EP3245276A1 - Zusammensetzungen aus thermoassoziativen additiven mit gesteuerter assoziation und schmiermittelzusammensetzungen damit - Google Patents

Zusammensetzungen aus thermoassoziativen additiven mit gesteuerter assoziation und schmiermittelzusammensetzungen damit

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Publication number
EP3245276A1
EP3245276A1 EP16700342.5A EP16700342A EP3245276A1 EP 3245276 A1 EP3245276 A1 EP 3245276A1 EP 16700342 A EP16700342 A EP 16700342A EP 3245276 A1 EP3245276 A1 EP 3245276A1
Authority
EP
European Patent Office
Prior art keywords
random copolymer
group
monomer
copolymer
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP16700342.5A
Other languages
English (en)
French (fr)
Other versions
EP3245276B1 (de
Inventor
Renaud Nicolay
Thi Hang Nga NGUYEN
Raphaele IOVINE
Gregory DESCROIX
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Centre National de la Recherche Scientifique CNRS
Ecole Superieure de Physique et Chimie Industrielles de Ville Paris
TotalEnergies Onetech SAS
Original Assignee
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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Publication of EP3245276A1 publication Critical patent/EP3245276A1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • 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
    • 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 at least one compound for controlling the combination of these two copolymers.
  • the invention also relates to a lubricant composition which results from the mixture of at least one lubricating base oil, at least two thermoassociative and exchangeable copolymers and at least one compound making it possible to control the combination of these two copolymers.
  • the present invention also relates to a method for modulating the viscosity of a lubricating composition which results from mixing at least one lubricating base oil with at least two thermoassociative and exchangeable copolymers; and the use of a diol compound for modulating the viscosity of a lubricating composition.
  • High molecular weight polymers are widely used to increase the viscosity of solutions in many fields, such as the petroleum, paper, water treatment, mining, cosmetics, textile and generally in all industrial techniques using thickened solutions.
  • these high molecular weight polymers have the disadvantage of having a low permanent shear strength compared to the same polymers of smaller sizes. These shear stresses on high molecular weight polymers result in cuts in the macromolecular chains. The polymer thus degraded has diminished 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 use temperature of the composition.
  • the Applicant has set itself the objective of formulating new additive compositions which are more stable in shear with respect 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.
  • thermoreversible associative and exchangeable additives and an agent which makes it possible to control the association and the dissociation of these additives.
  • 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 carrying diols functions and a compound having at least two boronic ester 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 with respect to the additive compositions of the prior art.
  • the additives of the composition of the invention have an inverted behavior vis-à-vis a temperature change with respect to the behavior of the solution and 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, 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.
  • a lubricating composition that is too viscous at the starting temperature can interfere with the movement of the moving parts and thus prevent the motor from rotating fast enough.
  • a lubricating composition must also be on the one hand sufficiently fluid to be able to reach the bearings quickly and prevent the wear thereof and on the other hand, sufficiently thick to ensure good protection of the engine when it reaches its operating temperature.
  • the viscosity-improving additives are polymers such as polyalpha-olefins, polymethylmethacrylates, 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.
  • high molecular weight polymers have the disadvantage of having a low permanent shear strength over polymers of the same nature but of smaller sizes.
  • they thicken the lubricant compositions whatever the operating temperature of the lubricating composition, and especially at low temperature.
  • Lubricating compositions of the prior art comprising viscosity improving additives may exhibit poor lubricating properties during engine start-up phases.
  • the lubricant composition according to the invention overcomes the aforementioned drawbacks by virtue of 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 a compound diol in a basic lubricating oil.
  • the Applicant has observed that the addition of a diol compound makes it possible to control the association between a copolymer carrying diol functions and a compound comprising boronic ester functions.
  • the polydiol copolymer is not or hardly associated with the compounds comprising boronic ester functions; the latter reacts with the added diol compound.
  • 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 polydiols random 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 of formation of these associations, thus to modulate the rheological behavior of the lubricant composition as a function of the desired use. It is possible, by virtue of the compositions of the invention, to provide lubricating compositions which have good lubricating properties during the engine starting phases (cold phase) and good lubricating properties when the engine is operating at its temperature. service (hot phase).
  • the subject of the invention is an additive composition resulting from the mixture of at least:
  • a random copolymer A2 comprising at least two boronic ester functional groups and capable of associating with said polydiol Al random copolymer by at least one transesterification reaction
  • an exogenous compound A4 chosen from 1,2-diols and 1,3-diols.
  • the molar percentage of exogenous compound A4 in the additive composition relative to the boronic ester functions of the random copolymer A2 is from 0.025 to 5000%, preferably from 0.1% to 1000%), more preferably from 0.5% to 500%, even more preferably from 1% to 150%.
  • the random copolymer Al results from the copolymerization:
  • R 1 is selected from the group consisting of -H, -C3 ⁇ 4, and -CH 2 -CH 3;
  • x is an integer ranging from 1 to 18; preferably from 2 to 18;
  • y is an integer equal to 0 or 1;
  • - X 1 and X 2 which are identical or different, are chosen from the group formed by hydrogen, tetrahydropyranyl, methyloxymethyl, tert-butyl, benzyl, trimethylsilyl and t-butyl dimethylsilyl;
  • R'2 and R "2, which are identical or different, are chosen from the group formed by hydrogen and a Ci-Cu alkyl, preferably methyl;
  • R '"2 is chosen from the group formed by a C 6 -C 18 aryl, a C 7 -C 18 aralkyl and a C 2 -C 18 alkyl, preferably an aryl
  • R2 is selected from the group consisting of -H, -Ct3 ⁇ 4 and -CH2-CH3,
  • R3 is selected from the group consisting of C6-C6 aryl, C6-C18 aryl substituted with R'3, -C (O) -O-R'3 ; -O-R ' 3 , -S-R' 3 and -C (O) -N (H) -R ' 3 with R' 3 an alkyl group
  • the random copolymer Al results from the copolymerization of at least one monomer M1 with at least two monomers M2 having different R3 groups.
  • one of the monomers M2 of the random copolymer Al has the general formula (II-A):
  • R2 is selected from the group consisting of -H, -CH3 and -CH2-C11,
  • R "3 is a C1-C14 alkyl group
  • R2 is selected from the group consisting of -H, -CH3 and -CH2-C11,
  • R "'3 is a C15-C30 alkyl group.
  • the side chains of the statistical copolymer are identical to one embodiment of the invention.
  • Al 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 M 1 of formula (I) in said copolymer ranging from 1 to 30%, preferably from 5 to 25%, more preferably ranging from from 9 to 21%>.
  • the random copolymer A2 results from the copolymerization:
  • t is an integer equal to 0 or 1;
  • u is an integer equal to 0 or 1;
  • M and R8 are divalent linking groups, which may be identical or different, chosen from the group formed by a C 6 -C 18 aryl, a C 7 -C 24 aralkyl and a C 2 -C 24 alkyl, preferably an C 6 -C 6 aryl; ,
  • X is a function chosen from the group formed by -OC (O) -, -C (O) -O-, -C (O) -N (H) -, -N (H) -C (O) - , -S-, -N (H) -, -N (R ' 4 ) - and -O- with R' 4 a hydrocarbon chain comprising from 1 to 15 carbon atoms;
  • R9 is selected from the group consisting of -H, -Ct3 ⁇ 4 and -CH2-Cf3 ⁇ 4;
  • - Rio and Ru identical or different are selected from the group consisting of hydrogen and a hydrocarbon group having 1 to 24 carbon atoms, preferably between 4 and 18 carbon atoms, preferably between 6 and 14 carbon atoms;
  • R12 is chosen from the group formed by -H, -Ct3 ⁇ 4 and -CH2-CH3,
  • R13 is selected from the group consisting of C6-C6 aryl, C6-C18 aryl substituted with a group R 'B, -C (O) -O-R' B ; -OR 'B, -S-
  • the chain formed by the linking of the groups Rio, M, X and (Rs) u with u equal to 0 or 1 of the monomer of general formula (IV) of the random copolymer A2 has a total number of carbon atoms ranging from 8 to 38, preferably from 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 exogenous compound A4 has the general formula (VI):
  • W3 an integer equal to 0 or 1;
  • R14 and R15 identical or different selected from the group consisting of hydrogen and a hydrocarbon group having 1 to 24 carbon atoms.
  • the substituents Rio, Ru and the value of the index (t) of the monomer of formula (IV) of the random copolymer A2 are identical respectively to the substituents R14, Ris and the value of the index W3, of the exogenous compound A4 of formula (VI).
  • At least one of the substituents Rio, Rn or the value of the index (t) of the monomer of formula (IV) of the random copolymer A2 is different from the substituents R14, Ris or from the value of the index W3, of the exogenous compound A4 of formula (VI).
  • the mass ratio between the polydiol random copolymer Al and the statistical copolymer A2 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 present invention also relates to a lubricant composition resulting from the mixture of at least:
  • the lubricating oil is chosen from oils of 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 Al and the statistical copolymer A2 ranges from 0.001 to 100, preferably from 0.05 to 20, even more preferably from 0 to , 1 to 10, even more preferably 0.2 to 5.
  • the molar percentage of exogenous compound A4 relative to the boronic ester functions of the random copolymer A2 ranges from 0.05 to 5000%, preferably from 0.1% to 1000%) even more preferably from 0.5% to 500%, more preferably from 1% to 150%.
  • the lubricant composition of the invention results from the addition of a functional additive selected from the group consisting of detergents, anti-wear additives, extreme pressure additives, additional antioxidants. , viscosity index improver polymers, pour point improvers, defoamers, anticorrosive additives, thickeners, dispersants, friction modifiers, and mixtures thereof.
  • the present invention also relates to a method for modulating the viscosity of a lubricating composition, the method comprising at least: the provision of a lubricant composition resulting from the mixing of at least one lubricating oil, at least one polydiol random copolymer Al and at least one random copolymer A2 comprising at least two boronic ester functions and which can associate with said polydiol random copolymer Al by at least one transesterification reaction,
  • the invention also proposes the use of at least one compound selected from 1,2-diols or 1,3 diols for modulating the viscosity of a lubricating composition, said lubricating composition resulting from mixing at least one oil lubricant, at least one polydiol random copolymer Al and at least one random copolymer A2 comprising at least two boronic ester functions and capable of associating with said polydiol random copolymer Al by at least one transesterification reaction.
  • FIG. 1 schematically represents a random copolymer (PI), a gradient copolymer (P2) and a block copolymer (P3), each circle represents a monomer unit. The difference in chemical structure between the monomers is symbolized by a different color (light gray / black).
  • Figure 2 schematically shows a comb copolymer.
  • FIG. 3 schematically illustrates the crosslinking of the composition according to the invention in tetrahydrofuran (THF) in the presence of exogenous diol A4 compounds.
  • Figure 4 shows schematically the behavior of the composition of the invention as a function of temperature.
  • a random copolymer having diol functions (function A) can associate thermoreversibly with a random copolymer having boronic ester functions (function B) via a reversible transesterification reaction.
  • a boronic ester chemical bond is formed between the two polymers.
  • the free diol compounds (function C) present in the medium in the form of small organic molecules make it possible to adjust the level of association between the copolymers bearing the diol A functions and the copolymers bearing the boronic ester B functions.
  • FIG. 5 represents the evolution of the relative viscosity (without unit, the ordinate axis) as a function of the temperature (° C, the abscissa axis) of the compositions A, C, D and E.
  • FIG. 6 represents the evolution of the relative viscosity (without unit, the ordinate axis) as a function of the temperature (° C, the abscissa axis) of the compositions A, B and F.
  • FIG. 7 represents the evolution of the elastic modulus (G ') and the viscous modulus (G ")
  • FIG. 8 represents the evolution of the elastic modulus (G ') and the viscous modulus (G ") (Pa, the ordinate axis) as a function of the temperature (° C, the abscissa axis) of the composition H.
  • FIG. 9 schematically illustrates the boronic ester exchange exchange reactions between two random polydiols (Al-1 and Al -2) and two random boronic esters (A2-1 and A2-2) in the presence of exogenous compounds diol (A4) and diol compounds released in situ (A3).
  • a first object of the present invention is an associative additive composition and thermoreversibly exchangeable and whose level of association is controlled by the presence of a so-called exogenous compound, the composition resulting from the mixture of at least:
  • a compound A2 in particular a random copolymer A2, comprising at least two boronic ester functional groups and capable of associating with said polydiol Al random copolymer by a transesterification reaction,
  • an exogenous compound A4 chosen from 1,2-diols and 1,3-diols.
  • the medium may be a hydrophobic medium, especially apolar, such as a solvent, a mineral oil, a natural oil, a synthetic oil.
  • the polydiol random copolymer Al 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 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. For example, a copolymer is said to be random when it consists of monomeric units whose distribution is a marko distribution in Vienna.
  • a schematic statistical polymer (PI) is illustrated in FIG. 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 copolymers.
  • 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 FIG. 1.
  • a gradient copolymer designates a copolymer of at least two monomeric units of different structures whose monomer composition gradually changes along the polymer chain, thus changing from progressively from one end of the polymer chain rich in a monomeric unit, to the other end rich in the other comonomer.
  • a schematic gradient polymer (P2) is illustrated in FIG.
  • 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
  • C1-C4 alkyl is meant a saturated hydrocarbon chain, linear or branched, comprising from 1 to 1 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 6 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.
  • C2-C10 alkenyl is meant a linear or branched hydrocarbon chain containing at least one unsaturation, preferably a carbon-carbon double bond, and comprising from 2 to 10 carbon atoms.
  • C7-C18 aralkyl means an aromatic hydrocarbon compound, preferably monocyclic, substituted by at least one linear or branched alkyl chain and in which the total number of carbon atoms of the aromatic ring and its substituents ranges from at 18 carbon atoms.
  • a C 7 -C 18 aralkyl may be selected from the group consisting of benzyl, tolyl and xylyl.
  • C 6 CIS-aryl group substituted with an R 3 group is meant 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 R'3 group.
  • Hal or halogen is meant a halogen selected from the group consisting of chlorine, bromine, fluorine and iodine. • Monomer Ml
  • R 1 is selected from the group consisting of -H, -Cf3 ⁇ 4 and -CH 2 -CH 3 , preferably -H and -CH 3 ;
  • x is an integer ranging from 1 to 18, preferably ranging from 2 to 18; more preferably from 3 to 8; even more preferably x is 4;
  • y is an integer equal to 0 or 1; preferably y is 0;
  • - X 1 and X 2 which are identical or different, are chosen from the group formed by hydrogen, tetrahydropyranyl, methyloxymethyl, tert-butyl, benzyl, trimethylsilyl and t-butyl dimethylsilyl;
  • R'2 and R "2, which are identical or different, are chosen from the group formed by hydrogen and a C1-C18 alkyl group;
  • R '"2 is selected from the group consisting of C 6 -C 18 aryl, C 7 -C 18 aralkyl and C 2 -C 18 alkyl, preferably C 6 -C 18 aryl, more preferably phenyl.
  • R '2 and R "2 is a C 1 -C 11 alkyl group
  • the hydrocarbon chain is a linear chain
  • the C 1 -C 4 alkyl group is selected from the group consisting of methyl, ethyl and n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decycling and n-undecyl.
  • the Ci-C n alkyl group is methyl.
  • R '"2 is a C 2 -C 18 alkyl group
  • the hydrocarbon chain is a linear chain
  • the monomers corresponding to formula (I-A) are among the preferred ones:
  • R 1 is selected from the group consisting of -H, -CH 3 and -CH 2 -CH 3 , preferably -H and -CH 3 ;
  • x is an integer ranging from 1 to 18, preferably ranging from 2 to 18; more preferably from 3 to 8; even more preferably x is 4;
  • y is an integer equal to 0 or 1; preferably y is 0.
  • the monomers corresponding to formula (I-B) are among the preferred ones:
  • R 1 is selected from the group consisting of -H, -C3 ⁇ 4 and -CH 2 -CH 3 , preferably -H and -CH 3 ;
  • x is an integer ranging from 1 to 18, preferably ranging from 2 to 18; more preferably from 3 to 8; even more preferably x is 4;
  • y is an integer equal to 0 or 1; preferably y is 0;
  • Y 1 and Y 2 which are identical or different, are chosen from the group formed by tetrahydropyranyl, methyloxymethyl, tert-butyl, benzyl, trimethylsilyl and t-butyl dimethylsilyl;
  • Y 1 and Y 2 form oxygen atoms a bridge of the following formula:
  • R'2 and R "2, which are identical or different, are chosen from the group formed by hydrogen and a C1-C11 alkyl group;
  • Y 1 and Y 2 form, with the oxygen atoms, a boronic ester of the following formula:
  • R '"2 is selected from the group consisting of C 6 -C 18 aryl, C 7 -C 18 aralkyl and C 2 -C 18 alkyl, preferably aryl C6-C18, more preferably phenyl.
  • the hydrocarbon chain is a linear chain
  • the Ci-Cu alkyl group is selected from the group consisting of methyl, ethyl n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decycling and n-undecyl.
  • the Ci-C n alkyl group is methyl.
  • R '"2 is a C 2 -C 18 alkyl group
  • the hydrocarbon chain is a linear chain
  • the monomer M 1 of general formula (I-A) is obtained by deprotection of the alcohol functional groups of the monomer of general formula (I-B) according to reaction scheme 1 below:
  • the monomer M 1 of general formula (IB) can be obtained by reacting a compound of general formula (Ic) with an alcohol compound of general formula (Ib) according to reaction scheme 2 below:
  • Y 3 is selected from the group consisting of a halogen atom, preferably chlorine, -OH and O-C (O) -R'i with R'i selected from the group consisting of -H, -CH3 and -CH2 -CH3, preferably -H and -CH3 ;
  • R 1, Y 1, Y 2, x and y have the same meaning as that given in general formula (I-B).
  • the compound of general formula (I-c) is commercially available from the suppliers: Sigma-Aldrich® and Alfa Aesar®.
  • the alcohol compound of general formula (I-b) is obtained from the corresponding polyol of formula (I-a) by protecting the diol functions according to the following reaction scheme 3:
  • the protective reaction of the diol functions of the compound of general formula (I-a) 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®. • Monomer M2
  • the second monomer of the copolymer has the general formula (II):
  • P2 is chosen from the group formed by -H, -CH3 and -CH2-CH3, preferably -H and
  • R3 is chosen from the group formed by a C6-C16 aryl group, an aryl
  • R'3 is a C1-C30 alkyl group whose hydrocarbon chain is linear.
  • the monomers corresponding to formula (II-A) are among the preferred ones:
  • R2 is selected from the group consisting of -H, -CH3 and -CH2-CH3, preferably -H and
  • R "3 is a C1-C14 alkyl group.
  • C1-C14 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.
  • the monomers corresponding to formula (II-B) are also among the preferred ones:
  • R2 is selected from the group consisting of -H, -CH3 and -CH2-CH3, preferably -CH 3 ;
  • R '"3 is a C 15 -C 30 alkyl group.
  • C 15 -C 30 alkyl group is meant a saturated hydrocarbon chain, linear or branched 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), ( ⁇ - ⁇ ) and (II-B) are well known to those skilled in the art. They are marketed by Sigma-Aldrich® and TCI®.
  • a preferred random copolymer results from the copolymerization of at least:
  • a preferred random copolymer results from the copolymerization of at least:
  • a preferred random copolymer results from the copolymerization of at least:
  • R2 is -CH3 and R '"3 is a C16-C24 alkyl group, preferably a linear C16-C24 alkyl.
  • a preferred random copolymer results from the copolymerization of at least:
  • a second monomer M2 chosen from the group formed by methacrylate of n-octyl, n-decyl methacrylate and n-dodecyl methacrylate;
  • a third monomer M2 chosen from the group formed by palmityl methacrylate, stearyl methacrylate, arachidyl methacrylate and behenyl methacrylate.
  • the copolymerization can be initiated in bulk or in solution in an organic solvent with compounds generating free radicals.
  • the copolymers of the invention are obtained by the known methods of radical copolymerization, in particular controlled such as the so-called method controlled radical polymerization controlled reversible chain transfer by addition-fragmentation (in English: Reversible Addition-Fragmentation Chain Transfer (RAFT )) and the method called Atom Transfer Radical Polymerization (ARTP).
  • RAFT Reversible Addition-Fragmentation Chain Transfer
  • ARTP Atom Transfer Radical Polymerization
  • the polydiol random copolymer Al is prepared according to a preparation process which comprises at least one polymerization step (a) in which at least: i) a first monomer M1 of general formula (I) as described above:
  • the method may further include iv) at least one chain transfer agent.
  • a source of free radicals is meant a chemical compound 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 and adapted to 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 hydrogen peroxide, the systems are preferably exemplified.
  • redox such as oxidation of Fe 2+ , persulfate / sodium-metabisulfite mixtures, or ascorbic acid / hydrogen peroxide, or photochemically cleavable compounds or ionizing radiation, for example ultraviolet or by beta or gamma radiation.
  • chain transfer agent is meant a compound whose purpose is to ensure homogeneous growth of the 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.
  • S thiocarbonylthio group
  • chain transfer agent mention may be made of dithioesters, trithiocarbonates, xanthates and dithiocarbamates.
  • 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 process for preparing a polydiol random copolymer comprises:
  • step (b) of the diol functions of the copolymer obtained at the end of step (a), so as to obtain a copolymer in which X 1 and X 2 are identical and are a hydrogen atom.
  • the polymerization step (a) comprises contacting at least one monomer M1 with at least two monomers M2 having different R3 groups.
  • one of the monomers M2 has the general formula (II-A) as defined above and the other monomer M2 has the general formula ( ⁇ - ⁇ ) as defined above.
  • the polydiol random copolymers Al 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.
  • Figure 2 schematically shows a comb polymer.
  • the Al copolymers have a skeleton of polymerizable functions, in particular a skeleton of methacrylate functions or styrene functions, and a mixture of hydrocarbon side chains which may or may not be substituted by diol functions.
  • the polydiol Al random copolymers 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.
  • the random copolymer Al is a thermosensitive copolymer, that is to say that it is sensitive to changes in temperature.
  • the side chains of the polydiol Al 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 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. The choice of this average chain length makes it possible to obtain a polymer that is soluble in a hydrophobic medium, whatever the temperature at which the copolymer is dissolved. The polydiol random copolymer Al is therefore miscible in a hydrophobic medium.
  • 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 Al has a molar percentage of monomer M 1 of formula (I) in said copolymer ranging from 1 to 30%, preferably 5 to 25%, more preferably from 9 to 21%.
  • the polydiol random copolymer Al has a mole percentage of M1 monomer of formula (I) in said copolymer ranging from 1 to 30%, preferably 5 to 25%, more preferably from 9 to 21 %, a molar percentage of monomer M2 of formula ( ⁇ - ⁇ ) in said copolymer ranging from 8 to 92% and a molar percentage of monomer M2 of formula ( ⁇ - ⁇ ) 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 random copolymer Al has a molar percentage of monomer M1 of formula (I) in said copolymer ranging from 1 to 30%, a mole percentage of monomer M2 of formula ( ⁇ - ⁇ ) in said copolymer ranging from 8 to 62% and a molar percentage of M2 monomer of formula ( ⁇ - ⁇ ) 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 Al 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 free radical polymerization.
  • the polydiol random copolymer Al 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 Al 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 chromatography measurement. Steric exclusion using a polystyrene calibration.
  • the compound A2 comprising two boronic ester functions has the general formula (III)
  • R 5, R 6 and R 7, which are identical or different, are chosen from the group formed by hydrogen and a hydrocarbon group containing from 1 to 24 carbon atoms, preferably from 4 to 18 carbon atoms, preferably from 6 to at 14 carbon atoms;
  • L is a divalent linking group and chosen from the group formed by a C 6 -C 18 aryl, a C 7 -C 24 aralkyl and a C 2 -C 24 hydrocarbon chain, preferably a C 6 -C 18 aryl.
  • hydrocarbon group having 1 to 24 carbon atoms is meant a group alkyl or alkenyl, linear or branched, having 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.
  • C2-C24 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 compound A2 is a compound of the general formula (III) above in which:
  • w 1 and W 2 identical or different, are integers equal to 0 or 1;
  • R and R are identical and are hydrogen atoms
  • R5 and R7 are identical and are a hydrocarbon group, preferably a linear alkyl, having 1 to 24 carbon atoms, preferably 4 to 18 carbon atoms, preferably 6 to 16 carbon atoms;
  • L is a divalent linking group and is a C 6 -C 6 aryl, preferably phenyl.
  • 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:
  • 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. 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 functional groups is a random poly (boronic ester) copolymer resulting from the copolymerization of at least one M3 monomer of formula (IV) as described below with minus an M4 monomer of formula (V) as described below.
  • the monomer M3 of the boronic ester random copolymer compound A2 has the general formula (IV) in which:
  • t is an integer equal to 0 or 1;
  • u is an integer equal to 0 or 1;
  • M and R8 are divalent, identical or different linking groups, and are selected from the group consisting of C 6 -C 18 aryl, C 7 -C 24 aralkyl and C 2 -C 24 alkyl, preferably C 6 -C 6 aryl; Cis,
  • X is a function chosen from the group formed by -OC (O) -, -C (O) -O-, -C (O) -N (H) -, -N (H) -C (O) - , -S-, -N (H) -, -N (R ' 4 ) - and -O- with R' 4 a hydrocarbon chain comprising from 1 to 15 carbon atoms;
  • - R9 is selected from the group consisting of -H, -Ct3 ⁇ 4 and -CH2-CH3; preferably -H and -CH 3 ;
  • - Rio and Ru identical or different, are chosen from the group formed by hydrogen and a hydrocarbon chain having from 1 to 24 carbon atoms, preferably from 4 to 18 carbon atoms, preferably from 6 to 12 carbon atoms;
  • C2-C24 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 monomer M3 has the general formula (IV) in which:
  • t is an integer equal to 0 or 1;
  • u is an integer equal to 0 or 1;
  • M and P 8 are divalent linking groups and are different, M is C 6 -C 6 aryl, preferably phenyl, R 5 is C 7 -C 24 aralkyl, preferably benzyl;
  • X is a function chosen from the group formed by -OC (O) -, -C (O) -O-, -C (O) -N (H) - and -O-, preferably -C (O) -O- or -OC (O) -;
  • P9 is selected from the group consisting of -H, -CH3, preferably -H;
  • - Rio and Ru are different, one of the groups Rio or Ru is H and the other Rio or Ru group is a hydrocarbon chain, preferably a linear alkyl group, having 1 to 24 carbon atoms, preferably between 4 and 18 carbon atoms, preferably between 6 and 12 carbon atoms.
  • the monomer 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 compounds of formula (IV-g) are commercially available from the following suppliers: Sigma-Aldrich®, Alfa Aesar® and TCI®.
  • z an integer equal to 0 or 1;
  • R12 is selected from the group consisting of -H, -CH3 and -CH2-CH3; u, X, M, R8 and R9 as defined above.
  • the compound of formula (IV-e) is obtained by reaction of a compound of formula (IV-c) with
  • X represents -O-C (O) -
  • Y4 represents an alcohol function -OH or a halogen atom, preferably chlorine or bromine and Y5 is a carboxylic acid function -C (O) -OH;
  • X represents -C (O) -O-, then Y4 represents a carboxylic acid function -C (O) -OH and Y5 is an alcohol function -OH or a halogen atom, and preferably chlorine or bromine;
  • X represents -C (O) -N (H) -, then Y4 represents a carboxylic acid function -C (O) -OH or a -C (O) -Hal function, and Y5 is an amino function N3 ⁇ 4;
  • X represents -N (H) -C (O) -, then Y4 represents an amino function N3 ⁇ 4 and Y5 is a carboxylic acid function -C (O) -OH or a -C (O) -Hal function;
  • X represents -N (H) -, then Y4 is a halogen atom and Y5 is an amino function -NH2 or Y4 is an amino function -NH2 and Y5 is a halogen atom;
  • X represents -N (R ' 4 ) -, then Y4 is a halogen atom and Y5 is an amino function -N (H) (R' 4 ) or Y4 is an amino function -N (H) (R) 4 ) and Y5 is a halogen atom;
  • X represents -O-, then Y4 is a halogen atom and Y5 is an alcohol function -OH or Y4 is an alcohol function -OH and Y5 is a halogen atom.
  • the compounds of formula (IV-d) are commercially available from the suppliers: Sigma-Aldrich®, TCI® and Acros Organics®.
  • 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:
  • the monomer M4 of the boronic ester random copolymer compound A2 has the general formula (V)
  • R12 is selected from the group consisting of -H, -Ct3 ⁇ 4 and -CH2-CH3, preferably -H and -Ct3 ⁇ 4;
  • R 13 is selected from the group consisting of C 6 -C 18 aryl, C 6 -C 18 aryl substituted with R 'B, -C (O) -O-R' B ; -OR 'B,
  • C1-C25 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 6 aryl group substituted with an R group is meant an aromatic hydrocarbon compound comprising from 6 to 18 carbon atoms, at least one carbon atom of the aromatic ring is substituted with a C 1 -C 25 alkyl group such as as defined above.
  • the monomers corresponding to formula (VA) are among the preferred ones:
  • - R.2 is chosen from the group formed by -H, -C3 ⁇ 4 and-CLh-CLh, preferably -
  • - R 'B is a C1-C25 alkyl group, preferably a linear C1-C25 alkyl, even more preferably a linear C5-C15 alkyl.
  • the boronic ester random copolymers are obtained by the known processes of radical copolymerization, in particular controlled such as the method called controlled radical polymerization controlled reversible chain transfer by addition-fragmentation (in English: Reversible Addition-Fragmentation Chain Transfer (RAFT) ) and the method called Atom Transfer Radical Polymerization (ARTP).
  • controlled radical polymerization controlled reversible chain transfer by addition-fragmentation in English: Reversible Addition-Fragmentation Chain Transfer (RAFT)
  • ARTP Atom Transfer Radical Polymerization
  • the boronic ester statistical copolymer is prepared according to a process which comprises at least one polymerization step (a) in which at least:
  • the method may further include iv) at least one agent chain transfer.
  • 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 M3 of general formula (IV) has a total number of atoms of carbon ranging from 8 to 38, preferably from 10 to 26.
  • the side chains of the boronic ester statistical copolymer have an average length greater than 8 carbon atoms, preferably ranging from 11 to 16. This length of chains 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) in said copolymer 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) in said copolymer ranging from 0.25 to 20%, preferably from 1 to 10% and a molar percentage of monomer of formula (V) in said copolymer ranging from 80 to 99.75%, preferably from 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 molar mass 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 compound A2 in particular the boronic ester random copolymer, has the property of being able to react in a hydrophobic medium, in particular apolar medium, with a compound carrying diol function (s) by a transesterification reaction.
  • This transesterification reaction can be represented according to the following scheme 9:
  • exogenous compound A4 is selected from 1,2 diols and 1,3 diols.
  • exogenous compound is intended to mean a compound which is added to the additive composition resulting from the mixing of at least one random polydiol Al copolymer and at least one A2 compound, in particular the poly random copolymer. (boronic ester).
  • w3 is an integer equal to 0 or 1
  • R14 and R15 which are identical or different, are chosen from the group formed by hydrogen and a hydrocarbon chain containing from 1 to 24 carbon atoms, preferably from 4 to 18 carbon atoms, preferably from 6 to 12 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 exogenous compound A4 has the general formula (VI) in which:
  • - W3 is an integer equal to 0 or 1;
  • R14 and R15 are different, one of the groups R14 or R15 is H and the other group R14 or R 15 is a hydrocarbon chain, preferably a linear alkyl group, having 1 to 24 carbon atoms, preferably 4 to 18 carbon atoms, preferably 6 to 12 carbon atoms.
  • the exogenous compound A4 has a different chemical structure from the diol compound A3 released in situ by transesterification reaction.
  • at least one of the substituents R14, Ris or the value of the index W3 of the exogenous compound A4 of formula (VI) is different respectively from the substituents R and R5 or from the value of the index wi or substituents R5 and R7 or the value of the index W2 of the compound A2 diester boronic of formula (III) or is different respectively from the substituents Rio, Rn or the value of the index t of the monomer (IV) of the poly random copolymer (boronic ester) A2.
  • the exogenous compound A4 has a chemical structure identical to the diol compound A3 released in situ by transesterification reaction.
  • the substituents R14, R15 and the value of the index W3 of the exogenous compound A4 of formula (VI) are identical respectively to the substituents R and R5 and to the value of the index wi or to R5 and R7 and at the value of the W2 index of the boronic diester compound A2 of formula (III) or is identical to the substituents Rio, Rn and to the value of the monomer index (IV), respectively, of the poly (boronic ester) random copolymer A2.
  • the additive composition results from the mixture of at least one polydiol random copolymer Al, of at least one compound A2, in particular a statistical copolymer A2, comprising at least two boronic ester functions and which can be to associate with said polydiol Al 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 poly (boronic ester) random copolymer during the transesterification reaction.
  • the random polymer Al polydiol is not a diol released in situ within the meaning of the present invention.
  • the compounds of formula (VI) are commercially available from the following suppliers: Sigma-Aldrich®, Alfa Aesar® and TCI®.
  • the additive compositions of the invention resulting from the mixture of at least one polydiol random copolymer Al as defined above, of at least one compound A2 as defined above, in particular at least one poly ( boronic ester) as defined above, and at least one exogenous compound A4 as defined above have very varied rheological properties depending on the temperature and the proportion of compounds Al, A2 and A4 used.
  • the polydiols random copolymers Al and the compounds A2 as defined above have the advantage of being associative and of exchanging chemical bonds in a thermoreversible manner, in particular in a hydrophobic medium, in particular an apolar hydrophobic medium.
  • the polydiols random copolymers Al and the compounds A2 as defined above can be crosslinked.
  • the polydiols random copolymers Al 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 polydiol random copolymers Al and the compounds A2 comprising at least two boronic ester functional groups, in particular with the poly (boronic ester) random copolymer.
  • the formation of covalent bonds between the Al polydiols and the A2 compounds may or may not lead to the formation of a three-dimensional polymeric network.
  • chemical bond is meant a covalent chemical bond of the boronic ester type.
  • exchangeable is meant that the compounds are able to exchange chemical bonds between them without the total number and nature of chemical functions being changed.
  • the boronic ester bonds of the A2 compounds, the boronic ester bonds formed by transesterification reaction between the boronic esters of the A2 compounds and the exogenous compounds A4, as well as the boronic ester bonds formed by the combination of the polydiols Al random copolymers and the A2 compounds can be exchange with diol functions carried by the exogenous compounds A4 or carried by the released compounds A3 in situ to form new boronic esters and new diol functions without the total number of boronic ester functions and diol functions being affected.
  • the boronic ester bonds of the compounds A2 as well as the boronic ester bonds formed by the combination of the polydiols random copolymers Al and the compounds A2 can also be exchanged to form new boronic esters without the total number of functions boronic esters is affected.
  • This other process of exchange of chemical bonds is carried out by metathesis reaction, via successive exchanges of boronic ester functions in the presence of diol compounds (compounds released in situ A3 and exogenous compounds A4); this process is illustrated in FIG. 9.
  • the polydiol random copolymer Al-1 which was associated with the A2-1 polymer, exchanged a boronic ester bond with the boronic ester random copolymer A2-2.
  • the polydiol random copolymer Al -2 which was in association with the A2-2 polymer, exchanged a boronic ester bond with the boronic ester random copolymer A2-1; the total number of boronic ester bond in the composition being unchanged and is 4.
  • the Al-1 copolymer is then combined with both the A2-1 polymer and the A2-2 copolymer.
  • the copolymer Al -2 is then combined with both the copolymer A2-1 and the copolymer A2-2.
  • Another chemical link exchange process is illustrated in FIG. 9, in which it can be observed that the polydiol random copolymer Al-1, which was associated with the polymer A2-1, exchanged two boronic ester bonds with the boronic ester statistical copolymer.
  • A2-2 Another chemical link exchange process is illustrated in FIG. 9, in which it can be observed that the polydiol random copolymer Al-1, which was associated with the polymer A2-1, exchanged two boronic ester bonds with the boronic este
  • the polydiol random copolymer Al -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 bonds in the composition being unchanged and is equal to 4.
  • the Al-1 copolymer is then combined with the A2-2 polymer.
  • the copolymer Al -2 is then combined 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. 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 functions of a random copolymer (Al copolymer) and boronic ester functions of a crosslinking agent (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.
  • thermosible crosslinked is meant a copolymer crosslinked by a reversible reaction whose displacement in one direction or the other direction is controlled by the temperature.
  • thermoreversible crosslinking mechanism of the additive composition of the invention in the presence of exogenous compounds A4 is shown schematically in FIG. 4.
  • the Applicant has observed that at low temperature, the polydiol copolymer Al (symbolized by the copolymer bearing functions A in FIG. 4) is not or very little crosslinked by the boronic ester compounds A2 (symbolized by the compound carrying functions B in Figure 4).
  • the boronic ester compounds A2 establish boronic ester bonds with the exogenous compound A4 (symbolized by the compound C in Figure 4) by transesterification reaction.
  • the polydiol random copolymer Al is a thermosensitive copolymer. When the temperature increases, the conformation in the space of the chains of this copolymer is modified; diol functions are made more accessible to association reactions. Thus, when the temperature increases, the diol functions of the copolymer Al react with the boronic ester functions of the compound A2 by a transesterification reaction and release in situ an A3 diol.
  • the polydiols random copolymers Al and the compounds A2 comprising at least two boronic ester functions then bind together and can be exchanged.
  • a gel may form in the medium, especially when the medium is apolar.
  • the boronic ester bonds between the polydiols random copolymers A1 and the A2 compounds are broken, and if necessary, the composition loses its gel character.
  • the compounds A2, in particular the random poly (boronic ester) 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.
  • the exogenous compound A4 is of the same chemical nature as the diol compound A3 released in situ by transesterification reaction between the polydiol random copolymer Al and the compound A2, in particular the poly (ester) random copolymer. boronic acid).
  • the total amount of free diols present in said composition is strictly greater than the amount of diol compounds released in situ.
  • free diols is meant diol functions which are capable of forming a chemical bond of boronic ester type by transesterification reaction.
  • total amount of free diols is meant in the sense of the present application, the total number of diol functions capable of forming a boronic ester chemical bond by transesterification.
  • the total amount of free diols is always equal to the sum of the number of moles of exogenous diol compounds A4 and the number (expressed in moles) of diol functional groups of the polydiol Al copolymer.
  • the additive composition we have:
  • Al and A2 is equal to the number of boronic ester functions connecting the copolymers Al and A2.
  • the amount of boronic ester bonds (or boronic ester link) which can be established between the polydiols random copolymers Al and the compounds A2, in particular the random copolymers poly (boronic ester), is adjusted by those skilled in the art by means of a appropriate selection of the polydiol Al random copolymer, the compound A2 and the composition of the mixture.
  • the compound A2 in particular random poly (boronic ester) copolymer, as a function of the structure of the random copolymer Al.
  • the content of random copolymer Al 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 1% to 50% by weight based on 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 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 mole percentage of exogenous compound A4 in the additive composition is from 0.025% to 5000%, preferably from 0.1% to 1000%, more preferably 0.5%. at 500%, even more preferably from 1% to 150%) relative to the boronic ester functions of compound A2, especially 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, all multiplied by one hundred.
  • the number of moles of boronic ester function of compound A2 can be determined by those skilled in the art by NMR analysis of the proton of compound A2, or by following the conversion to monomers during the synthesis of the copolymer A2, when the compound A2 is a random poly (boronic ester) copolymer.
  • the mass ratio (ratio A1 / A2) between the polydiol Al statistical compound and the A2 compound, in particular the poly (boronic ester) random copolymer, in the additive composition ranges from 0.005 to 200, preferably 0.05. at 20, even more preferably from 0.1 to 10, still more preferably from 0.2 to 5.
  • the composition of the invention may also 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, antifoam agents, dispersant additives, adhesion promoters and stabilizers.
  • novel additive compositions of the invention are prepared by means well known to those skilled in the art. For example, it suffices for the person skilled in the art to:
  • the person skilled in the art also knows how to adjust the various parameters of the composition of the invention to obtain either a composition in which the polydiol random copolymer Al and the compound A2, in particular the boronic ester random copolymer, are associated either with a composition in which the random copolymer polydiol Al and the compound A2, in particular the boronic ester random copolymer, are crosslinked and to modulate the degree of association or the degree of crosslinking for a given use temperature.
  • a person skilled in the art knows how to adjust in particular:
  • 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 the improved recovery of oil, the paper industry, paints, food additives, cosmetic or pharmaceutical formulation.
  • Another subject of the present invention relates to a lubricant composition resulting from the mixture of at least:
  • a random copolymer A2 as defined above, comprising at least two boronic ester functional groups and capable of associating with said polydiol Al random copolymer by at least one transesterification reaction,
  • an exogenous compound A4 chosen from 1,2-diols and 1,3-diols, and in particular as defined above.
  • the lubricating compositions according to the invention have an inverted behavior with respect to a modification of the temperature with respect to the behavior of the base oil and the polymer type rheological additives of the prior art and have the advantage that this rheological behavior can be modulated according to the temperature of use.
  • the compositions of the present invention have the advantage of thickening as the temperature increases.
  • the formation of reversible covalent bonds makes it possible to increase (reversibly) the molar mass of the polymers and thus 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 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 or animal origin, preferably oils of vegetable origin such as rapeseed oil, sunflower oil, palm oil, coconut oil, coconut ...
  • 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 products whose viscosity index is between 120 and 130, the hydroisomerized mineral bases whose viscosity index is between 140 and 150.
  • Lubricating oils of synthetic origin come as their name suggests chemical synthesis such as the addition of a product on itself or polymerization, or the addition of a product on another such as esterification, alkylation, fluorination, etc., of components derived from petrochemistry, carbochemistry, and mineral chemistry such as: olefins, aromatics, alcohols, acids, halogenated compounds, phosphorus compounds, silicones, etc.
  • chemical synthesis such as the addition of a product on itself or polymerization, or the addition of a product on another such as esterification, alkylation, fluorination, etc., of components derived from petrochemistry, carbochemistry, and mineral chemistry such as: olefins, aromatics, alcohols, acids, halogenated compounds, phosphorus compounds, silicones, etc.
  • synthetic oils based on synthetic hydrocarbons such as polyalphaolefins (PAO), internal polyolefins (IOPs), polybutenes and polyisobutenes (PIB), dialkylbenenes, alkylated polyphenyls;
  • PAO polyalphaolefins
  • IOPs internal polyolefins
  • PIB polyisobutenes
  • dialkylbenenes alkylated polyphenyls
  • synthetic polyglycol oils such as monoalkylene glycols, polyalkylene glycols and monoethers of polyalkylene glycols;
  • the 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 American Petroleum Institute (API) Basic Oil Interchangeability Guidelines. equivalent according to the ATIEL classification (Technical Association of the European Lubricants Industry) as summarized below:
  • compositions of the invention may comprise one or more lubricating oils.
  • the lubricating oil or the lubricating oil mixture is the major ingredient in the lubricating composition. This is called lubricating base oil.
  • major ingredient is meant that the lubricating oil or the lubricating oil mixture represents at least 51% 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 preferably from grade SAE 20W to grade SAE 50 (SAE stands for Society of Automotive Engineers or Functional Additives).
  • 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 (s) which are added to the composition of the invention are chosen according to the end use of the lubricating composition. These additives can be introduced in two different ways:
  • each additive is added separately and sequentially in the composition, or all of the additives are added simultaneously in the composition, the additives are in this case generally available in the form of a package, called package of additives.
  • 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 Lubricating 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 excess of 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.
  • Anti-wear additives and extreme pressure additives are preferably calcium, magnesium, sodium or barium.
  • anti-wear and extreme pressure additives there is a wide variety of anti-wear and extreme pressure additives.
  • phosphosulfur additives such as metal alkylthiophosphates, in particular zinc alkylthiophosphates, and more specifically zinc dialkyldithiophosphates or ZnDTPs, amine phosphates, 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.
  • Anticorrosions 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). Polymers improving the viscosity index:
  • 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.
  • lubricant compositions of the invention are prepared by means well known to those skilled in the art. For example, it suffices for the person skilled in the art to:
  • the lubricant compositions of the invention result from the mixture of associative polymers which have the property of increasing the viscosity of the lubricating oil by combinations, and in particular in some cases by crosslinking.
  • the lubricating compositions according to the invention have the advantage that these combinations or crosslinking are thermoreversible and that the level of association or crosslinking can be controlled by the addition of an additional diol compound.
  • the amount of boronic ester bonds (or boronic ester bond) which can be established between the polydiols random copolymers Al and the compounds A2, in particular the boronic ester random copolymer A2, is adjusted by those skilled in the art by means of an appropriate selection.
  • polydiol Al random copolymer especially that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula ( ⁇ - ⁇ ) and at least one monomer of formula ( ⁇ - ⁇ ), of the compound A2, in particular the boronic ester random copolymer A2, of the exogenous compound A4, and in particular the molar percentage of exogenous compound A4.
  • the person skilled in the art knows how to select the structure of the compound A2, in particular of the boronic ester statistical copolymer, as a function of the structure of the random copolymer Al, in particular that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula ( ⁇ - ⁇ ) and at least one monomer of formula ( ⁇ - ⁇ ).
  • the average length of the side chains of the polydiol Al random copolymer especially 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);
  • the length of the monomer M3 of the boronic ester random copolymer A2 the average degree of polymerization of the polydiol Al random copolymers, 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 ( ⁇ - ⁇ ), and random copolymers boronic esters A2, the weight percentage of the polydiols random copolymer Al, in particular that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula ( ⁇ - ⁇ ) and at least one monomer of formula ( ⁇ - ⁇ ), the weight percentage of the boronic ester random copolymer A2,
  • the content of the random copolymer Al, 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 is 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 content of compound A2 in particular the content of random boronic ester copolymer, ranges from 0.25% to 20% by weight relative to the total weight of the lubricating composition, preferably from 0.5 to 10% by weight. %> by weight relative to the total weight of the lubricating composition.
  • the mass ratio (ratio A1 / A2) between the polydiol Al 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) and at least one a monomer of formula ( ⁇ - ⁇ ), and the compound A2, in particular the boronic ester statistical copolymer ranges from 0.001 to 100, preferably from 0.05 to 20, even more preferably from 0.1 to 10, of more preferably from 0.2 to 5.
  • the sum of the masses of the random copolymer Al in particular that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula ( ⁇ - ⁇ ) and at least one monomer of formula (II-A2), and of the compound A2, in particular of the boronic ester random copolymer, is from 0.5 to 20% relative to the total mass of the lubricating composition, preferably from 4% to 15% relative to the total mass of the lubricating composition and the lubricating oil mass is from 60%> to 99%> relative to the total mass of the lubricating composition.
  • the molar percentage of exogenous compound A4 in the lubricating composition is from 0.05% to 5000%, preferably from 0.1% to 1000%, more preferably 0.5%. at 500%, even more preferably from 1% to 150%) relative to the boronic ester functions of compound A2, especially the poly (boronic ester) random copolymer.
  • the lubricant composition of the invention results from the mixture of:
  • the lubricating composition of the invention results from the mixture of:
  • Another object of the present invention is a method for modulating the viscosity of a lubricating composition, the process comprising at least:
  • a lubricant composition resulting from the mixing of at least one lubricating oil, at least one polydiol random copolymer Al and at least one random copolymer A2 comprising at least two boronic ester functions and which can associate with said polydiol random copolymer Al by at least one transesterification reaction,
  • modulating the viscosity of a lubricating composition is meant in the sense of the present invention, an adaptation of the viscosity at a given temperature depending on the use of the lubricant composition. This is achieved by adding an exogenous compound A4 as defined above. This compound makes it possible to control the degree of association and crosslinking of the two copolymers polydiol Al and poly (boronic ester) A2.
  • R14 and R15 identical or different selected from the group consisting of hydrogen and a hydrocarbon group having 1 to 24 carbon atoms.
  • these 1, 2-diol or 1, 3 diols have the general formula (VI) in which:
  • - W3 is an integer equal to 0 or 1;
  • R14 and R15 are different, one of the groups R14 or R15 is H and the other group R14 or R15 is a hydrocarbon chain, preferably a linear alkyl group, having 1 to 24 carbon atoms, preferably between 4 and 18 carbon atoms, preferably between 6 and 12 carbon atoms.
  • 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 ( ⁇ - ⁇ ) and at least one monomer of formula ( ⁇ - ⁇ ), Boronic ester random copolymer A2 and exogenous compound A4 also apply to processes for modulating the viscosity of a lubricating composition.
  • Another object of the present invention is the use of the lubricant 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.
  • composition for lubricating at least one engine comprising, in particular essentially, a composition resulting from the mixture of:
  • composition having a kinematic viscosity at 100 ° C measured according to ASTM D445 ranging from 3.8 to 26.1 cSt; the percentages by weight being expressed relative to the total weight of said composition.
  • the random copolymers Al 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 ( ⁇ - ⁇ ), and the boronic ester random copolymers A2 as defined above can associate and exchange thermoreversibly in the presence of the exogenous compound A4; but they do not form three-dimensional networks. They are not crosslinked.
  • the composition for lubricating at least one engine further comprises at least one functional additive selected from the group consisting of detergents, anti-wear additives, extreme pressure additives, additional antioxidants, anti-corrosion additives, viscosity index improvers, pour point improvers, defoamers, thickeners, dispersants, friction modifiers and mixtures thereof.
  • at least one functional additive selected from the group consisting of detergents, anti-wear additives, extreme pressure additives, additional antioxidants, anti-corrosion additives, viscosity index improvers, pour point improvers, defoamers, thickeners, dispersants, friction modifiers and mixtures thereof.
  • the composition for lubricating at least one engine comprising, in particular, essentially consists of a composition resulting from the mixture of:
  • At least one exogenous compound A4 as defined above; 0.5 to 15% by weight of at least one functional additive selected from the group consisting of detergents, anti-wear additives, extreme pressure additives, additional antioxidants, anti-corrosion additives, index-improving polymers viscosity, pour point improvers, defoamers, thickeners, dispersants, friction modifiers and mixtures thereof;
  • composition having a kinematic viscosity at 100 ° C measured according to ASTM D445 ranging from 3.8 to 26.1 cSt; the percentages by weight being expressed relative to the total weight of said composition.
  • Another object of the present invention is a composition for lubricating at least one transmission, such as manual or automatic gearboxes.
  • composition for lubricating at least one transmission comprising, in particular essentially, a composition resulting from the mixture of:
  • At least random copolymer Al 0.5% to 15% by weight of at least random copolymer Al 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 ( ⁇ - ⁇ ) and at least one monomer of formula (II-B), at least one boronic ester random copolymer A2 as defined above;
  • composition having a kinematic viscosity at 100 ° C. measured according to ASTM D445 ranging from 4.1 to 41 cSt, the percentages by weight being expressed relative to the total weight of said composition.
  • the random copolymers Al 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 ( ⁇ - ⁇ ), and the boronic ester random copolymers A2 as defined above can associate and exchange thermoreversibly in the presence of the exogenous compound A4; 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 composition for lubricating to lubricate at least one transmission comprising, in particular essentially consists of, a composition resulting from the mixture of:
  • At least one functional additive selected from the group consisting of detergents, anti-wear additives, extreme pressure additives, additional antioxidants, anticorrosive additives, polymers improving viscosity number, pour point impreners, defoamers, thickeners, dispersants, friction modifiers and mixtures thereof;
  • composition having a kinematic viscosity at 100 ° C. measured according to the ASTM D445 standard ranging from 4.1 to 41 cSt, the percentages by weight being expressed relative to the total weight of said composition.
  • 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 lubricant 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 ( ⁇ - ⁇ ) and at least one monomer of formula ( ⁇ - ⁇ ), the boronic ester random copolymer A2 and the exogenous compound A4 also apply to the method of lubricating at least one mechanical part.
  • Another subject of the present invention relates to the use of at least one compound chosen from 1,2-diols or 1,3 diols for modulating the viscosity of a lubricating composition, said lubricating composition resulting from the mixing of at least one lubricating oil, at least one polydiol random copolymer Al and at least one random copolymer A2 comprising at least two boronic ester functions and capable of associating with said polydiol Al random copolymer by at least one transesterification reaction.
  • these 1, 2-diol or 1, 3 diols have the general formula (VI):
  • R14 and R15 identical or different selected from the group consisting of hydrogen and a hydrocarbon group having 1 to 24 carbon atoms.
  • these 1, 2-diol or 1, 3 diols have the general formula (VI) in which:
  • - W3 is an integer equal to 0 or 1;
  • R14 and R15 are different, one of the groups R14 or R15 is H and the other group R14 or R15 is a hydrocarbon chain, preferably a linear alkyl group, having 1 to 24 carbon atoms, preferably between 4 and 18 carbon atoms, preferably between 6 and 12 carbon atoms.
  • the random copolymer Al of the invention is obtained according to the following reaction scheme 10:
  • 2nd step 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 an aqueous solution of 0.5 M hydrochloric acid, 6 ⁇ 300 ml of a saturated aqueous solution of NaHCO 3 and again 4 x 300 mL of water.
  • the organic phase is dried over MgSO 4, filtered and then concentrated under vacuum using a rotary evaporator to give 64.9 g (85.3% yield) of protected diol monomer in the form of a light yellow liquid. whose characteristics are as follows:
  • 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 methanol, filtration and drying under vacuum at 30 ° C overnight.
  • the deprotection of the copolymer is carried out according to the following protocol:
  • a poly (alkyl methacrylate-co-alkyldiol methacrylate) copolymer containing about 20 mol% of monomer diol M1 units and having an average length of pendant alkyl chains of 13.8 carbon atoms is obtained.
  • the boronic ester monomer is synthesized according to the following reaction scheme 11
  • 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 the 4-carboxyphenylboronic acid. The reaction medium is then transparent and homogeneous. 1,2-Propanediol (2.78 g, 36.6 mmol) is then added slowly, followed by an excess of magnesium in order to trap the water initially introduced as well as the water released by the condensation between the CPBA and the 1,2 propanediol. The reaction medium is stirred for 1 hour at 25 ° C before being filtered.
  • CPBA 4-carboxyphenylboronic acid
  • 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 x 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 as well. that the water released by the condensation between the boronic acid monomer and 1,2-dodecanediol.
  • reaction medium After stirring for 3 hours at ambient temperature, the reaction medium is filtered. The solvent is then removed from the filtrate using a rotary evaporator to give 10.2 g of a mixture of boronic ester monomer and 1,2-dodecanediol as a light yellow solid.
  • the statistical copolymer A2 is obtained according to the following protocol:
  • the boronic ester copolymer obtained has a number average molecular weight ( 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%. molar boronic ester monomer and 96% lauryl methacrylate. 3. Rheological studies o 3.1 Ingredients for the formulation of compositions A to H
  • the lubricating base oil used in the compositions to be tested is a Group III API oil sold by SK under the name Yubase 4. It has the following characteristics:
  • 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 51,400 g / mol. Its polydispersity index is 1.20. Its number-average degree of polymerization (DPn) is 184. The number average molecular weight and the polydispersity index are measured by steric exclusion chromatography using a polystyrene calibration. This copolymer is obtained according to the implementation of the protocol described in paragraph 1 above.
  • This copolymer comprises 4 mol% of monomers having boronic end functions.
  • the average side chain length is greater than 12 carbon atoms. Its 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 molecular weight and the polydispersity index are measured by size exclusion chromatography using a polystyrene calibration. This copolymer is obtained by the implementation of the protocol described in paragraph 2 above.
  • 1,2-Docecanediol comes from the TCI® supplier.
  • composition A (comparative) is obtained as follows:
  • 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 (Mn) equal to 10600 g / mol, a polydispersity index (Ip) equal to 3.06, a number average polymerization degree of 466 and the average length of the pendant chains is of 14 carbon atoms.
  • This polymethacrylate is used as a viscosity index improving additive.
  • 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 E (according to the invention) is obtained as follows:
  • composition C previously prepared are introduced into a flask. 97.6 mg of a 5% by weight solution of 1, 2-dodecanediol (compound A-4) in a base oil group III are added to this solution. The solution thus obtained is stirred at 90 ° C. for two hours.
  • 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 polymer formulations that do not form gels in a Group III base oil over the temperature range of the study (compositions A to F), the rheology measurements were performed using a cylindrical geometry of reference DG 26.7 Viscosity was measured as a function of shear rate for a temperature range of 10 ° C to 110 ° C. For each temperature, the viscosity of the system was measured as a function of the shear rate from 0.01 to 1000 sec -1 .
  • Viscosity measurements as a function of shear rate at T 10 ° C, 20 ° C, 30 ° C, 50 ° C, 70 ° C, 90 ° C and 110 ° C were made (ranging from 10 ° C to 110 ° C) followed by further measurements at 10 ° C and / or 20 ° C to To evaluate the reversibility of the systems, an average viscosity was then calculated for each temperature using the measuring points situated on the same plate.
  • Base oil was chosen to represent the evolution of the system's viscosity as a function of temperature, since this quantity directly reflects the compensation for the natural viscosity loss of a Group III base oil of the polymer systems studied.
  • the elastic modulus and the viscous modulus were measured as a function of temperature over a temperature range of 10 ° C to 110 ° C.
  • the heating (and cooling) speed was set at 0.003 ° C / s, the angular frequency was chosen at 1 rad / s with the deformation rate of 1%. o 3.4 Results obtained in rheology
  • compositions A to F has been studied for a temperature range of between 10 ° and 110 ° C.
  • the relative viscosity of these compositions is illustrated in FIGS. 5 and 6.
  • the polydiol Al random copolymer, alone in composition B, does not allow compensation for the natural viscosity loss of the Group III base oil. It is the same 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), compensation for the natural viscosity loss of the group base oil is observed. III greater than that resulting from the addition of the polymethacylate polymer in the Group III base oil (composition A).
  • composition C additionally comprises 10 mol% of free 1,2-dodecanediol (compound A-4) relative to the boronic ester functions of the poly (boronic ester) copolymer A-2 (composition D); a slight decrease in 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 additionally 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), observed a decrease in relative viscosity at low temperatures (temperatures below 45 ° C).
  • composition resulting from mixing the random copolymer polydiols A-1, poly (boronic ester) copolymer A-2 and 1,2-dodecanediol (compound A-4) compensates for the loss of viscosity of the oil.
  • Group III base in a manner comparable to that obtained with the polymethacrylate polymer in the Group III base oil (Composition A).
  • 1,2-dodecanediol makes it possible to modify, as a function of temperature, the viscosity of a lubricant composition resulting from the mixing of at least one random polydiol copolymer A-1 and at least one random copolymer A-2 poly (ester boronic) by controlling the level of association of the chains of these two copolymers.
  • compositions G and H were studied as a function of temperature (hysteresis curve of FIGS. 7 and 8). These two compositions result from the mixture in a Group III base oil of the polydiol random copolymer A-1 and the statistical copolymer A-2 poly (boronic ester).
  • the composition H further comprises 1,2-dodecanediol (compound A-4).
  • intersection of the curves G 'and G "illustrates the change of state of the compositions, that is to say the transition from a liquid state to a gelled state when the temperature increases and the transition 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 transition from a liquid state to a gelled state occurs between 95 ° C and 100 ° C. At this temperature, the chains of the copolymers Al and A-2 combine, exchange and form a three-dimensional network crosslinked. When the temperature is lowered, a new change of state is observed for a temperature of between 65 ° and 70 ° C. The composition changes from a gelled state to a liquid state in which the copolymer chains no longer associate with each other.
  • composition H (FIG. 8)
  • the composition H gels for a temperature between 105 and 110 ° C and goes 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 the composition H.

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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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
EP16700342.5A 2015-01-15 2016-01-11 Zusammensetzungen aus thermoassoziativen additiven mit gesteuerter assoziation und schmiermittelzusammensetzungen damit Active EP3245276B1 (de)

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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
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
FR3081466B1 (fr) * 2018-05-24 2020-06-12 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
EP4441176A1 (de) 2021-12-03 2024-10-09 Evonik Operations GmbH Borestermodifizierte polyalkyl(meth)acrylatpolymere
EP4441180A1 (de) 2021-12-03 2024-10-09 TotalEnergies OneTech Schmiermittelzusammensetzungen
EP4441178A1 (de) 2021-12-03 2024-10-09 TotalEnergies OneTech Schmiermittelzusammensetzungen
WO2023099630A1 (en) 2021-12-03 2023-06-08 Evonik Operations Gmbh Boronic ester modified polyalkyl(meth)acrylate polymers
WO2023099632A1 (en) 2021-12-03 2023-06-08 Evonik Operations Gmbh Boronic ester modified polyalkyl(meth)acrylate polymers
EP4441179A1 (de) 2021-12-03 2024-10-09 TotalEnergies OneTech Schmiermittelzusammensetzungen

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MA40661B1 (fr) 2018-11-30
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BR112017015040A2 (pt) 2019-11-19
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CA2971690A1 (fr) 2016-07-21
FR3031744B1 (fr) 2017-02-10
FR3031744A1 (fr) 2016-07-22

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