.9 cSt.
  • the problem usually arising from using known processes is that the reaction mixtures used to prepare commonly known polyalkyl (meth)acrylates contain monomers with different reactivities leading to polymers with an inhomogenous distribution of the apolar and polar monomers. If one monomer is more reactive than another second monomer, this monomer will be copolymerized in a higher amount in the beginning of the monomer feed leading to polymer compositions with increased amounts of this monomer at the beginning, while the second monomer will be enriched in the polymers formed during a later time in the feed process.
  • the final product then contains a mixture of all the different fractions of the polymer compositions formed during the whole process, from more polar to less polar fractions as compared to the average polymer composition. Typically, these are only very small deviations. But for polymerizations where macromonomers are used and especially in combination with dispersant monomers like DMAEMA the deviations are extremely large.
  • Table 3 shows the polymerization kinetics of Polymer 1.1 during the original process 1.1.
  • the composition of generated and accumulated polymer is shown over the time.
  • Table 4 shows the polymerization kinetics of Polymer 1.2 having the same total composition as Polymer 1.1 but was produced using the "split-feed" process 1.2. The composition of generated and accumulated polymer is shown over the time.
  • This ratio can be used as an estimate for the overall polarity of the polymer in each fraction prepared in the respective time intervals and is therefore used as an estimate for the solubility/HAZE of the polymer in this fraction. Comparing the polarity ratios of the two process variants leads to the result that for the original process larger deviations from the average polarity ratio of the polymer exist.
  • the kinetics can be calculated via the residual monomer content(s).
  • Formulations with Yubase 4+ as base oil were prepared by using formulation targets 0W30 according to SAE J300; i.e. it was formulated on an HTHS 150 target of 2.9 mPas by adding the polymers prepared according to the present invention.
  • the resulting polymer content was typically between 3 and 3.5% by weight.
  • Characteristic EO formulation properties (KV 40 , KV 100 , HTHS 100 , HTHS 80 ) were measured and are summarized in Table 7 below.

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Claims (9)

  1. Procédé pour la préparation de polymères de type poly((méth)acrylate d'alkyle) constitués de :
    (a) 10 à 20% en poids d'esters d'acide (méth)acrylique et d'un polybutadiène hydrogéné hydroxylé;
    (b1) 45% à 60% en poids de (méth)acrylates de C1-4 alkyle;
    (b2) 10% à 25% en poids de méthacrylates de C10-15 alkyle, plus préférablement de méthacrylates de C12-14 alkyle;
    (b3) 10% à 15% en poids de styrène; et
    (b4) 5% à 7% en poids de monomères contenant N choisis dans le groupe constitué par méthacrylate de N,N-diméthylaminoéthyle (DMAEMA), N-(3-(diméthylamino)propyl)méthacrylamide (DMAPMAm) et N-vinylpyrrolidinone (NVP), de préférence DMAEMA,
    sur la base de la quantité totale des polymères de type poly((méth)acrylate d'alkyle),
    le procédé comprenant les étapes de:
    (i) préparation d'un mélange de monomères 1 comprenant 130 à 145% de la teneur cible de monomères (a) et 90% à 96% de la teneur cible de monomères (b), la concentration des monomères dans le mélange 1 étant de 50 à 60%;
    (ii) ajout d'un mélange de monomères 2 comprenant 50 à 60% de la teneur cible de monomères (a) et 105% à 110% de la teneur cible de monomères (b), la concentration des monomères dans le mélange 2_ étant de 50 à 60%;
    caractérisé en ce que le mélange de monomères 1 comprend 50 à 60% de la quantité totale de monomères utilisés dans le processus et le mélange de monomères 2 comprend 40 à 50% de la quantité totale de monomères utilisés dans le processus.
  2. Procédé selon la revendication 1, dans lequel le mélange de monomères 2_ peut être en outre divisé en un mélange de monomères 2a et un mélange de monomères 2b, dans lequel
    le mélange 2a comprend 100% de la teneur cible de monomères (a) et 100% de la teneur cible de monomères (b), la concentration des monomères dans le mélange 2a étant de 50 à 60%, et
    le mélange de monomères 2b comprend 0% de la teneur cible de monomères (a) et 115 à 125% de la teneur cible de monomères (b), la concentration des monomères dans le mélange 2b étant de 50 à 60%, caractérisé en ce que le mélange de monomères 2a comprend 20 à 30% de la quantité totale de monomères utilisés dans le processus, et le mélange de monomères 2b comprend 20 à 25% de la quantité totale de monomères utilisés dans le processus.
  3. Procédé selon l'une quelconque des revendications précédentes, dans lequel le polymère de type poly((méth)acrylate d'alkyle) est constitué de:
    (a) 10 à 20% en poids d'esters d'acide (méth)acrylique et d'un polybutadiène hydrogéné hydroxylé;
    (b1) 45% à 60% en poids de méthacrylates de C1-4 alkyle;
    (b2) 10% à 25% en poids de méthacrylates de C10-15 alkyle, plus préférablement de méthacrylates de C12-14 alkyle;
    (b3) 10% à 15% en poids de styrène; et
    (b4) 5% à 7% en poids de méthacrylate de N,N-diméthylaminoéthyle (DMAEMA).
  4. Procédé selon l'une quelconque des revendications précédentes, le poids moléculaire moyen en poids des polymères de type poly((méth)acrylate d'alkyle) étant dans la plage de 100 000 à 1 000 000 g/mole, préférablement dans la plage de 400 000 à 700 000 g/mole.
  5. Procédé selon l'une quelconque des revendications précédentes, les mélanges de monomères comprenant en outre une huile de base choisie dans le groupe constitué par des huiles du groupe I, II, III, IV ou V de l'API et des mélanges correspondants.
  6. Procédé selon l'une quelconque des revendications précédentes, les mélanges de monomères comprenant en outre une huile de base qui comprend un mélange d'huiles du groupe III de l'API et du groupe V de l'API.
  7. Procédé selon l'une quelconque des revendications précédentes,
    le mélange 1 comprenant 60% à 75% en poids d'huile du groupe III de l'API ou des mélanges correspondants et 25% à 40% en poids d'huile de base du groupe V et des mélanges correspondants, et
    le mélange 2 comprenant 75% à 85% en poids d'huile du groupe III de l'API ou des mélanges correspondants et 15% à 25% en poids d'huile de base du groupe V et des mélanges correspondants; ou
    le mélange 1 comprenant 65% à 75% en poids d'huile du groupe III de l'API ou des mélanges correspondants et 25% à 35% en poids d'huile de base du groupe V et des mélanges correspondants, et
    le mélange 2a comprenant 65% à 75% en poids d'huile du groupe III de l'API ou des mélanges correspondants et 25% à 35% en poids d'huile de base du groupe V et des mélanges correspondants, et
    le mélange 2b comprenant 65% à 75% en poids d'huile du groupe III de l'API ou des mélanges correspondants et 25% à 35% en poids d'huile de base du groupe V et des mélanges correspondants,
    sur la base du poids total de l'huile de base.
  8. Procédé pour la préparation de polymères de type poly((méth)acrylate d'alkyle), le polymère de type poly((méth)acrylate d'alkyle) étant constitué de :
    (a) 10 à 20% en poids d'esters d'acide (méth)acrylique et d'un polybutadiène hydrogéné hydroxylé;
    (b1) 45% à 60% en poids de (méth)acrylates de C1-4 alkyle;
    (b2) 10% à 25% en poids de méthacrylates de C10-15 alkyle, plus préférablement de méthacrylates de C12-14 alkyle;
    (b3) 10% à 15% en poids de styrène; et
    (b4) 5% à 7% en poids de monomères contenant N choisis dans le groupe constitué par méthacrylate de N,N-diméthylaminoéthyle (DMAEMA), N-(3-(diméthylamino)propyl)méthacrylamide (DMAPMAm) et N-vinylpyrrolidinone (NVP), de préférence DMAEMA,
    sur la base de la quantité totale des polymères de type poly((méth)acrylate d'alkyle),
    le procédé comprenant les étapes de:
    (i) préparation d'un mélange de monomères 1 comprenant 18 à 23% en poids de monomères (a), 45% à 52% en poids de monomères (b1), 14% à 18% en poids de monomères (b2), 9% à 11% en poids de monomères (b3) et 2,5 à 6,5% en poids de monomères (b4), sur la base de la quantité totale de monomères dans le mélange 1, dans une huile de base, la concentration des monomères dans le mélange 1 étant de 50 à 60%; et
    (ii) ajout d'un mélange de monomères 2 comprenant 6% à 11% en poids de monomères (a), 53% à 60% en poids de monomères (b1), 16 à 20% en poids de monomères (b2), 10 à 13% en poids de monomères (b3) et 3 à 7% en poids de monomères (b4), sur la base de la quantité totale de monomères dans le mélange 2, dans une huile de base, la concentration des monomères dans le mélange 2 étant de 50 à 60%;
    caractérisé en ce que le mélange de monomères 1 comprend 54 à 59% de la quantité totale de monomères utilisés dans le processus et le mélange de monomères 2 comprend 41 à 46% de la quantité totale de monomères utilisés dans le processus, ou
    (ii) ajout d'un mélange de monomères 2a comprenant 13 à 17% en poids de monomères (a), 49% à 55% en poids de monomères (b1), 15 à 19% en poids de monomères (b2), 10 à 12% en poids de monomères (b3) et 2,5% à 7% en poids de monomères (b4), sur la base de la quantité totale de monomères dans le mélange 2a, dans une huile de base, la concentration des monomères dans le mélange 2a étant de 53 à 57%; et
    (iii) ajout d'un mélange de monomères 2b comprenant 0% à 1% en poids de monomères (a), 58% à 65% en poids de monomères (b1), 18% à 22% en poids de monomères (b2), 12 à 14% en poids de monomères (b3) et 3% à 8% en poids de monomères (b4), sur la base de la quantité totale de monomères dans le mélange 2b, dans une huile de base, la concentration des monomères dans le mélange 2b étant de 51 à 55%; et
    caractérisé en ce que le mélange de monomères 2a comprend 23 à 27% de la quantité totale de monomères utilisés dans le processus et le mélange de monomères 2b comprend 20 à 24% de la quantité totale de monomères utilisés dans le processus dans lequel
    le mélange 1 comprend 60% à 75% en poids d'huile du groupe III de l'API ou des mélanges correspondants et 25% à 40% en poids d'huile de base du groupe V et des mélanges correspondants, sur la base de la quantité totale d'huile de base utilisée dans le mélange 1; et
    le mélange 2 comprend 75% à 85% en poids d'huile du groupe III de l'API ou des mélanges correspondants et 15% à 25% en poids d'huile de base du groupe V et des mélanges correspondants, sur la base de la quantité totale d'huile de base utilisée dans le mélange 2; ou
    le mélange 1 comprend 65% à 75% en poids d'huile du groupe III de l'API ou des mélanges correspondants et 25% à 35% en poids d'huile de base du groupe V et des mélanges correspondants, sur la base de la quantité totale d'huile de base utilisée dans le mélange 1;
    le mélange 2a comprend 65% à 75% en poids d'huile du groupe III de l'API ou des mélanges correspondants et 25% à 35% en poids d'huile de base du groupe V et des mélanges correspondants, sur la base de la quantité totale d'huile de base utilisée dans le mélange 2a; et
    le mélange 2b comprend 65% à 75% en poids d'huile du groupe III de l'API ou des mélanges correspondants et 25% à 35% en poids d'huile de base du groupe V et des mélanges correspondants, sur la base de la quantité totale d'huile de base utilisée dans le mélange 2b.
  9. Procédé selon la revendication 8, le polymère de type poly((méth)acrylate d'alkyle) étant constitué de:
    (a) 10 à 20% en poids d'esters d'acide méthacrylique et d'un polybutadiène hydrogéné hydroxylé;
    (b1) 45% à 60% en poids de méthacrylates de C1-4 alkyle;
    (b2) 10% à 25% en poids de méthacrylates de C10-15 alkyle, plus préférablement de méthacrylates de C12-14 alkyle;
    (b3) 10% à 15% en poids de styrène; et
    (b4) 5% à 7% en poids de méthacrylate de N,N-diméthylaminoéthyle (DMAEMA).
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Family Cites Families (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4048413A (en) * 1975-12-08 1977-09-13 Scm Corporation High-conversion drift-free batch-type addition copolymerization
NO924031L (no) * 1992-03-20 1993-09-21 Rohm & Haas Fremgangsmaate til styring av molekylvektfordelingen i polymerer
US5393843A (en) 1992-08-31 1995-02-28 Shell Oil Company Butadiene polymers having terminal functional groups
EP0668342B1 (fr) 1994-02-08 1999-08-04 Shell Internationale Researchmaatschappij B.V. Procédé de préparation d'une huile lubrifiante de base
EP1365005B1 (fr) 1995-11-28 2005-10-19 Shell Internationale Researchmaatschappij B.V. Procédé pour la production d'huiles lubrifiantes
BR9611898A (pt) 1995-12-08 2000-05-16 Exxon Research Engineering Co Processo para a produção de um óleo de base de hidrocarboneto biodegradável de alto desempenho, e, respectivo óleo
US6140431A (en) * 1997-02-27 2000-10-31 Rohm And Haas Company Process for preparing continuously variable-composition copolymers
US6090989A (en) 1997-10-20 2000-07-18 Mobil Oil Corporation Isoparaffinic lube basestock compositions
DE69810810T2 (de) * 1997-10-21 2003-09-11 Solutia Inc Schaumarme kohlenwasserstoffölzusammensetzungen
US6059955A (en) 1998-02-13 2000-05-09 Exxon Research And Engineering Co. Low viscosity lube basestock
US6008164A (en) 1998-08-04 1999-12-28 Exxon Research And Engineering Company Lubricant base oil having improved oxidative stability
US6475960B1 (en) 1998-09-04 2002-11-05 Exxonmobil Research And Engineering Co. Premium synthetic lubricants
US6165949A (en) 1998-09-04 2000-12-26 Exxon Research And Engineering Company Premium wear resistant lubricant
US6080301A (en) 1998-09-04 2000-06-27 Exxonmobil Research And Engineering Company Premium synthetic lubricant base stock having at least 95% non-cyclic isoparaffins
US6103099A (en) 1998-09-04 2000-08-15 Exxon Research And Engineering Company Production of synthetic lubricant and lubricant base stock without dewaxing
US6332974B1 (en) 1998-09-11 2001-12-25 Exxon Research And Engineering Co. Wide-cut synthetic isoparaffinic lubricating oils
FR2798136B1 (fr) 1999-09-08 2001-11-16 Total Raffinage Distribution Nouvelle huile de base hydrocarbonee pour lubrifiants a indice de viscosite tres eleve
US7067049B1 (en) 2000-02-04 2006-06-27 Exxonmobil Oil Corporation Formulated lubricant oils containing high-performance base oils derived from highly paraffinic hydrocarbons
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
DE102009001446A1 (de) 2009-03-10 2010-09-23 Evonik Rohmax Additives Gmbh Verwendung von Kammpolymeren als Antifatigue-Additive
DE102009001447A1 (de) 2009-03-10 2010-09-16 Evonik Rohmax Additives Gmbh Verwendung von Kammpolymeren zur Verbesserung des Lasttragevermögens
JP6417321B2 (ja) 2012-06-21 2018-11-07 シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイＳｈｅｌｌ Ｉｎｔｅｒｎａｔｉｏｎａｌｅ Ｒｅｓｅａｒｃｈ Ｍａａｔｓｃｈａｐｐｉｊ Ｂｅｓｌｏｔｅｎ Ｖｅｎｎｏｏｔｓｈａｐ 潤滑組成物
WO2014170169A1 (fr) 2013-04-18 2014-10-23 Evonik Industries Ag Formulation d'huile pour boîte de vitesses réduisant la consommation de carburant
SG11201901623TA (en) 2016-08-31 2019-03-28 Evonik Oil Additives Gmbh Comb polymers for improving noack evaporation loss of engine oil formulations
MX2019007208A (es) 2016-12-19 2019-08-16 Evonik Oil Additives Gmbh Composicion de aceites lubricantes que comprende polimeros peine dispersantes.
WO2019012031A1 (fr) 2017-07-14 2019-01-17 Evonik Oil Additives Gmbh Polymères en peigne à fonctionnalité imide
ES2847382T3 (es) * 2017-09-04 2021-08-03 Evonik Operations Gmbh Nuevos mejoradores del índice de viscosidad con distribuciones de peso molecular definidas
JP6456468B1 (ja) * 2017-12-13 2019-01-23 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 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

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CN115485354B (zh) 2023-08-25
JP2023523755A (ja) 2023-06-07
EP4143279A1 (fr) 2023-03-08
CN115485354A (zh) 2022-12-16
WO2021219679A1 (fr) 2021-11-04
CA3172828A1 (fr) 2021-11-04

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