EP3245276B1 - Zusammensetzungen aus thermoassoziativen additiven mit gesteuerter assoziation und schmiermittelzusammensetzungen damit - Google Patents

Zusammensetzungen aus thermoassoziativen additiven mit gesteuerter assoziation und schmiermittelzusammensetzungen damit Download PDF

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Publication number
EP3245276B1
EP3245276B1 EP16700342.5A EP16700342A EP3245276B1 EP 3245276 B1 EP3245276 B1 EP 3245276B1 EP 16700342 A EP16700342 A EP 16700342A EP 3245276 B1 EP3245276 B1 EP 3245276B1
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Prior art keywords
random copolymer
monomer
composition
formula
boronic ester
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English (en)
French (fr)
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EP3245276A1 (de
Inventor
Renaud Nicolay
Thi Hang Nga NGUYEN
Raphaele IOVINE
Gregory DESCROIX
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Centre National de la Recherche Scientifique CNRS
Ecole Superieure de Physique et Chimie Industrielles de Ville Paris
TotalEnergies Onetech SAS
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Centre National de la Recherche Scientifique CNRS
Ecole Superieure de Physique et Chimie Industrielles de Ville Paris
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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
    • 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
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • 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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/04—Hydroxy compounds
    • C10M129/06—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M129/08—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least 2 hydroxy groups
    • 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
    • C10M155/00—Lubricating compositions characterised by the additive being a macromolecular compound containing atoms of elements not provided for in groups C10M143/00 - C10M153/00
    • C10M155/04—Monomer containing boron
    • 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
    • C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
    • 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
    • C10M2203/003—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/022—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/024—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amido or imido group
    • 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
    • C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2221/02—Macromolecular compounds obtained by reactions of monomers involving only carbon-to-carbon unsaturated bonds
    • 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
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • 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
    • 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
    • C10N2070/00—Specific manufacturing methods for lubricant compositions
    • C10N2070/02—Concentrating of additives

Definitions

  • the present invention relates to novel additive compositions which result from the mixture of at least two thermoassociative and exchangeable copolymers and of at least one compound making it possible to control the association of these two copolymers.
  • the invention also relates to a lubricating composition which results from the mixture of at least one lubricating base oil, of at least two thermoassociative and exchangeable copolymers and of at least one compound making it possible to control the association of these two copolymers.
  • the present invention also relates to a process for modulating the viscosity of a lubricating composition which results from the mixture of at least one lubricating base oil, of at least two thermoassociative and exchangeable copolymers; as well as the use of a diol compound to modulate the viscosity of a lubricating composition.
  • Polymers of high molecular weight are widely used to increase the viscosity of solutions in many fields, such as petroleum, paper, water treatment, mining, cosmetics, textiles, and other industries. generally in all industrial techniques using thickened solutions.
  • these polymers of high molecular weight have the drawback of having a low resistance to permanent shear compared to the same polymers of smaller sizes. These shear stresses on polymers of high molecular weight lead to cleavages at the level of the macromolecular chains. The polymer thus degraded has reduced thickening properties, and the viscosity of the solutions containing it drops irreversibly. In addition, these polymers do not make it possible to modulate the thickening of the composition in which they are added as a function of the temperature of use of the composition.
  • the Applicant has set itself the objective of formulating new additive compositions which are more stable to shear compared to the compounds of the prior art and whose rheological behavior can be adapted as a function of the use of the composition in which these additives are added.
  • the associated (potentially crosslinked) and exchangeable copolymers have the advantage of being more stable to shear stresses. This characteristic results from the combined use of two particular compounds, a random copolymer bearing diol functions and a compound comprising at least two boronic ester functions.
  • aqueous fluid used in the exploitation of oil or gas deposits comprising at least one boronate polymer comprising at least one boronate or precursor function, and at least one ligand polymer having at least two groups capable of reacting with the one or more boronate or precursor functions.
  • the additive composition according to the invention has many advantages. It makes it possible to increase the viscosity of solutions, in particular of hydrophobic solutions, comprising them relative to the additive compositions of the prior art.
  • the additives of the composition of the invention have an inverse behavior with respect to a modification of the temperature with respect to the behavior of the solution and of the rheological additives of polymer type of the prior art. It also makes it possible to adapt the increase in viscosity and the rheological behavior of these solutions as a function of their temperature of use.
  • the Applicant has also set itself the objective of formulating new lubricating compositions which make it possible to reduce the friction between two mechanical parts during cold use and during hot use.
  • 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 when the temperature is varied.
  • the thickness of the protective film is proportional to the viscosity, and therefore also depends on the temperature.
  • a composition exhibits good lubricating properties if the thickness of the protective film remains substantially constant whatever the conditions and the duration of use of the lubricant.
  • polymers of high molecular weight have the drawback of having a low resistance to permanent shear compared to polymers of the same nature but of smaller sizes.
  • the lubricating compositions of the prior art comprising additives improving viscosity can exhibit poor lubricating properties during the starting phases of an engine.
  • the lubricating composition according to the invention makes it possible to overcome the aforementioned drawbacks thanks to the combined use of a mixture of two thermoassociative and exchangeable compounds (a copolymer bearing diol functions and a compound comprising boronic ester functions) and of a compound diol in a lubricating base oil.
  • a gel may form in the base oil.
  • the boronic ester bonds between the random polydiol copolymers and the compounds comprising them break; the composition loses its gelled character if necessary.
  • the Boronic ester functions of the compound comprising them react with the added diol compound. It is possible to modulate the kinetics and the temperature window for the formation of these associations, and therefore to modulate the rheological behavior of the lubricating composition as a function of the desired use.
  • compositions of the invention it is possible, thanks to the compositions of the invention to provide lubricating compositions which have good lubricating properties during the starting phases of an engine (cold phase) and good lubricating properties when the engine is operating at its temperature. service (hot phase).
  • the molar percentage of exogenous compound A4, in the additive composition, relative to the boronic ester functions of the statistical copolymer A2 ranges from 0.025 to 5000%, preferably ranges from 0.1% to 1000%, from even more preferably from 0.5% to 500%, even more preferably from 1% to 150%.
  • the random copolymer A1 results from the copolymerization of at least one monomer M1 with at least two monomers M2 having different R 3 groups.
  • the side chains of the random copolymer A1 have an average length ranging from 8 to 20 carbon atoms, preferably from 9 to 15 carbon atoms.
  • the random copolymer A1 has a molar percentage of monomer M1 of formula (I) in said copolymer ranging from 1 to 30%, preferably from 5 to 25%, more preferably ranging from 9 to 21%.
  • the chain formed by the linking of groups R 10 , M, X and (R 8 ) u with u equal to 0 or 1 of the monomer of general formula (IV) of the statistical copolymer A2 has a total number of carbon atoms ranging from 8 to 38, preferably 10 to 26.
  • the side chains of the random copolymer A2 have an average length greater than or equal to 8 carbon atoms, preferably ranging from 11 to 16 carbon atoms.
  • the random copolymer A2 has a molar percentage of monomer of formula (IV) in said copolymer ranging from 0.25 to 20%, preferably from 1 to 10%.
  • the substituents R 10 , R 11 and the value of the index (t) of the monomer of formula (IV) of the random copolymer A2 are identical respectively to the substituents R 14 , R 15 and to the value of the index w 3 , of the exogenous compound A4 of formula (VI).
  • At least one of the substituents R 10 , R 11 or the value of the index (t) of the monomer of formula (IV) of the random copolymer A2 is respectively different from the substituents R 14 , R 15 or the value of the index w 3 , of the exogenous compound A4 of formula (VI).
  • the mass ratio between the polydiol A1 random copolymer and the A2 random copolymer ranges from 0.005 to 200, preferably from 0.05 to 20, even more preferably from 0.1 to 10, even more preferably from 0.2 to 5.
  • the lubricating oil is chosen from oils from group I, group II, group III, group IV, group V of the API classification and one of their mixture.
  • the mass ratio between the random copolymer A1 and the random copolymer A2 ranges from 0.005 to 100, preferably from 0.05 to 20 and even more preferably from 0 , 1 to 10, even more preferably from 0.2 to 5.
  • the molar percentage of exogenous compound A4 relative to the boronic ester functions of the statistical copolymer A2 ranges from 0.05 to 5000%, preferably ranges from 0.1% to 1000%, so even more preferably from 0.5% to 500%, even more preferably from 1% to 150%.
  • the polydiol A1 random copolymer results from the copolymerization of at least one first monomer M1 carrying diol functions and at least one second monomer M2, with a chemical structure different from that of the monomer M1.
  • C 6 -C 18 aryl group substituted with an R ′ 3 group is understood to mean an aromatic hydrocarbon compound, preferably monocyclic, comprising from 6 to 18 carbon atoms of which at least one carbon atom of the aromatic ring is substituted. by a group R ' 3 .
  • R '" 2 is a C 2 -C 18 alkyl group
  • the hydrocarbon chain is a straight chain
  • 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-decycle 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 straight chain
  • the compound of general formula (I-c) is commercially available from the suppliers: Sigma-Aldrich® and Alfa Aesar®.
  • the monomers of formula (II), (II-A) and, (II-B) are well known to those skilled in the art. They are marketed by Sigma-Aldrich® and TCI®.
  • a source of free radicals is meant a chemical compound making it possible to generate 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 and suitable for polymerization processes, in particular controlled radical polymerization.
  • benzoyl peroxide tert-butyl peroxide, diazo compounds such as azobisisobutyronitrile, peroxygen compounds such as persulphates or hydrogen peroxide, systems redox such as the oxidation of Fe 2+ , persulphate / sodium-metabisulphite mixtures, or ascorbic acid / hydrogen peroxide or else compounds cleavable photochemically or by ionizing radiation, for example ultraviolet rays or by beta or gamma radiation.
  • diazo compounds such as azobisisobutyronitrile
  • peroxygen compounds such as persulphates or hydrogen peroxide
  • systems redox such as the oxidation of Fe 2+ , persulphate / sodium-metabisulphite mixtures, or ascorbic acid / hydrogen peroxide or else compounds cleavable photochemically or by ionizing radiation, for example ultraviolet rays or by beta or gamma radiation.
  • the polymerization step (a) comprises bringing at least one M1 monomer into contact with at least two M2 monomers having different groups.
  • one of the monomers M2 has the general formula (II-A) as defined above and the other monomer M2 has the general formula (II-B) as defined above.
  • the polydiol A1 random copolymers are comb copolymers.
  • comb copolymers is meant a copolymer having a main chain (also called backbone) and side chains.
  • the side chains are dangling on either side 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.
  • the A1 copolymers have a backbone of polymerizable functions, in particular a backbone of methacrylate functions or of styrene functions, and a mixture of hydrocarbon side chains substituted or not by diol functions.
  • Polydiol A1 random copolymers have the advantage of being sensitive to external stimuli, such as temperature, pressure, shear rate; this sensitivity resulting in a change in properties.
  • external stimuli such as temperature, pressure, shear rate
  • the conformation in space of the copolymer chains is modified and the diol functions are made more or less accessible to association reactions, which can generate crosslinking, as well as to exchange reactions. These processes of association and exchange are reversible.
  • the random copolymer A1 is a thermosensitive copolymer, that is to say it is sensitive to changes in temperature.
  • the side chains of the polydiol A1 random copolymer 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 length of the side chains of each monomer constituting the copolymer.
  • Those skilled in the art know how to obtain this average length by appropriately selecting the types and the ratio of monomers constituting the polydiol random copolymer.
  • the choice of this average chain length makes it possible to obtain a polymer which is soluble in a hydrophobic medium, whatever the temperature at which the copolymer is dissolved.
  • the polydiol A1 random copolymer is therefore miscible in a hydrophobic medium.
  • hydrophobic medium is meant a medium which does not have or has a very low affinity for water, that is to say that it is not miscible in water or in an aqueous medium.
  • the polydiol A1 random copolymer has a molar percentage of M1 monomer of formula (I) in said copolymer ranging from 1 to 30%, preferably 5 to 25%, more preferably ranging from 9 to 21%.
  • the polydiol A1 random copolymer has a molar percentage of M1 monomer 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 M2 monomer of formula (II-A) in said copolymer ranging from 8 to 92% and a molar percentage of M2 monomer of formula (II-B) 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 polydiol A1 random copolymer 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 monomer M2 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 A1 random copolymer has a number-average degree of 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 free radical source when the copolymers of the invention are prepared by conventional radical polymerization.
  • the polydiol A1 random copolymer has a polydispersity index (Ip) ranging from 1.05 to 3.75; preferably ranging from 1.10 to 3.45.
  • the polydispersity index is obtained by measurement of size exclusion chromatography using a polystyrene calibration.
  • the polydiol A1 random copolymer has a number-average molar mass ranging from 10,000 to 400,000 g / mol, preferably from 25,000 to 150,000 g / mol, the number-average molar mass being obtained by measurement of chromatography d steric exclusion using polystyrene calibration.
  • hydrocarbon-based group having from 1 to 24 carbon atoms is understood to mean an alkyl or alkenyl group, linear or branched, having from 1 to 24 carbon atoms.
  • group hydrocarbon comprises 4 to 18 carbon atoms, preferably 6 to 14 carbon atoms.
  • the hydrocarbon group is linear alkyl.
  • C 2 -C 24 hydrocarbon-based chain means an alkyl or alkenyl group, linear or branched, 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 compound A2 boronic diester 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 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 shift the chemical equilibria between the boronic acid molecules of formula (III-a) and the boroxine molecules obtained from the boronic acids of formula (III-a).
  • boronic acids can spontaneously form boroxine molecules at room temperature.
  • the presence of boroxine 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 which are 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 the same.
  • compound A2 comprising at least two boronic ester functions is a poly (boronic ester) random copolymer resulting from the copolymerization of at least one M3 monomer of formula (IV) as described below with at minus one M4 monomer of formula (V) as described below.
  • C 2 -C 24 alkyl means a saturated, linear or branched hydrocarbon chain 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 from 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 from 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 between 6 and 12 carbon atoms.
  • C 1 -C 25 alkyl group means a saturated, linear or branched hydrocarbon chain comprising from 1 to 25 carbon atoms. Preferably, the hydrocarbon chain is linear.
  • C 6 -C 18 aryl group substituted with an R 13 group is understood to mean an aromatic hydrocarbon compound comprising from 6 to 18 carbon atoms of which at least one carbon atom of the aromatic ring is substituted by a C alkyl group. 1 -C 25 as defined above.
  • the sources of radicals and the transfer agents are those which have been described for the synthesis of random polydiol copolymers.
  • the preferences described for radical sources and transfer agents also apply to this process.
  • the exogenous compound A4 has a chemical structure identical to the diol compound A3 released in situ by a transesterification reaction.
  • the substituents R 14 , R 15 and the value of the index w 3 of the exogenous compound A4 of formula (VI) is identical respectively to the substituents R 4 and R 5 and to the value of the index w 1 or to R 5 and R 7 and to the value of the index w 2 of the boronic diester compound A2 of formula (III) or is identical respectively to the substituents R 10 , R 11 and to the value of the index t of the monomer (IV) of the poly (boronic ester) random copolymer A2.
  • the composition of additives resulting from the mixture of at least one polydiol A1 random copolymer, of at least one A2 compound, in particular an A2 random copolymer, comprising at least two boronic ester functions and which may s' associate with said polydiol A1 random copolymer by a transesterification reaction, and an addition of at least one exogenous compound A4 as defined above may further comprise a compound A3 diol released in situ, identical to the exogenous compound A4 added in the composition.
  • the term “diol released in situ” means the compound carrying a diol function, this compound being produced in the additive composition during the exchange of the hydrocarbon groups of the boronic ester compound A2, in particular of the random poly (boronic ester) copolymer, during the transesterification reaction.
  • the random polymer A1 polydiol is not a diol released in situ within the meaning of the present invention.
  • compositions of the invention resulting from the mixture of at least one polydiol A1 random copolymer as defined above, of at least one A2 compound as defined above, in particular of at least one poly ( boronic ester) as defined above, and at least one exogenous compound A4 as defined above exhibit very varied rheological properties as a function of the temperature and according to the proportion of compounds A1, A2 and A4 used.
  • association is understood to mean that covalent chemical bonds of the boronic ester type are established between the polydiol A1 random copolymers and the A2 compounds comprising at least two boronic ester functions, in particular with the poly (boronic ester) random copolymer.
  • the formation of covalent bonds between the A1 polydiols and the A2 compounds may or may not lead to the formation of a three-dimensional polymer network.
  • the polydiol A1-1 random copolymer which was associated with the A2-1 polymer, exchanged a boronic ester bond with the A2-2 boronic ester random copolymer.
  • the polydiol A1-2 random copolymer which was associated with the A2-2 polymer, exchanged a boronic ester bond with the A2-1 boronic ester random copolymer; the total number of boronic ester bonds in the composition being unchanged and is equal to 4.
  • the copolymer A1-1 is then combined both with the polymer A2-1 and with the copolymer A2-2.
  • the A1-2 copolymer is then combined both with the A2-1 copolymer and with the A2-2 copolymer.
  • the reversible chemical reaction is a transesterification reaction between diol functions of a random copolymer (copolymer A1) and boronic ester functions of a crosslinking agent (compound A2).
  • the bridges formed are bonds of the boronic ester type. These boronic ester bonds are covalent and labile due to the reversibility of the transesterification reaction.
  • thermosibly crosslinked means a copolymer crosslinked by virtue of a reversible reaction, the movement of which in one direction or the other direction is controlled by temperature.
  • the boronic ester bonds between the polydiol random copolymers A1 and the compounds A2 break, and where appropriate, the composition loses its gelled character.
  • the compounds A2, in particular the poly (boronic ester) random copolymer then establish boronic ester bonds by transesterification reaction with the exogenous compound A4 or with the diol compound A3 released in situ.
  • the viscosity and the rheological behavior of this composition are modulated.
  • the exogenous compound A4 makes it possible to modulate the viscosity of this composition as a function of the temperature and according to the desired use.
  • boronic ester bonds (or boronic ester bonds) which can be established between the polydiol A1 random copolymers and the A2 compounds, in particular the poly (boronic ester) random copolymers, is adjusted by a person skilled in the art by means of a appropriate selection of polydiol A1 random copolymer, A2 compound and mixture composition.
  • the structure of compound A2 in particular of a poly (boronic ester) random copolymer, as a function of the structure of the A1 random copolymer.
  • the content of random copolymer A1 in the composition ranges from 0.1% to 99.5% by weight relative to the total weight of the additive composition, preferably ranges from 0.25% to 80% by weight per relative to the total weight of the additive composition, more preferably from 1% to 50% by weight relative to the total weight of the additive composition.
  • the content of compound A2, in particular of poly (boronic ester) random copolymer, in the composition ranges from 0.1% to 99.5% by weight relative to the total weight of the additive composition, preferably ranges from 0.25% to 80% by weight relative to the total weight of the additive composition, more preferably from 0.5% to 50% by weight relative to the total weight of the additive composition.
  • the molar percentage of exogenous compound A4 in the additive composition ranges from 0.025% to 5000%, preferably ranges from 0.1% to 1000%, more preferably from 0.5 to 500%, even more preferably from 1% to 150% relative to the boronic ester functions of compound A2, in particular of the poly (boronic ester) random copolymer.
  • the molar percentage of exogenous compound A4 relative to the number of boronic ester functions of compound A2 is the ratio of the number of moles of exogenous compound A4 to the number of moles of boronic ester function of compound A2, the whole multiplied by one hundred.
  • the number of moles of boronic ester function of compound A2 can be determined by a person skilled in the art by proton NMR analysis of compound A2, or by following the conversion into monomers during the synthesis of copolymer A2, when compound A2 is a poly (boronic ester) random copolymer.
  • the mass ratio (ratio A1 / A2) between the polydiol statistical compound A1 and the compound A2, in particular the poly (boronic ester) random copolymer, in the additive composition ranges from 0.005 to 200, preferably from 0.05 to 20 , even more preferably from 0.1 to 10, even more preferably from 0.2 to 5.
  • the composition of the invention may further comprise at least one additive chosen from the group formed by thermoplastics, elastomers, thermoplastic elastomers, thermosetting polymers, pigments, dyes, fillers, plasticizers, fibers, antioxidants, lubricant additives, compatibilizers, anti-foaming agents, dispersant additives, adhesion promoters and stabilizers.
  • at least one additive chosen from the group formed by thermoplastics, elastomers, thermoplastic elastomers, thermosetting polymers, pigments, dyes, fillers, plasticizers, fibers, antioxidants, lubricant additives, compatibilizers, anti-foaming agents, dispersant additives, adhesion promoters and stabilizers.
  • compositions of the invention can be used in all media whose viscosity varies as a function of temperature.
  • the compositions of the invention make it possible to thicken a fluid and to modulate the viscosity as a function of the temperature of use.
  • the additive composition according to the invention can be used in fields as varied as improved oil recovery, the paper industry, paints, food additives, cosmetic or pharmaceutical formulation.
  • the lubricating compositions according to the invention have an inverted behavior with respect to a modification of the temperature compared to the behavior of the base oil and of the rheological additives of polymer type of the prior art and have the advantage that this rheological behavior can be modulated as a function of the temperature of use.
  • the compositions of the present invention have the advantage of thickening when the temperature increases.
  • the formation of reversible covalent bonds makes it possible to (reversibly) increase the molar mass of the polymers and therefore limits the drop in the viscosity of the base oil at high temperatures.
  • the additional addition of diol compounds makes it possible to control the rate of formation of these reversible bonds.
  • the viscosity of the lubricating composition is thus controlled and depends less on temperature fluctuations.
  • oil is understood to mean a fatty substance that is liquid at ambient temperature (25 ° C.) and atmospheric pressure (760 mmm of Hg evening 105 Pa).
  • Lubricating oil is meant an oil which attenuates the friction between two moving parts in order to facilitate the operation of these parts.
  • Lubricating oils can be of natural, mineral or synthetic origin.
  • the lubricating oils of natural origin can be oils of vegetable or animal origin, preferably oils of vegetable origin such as rapeseed oil, sunflower oil, palm oil, olive oil. copra ...
  • Lubricating oils of mineral origin are of petroleum origin and are extracted from petroleum cuts resulting from the atmospheric and vacuum distillation of crude oil. Distillation can be followed by refining operations such as solvent extraction, dealphating, solvent dewaxing, hydrotreatment, hydrocracking, hydroisomerization, hydrofinishing, etc. cite paraffinic mineral base oils such as Bright Stock Solvent (BSS) oil, naphthenic mineral base oils, aromatic mineral oils, hydrorefined mineral bases with a viscosity index of approximately 100, mineral bases hydrocracked with a viscosity index between 120 and 130, hydroisomerized mineral bases with a viscosity index between 140 and 150.
  • BSS Bright Stock Solvent
  • the lubricating oils which can be used in the composition of the invention can be chosen from any of the oils of groups I to V specified in the guidelines of the API (Base Oil Interchangeability Guidelines of the American Petroleum Institute (API). ) (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 hydroisomerized oils ⁇ 90% ⁇ 0.03% ⁇ 120 Group IV (PAO) Polyalphaolefins Group V Esters and other bases not included in groups I to IV bases * measured according to ASTM D2007 ** measured according to ASTM D2622, ASTM D4294, ASTM D4927 and ASTM D3120 standards *** measured according to ASTM D2270
  • compositions of the invention can comprise one or more lubricating oils.
  • the lubricating oil or the lubricating oil mixture is the major ingredient in the lubricating composition. This is referred to as a lubricating base oil.
  • major ingredient is meant that the lubricating oil or the mixture of lubricating oils represents at least 51% by weight relative to the total weight of the composition.
  • the lubricating oil or the mixture of lubricating oils represents at least 70% by weight relative to the total weight of the composition.
  • the lubricating oil is selected from the group formed by 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 formed by oils of group III, of group IV, of group V of the API classification and their mixture.
  • the lubricating oil is an oil of group III of the API classification.
  • the lubricating oil has a kinematic viscosity at 100 ° C measured according to the ASTM D445 standard ranging from 2 to 150 cSt, preferably ranging from 5 to 15 cSt.
  • the lubricating oils can range from grade SAE 15 to grade SAE 250, and preferably from grade SAE 20W to grade SAE 50 (SAE stands for Society of Automotive Engineers
  • composition of the invention may further comprise a functional additive chosen from the group formed by detergents, anti-wear additives, extreme pressure additives, antioxidants, polymers improving the viscosity index. , pour point improvers, defoamers, thickeners, anti-corrosion additives, dispersants, friction modifiers and mixtures thereof.
  • the functional additive or the mixtures of functional additives, when they are present, represent from 0.1 to 10% by weight relative to the total weight of the composition.
  • antiwear and extreme pressure additives there is a wide variety of antiwear and extreme pressure additives.
  • phosphosulfur additives such as metal alkylthiophosphates, in particular zinc alkylthiophosphates, and more specifically zinc dialkyldithiophosphates or ZnDTP, amine phosphates, polysulphides, in particular sulfur olefins and metal dithiocarbamates.
  • antioxidants act as free radical inhibitors or destroyers of hydroperoxides.
  • antioxidants commonly used are antioxidants of the phenolic or amine type.
  • additives cover the surface with a film which prevents the access of oxygen to the surface of the metal. They can sometimes neutralize acids or certain chemicals to prevent corrosion of the metal.
  • DMTD dimercaptothiadiazole
  • benzotriazoles benzotriazoles
  • phosphites capture of free sulfur
  • additives make it possible to guarantee good resistance to cold and a minimum viscosity at high temperature of the composition.
  • OCP olefin copolymers
  • PMA polymethacrylates
  • additives improve the cold behavior of the compositions, by slowing the formation of paraffin crystals.
  • These additives are, for example, polymethacrylates of alkyl, polyacrylates, polyarylamides, polyalkylphenols, polyalkylnaphthalenes and alkylated polystyrenes.
  • Thickeners are additives used above all for industrial lubrication and make it possible to formulate lubricants of higher viscosity than lubricating compositions for engines.
  • polysiobutenes having a molar mass by weight of 10,000 to 100,000 g / mol.
  • additives improve the coefficient of friction of the composition.
  • molybdenum dithiocarbamate amines having at least one hydrocarbon chain of at least 16 carbon atoms, esters of fatty acids and of polyols such as esters of fatty acids and of glycerol, in particular glycerol monooleate.
  • the quantity of boronic ester bonds (or boronic ester bond) which can be established between the polydiol random copolymers A1 and the compounds A2, in particular the boronic ester statistical copolymer A2, is adjusted by a person skilled in the art by means of an appropriate selection.
  • the polydiol A1 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) and at least one monomer of formula (II-B), of the compound A2, in particular the boronic ester random copolymer A2, of the exogenous compound A4, and in particular of the molar percentage of exogenous compound A4.
  • 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) and at least one monomer of formula (II-B) in the lubricating composition ranges from 0.25% to 20% by weight relative to the total weight of the lubricating composition, preferably from 1% to 10% by weight relative to the total weight of the lubricating composition.
  • the molar percentage of exogenous compound A4 in the lubricating composition ranges from 0.05% to 5000%, preferably ranges from 0.1% to 1000%, more preferably from 0.5% to 500. %, even more preferably from 1% to 150% relative to the boronic ester functions of compound A2, in particular of the poly (boronic ester) random copolymer.
  • the term “modulating the viscosity of a lubricating composition” means an adaptation of the viscosity at a given temperature as a function of the use of the lubricating composition. This is obtained by adding an exogenous compound A4 as defined above. This compound makes it possible to control the rate of association and crosslinking of the two copolymers, polydiol A1 and poly (boronic ester) A2.
  • the definitions and preferences relating to lubricating oils, to random copolymers 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) and at least one monomer of formula (II-B), to the boronic ester random copolymer A2 and to the exogenous compound A4 also apply to the compositions for lubricating at least one engine.
  • the composition for lubricating at least one transmission further comprises at least one functional additive chosen from the group formed by detergents, anti-wear additives, extreme pressure additives, additional antioxidants, anti-corrosion additives, polymers improving the viscosity index, pour point improvers, antifoams, thickeners, dispersants, friction modifiers and mixtures thereof.
  • the definitions and preferences relating to lubricating oils, to random copolymers 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) and at least one monomer of formula (II-B), to the boronic ester random copolymer A2 and to the exogenous compound A4 also apply to the method of lubricating at least one mechanical part .
  • the random copolymer A1 of the invention is obtained according to the following reaction scheme:
  • 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 carrier d '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 100 mL Schlenk tube.
  • the deprotection of the copolymer is carried out according to the following protocol: 7.02 g of copolymer containing approximately 20% of protected diol function obtained previously are introduced into a 500 mL Erlenmeyer flask. 180 mL of dioxane are added and the reaction medium is placed under stirring at 30 ° C. 3 mL of a 1M aqueous hydrochloric acid solution and then 2.5 mL of a 35% mass hydrochloric acid aqueous solution 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 under stirring at 40 ° C. for 48 hours. The copolymer is recovered by precipitation in methanol, filtration and drying under vacuum at 30 ° C. overnight.
  • reaction medium After 3 hours with stirring at room temperature, the reaction medium is filtered. The solvent is then removed from the filtrate by means of a rotary evaporator to give 10.2 g of a mixture of boronic ester monomer and 1,2-dodecanediol in the form of a light yellow solid.
  • the reaction medium is then degassed for 30 minutes by bubbling argon before being brought to 65 ° C. for a period 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 molar mass ( 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 a polystyrene calibration and by monitoring the conversion into monomers during the copolymerization. Proton NMR analysis of the final copolymer gives a composition of 4 mol% of boronic ester monomer and 96% of lauryl methacrylate.
  • compositions A to H Ingredients for the formulation of compositions A to H
  • This copolymer comprises 20 mol% of monomers having diol functions.
  • the average side chain length is 13.8 carbon atoms.
  • Its number average molar mass is 51,400 g / mol.
  • Its polydispersity index is 1.20.
  • Its number-average degree of polymerization (DPn) is 184.
  • the number-average molar mass and the polydispersity index are measured by size exclusion chromatography measurement using a polystyrene calibration. This copolymer is obtained by following the implementation of the protocol described in paragraph 1 above.
  • This copolymer comprises 4 mol% of monomers having boronic ester functions.
  • the average side chain length is greater than 12 carbon atoms.
  • Its number average molar mass is 37,200 g / mol.
  • Its polydispersity index is 1.24.
  • Its number-average degree of polymerization (DPn) is 166. Its number-average molar mass and the polydispersity index are measured by measurement of size exclusion chromatography using a polystyrene calibration. This copolymer is obtained by implementing the protocol described in paragraph 2 above.
  • 1,2-Docecanediol comes from the supplier TCI®.
  • composition A (comparative) is obtained as follows :
  • the polymer contains a 4.2% by mass solution of a polymethacrylate polymer in a lubricating base oil of group III of the API classification.
  • the polymer has a number-average molar mass (Mn) equal to 106 00 g / mol, a polydispersity index (Ip) equal to 3.06, a number-average degree of polymerization of 466 and the average length of the pendant chains is 14 carbon atoms.
  • This polymethacrylate is used as an additive improving the viscosity index.
  • This composition is used as a reference for the study of viscosity. It represents the rheological behavior of the lubricating compositions marketed.
  • composition B (comparative) is obtained as follows :
  • composition C (comparative) is obtained as follows :
  • Composition D (according to the invention) is obtained as follows:
  • composition C prepared above 7.95 g of composition C prepared above are introduced into a flask. 19.2 mg of a solution at 5% by mass of 1,2-dodecanediol (compound A-4) in a group III base oil are added to this solution. The solution thus obtained is kept under stirring at 90 ° C. for two hours.
  • Composition E (according to the invention) is obtained as follows:
  • composition C prepared above 4.04 g of composition C prepared above are introduced into a flask. 97.6 mg of a solution at 5% by mass of 1,2-dodecanediol (compound A-4) in a group III base oil are added to this solution. The solution thus obtained is kept under stirring at 90 ° C. for two o'clock.
  • composition F (comparative) is obtained as follows :
  • composition G (comparative) is obtained as follows :
  • Composition H (according to the invention) is obtained as follows :
  • compositions A to F In the case of the polymer formulations which do not form gels in a base oil of group III over the temperature range of the study (compositions A to F), the rheology measurements were carried out using a cylindrical geometry of reference DG 26.7 The viscosity was measured as a function of the shear rate for a temperature range varying from 10 ° C to 110 ° C. For each temperature, the viscosity of the system was measured as a function of the speed shear rate from 0.01 to 1000 s -1 .
  • the viscosity measurements as a function of the shear rate at T 10 ° C, 20 ° C, 30 ° C, 50 ° C, 70 ° C, 90 ° C and 110 ° C were carried out (ranging from 10 ° C at 110 ° C) followed by further measurements at 10 ° C and / or 20 ° C in order to assess the reversibility of the systems. An average viscosity was then calculated for each temperature using the measurement points located on the same plate.
  • the elastic modulus and the viscous modulus were measured as a function of the temperature for a temperature range varying from 10 ° C to 110 ° C.
  • the heating (and cooling) rate was set 0.003 ° C / s, the angular frequency was chosen at 1 rad / s with the strain rate of 1%.
  • compositions A to F The viscosity of compositions A to F was studied for a temperature range from 10 ° to 110 ° C. The relative viscosity of these compositions is illustrated in figures 5 and 6 .
  • the polydiol A-1 random copolymer, alone in composition B, does not allow compensation for the loss of natural viscosity of the group III base oil.
  • the same is true for the poly (boronic ester) copolymer A-2 when this copolymer is used alone in composition F.
  • composition C When the polydiol random copolymer A-1 and the poly (boronic ester) copolymer A-2 are present together in the same lubricating composition (composition C), a compensation is observed for the loss of natural viscosity of the base oil of group III greater than that resulting from the addition of the polymethacylate polymer in the group III base oil (composition A).
  • composition C further comprises 10 mol% of 1,2-dodecanediol free (compound A-4) relative to the boronic ester functions of the poly (boronic ester) copolymer A-2 (composition D); a slight decrease in the relative viscosity is observed at low temperatures (temperatures below 45 ° C) while the compensation for the loss of hot viscosity is slightly greater than that of composition C which comprises the polydiol random copolymer A-1 and the poly (boronic ester) copolymer A-2.
  • composition C further comprises 100 mol% of free 1,2-dodecanediol (compound A-4) relative to the boronic ester functions of the poly (boronic ester) copolymer A-2 (composition E), it is observed a decrease in the relative viscosity at low temperatures (temperatures below 45 ° C).
  • composition resulting from the blend of polydiols A-1 random copolymer, A-2 poly (boronic ester) copolymer and 1,2-dodecanediol (compound A-4) compensates for the loss of viscosity of the oil base of group III in a manner comparable to that obtained with the polymethacrylate polymer in the base oil of group III (composition A).
  • composition E in the presence of 1,2-dodecanediol, the cold properties of composition E have been improved compared to those of composition C. In addition, composition E still retains the property of compensating for the loss of viscosity of the Group III base oil for high temperatures. 1,2-Dodecanediol therefore makes it possible to modify, as a function of temperature, the viscosity of a lubricating composition resulting from the mixture of at least one polydiol A-1 random copolymer and at least one A-2 poly (ester boronic) by controlling the rate of association of the chains of these two copolymers.
  • compositions G and H were studied as a function of temperature (hysteresis curve in FIGS. 7 and 8). These two compositions result from the mixture in a base oil of group III of the polydiol random copolymer A-1 and of the random copolymer A-2 poly (boronic ester).
  • Composition H further comprises 1,2-dodecanediol (compound A-4).
  • curves G ′ and G ′′ illustrates the change in state of the compositions, that is to say the passage from a liquid state to a gelled state when the temperature increases and the passage from a gelled state to a liquid state when the temperature decreases.
  • composition G For composition G (FIG. 7), it is observed that the temperature at which the composition changes from a liquid state to a gelled state is carried out between 95 ° C. and 100 ° C. At this temperature, the chains of copolymers A-1 and A-2 associate, exchange and form a three-dimensional crosslinked network. When the temperature is reduced, a new change of state is observed for a temperature between 65 ° and 70 ° C. The composition changes from a gelled state to a liquid state where the copolymer chains no longer associate with each other.
  • composition H (FIG. 8), a shift in the value of the temperature at which the composition changes state is observed. Indeed, composition H gels for a temperature between 105 and 110 ° C and passes to a liquid state for a temperature between 70 ° C and 75 ° C. 1,2 dodecanediol (compound A-4) makes it possible to modulate the rheological behavior of composition H.

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Claims (16)

  1. Additivzusammensetzung, die aus dem Mischen von mindestens Folgendem resultiert:
    - einem statistischen Polydiol-Copolymer A1;
    - einem statistischen Copolymer A2, das mindestens zwei Boronsäureesterfunktionen umfasst und mit dem statistischen Polydiol-Copolymer A1 durch mindestens eine Umesterungsreaktion assoziieren kann,
    - eine exogene Verbindung A4, die aus 1,2-Diolen und 1,3-Diolen ausgewählt ist,
    wobei das Massenverhältnis zwischen dem statistischen Polydiol-Copolymer A1 und dem statistischen Copolymer A2 (Verhältnis A1/A2) im Bereich von 0,005 bis 200 liegt, wobei der Molprozentanteil von exogener Verbindung A4, bezogen auf die Boronsäureesterfunktionen des statistischen Copolymers A2, im Bereich von 0,025 bis 5000 % liegt,
    wobei das statistische Copolymer A1 aus der Copolymerisation von Folgendem resultiert:
    ▪ mindestens einem ersten Monomer M1 der allgemeinen Formel (I):
    Figure imgb0062
     in der:
    - R1 aus der aus -H, -CH3 und -CH2-CH3 gebildeten Gruppe ausgewählt ist;
    - x eine ganze Zahl im Bereich von 1 bis 18, vorzugsweise von 2 bis 18, ist;
    - y eine ganze Zahl mit einem Wert von 0 oder 1 ist;
    - X1 und X2 gleich oder verschieden sind und aus der aus Wasserstoff, Tetrahydropyranyl, Methyloxymethyl, tert-Butyl, Benzyl, Trimethylsilyl und t-Butyldimethylsilyl gebildeten Gruppe ausgewählt sind;
    oder auch
    - X1 und X2 mit den Sauerstoffatomen eine Brücke der folgenden Formel bilden:
    Figure imgb0063
     in der:
    - die Sterne (*) die Bindungen an die Sauerstoffatome symbolisieren,
    - R'2 und R"2 gleich oder verschieden sind und aus der aus Wasserstoff und einem C1-C11-Alkyl, vorzugsweise Methyl, gebildeten Gruppe ausgewählt sind;
    oder auch
    - X1 und X2 mit den Sauerstoffatomen einen Boronsäureester der folgenden Formel bilden:
    Figure imgb0064
     in der:
    - die Sterne (*) die Bindungen an die Sauerstoffatome symbolisieren,
    - R'"2 aus der aus einem C6-C18-Aryl, einem C7-C18-Aralkyl und einem C2-C18-Alkyl, vorzugsweise einem C6-C18-Aryl, gebildeten Gruppe ausgewählt sind;
    ▪ mit mindestens einem zweiten Monomer M2 der allgemeinen Formel (II):
    Figure imgb0065
     in der:
    - R2 aus der aus -H, -CH3 und -CH2-CH3 gebildeten Gruppe ausgewählt ist;
    - R3 aus der aus einem C6-C18-Aryl, einem C6-C18-Aryl, das durch eine Gruppe R'3, -C(O)-O-R'3, -O-R'3, -S-R'3 und -C(O)-N(H)-R'3 bestehenden Gruppe ausgewählt ist, wobei R'3 eine C1-C30-Alkylgruppe ist,
    wobei der Molprozentanteil von Monomer M1 der Formel (I) in dem statistischen Copolymer A1 im Bereich von 1 bis 30 % liegt und der Molprozentanteil von Monomeren mit Boronsäureesterfunktionen in dem statistischen Copolymer A2 im Bereich von 0,25 bis 20 % liegt.
  2. Additivzusammensetzung nach Anspruch 1, wobei das statistische Copolymer A1 aus der Copolymerisation von mindestens einem Monomer M1 mit mindestens zwei Monomeren M2 mit verschiedenen Gruppen R3 resultiert.
  3. Additivzusammensetzung nach Anspruch 2, wobei eines der Monomere M2 des statistischen Copolymers A1 die allgemeine Formel (II-A) aufweist:
    Figure imgb0066
     in der:
    - R2 aus der aus -H, -CH3 und -CH2-CH3 gebildeten Gruppe ausgewählt ist;
    - R"3 eine C1-C14-Alkylgruppe ist,
    und das andere Monomer M2 des statistischen Copolymers A1 die allgemeine Formel (II-B) aufweist:
    Figure imgb0067
     in der:
    - R2 aus der aus -H, -CH3 und -CH2-CH3 gebildeten Gruppe ausgewählt ist;
    - R"3 eine C15-C30-Alkylgruppe ist.
  4. Additivzusammensetzung nach einem der Ansprüche 1 bis 3, wobei das statistische Copolymer A1 einen Molprozentanteil von Monomer M1 der Formel (I) in dem Copolymer im Bereich von 5 bis 25 %, bevorzugt im Bereich von 9 bis 21 %, aufweist.
  5. Additivzusammensetzung nach einem der Ansprüche 1 bis 4, wobei das statistische Copolymer A2 aus der Copolymerisation von Folgendem resultiert:
    ▪ mindestens einem Monomer M3 der Formel (IV):
    Figure imgb0068
     in der:
    - t eine ganze Zahl mit einem Wert von 0 oder 1 ist;
    - u eine ganze Zahl mit einem Wert von 0 oder 1 ist;
    - M und R8 gleich oder verschieden zweiwertige Verbindungsgruppen sind, die aus der aus einem C6-C18-Aryl, einem C7-C24-Aralkyl und einem C2-C24-Alkyl, vorzugsweise einem C6-C18-Aryl, gebildeten Gruppe ausgewählt sind,
    - X eine aus der aus -O-C(O)-, -C(O)-O-, -C(O)-N(H)-, -N(H)-C(O)-, -S-, - N(H)-, -N(R')4 und -O- gebildeten Gruppe ausgewählte Funktion ist, wobei R'4 eine Kohlenwasserstoffkette mit 1 bis 15 Kohlenstoffatomen ist;
    - R9 aus der aus -H, -CH3 und -CH2-CH3 gebildeten Gruppe ausgewählt ist;
    - R10 und R11 gleich oder verschieden sind und aus der aus Wasserstoff und einer Kohlenwasserstoffgruppe mit 1 bis 24 Kohlenstoffatomen, vorzugsweise zwischen 4 und 18 Kohlenstoffatomen, vorzugsweise zwischen 6 und 14 Kohlenstoffatomen, gebildeten Gruppe ausgewählt ist;
    und wobei die durch die Verknüpfung der Gruppen R10, M, X und (R8)u mit u gleich 0 oder 1 des Monomers der allgemeinen Formel (IV) des statistischen Copolymers A2 gebildete Kette eine Gesamtzahl von Kohlenstoffatomen im Bereich von 8 bis 38, vorzugsweise von 10 bis 26, aufweist,
    ▪ mit mindestens einem zweiten Monomer M4 der allgemeinen Formel (V):
    Figure imgb0069
     in der:
    - R12 aus der aus -H, -CH3 und -CH2-CH3 gebildeten Gruppe ausgewählt ist;
    - R13 aus der aus einem C6-C18-Aryl, einem C6-C18-Aryl, das durch eine Gruppe R'13, -C(O)-O-R'13, -O-R'13, -S-R'13 und -C(O)-N(H)-R'13 bestehenden Gruppe ausgewählt ist, wobei R'13 eine C1-C25-Alkylgruppe ist.
  6. Additivzusammensetzung nach Anspruch 5, wobei das statistische Copolymer A2 einen Molprozentanteil von Monomer der Formel (IV) in dem Copolymer im Bereich von 1 bis 10 % aufweist.
  7. Additivzusammensetzung nach einem der Ansprüche 1 bis 6, wobei die exogene Verbindung A4 die folgende allgemeine Formel (VI) aufweist:
    Figure imgb0070
     wobei:
    w3 eine ganze Zahl mit einem Wert von 0 oder 1 ist;
    R14 und R15 gleich oder verschieden sind und aus der aus Wasserstoff und einer Kohlenwasserstoffgruppe mit 1 bis 24 Kohlenstoffatomen gebildeten Gruppe ausgewählt sind.
  8. Additivzusammensetzung nach Anspruch 7, wobei die Substituenten R10, R11 und der Wert des Indexes (t) des Monomers der Formel (IV) des statistischen Copolymers A2 mit den Substituenten R14, R15 bzw. dem Wert des Indexes w3 der exogenen Verbindung A4 der Formel (VI) identisch sind.
  9. Additivzusammensetzung nach Anspruch 7, wobei mindestens einer der Substituenten R10, R11 oder der Wert des Indexes (t) des Monomers der Formel (IV) des statistischen Copolymers A2 von den Substituenten R14, R15 bzw. dem Wert des Indexes w3 der exogenen Verbindung A4 der Formel (VI) verschieden ist.
  10. Additivzusammensetzung nach einem der Ansprüche 1 bis 9, wobei das Massenverhältnis zwischen dem statistischen Polydiol-Copolymer A1 und dem statistischen Copolymer A2 (Verhältnis A1/A2) 0,05 bis 20, bevorzugt 0,1 bis 10, noch weiter bevorzugt 0,2 bis 5, beträgt.
  11. Schmiermittelzusammensetzung, die aus dem Mischen von mindestens Folgendem resultiert:
    - einem Schmieröl und
    - einer Additivzusammensetzung gemäß einem der Ansprüche 1 bis 10.
  12. Schmiermittelzusammensetzung nach Anspruch 11, wobei das Massenverhältnis zwischen dem statistischen Copolymer A1 und dem statistischen Copolymer A2 (Verhältnis A1/A2) 0,005 bis 100, bevorzugt 0,05 bis 20, noch weiter bevorzugt 0,1 bis 10, noch weiter bevorzugt 0,2 bis 5 beträgt.
  13. Schmiermittelzusammensetzung nach Anspruch 11 oder Anspruch 12, wobei der Molprozentanteil von exogener Verbindung A4, bezogen auf die Boronsäureesterfunktionen des statistischen Copolymers A2, im Bereich von 0,05 bis 5000 %, bevorzugt von 0,1 % bis 1000 %, noch weiter bevorzugt von 0,5 % bis 500 %, noch weiter bevorzugt von 1 % bis 150 %, liegt.
  14. Schmiermittelzusammensetzung nach einem der Ansprüche 11 bis 13, die aus dem zusätzlichen Mischen mit einem funktionalen Additiv resultiert, welches aus der aus Detergentien, Verschleißschutzmitteln, Höchstdruckadditiven, zusätzlichen Antioxidantien, Polymeren, die den Viskositätsindex verbessern, Pour-Point-Verbesserern, Entschäumern, Korrosionsschutzadditiven, Verdickern, Dispergiermitteln, Reibungsmodifikatoren und Mischungen davon gebildeten Gruppe ausgewählt ist.
  15. Verfahren zur Modulierung der Viskosität einer Schmiermittelzusammensetzung, wobei das Verfahren mindestens Folgendes umfasst:
    - Bereitstellen einer Schmiermittelzusammensetzung, die aus dem Mischen von mindestens einem Schmieröl, mindestens einem statistischen Polydiol-Copolymer A1 und mindestens einem statistischen Copolymer A2, das mindestens zwei Boronsäuresterefunktionen umfasst und mit dem statistischen Polydiol-Copolymer A1 durch mindestens eine Umesterungsreaktion assoziieren kann, resultiert,
    - Zugeben mindestens einer exogenen Verbindung A4, die aus 1,2-Diolen und 1,3-Diolen ausgewählt ist,
    wobei das Massenverhältnis zwischen dem statistischen Polydiol-Copolymer A1 und dem statistischen Copolymer A2 (Verhältnis A1/A2) im Bereich von 0,005 bis 200 liegt, der Molprozentanteil von exogener Verbindung A4, bezogen auf die Boronsäureesterfunktionen des statistischen Copolymers A2, im Bereich von 0,025 bis 5000 % liegt und
    das statistische Copolymer A1 aus der Copolymerisation von Folgendem resultiert:
    ▪ mindestens einem ersten Monomer M1 der allgemeinen Formel (I):
    Figure imgb0071
     in der:
    - R1 aus der aus -H, -CH3 und -CH2-CH3 gebildeten Gruppe ausgewählt ist;
    - x eine ganze Zahl im Bereich von 1 bis 18, vorzugsweise von 2 bis 18, ist;
    - y eine ganze Zahl mit einem Wert von 0 oder 1 ist;
    - X1 und X2 gleich oder verschieden sind und aus der aus Wasserstoff, Tetrahydropyranyl, Methyloxymethyl, tert-Butyl, Benzyl, Trimethylsilyl und t-Butyldimethylsilyl gebildeten Gruppe ausgewählt sind;
    oder auch
    - X1 und X2 mit den Sauerstoffatomen eine Brücke der folgenden Formel bilden:
    Figure imgb0072
     in der:
    - die Sterne (*) die Bindungen an die Sauerstoffatome symbolisieren,
    - R'2 und R"2 gleich oder verschieden sind und aus der aus Wasserstoff und einem C1-C11-Alkyl, vorzugsweise Methyl, gebildeten Gruppe ausgewählt sind;
    oder auch
    - X1 und X2 mit den Sauerstoffatomen einen Boronsäureester der folgenden Formel bilden:
    Figure imgb0073
     in der:
    - die Sterne (*) die Bindungen an die Sauerstoffatome symbolisieren,
    - R'"2 aus der aus einem C6-C18-Aryl, einem C7-C18-Aralkyl und einem C2-C18-Alkyl, vorzugsweise einem C6-C18-Aryl, gebildeten Gruppe ausgewählt sind;
    ▪ mit mindestens einem zweiten Monomer M2 der allgemeinen Formel (II):
    Figure imgb0074
     in der:
    - R2 aus der aus -H, -CH3 und -CH2-CH3 gebildeten Gruppe ausgewählt ist;
    - R3 aus der aus einem C6-C18-Aryl, einem C6-C18-Aryl, das durch eine Gruppe R'3, -C(O)-O-R'3, -O-R'3, -S-R'3 und -C(O)-N(H)-R'3 bestehenden Gruppe ausgewählt ist, wobei R'3 eine C1-C30-Alkylgruppe ist,
    wobei der Molprozentanteil von Monomer M1 der Formel (I) in dem statistischen Copolymer A1 im Bereich von 1 bis 30 % liegt und der Molprozentanteil von Monomeren mit Boronsäureesterfunktionen in dem statistischen Copolymer A2 im Bereich von 0,25 bis 20 % liegt.
  16. Verwendung mindestens einer Verbindung, die aus 1,2-Diolen und 1,3-Diolen ausgewählt ist, zur Modulierung der Viskosität einer Schmiermittelzusammensetzung, wobei die Schmiermittelzusammensetzung aus dem Mischen von mindestens einem Schmieröl, mindestens einem statistischen Polydiol-Copolymer A1 und mindestens einem statistischen Copolymer A2, das mindestens zwei Boronsäuresterefunktionen umfasst und mit dem statistischen Polydiol-Copolymer A1 durch mindestens eine Umesterungsreaktion assoziieren kann, resultiert, wobei das Massenverhältnis zwischen dem statistischen Polydiol-Copolymer A1 und dem statistischen Copolymer A2 (Verhältnis A1/A2) im Bereich von 0,005 bis 200 liegt,
    wobei der Molprozentanteil der Verbindung, die aus aus 1,2-Diolen und 1,3-Diolen ausgewählt ist, bezogen auf die Boronsäureesterfunktionen des statistischen Copolymers A2, im Bereich von 0,025 bis 5000 % liegt und
    das statistische Copolymer A1 aus der Copolymerisation von Folgendem resultiert:
    ▪ mindestens einem ersten Monomer M1 der allgemeinen Formel (I):
    Figure imgb0075
     in der:
    - R1 aus der aus -H, -CH3 und -CH2-CH3 gebildeten Gruppe ausgewählt ist;
    - x eine ganze Zahl im Bereich von 1 bis 18, vorzugsweise von 2 bis 18, ist;
    - y eine ganze Zahl mit einem Wert von 0 oder 1 ist;
    - X1 und X2 gleich oder verschieden sind und aus der aus Wasserstoff, Tetrahydropyranyl, Methyloxymethyl, tert-Butyl, Benzyl, Trimethylsilyl und t-Butyldimethylsilyl gebildeten Gruppe ausgewählt sind;
    oder auch
    - X1 und X2 mit den Sauerstoffatomen eine Brücke der folgenden Formel bilden:
    Figure imgb0076
     in der:
    - die Sterne (*) die Bindungen an die Sauerstoffatome symbolisieren,
    - R'2 und R"2 gleich oder verschieden sind und aus der aus Wasserstoff und einem C1-C11-Alkyl, vorzugsweise Methyl, gebildeten Gruppe ausgewählt sind;
    oder auch
    - X1 und X2 mit den Sauerstoffatomen einen Boronsäureester der folgenden Formel bilden:
    Figure imgb0077
     in der:
    - die Sterne (*) die Bindungen an die Sauerstoffatome symbolisieren,
    - R'"2 aus der aus einem C6-C18-Aryl, einem C7-C18-Aralkyl und einem C2-C18-Alkyl, vorzugsweise einem C6-C18-Aryl, gebildeten Gruppe ausgewählt sind;
    ▪ mit mindestens einem zweiten Monomer M2 der allgemeinen Formel (II):
    Figure imgb0078
     in der:
    - R2 aus der aus -H, -CH3 und -CH2-CH3 gebildeten Gruppe ausgewählt ist;
    - R3 aus der aus einem C6-C18-Aryl, einem C6-C18-Aryl, das durch eine Gruppe R'3, -C(O)-O-R'3, -O-R'3, -S-R'3 und -C(O)-N(H)-R'3 substituiert ist, bestehenden Gruppe ausgewählt ist, wobei R'3 eine C1-C30-Alkylgruppe ist,
    wobei der Molprozentanteil von Monomer M1 der Formel (I) in dem statistischen Copolymer A1 im Bereich von 1 bis 30 % liegt und der Molprozentanteil von Monomeren mit Boronsäureesterfunktionen in dem statistischen Copolymer A2 im Bereich von 0,25 bis 20 % liegt.
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