EP3099721B1 - Compositions lubrifiantes comprenant des copolymeres thermoassociatifs et echangeables - Google Patents

Compositions lubrifiantes comprenant des copolymeres thermoassociatifs et echangeables Download PDF

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Publication number
EP3099721B1
EP3099721B1 EP15700905.1A EP15700905A EP3099721B1 EP 3099721 B1 EP3099721 B1 EP 3099721B1 EP 15700905 A EP15700905 A EP 15700905A EP 3099721 B1 EP3099721 B1 EP 3099721B1
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Prior art keywords
monomer
formula
group
chosen
copolymer
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German (de)
English (en)
French (fr)
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EP3099721A1 (fr
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Thi Hang Nga NGUYEN
Renaud Nicolay
Raphaële IOVINE
Ilias Iliopoulos
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Centre National de la Recherche Scientifique CNRS
Ecole Superieure de Physique et Chimie Industrielles de Ville de Paris ESPCI
TotalEnergies Marketing Services SA
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Centre National de la Recherche Scientifique CNRS
Ecole Superieure de Physique et Chimie Industrielles de Ville de Paris ESPCI
Total Marketing Services SA
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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
    • 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
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen 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
    • 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
    • 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
    • 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
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/08—Resistance to extreme temperature
    • 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
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • 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
    • C10N2030/18—Anti-foaming property

Definitions

  • the present invention relates to a composition resulting from the mixture of at least one lubricating oil, at least one random copolymer A1, and at least one compound A2 comprising at least two boronic ester functions; the random copolymer A1 results from the copolymerization of at least one first monomer M1 carrying diol functions and at least one second monomer M2 of chemical structure different from that of the monomer M1.
  • the invention also relates to the use of this composition for lubricating a mechanical part.
  • the field of the present invention is that of lubricants.
  • Lubricating compositions are compositions applied between the surfaces, in particular metal surfaces, of moving parts. They reduce the friction and wear between two parts in contact and in motion relative to each other. They also serve to dissipate some of the thermal energy generated by this friction. Lubricating compositions form a protective film between the surfaces of the parts to which they are applied.
  • compositions used for the lubrication of mechanical parts generally consist of a base oil and additives.
  • the base oil in particular of petroleum or synthetic origin, exhibits variations in viscosity with the temperature being varied.
  • the thickness of the protective film is proportional to the viscosity, so also depends on the temperature.
  • a composition has good lubricating properties if the thickness of the protective film remains substantially constant regardless of the conditions and the duration of use of the lubricant.
  • a lubricating composition may be subjected to external or internal temperature changes.
  • the external temperature changes are due to changes in ambient air temperature, such as temperature variations between summer and winter, for example.
  • the internal temperature changes result from the implementation of the motor.
  • the temperature of an engine is lower during its start-up phase, especially in cold weather, than during prolonged use. Therefore, the thickness of the protective film may vary in these different situations.
  • additives improving the viscosity of a lubricating composition have the function of modifying the rheological behavior of the lubricating composition. They promote a substantially constant viscosity over a temperature range at which the lubricant composition is used. For example, these additives limit the decrease in the viscosity of the lubricant composition when the temperature rises or limit the increase in the viscosity of the lubricating composition as the temperature decreases.
  • the viscosity-improving additives are polymers such as polyalpha-olefins, polymethyl methacrylates, copolymers resulting from the polymerization of an ethylenic monomer and an alpha-olefin. . These polymers are of high molecular weight. In general, the contribution of these polymers to the control of the viscosity is all the more important that their molecular weight is high.
  • the high molecular weight polymers have the disadvantage of having a low permanent shear strength compared to polymers of the same nature but of smaller size.
  • a lubricant composition is subjected to significant shear stresses, particularly in internal combustion engines, where the friction surfaces have a very small gap and the pressures exerted on the parts are high. These shear stresses on the high molecular weight polymers cause cuts in the macromolecular chains. The polymer thus degraded no longer has thickening properties, and the viscosity drops irreversibly. This loss of permanent shear strength therefore leads to a degradation of the lubricating properties of the lubricant composition.
  • the polymers of the prior art in particular PMMA (polymethylmethacrylates) have a rheo-thickening behavior. At a high shear rate, the PMMA chain breaks. This results in the formation of two molecules having approximately half the molar weight of the initial PMMA. The total hydrodynamic volume of these two small molecules is lower than that of the initial PPMA, which results in a lower viscosity contribution and results in a reduction in viscosity.
  • Ethylene-alphaolefin copolymers having a high ethylene content are viscosity improvers and are shear stable.
  • these polymers have the disadvantage of aggregating in the compositions containing them and lead to extremely viscous lubricating compositions, such as gels. This aggregation generally occurs at ambient conditions or during cooling.
  • the aim of the applicant is to formulate new lubricating compositions whose viscosity is better controlled with respect to the lubricant compositions of the prior art.
  • it aims to provide new rheological additives, which when introduced into a base oil, have an inverted behavior with respect to a modification of the temperature with respect to the behavior of the base oil and the rheological additives of polymer type of the prior art.
  • the additives of the present invention have the advantage of thickening the medium in which they are dispersed as the temperature increases.
  • the document EP0570073 discloses an additive which improves the viscosity index of a lubricating composition in which it is added.
  • This additive is a copolymer resulting from the polymerization of 1- (methacryloylethoxy) -4,4,6-trimethyl-dioxaborinane and a linear alkyl methacrylate (C 12 -C 18 ).
  • This additive belongs to the family of borate compounds which can be represented by the general formula B (OR) 3 with R an alkyl or aryl group.
  • This additive does not belong to the family of boronate compounds which may be represented by the general formula RB (OR) 2 with R an alkyl or aryl group.
  • This additive can not associate with other compounds via exchangeable chemical bonds.
  • the Applicant has observed that at low temperature, the polydiol copolymer of the invention is not or only slightly crosslinked by the compounds comprising boronic ester functions.
  • the diol functions of the copolymer react with the boronic ester functions of the compound comprising them by a transesterification reaction.
  • Polydiol random copolymers and compounds comprising boronic ester functions then bind together and can be exchanged.
  • a gel may form in the base oil.
  • the boronic ester linkages between the polydiol random copolymers and the compounds comprising them break; the composition loses its gelled character if necessary.
  • the Applicant has also set itself the objective of formulating new rheology additives which are more stable in shear with respect to the compounds of the prior art.
  • the random copolymer A1 results from the copolymerization of at least one monomer M1 with at least two monomers M2 having different R 31 groups.
  • the invention also relates to the use of a composition as described above for lubricating a mechanical part.
  • oil means a fatty substance liquid at room temperature (25 ° C) and atmospheric pressure (760 mmm Hg evening 105 Pa).
  • Lubricating oil is meant an oil that reduces the friction between two moving parts to facilitate the operation of these parts.
  • Lubricating oils can be of natural, mineral or synthetic origin.
  • Lubricating oils of natural origin may be oils of vegetable origin or animal, preferably vegetable oils such as rapeseed oil, sunflower oil, palm oil, coconut oil ...
  • Lubricating oils of mineral origin are of petroleum origin and are extracted from petroleum fractions from the atmospheric and vacuum distillation of crude oil. The distillation can be followed by refining operations such as solvent extraction, secondaryphatage, solvent dewaxing, hydrotreating, hydrocracking, hydroisomerisation, hydrofinition, etc.
  • paraffinic mineral base oils such as Bright Stock Solvent Oil (BSS), naphthenic mineral base oils, aromatic mineral oils, hydrorefined mineral bases with a viscosity number of about 100, mineral bases hydrocracked compounds whose viscosity index is between 120 and 130, the hydroisomerized mineral bases whose viscosity index is between 140 and 150.
  • Lubricating oils that can be used in the composition of the invention can be selected from any of the I to V oils specified in the API Guidelines (American Petroleum Institute's Basic Oil Interchangeability Guidelines). ) (or their equivalents according to the ATIEL classification (Technical Association of the European Lubricants Industry) as summarized below: Content of saturated compounds * Sulfur content ** Viscosity index (VI) ** Group I Mineral oils ⁇ 90% > 0.03% 80 ⁇ VI ⁇ 120 Group II Hydrocracked oils ⁇ 90% ⁇ 0.03% 80 ⁇ VI ⁇ 120 Group III Hydrocracked or hydro-isomerized oils ⁇ 90% ⁇ 0.03% ⁇ 120 Group IV (PAO) Polyalphaolefins Group V Esters and other bases not included in groups I to IV * measured according to ASTM D2007 ** measured according to ASTM D2622, ASTM D4294, ASTM D4927 and ASTM D3120 ** measured according to ASTM D2270
  • compositions of the invention may comprise one or more lubricating oils.
  • the lubricating oil or the mixture of lubricating oils represents at least 50% by weight relative to the total weight of the composition.
  • the lubricating oil or the lubricating oil mixture represents at least 70% by weight relative to the total weight of the composition.
  • the lubricating oil is selected from the group consisting of oils of group I, group II, group III, group IV, group V of the API classification and one of their mixture.
  • the lubricating oil is chosen from the group consisting of oils of group III, group IV, group V of the API classification and their mixture.
  • the lubricating oil is a Group III API oil.
  • the lubricating oil has a kinematic viscosity at 100 ° C measured according to ASTM D445 ranging from 2 to 150 cSt, preferably from 5 to 15 cSt.
  • Lubricating oils can range from SAE grade 15 to SAE grade 250, and most preferably SAE grade 20W to grade SAE 50 (SAE stands for Society of Automotive Engineers).
  • composition of the invention comprises at least one polydiol random copolymer resulting from the copolymerization of at least one first monomer M1 bearing diol functions and at least one second monomer M2, with a chemical structure different from that of the monomer M1.
  • copolymer is meant a linear or branched oligomer or macromolecule having a sequence consisting of several repeating units (or monomeric unit) of which at least two units have a different chemical structure.
  • monomeric unit or “monomer” is meant a molecule capable of being converted into an oligomer or a macromolecule by combination with itself or with other molecules of the same type.
  • a monomer refers to the smallest constituent unit whose repetition leads to an oligomer or a macromolecule.
  • random copolymer is understood to mean an oligomer or a macromolecule in which the sequential distribution of the monomeric units obeys known statistical laws.
  • a copolymer is said to be random when it consists of monomeric units whose distribution is a Markovian distribution.
  • a schematic statistical polymer (P1) is illustrated in figure 1 . The distribution in the polymer chain of the monomer units depends on the reactivity of the polymerizable functions of the monomers and the relative concentration of the monomers.
  • the polydiol random copolymers of the invention are distinguished from block copolymers and gradient polymers.
  • block is meant a part of a copolymer comprising several identical or different monomer units and which have at least one particular constitution or configuration to distinguish it from its adjacent parts.
  • a schematic block copolymer (P3) is illustrated in figure 1 .
  • a gradient copolymer refers to a copolymer of at least two monomeric units of different structures whose monomer composition gradually changes along the polymer chain, thus progressively passing from one end of the rich polymer chain into a pattern. monomer, at the other end rich in the other comonomer.
  • a schematic gradient polymer (P2) is illustrated in figure 1 .
  • copolymerization is meant a process which makes it possible to convert a mixture of at least two monomeric units of different chemical structures into an oligomer or a copolymer.
  • B represents a boron atom
  • C i -C j means a saturated hydrocarbon chain, linear or branched, comprising from i to j carbon atoms.
  • C 1 -C 10 alkyl is meant a saturated hydrocarbon chain, linear or branched, comprising from 1 to 10 carbon atoms.
  • C 6 -C 18 aryl is meant a functional group derived from an aromatic hydrocarbon compound having from 6 to 18 carbon atoms. This functional group can be monocyclic or polycyclic.
  • a C 6 -C 18 aryl may be phenyl, naphthalene, anthracene, phenanthrene and tetracene.
  • C 2 -C 10 alkenyl is meant a linear or branched hydrocarbon chain containing at least one unsaturation, preferably a double bond, and comprising from 2 to 10 carbon atoms.
  • C 7 -C 18 aralkyl is meant an aromatic hydrocarbon compound, preferably monocyclic, substituted by at least one linear or branched alkyl chain and the total number of carbon atoms of the aromatic ring and its substituents ranging from 7 to 18 carbon atoms.
  • a C 7 -C 18 aralkyl may be chosen from the group formed by benzyl, tolyl and xylyl.
  • C 6 -C 18 aryl group substituted by a group R ' 3 is meant an aromatic hydrocarbon compound preferably monocyclic, comprising from 6 to 18 carbon atoms, at least one carbon atom of the aromatic ring is substituted by a group R ' 3 .
  • Hal or halogen is meant a halogen selected from the group consisting of chlorine, bromine, fluorine and iodine.
  • R ' 2 and R " 2 is a C 1 -C 11 alkyl group
  • the hydrocarbon chain is a linear chain
  • the C 1 -C 11 alkyl group is chosen from the group formed by methyl ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decycling and n-undecyl.
  • the C 1 -C 11 alkyl group is methyl.
  • R "' 2 is a C 2 -C 18 alkyl group
  • the hydrocarbon chain is a linear chain.
  • R ' 2 and R " 2 is a C 1 -C 11 alkyl group
  • the chain hydrocarbon is a linear chain.
  • the C 1 -C 11 alkyl group is chosen from the group formed by methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decycling and n-undecyl. More preferably, the C 1 -C 11 alkyl group is methyl.
  • R "' 2 is a C 2 -C 18 alkyl group
  • the hydrocarbon chain is a linear chain.
  • the monomer M1 of general formula (IA) is obtained by deprotection of the alcohol functional groups of the monomer of general formula (IB) according to reaction scheme 1 below: with R 1 , Y 1 , Y 2 , x and y as defined in the general formula (IB) described above.
  • the compound of general formula (I-c) is commercially available from suppliers: Sigma-Aldrich® and Alfa Aesar®.
  • the alcohol compound of general formula (Ib) is obtained from the corresponding polyol of formula (Ia) by protecting the diol functions according to the following reaction scheme 3: with x, y, Y 1 and Y 2 as defined in the general formula (IB).
  • the protective reaction of the diol functions of the compound of general formula (Ia) is well known to those skilled in the art. It knows how to adapt the reaction protection conditions according to the nature of the protective groups Y 1 and Y 2 used.
  • the polyol of general formula (Ia) is commercially available from suppliers: Sigma-Aldrich® and Alfa Aesar®.
  • R ' 3 is a C 1 -C 30 alkyl group whose hydrocarbon chain is linear.
  • R ' 3 is a C 1 -C 30 alkyl group whose hydrocarbon chain is linear.
  • C 1 -C 14 alkyl group is meant a saturated hydrocarbon chain, linear or branched comprising from 1 to 14 carbon atoms.
  • the hydrocarbon chain is linear.
  • the hydrocarbon chain comprises from 4 to 12 carbon atoms.
  • C 15 -C 30 alkyl group is meant a linear or branched saturated hydrocarbon chain comprising from 15 to 30 carbon atoms.
  • the hydrocarbon chain is linear.
  • the hydrocarbon chain comprises from 16 to 24 carbon atoms.
  • the monomers of formula (II), (II-A), especially (II-A1) and (II-A2), (II-B) are well known to those skilled in the art. They are marketed by Sigma-Aldrich® and TCI®.
  • the copolymerization can be initiated in bulk or in solution in an organic solvent with compounds generating free radicals.
  • the copolymers of the invention in particular those resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula (I) ) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), are obtained by the known methods of radical copolymerization, controlled in particular such as the method called controlled radical polymerization controlled by reversible addition-fragmentation chain transfer (in English: Reversible Addition-Fragmentation Chain Transfer (RAFT)) and the so-called atom controlled transfer radical polymerization method (in English Atom Transfer Radical Polymerization (ARTP)).
  • RAFT Reversible Addition-Fragmentation Chain Transfer
  • atom controlled transfer radical polymerization method in English Atom Transfer Radical Polymerization (ARTP)
  • the method may further include iv) at least one chain transfer agent.
  • a source of free radicals is meant a chemical compound or for generating a chemical species having one or more unpaired electrons on its outer layer.
  • Those skilled in the art can use any source of free radicals known per se as suitable for polymerization processes, especially controlled radical polymerization.
  • the sources of free radicals benzoyl peroxide, tert-butyl peroxide, diazo compounds such as azobisisobutyronitrile, peroxygen compounds, such as persulfates or the like, are preferred by way of illustration.
  • oxygenated water oxygenated water
  • redox systems such as oxidation of Fe 2+ , persulfate / sodium-metabisulphite mixtures, or ascorbic acid / hydrogen peroxide, or photochemically cleavable compounds or by ionizing radiation, for example ultraviolet rays or by beta or gamma radiation.
  • Chain transfer agent means a compound the purpose of which is to ensure homogeneous growth of macromolecular chains by reversible transfer reactions between growing species, ie polymer chains terminated by a carbon radical, and dormant species, ie polymer chains terminated by a transfer agent. This reversible transfer process makes it possible to control the molecular masses of copolymers thus prepared.
  • S thiocarbonylthio group
  • a preferred transfer agent is cumyl dithiobenzoate or 2-cyano-2-propyl benzodithioate.
  • chain transfer agent is also meant a compound whose purpose is to limit the growth of the macromolecular chains being formed by addition of monomer molecules and to start new chains, which makes it possible to limit the molecular masses final, even to control them.
  • transfer agent is used in telomerization.
  • a preferred transfer agent is cysteamine.
  • the polymerization step (a) comprises contacting at least one monomer M1 with at least two monomers M2 having different R 31 groups.
  • the polydiol random copolymers A1 of the invention are comb copolymers.
  • Comb copolymers means a copolymer having a main chain (also called backbone) and side chains.
  • the side chains are hanging on both sides of the main chain.
  • the length of each side chain is less than the length of the main chain.
  • the figure 2 schematically represents a comb polymer.
  • copolymers of the invention in particular those resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula (I) with at least one a monomer of formula (II-A1) and at least one monomer of formula (II-A2), have a skeleton of polymerizable functions, in particular a skeleton of methacrylate functions, and a mixture of hydrocarbon side chains substituted or not by diol functions .
  • the polydiol random copolymers of the invention especially those resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), have the advantage of being sensitive to external stimuli, such as temperature, pressure, shear rate ; this sensitivity translates into a change of properties.
  • external stimuli such as temperature, pressure, shear rate
  • the conformation in space of the copolymer chains is modified and the diol functions are rendered more or less accessible to the association reactions, which can generate crosslinking, as well as to the exchange reactions. These processes of association and exchange are reversible.
  • the copolymer of the invention A1 is a thermosensitive copolymer, that is to say that it is sensitive to changes in temperature.
  • the side chains of the polydiol random copolymer in particular that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula (I ) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), have an average length ranging from 8 to 20 carbon atoms, preferably from 9 to 15 carbon atoms.
  • average side chain length is meant the average side chain length of each monomer constituting the copolymer. Those skilled in the art can obtain this average length by appropriately selecting the types and ratio of monomers constituting the polydiol random copolymer.
  • hydrophobic medium is meant a medium that has no or a very low affinity for water, that is to say it is not miscible in water or in an aqueous medium.
  • the polydiol random copolymer of the invention especially that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula ( I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), has a molar percentage of monomer M1 of formula (I) in said copolymer ranging from 1 to 30%, preferably ranging from 5 to 25%, more preferably from 9 to 21%.
  • the copolymer of the invention has a molar percentage of monomer M1 of formula (I) in said copolymer ranging from 1 to 30%, preferably 5 to 25%, more preferably ranging from 9 to 21%, a molar percentage of monomer M2 of formula (II-A1) in said copolymer ranging from 8 to 92% and a molar percentage of monomer M2 of formula (II-A2) in said copolymer ranging from 0, 1 to 62%.
  • the molar percentage of monomers in the copolymer results directly from the adjustment of the amounts of monomers used for the synthesis of the copolymer.
  • the copolymer A1 has a molar percentage of monomer M1 of formula (I) in said copolymer ranging from 1 to 30%, a molar percentage of monomer M2 of formula (II-A) in said copolymer ranging from 8 to 62% and a molar percentage of M2 monomer of formula (II-B) in said copolymer ranging from 8 to 91%.
  • the molar percentage of monomers in the copolymer results directly from the adjustment of the amounts of monomers used for the synthesis of the copolymer.
  • the polydiol random copolymer of the invention especially that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula ( I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), at a degree of number-average polymerization ranging from 100 to 2000, preferably from 150 to 1000.
  • the degree of polymerization is controlled using a controlled radical polymerization technique, a telomerization technique or by adjusting the amount of source of free radicals when the copolymers of the invention are prepared by conventional radical polymerization.
  • the polydiol random copolymer of the invention especially that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula ( I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), has a polydispersity index (Ip) ranging from 1.05 to 3.75; preferably from 1.10 to 3.45.
  • the polydispersity index is obtained by measurement of size exclusion chromatography using a polystyrene calibration.
  • the polydiol random copolymer of the invention especially that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula ( I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), has a number-average molar mass ranging from 10,000 to 400,000 g / mol, preferably 25,000 at 150,000 g / mol, the number-average molar mass being obtained by steric exclusion chromatography using a polystyrene calibration.
  • hydrocarbon group having 1 to 24 carbon atoms is meant a linear or branched alkyl or alkenyl group having from 1 to 24 carbon atoms.
  • the hydrocarbon group comprises from 4 to 18 carbon atoms, preferably from 6 to 14 carbon atoms.
  • the hydrocarbon group is a linear alkyl.
  • C 2 -C 24 hydrocarbon chain is meant a linear or branched alkyl or alkenyl group comprising from 2 to 24 carbon atoms.
  • the hydrocarbon chain is a linear alkyl group.
  • the hydrocarbon chain comprises from 6 to 16 carbon atoms.
  • the boronic diester A2 compound of formula (III) as described above is obtained by a condensation reaction between a boronic acid of general formula (III-a) and diol functions of the compounds of general formula (III-b) and (III-c) according to reaction scheme 4 below: with w 1 , w 2 L, R 4 , R 5 , R 6 and R 7 , as defined above.
  • the compound of general formula (III-a) is dissolved, in the presence of water, in a polar solvent such as acetone.
  • a polar solvent such as acetone.
  • the presence of water makes it possible to displace the chemical equilibria between the boronic acid molecules of formula (III-a) and the boroxin molecules obtained from the boronic acids of formula (III-a).
  • boronic acids can spontaneously form boroxine molecules at room temperature.
  • the presence of boroxin molecules is undesirable in the context of the present invention.
  • the condensation reaction is carried out in the presence of a dehydrating agent such as magnesium sulfate.
  • a dehydrating agent such as magnesium sulfate. This agent makes it possible to trap the water molecules initially introduced as well as those released by the condensation between the compound of formula (III-a) and the compound of formula (III-b) and between the compound of formula (III- a) and the compound of formula (III-c).
  • the compound (III-b) and the compound (III-c) are identical.
  • the compound A2 comprising at least two boronic ester functions is a boronic ester random copolymer resulting from the copolymerization of at least one monomer M3 of formula (IV) as described herein. below with at least one M4 monomer of formula (V) as described below.
  • C 2 -C 24 alkyl is meant a saturated hydrocarbon chain, linear or branched, comprising from 2 to 24 carbon atoms.
  • the hydrocarbon chain is linear.
  • the hydrocarbon chain comprises from 6 to 16 carbon atoms.
  • hydrocarbon chain comprising 1 to 15 carbon atoms is meant a linear or branched alkyl or alkenyl group comprising from 1 to 15 carbon atoms.
  • the hydrocarbon chain is a linear alkyl group.
  • it comprises from 1 to 8 carbon atoms.
  • hydrocarbon chain comprising 1 to 24 carbon atoms is meant a linear or branched alkyl or alkenyl group comprising from 1 to 24 carbon atoms.
  • the hydrocarbon chain is a linear alkyl group.
  • it comprises from 4 to 18 carbon atoms, preferably from 6 to 12 carbon atoms.
  • the monomers M3 of formula (IV) are obtained in particular from a preparation process comprising at least one step of condensation of a boronic acid of general formula (IV-f) with a diol compound of general formula (IV-g ) according to reaction scheme 5 below:
  • the compound of general formula (IV-f) is dissolved, in the presence of water, in a polar solvent such as acetone.
  • the condensation reaction is carried out in the presence of a dehydrating agent, such as magnesium sulfate.
  • the compound of formula (IV-c) is obtained by a condensation reaction between a boronic acid of formula (IV-a) with at least one diol compound of formula (IV-b) according to the following reaction scheme 8: with M, Y 4 , z and R 12 as defined above,
  • the compounds of formula (IV-a) and (IV-b) are commercially available from the following suppliers: Sigma-Aldrich®, Alfa Aesar® and TCI®.
  • C 1 -C 25 alkyl group is meant a saturated hydrocarbon chain, linear or branched, comprising from 1 to 25 carbon atoms.
  • the hydrocarbon chain is linear.
  • C 6 -C 18 aryl group substituted by a group R 13 is meant an aromatic hydrocarbon compound comprising from 6 to 18 carbon atoms, at least one carbon atom of the aromatic ring is substituted by a C 1 -C 4 alkyl group. 1 -C 25 as defined above.
  • the boronic ester random copolymers are obtained by the known methods of radical copolymerization, in particular controlled such as the method called controlled radical polymerization controlled by reversible addition-fragmentation chain transfer (in English: Reversible Addition-Fragmentation Chain Transfer (RAFT) ) and the method called Atom Transfer Radical Polymerization (ARTP).
  • controlled radical polymerization controlled by reversible addition-fragmentation chain transfer in English: Reversible Addition-Fragmentation Chain Transfer (RAFT)
  • ARTP Atom Transfer Radical Polymerization
  • the method may further comprise iv) at least one chain transfer agent.
  • Radical sources and transfer agents are those which have been described for the synthesis of polydiol random copolymers. The preferences described for radical sources and transfer agents also apply to this process.
  • X of the monomer M 3 of general formula (IV) has a total number of carbon atoms ranging from 8 to 38, preferably from 10 to 26 carbon atoms.
  • the side chains of the boronic ester random copolymer have an average length greater than 8 carbon atoms, preferably ranging from 11 to 16 carbon atoms.
  • This chain length makes it possible to solubilize the boronic ester random copolymer in a hydrophobic medium.
  • average side chain length is meant the average side chain length of each monomer constituting the copolymer. The person skilled in the art knows how to obtain this average length by appropriately selecting the types and the ratio of monomers constituting the boronic ester statistical copolymer.
  • the boronic ester statistical copolymer has a molar percentage of monomer of formula (IV) ranging from 0.25 to 20%, preferably from 1 to 10%.
  • the boronic ester statistical copolymer has a molar percentage of monomer of formula (IV) ranging from 0.25 to 20%, preferably from 1 to 10% and a molar percentage of monomer of formula (V) ranging from 80 to 99 , 75%, preferably 90 to 99%.
  • the boronic ester statistical copolymer has a number-average degree of polymerization ranging from 50 to 1500, preferably from 80 to 800.
  • the boronic ester statistical copolymer has a polydispersity index (Ip) ranging from 1.04 to 3.54; preferably ranging from 1.10 to 3.10. These values are obtained by size exclusion chromatography using tetrahydrofuran as eluent and a polystyrene calibration.
  • the boronic ester statistical copolymer has a number-average molecular weight ranging from 10,000 to 200,000 g / mol, preferably from 25,000 to 100,000 g / mol. These values are obtained by size exclusion chromatography using tetrahydrofuran as eluent and a polystyrene calibration.
  • the new compositions of the invention have the advantage of being thermoreversibly crosslinkable.
  • the polydiols random copolymers A1 especially those resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), and compounds A2 as defined above have the advantage of being associative and of exchanging chemical bonds thermoreversibly, especially in a hydrophobic medium, in particular an apolar hydrophobic medium.
  • the polydiols random copolymers A1 in particular those resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula (I) ) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), and compounds A2 as defined above can be crosslinked.
  • Polydiols random copolymers A1 especially those resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula (I) with at least one a monomer of formula (II-A1) and at least one monomer of formula (II-A2), and the compounds A2 also have the advantage of being exchangeable.
  • association is understood to mean that covalent boronic ester-type chemical bonds are established between the polydiols random copolymers A1, in particular those resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), and the compounds A2 comprising at least minus two boronic ester functions.
  • the figure 4 illustrates associative polymers.
  • polydiols A1 especially those resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula (I) with at least minus one monomer of formula (II-A1) and at least one monomer of formula (II-A2), and compounds A2 and according to the composition of the mixtures, the formation of covalent bonds between polydiols A1 and compounds A2 may lead to no to the formation of a three-dimensional polymeric network.
  • chemical bond is meant a covalent chemical bond of the boronic ester type.
  • FIG 9 Another chemical link exchange process is illustrated in figure 9 in which it can be seen that the polydiol random copolymer A1-1, which was associated with the A2-1 polymer, exchanged two boronic ester bonds with the boronic ester random copolymer A2-2.
  • the polydiol random copolymer A1-2 which was in association with the A2-2 polymer, exchanged two boronic ester bonds with the boronic ester random copolymer A2-1; the total number of boronic ester bond in the composition being unchanged and is equal to 4.
  • the A1-1 copolymer is then combined with the A2-2 polymer.
  • the copolymer A1-2 is then with the polymer A2-1.
  • the A2-1 copolymer was exchanged with the A2-2 polymer.
  • crosslinked is meant a copolymer in the form of a network obtained by the establishment of bridges between the macromolecular chains of the copolymer. These interconnected chains are for the most part distributed in the three dimensions of space.
  • a crosslinked copolymer forms a three-dimensional network.
  • the formation of a copolymer network is ensured by a solubility test. It can be ensured that a network of copolymers has been formed by placing the copolymer network in a known solvent to dissolve the uncrosslinked copolymers of the same chemical nature. If the copolymer swells instead of dissolving, the person skilled in the art knows that a network has been formed. The figure 3 illustrates this solubility test.
  • crosslinkable is meant a copolymer capable of being crosslinked.
  • reversibly crosslinked is meant a crosslinked copolymer whose bridges are formed by a reversible chemical reaction.
  • the reversible chemical reaction can move in one direction or another, resulting in a change in structure of the polymer network.
  • the copolymer can pass from an uncrosslinked initial state to a crosslinked state (three-dimensional network of copolymers) and from a crosslinked state to an uncrosslinked initial state.
  • the bridges that form between the copolymer chains are labile. These bridges can form or exchange through a chemical reaction that is reversible.
  • the reversible chemical reaction is a transesterification reaction between diol functional groups of a random copolymer (copolymer A1, especially that resulting from the copolymerization of at least one monomer of formula (I) with at least one a monomer of formula (II-A) or of at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2)) and ester functions boronic compound A2.
  • the bridges formed are boronic ester type bonds. These boronic ester bonds are covalent and labile because of the reversibility of the transesterification reaction.
  • thermoreversible crosslinked is meant a copolymer crosslinked by a reversible reaction whose displacement in one direction or the other direction is controlled by the temperature.
  • the thermoreversible crosslinking mechanism of the composition of the invention is schematically presented in figure 4 .
  • the applicant has observed that at low temperature, the polydiol copolymer A1, in particular that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one a monomer of formula (II-A2) (symbolized by the copolymer carrying A functions on the figure 4 ), is not or only slightly crosslinked by the boronic ester compounds A2 (symbolized by the compound carrying B functions on the figure 4 ).
  • the diol functions of the copolymer react with the boronic ester functions of compound A2 by a transesterification reaction.
  • Polydiols random copolymers A1 especially those resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula (I) with at least one a monomer of formula (II-A1) and at least one monomer of formula (II-A2), and the compounds A2 comprising at least two boronic ester functions then bind together and can be exchanged.
  • a gel can be formed in the medium, especially when the medium is nonpolar .
  • the boronic ester bonds between the polydiols random copolymers A1 in particular those resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), and the A2 compounds are broken, and if necessary, the composition loses its gelled character.
  • the amount of boronic ester bonds (or boronic ester bond) which can be established between the polydiols random copolymers A1 and the A2 compounds is adjusted by those skilled in the art by means of an appropriate selection of the polydiol A1 random copolymer, in particular the resulting one. of the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), and compound A2 and the composition of the mixture.
  • the content of random copolymer A1, in particular that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2) in the composition ranges from 0.25% to 20% by weight relative to the total weight of the final composition, preferably from 1 to 10% by weight relative to the total weight of the final composition.
  • the content of compound A2 in the composition ranges from 0.25% to 20% by weight relative to the total weight of the final composition, preferably preferably from 0.5% to 10% by weight relative to the total weight of the composition. the final composition.
  • the mass ratio between the polydiol A1 statistical compound, in particular that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), and the compound A2 (ratio A1 / A2) in the composition ranges from 0.001 to 100, preferably from 0.05 to 20, even more preferably 0.1 to 10, more preferably 0.2 to 5.
  • the sum of the masses of the random copolymer A1, in particular that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), and of compound A2 is from 0.5 to 20% with respect to the total mass of the lubricating composition and the lubricating oil mass ranges from 80% to 99.5% relative to the total mass of the lubricating composition.
  • composition of the invention may further comprise a functional additive selected from the group consisting of detergents, anti-wear additives, extreme pressure additives, antioxidants, viscosity index improving polymers. , pour point improvers, defoamers, thickeners, anticorrosive additives, dispersants, friction modifiers and mixtures thereof.
  • a functional additive selected from the group consisting of detergents, anti-wear additives, extreme pressure additives, antioxidants, viscosity index improving polymers. , pour point improvers, defoamers, thickeners, anticorrosive additives, dispersants, friction modifiers and mixtures thereof.
  • the functional additive or functional additive mixtures when present, represent from 0.1 to 10% by weight relative to the total weight of the composition.
  • the detergents that can be used in the lubricant compositions according to the present invention are well known to those skilled in the art.
  • the detergents commonly used in the formulation of lubricating compositions are typically anionic compounds having a long lipophilic hydrocarbon chain and a hydrophilic head.
  • the associated cation is typically a metal cation of an alkali or alkaline earth metal.
  • the detergents are preferably chosen from alkali metal or alkaline earth metal salts of carboxylic acids, sulphonates, salicylates and naphthenates, as well as the salts of phenates.
  • the alkali and alkaline earth metals are preferably calcium, magnesium, sodium or barium. These metal salts may contain the metal in an approximately stoichiometric amount or in excess (in an amount greater than the stoichiometric amount). In the latter case, we are dealing with so-called overbased detergents.
  • the excess metal providing the overbased detergent character is in the form of oil insoluble metal salts, for example carbonate, hydroxide, oxalate, acetate, glutamate, preferably carbonate.
  • additives protect the friction surfaces by forming a protective film adsorbed on these surfaces.
  • anti-wear and extreme pressure additives include phosphosulfur additives such as metal alkylthiophosphates, in particular zinc alkylthiophosphates, and more specifically zinc dialkyldithiophosphates or ZnDTPs, amine phosphates and polysulfides, especially sulfur-containing olefins and metal dithiocarbamates.
  • antioxidants act as free radical inhibitors or destroyers of hydroperoxides.
  • antioxidants are antioxidants of phenolic or amine type.
  • additives cover the surface of a film that prevents access of oxygen to the surface of the metal. They can sometimes neutralize acids or certain chemicals to prevent metal corrosion.
  • Illustrative examples include dimercaptothiadiazole (DMTD), benzotriazoles, phosphites (free sulfur capture).
  • additives make it possible to guarantee a good cold behavior and a minimum viscosity at high temperature of the composition.
  • OCP copolymer olefins
  • PMA polymethacrylates
  • additives improve the cold behavior of the compositions by slowing down the formation of paraffin crystals.
  • They are, for example, alkyl polymethacrylates, polyacrylates, polyarylamides, polyalkylphenols, polyalkylnaphthalenes and alkylated polystyrenes.
  • Thickeners are additives used mainly for industrial lubrication and make it possible to formulate lubricants of higher viscosity than engine lubricating compositions.
  • polysiobutenes having a molar mass by weight of 10,000 to 100,000 g / mol.
  • additives ensure the maintenance in suspension and the evacuation of insoluble solid contaminants constituted by the by-products of oxidation which are formed during the use of the composition.
  • succinimides for example, of succinimides, PIBs (polyisobutene) succinimides and Mannich bases.
  • additives improve the coefficient of friction of the composition.
  • molybdenum dithiocarbamate amines having at least one chain hydrocarbon of at least 16 carbon atoms, esters of fatty acids and polyols such as esters of fatty acids and glycerol, in particular glycerol monooleate.
  • Another object of the present invention is the use of the composition as defined above for lubricating a mechanical part.
  • compositions of the invention are useful for lubricating the surfaces of parts that are conventionally found in an engine such as the pistons, segments, shirts system.
  • At least one random copolymer A1 especially that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or from at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), and at least one compound A2 comprising at least two boronic ester functions as defined above can associate and exchange in a thermoreversible way; but they do not form three-dimensional networks. They are not crosslinked.
  • the composition for lubricating at least one motor further comprises at least one functional additive selected from the group consisting of detergents, anti-wear additives, extreme pressure additives, additional antioxidants, anticorrosive additives, viscosity index improvers, dots improvers and the like. flow, antifoams, thickeners, dispersants, friction modifiers and mixtures thereof.
  • the definitions and preferences relating to lubricating oils, random copolymers A1, especially that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or at least one monomer of formula (I) with minus one monomer of formula (II-A1) and at least one monomer of formula (II-A2), and compounds A2 also apply to compositions for lubricating at least one engine.
  • Another object of the present invention is a composition for lubricating at least one transmission, such as manual or automatic gearboxes.
  • At least one random copolymer A1 especially that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or from at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), and at least one compound A2 comprising at least two boronic ester functions as defined above can associate and exchange in a thermoreversible way; but they do not form three-dimensional networks. They are not crosslinked.
  • the composition for lubricating at least one transmission further comprises at least one functional additive selected from the group consisting of detergents, antiwear additives, extreme pressure additives, additional antioxidants, anticorrosion additives, viscosity index improver polymers, pour point improvers, defoamers, thickeners, dispersants, friction modifiers and mixtures thereof.
  • at least one functional additive selected from the group consisting of detergents, antiwear additives, extreme pressure additives, additional antioxidants, anticorrosion additives, viscosity index improver polymers, pour point improvers, defoamers, thickeners, dispersants, friction modifiers and mixtures thereof.
  • the definitions and preferences relating to lubricating oils, random copolymers A1, especially that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), and compounds A2 also apply to the compositions for lubricating at least one transmission.
  • compositions of the invention can be used for engines or transmissions of light vehicles, trucks but also ships.
  • Another object of the present invention is a method of lubricating at least one mechanical part, in particular at least one motor or at least one transmission, said method comprising a step in which said mechanical part is brought into contact with at least one composition as defined above.
  • the definitions and preferences relating to lubricating oils, random copolymers A1, especially that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), and compounds A2 also apply to the method of lubricating at least one mechanical part.
  • Another subject of the present invention relates to a parent composition resulting from the mixture of at least at least one random copolymer A1 as defined above, in particular that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), at least a compound A2 comprising at least two boronic ester functions, at least one functional additive selected from the group consisting of detergents, anti-wear additives, extreme pressure additives, antioxidants, viscosity index improving polymers, improvers pour point, antifoams, thickeners, dispersants, friction modifiers and their mixtures.
  • mother composition is meant a composition which a person skilled in the art can make daughter solutions by removing a certain amount of mother solution supplemented by the addition of a necessary quantity of diluent (solvent or other) to obtain a desired concentration.
  • a daughter composition is thus obtained by dilution of a parent composition.
  • the lubricating compositions of the invention can be obtained by diluting in a lubricating oil, especially a Group I, Group II, Group III, Group IV, Group V API classification base oil. or a mixture thereof, the parent composition as defined above.
  • the random copolymer A1 of the invention is obtained according to the following reaction scheme:
  • the product thus obtained is then introduced into an IL flask surmounted by a dropping funnel.
  • the glassware used was first dried overnight in a thermostatically controlled oven at 100 ° C. 500 ml of anhydrous dichloromethane are then introduced into the flask followed by 36.8 g (364 mmol) of triethylamine.
  • a solution of 39.0 g (373 mmol) of methacryloyl chloride (MAC) in 50 mL of anhydrous dichloromethane is introduced into the dropping funnel.
  • the flask is then placed in an ice bath to lower the temperature of the reaction medium to around 0 ° C.
  • the methacryloyl chloride solution is then added dropwise with vigorous stirring.
  • the reaction medium is left stirring for 1 hour at 0 ° C. and then 23 hours at room temperature.
  • the reaction medium is then transferred into a 3 L Erlenmeyer flask and 1 L of dichloromethane is added.
  • the organic phase is then successively washed with 4 ⁇ 300 ml of water, 6 ⁇ 300 ml of a 0.5 M aqueous hydrochloric acid solution, 6 ⁇ 300 ml of a saturated aqueous solution of NaHCO 3 and new 4 ⁇ 300 mL of water.
  • the synthesis of the copolymer is carried out according to the following protocol: 10.5 g (31.0 mmol) of stearyl methacrylate (StMA), 4.76 g (18.7 mmol) of lauryl methacrylate (LMA), 3.07 g (12.7 mmol) of methacrylate bearing a protected diol function in the form of a ketal obtained according to the protocol described in paragraph 1.1.1, 68.9 mg (0.253 mmol) of cumyl dithiobenzoate and 19.5 ml of anisole are introduced into a Schlenk tube of 100 ml.
  • StMA stearyl methacrylate
  • LMA lauryl methacrylate
  • methacrylate bearing a protected diol function in the form of a ketal obtained according to the protocol described in paragraph 1.1.1
  • 68.9 mg (0.253 mmol) of cumyl dithiobenzoate and 19.5 ml of anisole are introduced into a Schlenk tube of 100
  • the reaction medium is stirred and 8.31 mg (0.0506 mmol) of azobisisobutyronitrile (AIBN) in solution in 85 .mu.l of anisole are introduced into the Schlenk tube.
  • AIBN azobisisobutyronitrile
  • the reaction medium is then degassed for 30 minutes by bubbling argon before being heated to 65 ° C. for a duration of 16 hours.
  • Schlenk's tube is placed in a bath of ice to stop the polymerization, then the polymer is isolated by precipitation in methanol, filtration and drying under vacuum at 30 ° C overnight.
  • a copolymer having a number-average molar mass ( M n ) of 41,000 g / mol, a polydispersity index (Ip) of 1.22 and a number-average degree of polymerization (DP n ) of 167 are thus obtained. values are respectively obtained by size exclusion chromatography using tetrahydrofuran as eluent and polystyrene calibration and by monitoring the conversion to monomers during the copolymerization.
  • the deprotection of the copolymer is carried out according to the following protocol: 7.02 g of copolymer containing about 20% protected diol function obtained previously are introduced into a 500 ml Erlenmeyer flask. 180 ml of dioxane are added and the reaction mixture is stirred at 30 ° C. 3 ml of a 1M aqueous solution of hydrochloric acid and then 2.5 ml of an aqueous solution of 35% hydrochloric acid are added dropwise. The reaction medium then becomes slightly opaque and 20 ml of THF are introduced to make the medium completely homogeneous and transparent. The reaction medium is then left stirring at 40 ° C. for 48 hours. The copolymer is recovered by precipitation in methanol, filtration and drying under vacuum at 30 ° C overnight.
  • a poly (alkyl methacrylate-co-alkyldiol methacrylate) copolymer containing about 20 mol% of M1 diol monomer units and having an average length of pendant alkyl chains of 13.8 carbon atoms is obtained.
  • ⁇ 1.2 From a monomer carrying a protected diol function in the form of a boronic ester
  • random copolymer A1 of the invention is obtained according to the following reaction scheme 11:
  • Phenylboronic acid (PBA) 6.01 g (49.3 mmol) and 300 mL of acetone are added to a 500 mL beaker followed by 1.5 mL of water.
  • the reaction medium is stirred and 6.07 g (45.2 mmol) of 1,2,6-hexanetriol are slowly added.
  • An excess of magnesium sulphate is added to the reaction medium in order to trap the water initially introduced as well as the water released by the condensation between phenylboronic acid and 1,2,6-hexanetriol.
  • the reaction medium is left stirring at ambient temperature for 30 minutes before being filtered and then concentrated under vacuum using a rotavapor.
  • the light yellow liquid thus obtained in the preceding step is then introduced into an IL flask surmounted by a dropping funnel.
  • the glassware used having been previously pre-dried overnight in a thermostatically controlled oven at 100 ° C.
  • 90 ml of anhydrous dichloromethane are then introduced into the flask followed by 6.92 g (68.4 mmol) of triethylamine.
  • a solution of 5.82 g (55.7 mmol) of methacryloyl chloride (MAC) in 10 mL of anhydrous dichloromethane is introduced into the dropping funnel.
  • the flask is then placed in an ice bath to lower the temperature of the reaction medium to around 0 ° C.
  • the methacryloyl chloride solution is then added dropwise with vigorous stirring.
  • the reaction mixture is left stirring for 1 hour at 0 ° C. and then 17 hours at room temperature.
  • the reaction medium is then transferred to a 500 ml Erlenmeyer flask and 300 ml of dichloromethane are added.
  • the organic phase is then successively washed with 4 ⁇ 100 mL of water, 4 ⁇ 100 mL of a 0.1 M aqueous hydrochloric acid solution, 4 ⁇ 100 mL of a saturated aqueous solution of NaHCO 3 and new 4 ⁇ 100 mL of water.
  • the synthesis of the polymer is carried out according to the following protocol: 13.5 g (40 mmol) of stearyl methacrylate (StMA), 12 g (47.2 mmol) of lauryl methacrylate (LMA), 3.12 g (10.8 mmol) of methacrylate carrying a diol function protected in the form of a boronic ester, 92.1 mg (0.416 mmol) of cumyl dithiobenzoate and 34 ml of anisole are introduced into a 100 ml Schlenk tube. The reaction medium is stirred and 13.7 mg (0.0833 mmol) of azobisisobutyronitrile (AIBN) in solution in 135 .mu.l of anisole are introduced into the Schlenk tube.
  • AIBN azobisisobutyronitrile
  • the reaction medium is then degassed for 30 minutes by bubbling argon before being heated to 65 ° C. for a period of 24 hours.
  • the Schlenk tube is placed in an ice bath to stop the polymerization and 30 mL of tetrahydrofuran (THF) is then added to the reaction medium.
  • THF tetrahydrofuran
  • a copolymer having a number average molecular weight ( M n ) of 70,400 g / mol, a polydispersity index (Ip) of 3,11 and a number-average degree of polymerization (DP n ) of 228 are thus obtained. These values are respectively obtained by steric exclusion chromatography using tetrahydrofuran as eluent and polystyrene calibration and by monitoring the conversion to monomers during the copolymerization.
  • a poly (alkyl methacrylate-co-alkyldiol methacrylate) copolymer containing about 10 mol% of monomer diol units and having an average length of pendant alkyl chains of 13.8 carbon atoms is obtained.
  • 1,4-Benzenediboronic acid (1,4-BDBA) (1.5 g, 9.05 mmol) is introduced into a 500 mL beaker, followed by 300 mL of acetone.
  • the reaction medium is stirred and 0.300 g (16.7 mmol) of water are introduced dropwise.
  • the reaction medium then becomes transparent and homogeneous and 1,2-dodecanediol (4.02 g, 19.9 mmol) is slowly added. After complete dissolution of the latter, an excess of magnesium sulphate is added in order to trap the water initially introduced as well as the water released by the condensation between 1,4-BDBA and 1,2-dodecanediol.
  • the reaction medium is filtered.
  • the solvent is then removed from the filtrate using a rotary evaporator to give 4.41 g of boronic diester and 1,2-dodecanediol (98% yield) as a white solid.
  • the boronic ester monomer of the invention is synthesized according to the following reaction scheme 13:
  • the monomer is obtained according to the protocol in two steps: The first step is to synthesize a boronic acid and the second step is to obtain a boronic ester monomer.
  • the 4-carboxyphenylboronic acid (CPBA) (5.01 g, 30.2 mmol) is introduced into an IL beaker followed by 350 mL of acetone and the reaction medium is stirred 7.90 mL (439 mmol) ) of water are added dropwise until complete dissolution of 4-carboxyphenylboronic acid.
  • the reaction medium is then transparent and homogeneous.
  • 1,2-Propanediol (2.78 g, 36.6 mmol) is then slowly added, followed by an excess of magnesium sulfate to trap the initially introduced water as well as the water released by the condensation between the CPBA and 1,2 propanediol.
  • the reaction medium is stirred for 1 hour at 25 ° C before being filtered.
  • the solvent is then removed from the filtrate by means of a rotary evaporator.
  • the product thus obtained and 85 ml of DMSO are introduced into a 250 ml flask.
  • the reaction medium is stirred and then after complete homogenization of the reaction medium, 8.33 g (60.3 mmol) of K 2 CO 3 are added.
  • 4- (Chloromethyl) styrene (3.34 g, 21.9 mmol) is then slowly introduced into the flask.
  • the reaction medium is then left stirring at 50 ° C. for 16 hours.
  • the reaction medium is transferred to a 2 L Erlenmeyer flask, then 900 ml of water are added.
  • the aqueous phase is extracted with 8 ⁇ 150 mL of ethyl acetate.
  • the boronic acid monomer (5.7 g, 20.2 mmol) obtained in the first step and 500 mL of acetone are introduced into an Erlenmeyer flask.
  • the reaction medium is stirred and 2.6 ml (144 mmol) of water are added dropwise until complete dissolution of the boronic acid monomer.
  • the reaction medium is then transparent and homogeneous.
  • a solution of 1,2-dodecanediol (5.32 g, 26.3 mmol) in 50 mL of acetone is slowly added to the reaction medium, followed by an excess of magnesium sulfate to trap the initially introduced water and as the water released by the condensation between the boronic acid monomer and 1,2-dodecanediol.
  • the statistical copolymer A2 of the invention is obtained according to the following protocol: 2.09 g of a boronic ester monomer mixture and 1,2-dodecanediol previously prepared (containing 3.78 mmol of boronic ester monomer), 98.3 mg (0.361 mmol) of cumyl dithiobenzoate, 22.1 g (86.2 g). 9 mmol) of lauryl methacrylate (LMA) and 26.5 ml of anisole are introduced into a 100 ml Schlenk tube. The reaction medium is stirred and 11.9 mg (0.0722 mmol) of azobisisobutyronitrile (AIBN) in solution in 120 .mu.l of anisole are introduced into the Schlenk tube.
  • AIBN azobisisobutyronitrile
  • the reaction medium is then degassed for 30 minutes by bubbling argon before being heated to 65 ° C. for a duration of 16 hours.
  • the Schlenk tube is placed in an ice bath to stop the polymerization, then the polymer is isolated by precipitation in anhydrous acetone, filtration and drying under vacuum at 30 ° C overnight.
  • the boronic ester copolymer obtained has a number-average molecular weight ( M n ) equal to 37,200 g / mol, a polydispersity index (Ip) equal to 1.24 and a number-average degree of polymerization (DP n ) equal to 166. These values are respectively obtained by size exclusion chromatography using tetrahydrofuran as eluent and polystyrene calibration and by monitoring the conversion to monomers during the copolymerization. Proton NMR analysis of the final copolymer gives a composition of 4 mol% boronic ester monomer and 96% lauryl methacrylate.
  • Appare 3.1 Apparatuses and protocols for measuring viscosity
  • Relative viscosity ⁇ on ⁇ solution ⁇ oil of based was also chosen to represent the evolution of the viscosity of the system as a function of temperature, since this quantity directly reflects the compensation for the natural viscosity loss of the Group III base oil of the polymer systems studied.
  • compositions based on random copolymers polydiols A1 and compounds A2 diester boronic.
  • copolymers A1-1, A1-2, A1-3 and A1-4 are obtained according to one of the protocols described in paragraph 1.
  • Compound A2-1 is the boronic diester obtained according to the protocol described in section 2.1.
  • Composition A (outside the invention) is used as a reference.
  • the polymer contains a 4.2% by weight solution of a polymethacrylate polymer in API Group III lubricating base oil.
  • the polymer has a number average molecular weight ( M n ) equal to 106,000 g / mol, a polydispersity index (Ip) of 3.06, a number average polymerization degree of 466 and the average length of the pendant chains is 14 carbon atoms.
  • This polymethacrylate is used as a viscosity index improving additive.
  • Composition B-1 (except the invention) is obtained as follows:
  • Composition C-1 (according to the invention) is obtained as follows:
  • a 10% by weight solution of polydiol copolymer A1-1 and 20 mol% of boronic diester A2-1 is obtained relative to the diol functions of the polydiol copolymer A1-1.
  • Composition D-1 (according to the invention) is obtained as follows:
  • a 10% by weight solution of polydiol copolymer A1-1 and 80 mol% of boronic diester A2-1 is obtained relative to the diol functions of the polydiol copolymer A1-1.
  • Composition B-2 (except the invention) is obtained as follows:
  • Composition C-2 (according to the invention) is obtained as follows:
  • a 10% by weight solution of polydiol copolymer A1-2 and 20 mol% of boronic diester A2-1 is obtained relative to the diol functions of the polydiol copolymer A1-2.
  • Composition D-2 (according to the invention) is obtained as follows:
  • a 10% by weight solution of polydiol copolymer A1-2 and 80 mol% of boronic diester A2-1 is obtained relative to the diol functions of the polydiol copolymer A1-2.
  • Composition B-3 (except the invention) is obtained as follows:
  • Composition C-3 (according to the invention) is obtained in the following manner:
  • a 10% by weight solution of polydiol copolymer A1-3 and 20 mol% of boronic diester A2-1 is obtained relative to the diol functions of the polydiol copolymer A1-3.
  • Composition B-4 (except the invention) is obtained as follows:
  • Composition C-4 (according to the invention) is obtained as follows:
  • a 10% by weight solution of polydiol copolymer A1-4 and 20 mol% of boronic diester A2-1 is obtained relative to the diol functions of the polydiol copolymer A1-4.
  • Composition D-4 (according to the invention) is obtained as follows:
  • a 10% by weight solution of polydiol copolymer A1-4 and 80 mol% of boronic diester A2-1 is obtained relative to the diol functions of the polydiol copolymer A1-4.
  • composition C1-1 The rheological behavior of the composition C1-1 was studied for a temperature range from 10 ° C to 110 ° C. The results are presented in figure 5 .
  • the dynamic viscosity of composition C1-1 varies at low shear rates and at temperatures below 50 ° C. Composition C1-1 is deformed under shear stress for temperatures below 50 ° C.
  • composition C1-1 For temperatures above 50 ° C., the dynamic viscosity of composition C1-1 varies very slightly or does not vary at low shear rates. The composition C1-1 is no longer deformed under the shear stress at these temperatures.
  • compositions A, B-1, C-1, D-1, B-2, C-2, D-2, B-3, C-3, D-3, B-4, C-4 , D-4 has been studied.
  • the evolution of the relative viscosity of these compositions is illustrated in Figures 6A-6D .
  • the polydiols copolymers A1-1 and A1-3 have the same average length of the alkyl chains (L C ), comparable molar masses but a percentage of diol monomer (M1) per skeletal chain different (20% and 10% respectively).
  • the polydiols A1-3 and A1-4 have the same percentage of diol monomer (M1) per chain, the same average length of the alkyl chains (L C ) but substantially different molar masses (47,800 g / mol and 97,100 g / mol). mol respectively) and degrees of substantially different number average polymerization (DP n 198 and 228 respectively).
  • compositions based on random copolymers polydiols A1 and compounds A2 polymer boronic ester.
  • a random poly (alkyl methacrylate-co-alkyldiol methacrylate) copolymer of the invention is tested. It is the following copolymer: ⁇ Copolymer A1-1: This copolymer comprises 20 mol% of monomers having diol functions. The average side chain length is 13.8 carbon atoms. Its average molar mass is 49,600 g / mol. Its polydispersity index is 1.51. Its number-average degree of polymerization (DP n ) is 167. The number average molecular weight and the polydispersity index are measured by steric exclusion chromatography using a polystyrene calibration.
  • copolymer A1-1 is obtained according to one of the protocols described in paragraph 1.
  • Compound A2-2 is the boronic ester polymer obtained according to the protocol described in section 2.2.
  • This copolymer comprises 4 mol% of monomers having boronic ester functions.
  • the average side chain length is greater than 12 carbon atoms.
  • Its average molar mass is 37,200g / mol.
  • Its polydispersity index is 1.24.
  • Its number-average degree of polymerization (DP n ) is 166.
  • the number average molecular weight and the polydispersity index are measured by steric exclusion chromatography using a polystyrene calibration.
  • the lubricating base oil used in the compositions to be tested is the group III oil described above in section 3.1.
  • Composition A (outside the invention) is used as a reference and is the same as Composition A used in Section 3.1.
  • Composition B (except the invention) is obtained as follows:
  • Composition B is the same composition B-1 used in section 3.1.
  • Composition C (according to the invention) is obtained as follows:
  • a 5% by weight solution of polydiol copolymer A1-1 and 1% by weight of boron ester polymer A2-2 is obtained relative to the total mass of the composition.
  • Composition D (according to the invention) is obtained in the following manner:
  • a 5% by weight solution of polydiol copolymer A1-1 and 2% by weight of boron ester polymer A2-2 is obtained relative to the total mass of the composition.
  • Composition E (according to the invention) is obtained as follows:
  • a 5% by weight solution of polydiol copolymer A1-1 and 3% by weight of boron ester polymer A2-2 is obtained relative to the total mass of the composition.
  • composition E The rheological behavior of the composition E was studied for a temperature range from 10 ° C to 110 ° C. The results are presented in figure 7 .
  • the dynamic viscosity of composition E varies at low shear rates and at temperatures below 50 ° C.
  • Composition E deforms under shear stress for temperatures below 50 ° C.
  • composition E For temperatures above 50 ° C., the dynamic viscosity of the composition E varies very slightly or does not vary at low shear rates. Composition E does not no longer deforms under shear stress at these temperatures.
  • Composition F (outside the invention) is obtained as follows:
  • VI booster polymer (Viscoplex V6.850 sold by Rohmax) is added to the lubricating base oil described above.
  • Viscoplex 6.850 comprises 41.8% active ingredient of a linear polymethacrylate.
  • composition thus obtained has the following characteristics; the percentages indicated correspond to percentages by weight relative to the total weight of the composition F: % Lubricating base oil 80.86 Viscoplex V6.850 19.14 (corresponding to 8% active ingredient of polymethacrylate)

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
EP15700905.1A 2014-01-27 2015-01-26 Compositions lubrifiantes comprenant des copolymeres thermoassociatifs et echangeables Active EP3099721B1 (fr)

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FR3031744B1 (fr) * 2015-01-15 2017-02-10 Total Marketing Services Compositions d'additifs thermoassociatifs dont l'association est controlee et compositions lubrifiantes les contenant
FR3059005B1 (fr) 2016-11-23 2018-12-07 Total Marketing Services Copolymeres thermoassociatifs et echangeables, composition les comprenant
FR3059006B1 (fr) 2016-11-23 2020-06-12 Total Marketing Services Compositions d’additifs thermoassociatifs dont l’association est controlee et compositions lubrifiantes les contenant
CN107298737A (zh) * 2017-06-20 2017-10-27 西南科技大学 一种三维动态聚丙烯的制备方法
FR3078710B1 (fr) 2018-03-07 2020-10-30 Total Marketing Services Composition comprenant des copolymeres thermoassociatifs et echangeables
FR3078706B1 (fr) 2018-03-07 2020-12-18 Total Marketing Services Copolymeres thermoassociatifs et echangeables, composition les comprenant
FR3081467B1 (fr) * 2018-05-24 2020-07-10 Total Marketing Services Oligomeres associatifs et echangeables, composition les comprenant
FR3081464B1 (fr) * 2018-05-24 2020-09-18 Total Marketing Services Oligomeres associatifs et echangeables, composition les comprenant
FR3081465B1 (fr) * 2018-05-24 2020-06-12 Total Marketing Services Oligomeres associatifs et echangeables, composition les comprenant
FR3081466B1 (fr) * 2018-05-24 2020-06-12 Total Marketing Services Oligomeres associatifs et echangeables, composition les comprenant
EP4441175B1 (en) 2021-12-03 2025-08-27 Evonik Operations GmbH Boronic ester modified polyalkyl(meth)acrylate polymers
WO2023099631A1 (en) 2021-12-03 2023-06-08 Evonik Operations Gmbh Boronic ester modified polyalkyl(meth)acrylate polymers
EP4441177B1 (en) 2021-12-03 2025-08-06 Evonik Operations GmbH Boronic ester modified polyalkyl(meth)acrylate polymers
WO2023099634A1 (en) 2021-12-03 2023-06-08 Totalenergies Onetech Lubricant compositions
EP4441180A1 (en) 2021-12-03 2024-10-09 TotalEnergies OneTech Lubricant compositions
EP4441179A1 (en) 2021-12-03 2024-10-09 TotalEnergies OneTech Lubricant compositions
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JP6444430B2 (ja) 2018-12-26
MA39196A1 (fr) 2017-10-31
CA2937928A1 (fr) 2015-07-30
BR112016017393A2 (pt) 2018-02-06
MA39196B1 (fr) 2018-11-30
TR201905388T4 (tr) 2019-05-21
UA119160C2 (uk) 2019-05-10
WO2015110643A1 (fr) 2015-07-30
US10336960B2 (en) 2019-07-02
KR20170027693A (ko) 2017-03-10
CN106164114B (zh) 2018-10-12
KR102292997B1 (ko) 2021-08-26
FR3016887A1 (fr) 2015-07-31
CN106164114A (zh) 2016-11-23
US20170009176A1 (en) 2017-01-12
JP2017508055A (ja) 2017-03-23

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