WO2022077235A1 - Polymères hyperramifiés et compositions lubrifiantes les comprenant - Google Patents

Polymères hyperramifiés et compositions lubrifiantes les comprenant Download PDF

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WO2022077235A1
WO2022077235A1 PCT/CN2020/120700 CN2020120700W WO2022077235A1 WO 2022077235 A1 WO2022077235 A1 WO 2022077235A1 CN 2020120700 W CN2020120700 W CN 2020120700W WO 2022077235 A1 WO2022077235 A1 WO 2022077235A1
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meth
mole
acrylate
trithiocarbonate
hyperbranched polymer
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PCT/CN2020/120700
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English (en)
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Xinyuan Zhu
Xin Jin
Chao Wei
Pei Sun
Gangsheng TONG
Feifei Wang
Jing Feng
Stefan Karl Maier
Qi XIAO
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Evonik Operations Gmbh
Evonik Industries Ag
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Priority to PCT/CN2020/120700 priority Critical patent/WO2022077235A1/fr
Publication of WO2022077235A1 publication Critical patent/WO2022077235A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M151/00—Lubricating compositions characterised by the additive being a macromolecular compound containing sulfur, selenium or tellurium
    • C10M151/02—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/12—Esters of monohydric alcohols or phenols
    • C08F120/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F120/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)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
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2438/00—Living radical polymerisation
    • C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
    • 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
    • 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
    • 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
    • C10N2020/075—Dendrimers
    • 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
    • C10N2030/68—Shear stability

Definitions

  • the present disclosure is directed to hyperbranched polymers, their preparation, lubricant compositions comprising such polymers and their use as viscosity index improvers in lubricant compositions.
  • lubricating oil has a viscosity low enough at low temperatures to assist in cold starting and a viscosity high enough at high temperatures to maintain its load-bearing characteristics.
  • the viscosity index (VI) is one indicator used widely in the lubricating field to assess the variation of viscosity with temperature. Generally speaking, lubricants with high VI value could have better maintained viscosity constancy over a broad temperature range and are often preferred in various applications.
  • VIIs viscosity index improvers
  • polymer based VIIs are extensively studied and widely used as a viscosity additive to enhance the VI value of formulated lubricants.
  • VI viscosity index
  • VIIs viscosity index improvers
  • a basic prerequisite for employability as oil additives is, trivially, the oil solubility of the polymers which, in the case of the PA (M) As, is based on the presence of a sufficiently large number of alkyl side chains having typically 7-30 carbon atoms.
  • the VI of PA (M) As can be raised further frequently by copolymerizing short-chain alkyl (meth) acrylates, for example methyl (meth) acrylate or butyl (meth) acrylate (EP 0 637 332, the Lubrizol Corporation) .
  • the VIs achievable with such PA (M) As are, depending on the concentration, permanent shear stability index (PSSI) and base oil type, usually in the range between 150 and 250.
  • nitrogen-and/or oxygen-containing monomers such as dimethylaminoethyl (meth) acrylate (U.S. Pat. No. 2,737,496, E.I. du Pont de Nemours and Company) or dimethylaminopropyl (meth) acrylamide (U.S. Pat. No. 4,021,357 Texaco Inc. ) .
  • the viscosities of polymer solutions in mineral oils or synthetic oils are dependent on the molecular weight to a high degree. This has the consequence that the temperature dependence of the viscosity decreases or the VI increases with rising molecular weight (J. Bartz, Additive für Schmierstoffe, [Additives for Lubricants] , Expert-Verlag, Renningen-Malmsheim 1994, 197-252) . In connection with the temperature increase, reference is also made to disentanglement of the collapsed polymer chain to give the extended wormlike molecule.
  • Shear-stable VIIs as required for manual transmission oils, automatic transmission oils, hydraulic oils or motor oils, based on conventional polymer types such as the PAMAs are realizable only with higher addition amounts. VIIs with a low contribution to viscosity at low temperatures, normal thickening in the VI range from 40 to 100°C., high contribution to viscosity above 100°C and simultaneously ensured good oil solubility within the entire temperature range are therefore of particular interest.
  • a first object of the present invention is therefore directed to a hyperbranched polymer consisting of:
  • a further first object of the present invention is directed to a hyperbranched polymer, wherein the alky (meth) acrylate comprises one or more C4-C20 alkyl (meth) acrylate, preferably one or more C8-C20 alkyl (meth) acrylate, more preferably one or more C12-C18 alkyl (meth) acrylate.
  • a further first object of the present invention is directed to a hyperbranched polymer, wherein the trithiocarbonate is selected from the group consisting of bis (3, 4, 4-trifluoro-3-buten-1-yl) trithiocarbonate, S-3-buten-1-yl-S'-octyl trithiocarbonate, S-allyl-S'-octyl trithiocarbonate, S-phenylmethyl-S'-2-propen-1-yl trithiocarbonate, S-3, 4, 4-trifluoro-3-buten-1-yl-S'-butyl trithiocarbonate, S-3, 4, 4-trifluoro-3-buten-1-yl-S'-ethyl trithiocarbonate, S-4-vinylphenylmethyl-S'-butyl trithiocarbonate, and S-4-vinylphenylmethyl-S'-propyl trithiocarbonate.
  • the trithiocarbonate is selected from the group consisting of bis (3, 4, 4-
  • Preferred trithiocarbonates are S-4-vinylphenylmethyl S’-propyl trithiocarbonate and S- (4-vinyl) benzyl-S'-propyl trithiocarbonate. Even more preferred is S-4-vinylphenylmethyl S’-propyl trithiocarbonate.
  • a second object of the present invention is directed to an additive composition comprising, based on a total weight of the additive composition:
  • each component (A) and (B) is based on the total weight of the additive composition.
  • the proportions of components (A) and (B) add up to 100%by weight.
  • a third object of the present invention is directed to a lubricating oil composition, comprising:
  • a further third object of the present invention is directed to a lubricating oil composition, comprising:
  • each component (A) , (B) and (C) is based on the total composition of the lubricating oil composition. In a particular embodiment, the proportions of components (A) , (B) and (C) add up to 100%by weight.
  • Weight-average molecular weight M w and number-average molecular weight M n are determined by size exclusion chromatography (SEC) using commercially available polymethylmethacrylate standards. The determination is effected by gel permeation chromatography with THF as eluent.
  • a hyperbranched polymer in the context of this present disclosure is a highly branched three-dimensional macromolecule. It is usually a copolymer formed by a polymerization between at least two monomers and characterized in terms of molecular weight and degree of branching.
  • hyperbranched polymers can be synthesized by various approaches, including step-growth polymerization via polycondensation or addition polymerization of multifunctional monomers, or copolymerization of vinyl monomers in the presence of multifunctional vinyl comonomers.
  • Atom transfer radical polymerization, and reversible addition-fragmentation chain transfer (RAFT) polymerization have been efficiently used to synthesize a variety of hyperbranched and star polymers with controlled compositions and variable functionality.
  • the structure of the hyperbranched polymers prepared according to the present disclosure is shown in the following sketch.
  • the bracket indicates that the structure inside is repeated once or more.
  • the hyperbranched polymer according to the present disclosure is obtained by copolymerizing two categories of monomers, i.e. at least one alkyl (meth) acrylate and at least one trithiocarbonate with at least one unsaturated functionality.
  • (meth) acrylic acid is used herein to refer to acrylic acid, methacrylic acid, and mixtures thereof.
  • acrylate refers to esters of acrylic acid;
  • methacrylate refers to esters of methacrylic acid; and
  • (meth) acrylate refers to both, esters of acrylic acid, and esters of methacrylic acid.
  • alkyl (meth) acrylate is used to refer to alkyl acrylate monomers, alkyl methacrylate monomers, and mixtures thereof.
  • Alkyl refers to a substituent formed by removing one hydrogen atom from an alkane.
  • the alkyl (meth) acrylate used in the present disclosure is preferably one or more C4-20 alkyl (meth) acrylates. More preferred alkyl (meth) acrylates are C8-20 alkyl (meth) acrylates. Still more preferred alkyl (meth) acrylates are C12-18 alkyl (meth) acrylates.
  • C4-20 alkyl (meth) acrylates for use in accordance with the present disclosure are esters of (meth) acrylic acid and alcohols having 4 to 20 carbon atoms.
  • the term "C4-20 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.
  • the suitable C4-20 alkyl (meth) acrylates include, for example, butyl (meth) acrylates, pentyl (meth) acrylates, hexyl (meth) acrylates, heptyl (meth) acrylates, octyl (meth) acrylates, 2-ethylhexyl (meth) acrylates, nonyl (meth) acrylates, decyl (meth) acrylates, 3-isopropylheptyl (meth) acrylates, undecyl (meth) acrylates, dodecyl (meth) acrylate, 5-methylundecyl (meth) acrylate, 2-butyloctyl (meth) acrylate, tridecyl (meth) acrylate, 2-methyldodecyl (meth) acrylate, tetradecyl (meth) acrylate, 5-methyltridecyl (meth) acrylate
  • Particularly preferred C4-20 alkyl (meth) acrylates are butyl (meth) acrylates, octyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, (meth) acrylic esters of a linear C12-16 alcohol mixture (C12-16 alkyl (meth) acrylates) , and (meth) acrylic esters of a linear C16-18 alcohol mixture (C16-18 alkyl (meth) acrylates) .
  • the C8-20 alkyl (meth) acrylates for use in accordance with the present disclosure are esters of (meth) acrylic acid and straight chain or branched alcohols having 8 to 20 carbon atoms.
  • the term "C8-20 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 C8-20 alkyl (meth) acrylates include, for example, octyl (meth) acrylates, 2-ethylhexyl (meth) acrylates, nonyl (meth) acrylates, decyl (meth) acrylate, 3-isopropylheptyl (meth) acrylates, undecyl (meth) acrylate, dodecyl (meth) acrylate, 5-methylundecyl (meth) acrylate, 2-butyloctyl (meth) acrylate, tridecyl (meth) acrylate, 2-methyldodecyl (meth) acrylate, tetradecyl (meth) acrylate, 5-methyltridecyl (meth) acrylate, 2-butyldecyl (meth) acrylate, 2-hexyloctyl (meth) acrylate, pentadecyl (meth) acrylate,
  • C12-18 alkyl (meth) acrylates for use in accordance with the present disclosure are esters of (meth) acrylic acid and alcohols having 12 to 18 carbon atoms.
  • the term "C12-18 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.
  • the suitable C12-18 alkyl (meth) acrylates include, for example, dodecyl (meth) acrylate, 5-methylundecyl (meth) acrylate, 2-butyloctyl (meth) acrylate, tridecyl (meth) acrylate, 2-methyldodecyl (meth) acrylate, tetradecyl (meth) acrylate, 5-methyltridecyl (meth) acrylate, 2-butyldecyl (meth) acrylate, 2-hexyloctyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, 5-methylundecyl (meth) acrylate, 2-hexyldecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, 2-hexy
  • Particularly preferred C12-18 alkyl methacrylates are methacrylic esters of a linear C12-16 alcohol mixture (C12-16 alkyl methacrylate) , methacrylic esters of a linear C16-18 alcohol mixture (C16-18 alkyl methacrylate) , or mixture thereof.
  • the number-average molar mass 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 alkyl (meth) acrylate for use in accordance with the present disclosure can be prepared by transesterification of alcohols and (meth) acrylates. 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.
  • alkyl (meth) acrylate can be obtained by a direct esterification proceeding, for example, from (meth) acrylic acid or (meth) acrylic anhydride, preferably under acidic catalysis by p-toluene-sulfonic acid or methanesulfonic acid, or from free methacrylic acid by the DCC method (dicyclohexylcarbodiimide) .
  • alkyl (meth) acrylate can be prepared by reacting alcohol with an acid chloride such as (meth) acryloyl chloride.
  • trithiocarbonates are the most popular RAFT agents, as they balance activity and stability and can be obtained from simple synthetic procedures.
  • the trithiocarbonates used in the present disclosure include at least one unsaturated functionality.
  • the unsaturated functionality is not an aromatic radical.
  • the unsaturated functionality has a double or triple bond.
  • the unsaturated functionality is vital to forming a hyperbranched polymer.
  • the unsaturated functionality is an alkenyl.
  • the alkenyl is selected from a vinyl, an allyl, and a butenyl.
  • butenyl refers to all isomers of a butene based substituent, such as, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl, and 2-methyl-2-propenyl.
  • Particular trithiocarbonate includes bis (3, 4, 4-trifluoro-3-buten-1-yl) trithiocarbonate, S-3-buten-1-yl-S’-octyl trithiocarbonate, S-allyl-S’-octyl trithiocarbonate, S-phenylmethyl-S’-2-propen-1-yl trithiocarbonate, S-3, 4, 4-trifluoro-3-buten-1-yl-S’-butyl trithiocarbonate, S-3, 4, 4-trifluoro-3-buten-1-yl-S’-ethyl trithiocarbonate, S-4-vinylphenylmethyl-S’-butyl trithiocarbonate, and S-4-vinylphenylmethyl-S’-propyl trithiocarbonate.
  • Preferred trithiocarbonates are S-4-vinylphenylmethyl S’-propyl trithiocarbonate and S- (4-vinyl) benzyl-S'-propyl trithiocarbonate. Even more preferred is S-4-vinylphenylmethyl S’-propyl trithiocarbonate.
  • the hyperbranched polymers in accordance with the present disclosure can be prepared by controlled free-radical polymerization, for example RAFT (reversible addition fragmentation chain transfer) .
  • RAFT reversible addition fragmentation chain transfer
  • the trithiocarbonate plays the role of the RAFT agent and is also incorporated in the polymer chain via polymerization of the unsaturated function.
  • the usable initiators include azo initiators widely known in the technical field, such as azodiisobutyronitrile (AIBN) and 1, 1-azobiscyclohexanecarbonitrile, and also 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-ethylhexanoate, tert-butyl peroxy-3,
  • the amount of initiator is from 5 mole%to 40 mole%, preferably from 10 mole%to 30 mole%, and more preferably from 15 mole%to 25 mole%, based on the amount of RAFT agent trithiocarbonate.
  • RAFT is a reversible deactivation radical polymerization (RDRP) , which is based on an equilibrium between active and dormant chains, which can be achieved by one of two processes: (i) reversible deactivation and metal-mediated living radical polymerization/atom transfer radical polymerization or (ii) degenerative transfer.
  • RDRP reversible deactivation radical polymerization
  • a source of radicals is required, typically a radical initiator.
  • RAFT methods are described in detail, for example, in WO 98/01478 and WO 2004/083169.
  • the polymerization can be conducted under standard pressure, reduced pressure, or elevated pressure.
  • the polymerization temperature is also uncritical. In general, however, it is in the range from 50 °C to 90 °C and preferably 60 °C to 80 °C.
  • the polymerization can proceed for a duration of about 4 h to 24 h, preferably 8 h to 20 h, and more preferably 10 h to 12 h.
  • the polymerization can be conducted with solvent.
  • solvent should be understood here in a broad sense.
  • the solvent is selected according to the polarity of the monomers used, it being possible with preference to use 1, 4-dioxane, dimethyl sulfoxide (DMSO) , or a mixture thereof.
  • the weight-average molecular weight (Mw) of the polymers according to the invention is in the range of 15,000 to 350,000 g/mol, more preferably 30,000 to 350,000 g/mol, even more preferably 40,000 to 200,000 g/mol, most preferably 60,000 to 150,000 g/mol.
  • Polymers having this weight-average molecular weight are especially suited for use in transmission fluids, such as automatic transmission fluids, manual transmission fluids and belt-continuously variable transmission fluids.
  • the number-average molecular weight (Mn) of the polymers according to the invention is in the range of 20,000 to 200,000 g/mol, more preferably 50,000 to 150,000 g/mol, most preferably 100,000 to 150,000 g/mol.
  • the polydispersity index (PDI) of the polymers according to the invention is in the range of 1.5 to 5, more preferably 1.5 to 4, most preferably 2 to 3.
  • the polydispersity index is defined as the ratio of weight-average molecular weight to number-average molecular weight (Mw/Mn) .
  • the weight-average and number-average molecular weights are determined by gel permeation chromatography (GPC) using commercially available polymethylmethacrylate standards. The determination is effected according to DIN 55672-1 by gel permeation chromatography with THF as eluent (flow rate: 1mL/min; injected volume: 100 ⁇ L) .
  • the polymer according to the invention can be characterized on the basis of its molar degree of branching ( "f branch " ) .
  • the molar degree of branching refers to the percentage in mole%of macromonomers used, based on the total molar amount of all the monomers in the monomer composition.
  • the molar amount of the macromonomers used is calculated based on the number-average molecular weight Mn of the macromonomers. The calculation of the molar degree of branching is described in detail in WO 2007/003238 A1, especially on pages 13 and 14, to which reference is made here explicitly.
  • the polymers have a molar degree of branching f branch of 0.1 to 10 mole%, more preferably 0.5 to 8 mole%, even more preferably 1 to 5 mole%, and most preferably 2 to 5 mole%.
  • the base oil to be used in the additive composition 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 Ill are mineral oils which are classified by the amount of saturates and sulfur 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 disclosure is preferably in the range of 1 mm 2 /sto 10 mm 2 /s, more preferably in the range of 2 mm 2 /sto 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 disclosure 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.
  • the additive composition of the present disclosure comprises preferably 10 wt. %to 50 wt. %of base oil, preferably 20 wt. %to 40 wt. %, based on the total weight of the additive composition.
  • the concentration of the hyperbranched polymer in the additive composition is preferably in the range from 50 wt. %to 90 wt. %, more preferably in the range of 60 wt. %to 80 wt. %, based on the total weight of the additive composition.
  • the proportions of base oil and hyperbranched polymer add up to 100 wt. %.
  • a lubricating oil composition comprising:
  • the lubricating oil compositions according to the present disclosure are characterized by their high VI value and high shear stability.
  • the present disclosure also relates to the above-described lubricating oil composition, which is characterized by its reduced CCS (Cold-Cranking Simulator) apparent viscosity at -35 °C to ASTM D 5293.
  • CCS Cold-Cranking Simulator
  • the lubricating oil composition of the present disclosure comprises preferably 80 wt. %to 99.5 wt. %, more preferably 85 wt. %to 98 wt. %, most preferably 90 wt. %to 95 wt. %, of a base oil (A) , based on the total weight of the lubricating oil composition.
  • the concentration of the hyperbranched polymer (B) in the lubricating oil composition is preferably in the range of 0.5 wt. %to 20 wt. %, more preferably 2 wt. %to 15 wt. %, most preferably 5 wt. %to 10 wt. %, based on the total weight of the lubricating oil composition.
  • the proportions of base oil and hyperbranched polymer add up to 100 wt. %.
  • the lubricant compositions according to the invention can contain any types of lubricant base oils, mineral, synthetic or natural, animal or vegetable oils suited to their use.
  • the base oils used in formulating the improved lubricating oil compositions of the present invention include, for example, conventional base stocks selected from API (American Petroleum Institute) base stock categories known as Group I, Group II, Group III, Group IV, and Group V.
  • the Group I and II base stocks are mineral oil materials (such as paraffinic and naphthenic oils) having a viscosity index (or VI) of less than 120.
  • Group I is further differentiated from Group II in that the latter contains greater than 90%saturated materials and the former contains less than 90%saturated material (that is more than 10%unsaturated material) .
  • Group III is considered the highest level of mineral base oil with a VI of greater than or equal to 120 and a saturates level greater than or equal to 90%.
  • the base oil included in the lubricating oil composition of the present invention is selected from the group consisting of API Group II and III base oils.
  • the lubricant composition comprises an API Group III base oil.
  • Group IV base oils are poly-alpha-olefins (PAOs) .
  • Group V base oils are esters and any other base oils not included in Group I to IV base oils. These base oils can be used individually or as a mixture.
  • the base oil or mixture thereof represent at least 80 wt. %, with respect to the total weight of the lubricant composition, preferably at least 85 wt. %, more preferably at least 90 wt. %, even more preferably 92.5 wt. %.
  • the lubricant composition according to the present invention comprises 80 wt. %to 99.5 wt. %, more preferably 85 wt. %to 98 wt. %, even more preferably 90 wt. %to 95 wt. %of base oil or mixture thereof, based on the total weight of the lubricant composition.
  • the lubricating oil composition according to the present disclosure may also contain further additives (C) selected from the group consisting of dispersants, defoamers, detergents, antioxidants, pour point depressants, antiwear additives, extreme pressure additives, friction modifiers, anticorrosion additives, dyes, and mixtures thereof.
  • C further additives selected from the group consisting of dispersants, defoamers, detergents, antioxidants, pour point depressants, antiwear additives, extreme pressure additives, friction modifiers, anticorrosion additives, dyes, and mixtures thereof.
  • Appropriate dispersants include poly (isobutylene) derivatives, for example poly (isobutylene) succinimides (PIBSIs) , including borated PIBSIs; and ethylene-propylene oligomers having N/O functionalities.
  • PIBSIs poly (isobutylene) succinimides
  • Dispersants are preferably used in an amount of 0 to 5 wt. %, based on the total amount of the lubricating oil composition.
  • Suitable defoamers are silicone oils, fluorosilicone oils, fluoroalkyl ethers, etc.
  • the defoaming agent is preferably used in an amount of 0.005 wt. %to 0.1 wt. %, based on the total amount of the lubricating oil composition.
  • 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.
  • Detergents are preferably used in an amount of 0.2 wt. %to 1 wt. %, based on the total amount of the lubricating oil composition.
  • 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'-isobutylidenebis (4, 6-dimethylphenol) ; 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.; naphthylamines, concretely alpha-naphthylamine, phenyl
  • Antioxidants are used in an amount of 0 to 15 wt. %, preferably 0.1 wt. %to 10 wt. %, more preferably 0.5 wt. %to 5 wt. %, based on the total amount of the lubricating oil composition.
  • the 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 amount of the pour point depressant is preferably from 0.1 wt. %to 5 wt. %, based on the total amount of the lubricating oil composition.
  • the preferred antiwear and extreme pressure additives include sulfur-containing compounds such as zinc dithiophosphate, zinc di-C 3-12 -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 antiwear agent may be present in an amount of 0 to 3 wt. %, preferably 0.1 wt. %to 1.5 wt. %, more preferably 0.5 wt. %to 0.9 wt. %, based on the total amount of the lubricating oil composition.
  • 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
  • Friction modifiers may be used in an amount of 0 to 6 wt. %, preferably 0.05 wt. %to 4 wt. %, more preferably 0.1 wt. %to 2 wt. %, based on the total amount of the lubricating oil composition.
  • ZnDTP is primarily an antiwear additive and extreme pressure additive, but also has the character of an antioxidant and corrosion inhibitor (here: metal passivator/deactivator) .
  • the total concentration of the one or more additives is up to 20 wt. %, more preferably 0.05 wt. %to 15 wt. %, more preferably 5 wt. %to 15 wt. %, based on the total weight of the lubricating oil composition.
  • the proportions of base oil, hyperbranched polymer, and additive may add up to 100 wt. %.
  • Figure 1 Shear stability data of the linear polymers and hyperbranched polymer at 40°C.
  • the horizontal axis is for kinematic viscosity and the vertical axis is for shear loss.
  • Figure 2 Shear stability data of the linear polymers and hyperbranched polymer at 100°C.
  • the horizontal axis is for kinematic viscosity and the vertical axis is for shear loss.
  • C13-MA (CAS registry number: 90551-76-1) was purchased from Evonik as Terra C 13-MA. The mean molecular weight is 268.0 g/mol. It is a mixture of C12-C16 alkyl methacrylate.
  • CTA-1 was synthesized as in C. Zhang, etc., Macromolecules, 2011, 44, 2034.
  • a solution of sodium methoxide 95%, 11.5 g, 0.202 mol
  • CS 2 (19.0 g, 0.250 mol) was added dropwise to the solution after 2 h, and the mixture was further stirred at ambient temperature for 5 h.
  • 4-vinylbenzyl chloride 90%, 37.2 g, 0.219 mol
  • CTA-2 was purchased from Sigma Aldrich.
  • PAO6 has a VI value of 148.
  • the polymers according to the present disclosure and the comparative examples were characterized with respect to their molecular weight and PDI.
  • the weight-average molecular weights (Mw) of the polymers (B) were determined by gel permeation chromatography (GPC) using polystyrene calibration standards according to DIN 55672-1 using the following measurement conditions:
  • THF tetrahydrofuran
  • BHT butylhydroxytoluol
  • Detection device a refractive index detector from Agilent 1260 series.
  • the additive compositions including the polymers according to the present disclosure 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 shear stability.
  • VI viscosity index
  • KV 40 kinematic viscosity at 40°C
  • KV 100 100°C
  • the PSSI Permanent Shear Stability Index
  • ASTM D 6022-01 Standard Practice for Calculation of Permanent Shear Stability Index
  • ASTM D 2603-B Standard Test Method for Sonic Shear Stability of Polymer-Containing Oils
  • the lubricating oil compositions including the comb polymers according to the present disclosure 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, and high-temperature high-shear viscosity at 80°C, 100°C, and 150°C to CEC L-036.
  • Alkyl methacrylates were put into the reactor bottle according to the feed ratio.
  • the reaction system was then sealed, frozen in liquid nitrogen, then filled with nitrogen for 10 minutes, then thawed. The same procedure was repeated three times.
  • the reaction lasted 12 hours to 24 hours at 70 °C. After thawing, a small amount of THF was added to dissolve and dripped into methanol to settle and purify.
  • the final product is obtained by drying the precipitate in vacuum.
  • Linear polymers LP-1 through LP-4 with increasing molecular weights were synthesized from CTA-2 and C13 methacrylate by tuning the duration of polymerization.
  • C13-HBP was synthesized according to a similar protocol, except the trithiocarbonate CTA-2 replaced by CTA-1.
  • Molar ratio was calculated as the amount of trithiocarbonate in molar divided by the amount of methacrylate in molar. The reaction durations for each polymer were controlled to achieve a polydisperisty of 2 to 3 and an icreasing molecular weight.
  • Test for sonic shear stability of modified fluids Clean the sonic horn using a lint-free wiper and optional solvent and calibrate the apparatus. Introduce 30 mL of the sample to be tested into a clean 50 mL Griffin beaker and immerse in the constant temperature bath at 0 °C. The beaker should be in a vertical position. The samples were allowed to equilibrate for 12.5 min. Then the sonic horn was immersed in the reference fluid. The samples were irradiated for 40 min.
  • Table 1 is intended to demonstrate the synthesis and performance data of the linear polymers and hyperbranched polymer and lubricating oils formulated with the polymers.
  • FIG. 1 shows the shear stability data of the linear polymers and hyperbranched polymer at 40 °C .
  • FIG. 2 shows the shear stability data of the linear polymers and hyperbranched polymer at 100°C.
  • the horizontal axis is for kinematic viscosity and the vertical axis is for shear loss.
  • Lubricating oils with hyperbranched polymer and linear polymers all show significantly improved kinematic viscosity at both 40 °C and 100 °C.
  • C13-HBP has approximately the same molecular weight and similar kinematic viscosity to the linear polymer LP-3. However, regarding shear loss, C13-HBP outperformances the linear counterpart. Also, in view of the general trend exhibited by LP-1 through LP-4, C13-HBP is well below the curve.
  • the lubricating oil with hyperbranched polymer C13-HBP has a significantly reduced shear loss at both 40 °C and 100 °C, compared to linear polymer LP-3 with similar molecular weight and/or similar kinematic viscosity.
  • the difference in shear stability may come from the distinct geometries, i.e., the shape and configuration of molecular chains in the polymers.

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Abstract

L'invention concerne un polymère hyperramifié obtenu par copolymérisation de (a) 90 à 99,5 % en moles d'au moins un alkyle (méth) acrylate ; et (b) 0,5 à 10 % en moles d'au moins un trithiocarbonate, le trithiocarbonate comprenant au moins une fonctionnalité insaturée, et le total en moles de l'alkyle (méth) acrylate et du trithiocarbonate étant de 100 % en moles. L'invention concerne en outre une composition d'additif et une composition d'huile lubrifiante.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006047393A1 (fr) * 2004-10-25 2006-05-04 The Lubrizol Corporation Procede pour preparer des polymeres et des compositions de polymeres
CN110128605A (zh) * 2018-02-02 2019-08-16 雅富顿化学公司 用于润滑剂添加剂应用的聚(甲基)丙烯酸酯星形聚合物
CN110869478A (zh) * 2017-06-27 2020-03-06 路博润公司 内燃机的润滑组合物和润滑方法

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Publication number Priority date Publication date Assignee Title
WO2006047393A1 (fr) * 2004-10-25 2006-05-04 The Lubrizol Corporation Procede pour preparer des polymeres et des compositions de polymeres
CN110869478A (zh) * 2017-06-27 2020-03-06 路博润公司 内燃机的润滑组合物和润滑方法
CN110128605A (zh) * 2018-02-02 2019-08-16 雅富顿化学公司 用于润滑剂添加剂应用的聚(甲基)丙烯酸酯星形聚合物

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Title
ZHANG CHENGBO, ZHOU YUAN, LIU QIANG, LI SHIXIAN, PERRIER SÉBASTIEN, ZHAO YOULIANG: "Facile Synthesis of Hyperbranched and Star-Shaped Polymers by RAFT Polymerization Based on a Polymerizable Trithiocarbonate", MACROMOLECULES, vol. 44, no. 7, 12 April 2011 (2011-04-12), US , pages 2034 - 2049, XP055920967, ISSN: 0024-9297, DOI: 10.1021/ma1024736 *

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