Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
  • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
  • C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
  • C08J3/096—Nitrogen containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
  • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
  • C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
  • C08J3/092—Hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
  • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
  • C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
  • C08J3/095—Oxygen containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
  • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
  • C08J3/11—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids from solid polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/21—Urea; Derivatives thereof, e.g. biuret
• • 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
  • C10M115/00—Lubricating compositions characterised by the thickener being a non-macromolecular organic compound other than a carboxylic acid or salt thereof
  • C10M115/08—Lubricating compositions characterised by the thickener being a non-macromolecular organic compound other than a carboxylic acid or salt thereof containing nitrogen
• • 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
  • C10M119/00—Lubricating compositions characterised by the thickener being a macromolecular compound
  • C10M119/24—Lubricating compositions characterised by the thickener being a macromolecular compound containing nitrogen
• • 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
  • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
  • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
  • C10M133/16—Amides; Imides
  • C10M133/18—Amides; Imides of carbonic or haloformic acids
  • C10M133/20—Ureas; Semicarbazides; Allophanates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2323/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
  • C08J2323/36—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by reaction with nitrogen-containing compounds, e.g. by nitration
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
  • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
  • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C08J2333/08—Homopolymers or copolymers of acrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
  • C08J2371/02—Polyalkylene oxides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
  • C08J2383/04—Polysiloxanes
• • 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
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/10—Amides of carbonic or haloformic acids
  • C10M2215/102—Ureas; Semicarbazides; Allophanates
  • C10M2215/1026—Ureas; Semicarbazides; Allophanates used as thickening 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
  • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2217/045—Polyureas; Polyurethanes
  • C10M2217/0456—Polyureas; Polyurethanes used as thickening agents
• • 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
  • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
  • C10N2050/10—Semi-solids; greasy

Definitions

• the present invention is in the field of formulation and proposes new viscosizing solutions. More particularly, the present invention relates to a composition comprising conventional bis-ureas and bis-ureas functionalized by macromolecular chains, these bis-ureas including complementary aryl spacers, the mixture of said bisureas in a solvent leading to a stable physical gel. The present invention also relates to a process for the preparation of this composition and the use of this composition as an organizer, alone or in a cosmetic preparation, an ink, a fuel or a lubricant, especially automotive.
• the Applicant has developed a strong expertise in the field of supramolecular chemistry, and in particular in the use of non-covalent interactions of the hydrogen bonding type to control the assembly of complex architectures and the obtaining of materials with reversible properties. in particular from symmetrical bis-ureas of global structure:
• A represents a spacer between the urea functions (preferably an aryl group which may be substituted with alkyl groups, more preferably toluene, xylene or trimethylbenzene) and R 'represents an alkyl group of aliphatic type, preferentially ethylhexyl; the hydrogen bonds are established between the protons of the urea functions of a first molecule and the oxygen atoms of the urea functions of a second molecule.
• Filamentary assemblies lead to a liquid solution.
• the tubular assemblies lead to a viscoelastic gel.
• Obtaining viscoelastic gels is a goal frequently pursued by those skilled in the art.
• One of the difficulties then encountered by those skilled in the art is to achieve good solubilization of bisurea in the desired medium.
• Conventional bis-ureas are not soluble in certain solvents such as those comprising long (C 12 -C 10) alkyl chains, which greatly limits industrial applications, particularly in the lubricant field.
• one of the tracks pursued in the prior art is to functionalize the bisureas by means of macromolecular chains.
• Pensée et al. have reported the synthesis of a bis-urea functionalized by chains of poly (isobutene) having a toluene spacer (PIBUT):
• EHUT ethylhexylureidotoluene bis-urea
• EHUTMB ethylhexylureidotrimethylbenzene bis-urea
• EHUT alone with a toluene spacer makes it possible to form a gel which has a transition temperature lying between around 40 ° C and EHUTMB alone with the spacer TMB can form a gel that has a transition temperature of around -5 ° C.
• the invention thus relates to a composition
• a composition comprising a mixture of conventional bis-ureas and of bis-ureas functionalized with macromolecular chains, in which: the conventional bis-ureas are of general formula (I),
• X represents a group selected from aryl or heteroaryl groups; optionally substituted with one or more groups selected from halogens, alkyls, alkenes, alkynes, heteroalkyls, heteroalkenes or heteroalkynes; preferably, X represents a phenyl group substituted with at least one alkyl chain comprising 1 to 4 carbon atoms and / or at least one halogen selected from Cl or Br;
• R 1 and R 2 each independently represent a linear or branched group selected from alkyl, alkene, alkyne, aryl, arylalkyl, heteroaryl, heteroalkyl, heteroalkene or heteroalkyne; said linear or branched group being optionally substituted by a halogen, alkyl, alkene, alkyne, heteroalkyl, heteroalkene or heteroalkyne group; the bis-ureas functionalized by macromolecular chains are of general formula (II),
• Y represents a group selected from aryl or heteroaryl groups; optionally substituted with one or more groups selected from halogens, alkyls, alkenes, alkynes, heteroalkyls, heteroalkenes or heteroalkynes; preferably, Y represents a phenyl group substituted with at least one alkyl chain comprising 1 to 4 carbon atoms or at least one halogen chosen from Cl or Br;
• R 3 and R 4 represents a macromolecular chain, preferably chosen from the family comprising poly (acrylate), poly (methacrylate), polyolefins, polycarbonates, polyethers, poly (diene), poly (vinyl acetate), polycarbonate, polysiloxanes, polyesters, polynorbornenes, polycyclooctenes and polystyrenes; and the other of R 4 and R 4 represents a linear or branched group selected from alkyl, alkene, alkyne, aryl, arylalkyl, heteroaryl, heteroalkyl, heteroalkene or heteroalkyne; said linear or branched group being optionally substituted by a halogen, alkyl, alkene, alkyne, heteroalkyl, heteroalkene or heteroalkyne group, or a macromolecular chain, preferably selected from the family comprising poly (acrylate), poly (methacrylate), polyolefins, polycarbonates, polyether
• X and Y are complementary spacers.
• the conventional bis-ureas of formula (I) are chosen from ethylhexylureido toluene (EHUT), ethylhexylureidotrimethylbenzene (EHUTMB) and ethylhexylureidoxylene (EHUX), preferably bis-ureas of formula (I). ) are EHUTMB molecules.
• the bis-ureas functionalized with macromolecular chains of formula (II) are chosen from poly (isobutene) ureidotoluene (PIBUT), poly (isobutene) ureidotrimethylbenzene (PIBUTMB), poly (isobutene) ureidoxylene (PIBUX) and poly (butyl acrylate) ureidoxylene (PABUX); preferentially, the functionalized bis-urea is chosen from PIBUX and PABUX.
• the composition comprises the mixture described above, and at least one solvent, preferably chosen from apolar solvents having long alkyl chains or polar solvents.
• the invention also relates to a process for preparing the composition comprising mixing the conventional bisurea compounds of formula (I) and functionalized bisureas of formula (II) with at least one solvent, with gentle stirring and optionally, in the presence of of heating.
• the solvent is an apolar solvent having long alkyl chains or an oil.
• said oil comprises vegetable, animal, mineral or synthetic oils; liquid hydrocarbon fuels; fuels; lubricants; more preferably PA06 oil.
• the solvent is a polar solvent.
• the invention also relates to the use of the composition, as an additive in a cosmetic composition, or an ink, in a fuel or in a lubricant, especially automotive.
• the composition is used as an organogelling agent, alone or in a cosmetic preparation, an ink, a fuel or a lubricant, in particular an automobile.
• Alkene relates to an unsaturated hydrocarbon chain, linear or branched, comprising from 2 to 40 carbon atoms, characterized by the presence of at least one covalent double bond between two carbon atoms;
• Alkyne relates to an unsaturated hydrocarbon chain, linear or branched, comprising from 2 to 40 carbon atoms, characterized by the presence of at least one covalent triple bond between two carbon atoms;
• Alkyl relates to an optionally substituted linear or branched hydrocarbon chain having 1 to 40 carbon atoms; preferentially the term alkyl, including alkyl chains containing from 1 to 9 carbon atoms, in particular methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl ; the term alkyl also includes long alkyl chains containing from 10 to 40 carbon atoms including in particular decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, cetyl, heptadecyl, octadecyl, nonadecyl and eicosyl.
• Apolar refers to a solvent whose resulting dipole moment is weak or zero
• Aprotic refers to media or solvents that can not contain or provide protons
• Aryl relates to a mono- or polycyclic system of 5 to 32 atoms, preferably 6 to 14, most preferably 6 to 10 carbon atoms having one or more aromatic rings.
• the aryl group is preferably a phenyl group;
• “Assembly” or “Self-assembly” refers to the association of molecules in order to form a particular structure in a controlled manner.
• the term “assembly” is intended to mean the association by weak bonds, preferably by hydrogen bonds, of bis-ureas in solution.
• these assemblies can lead to filamentary or tubular structures; preferentially to tubular assemblies;
• Biogas or “Biodiesel” means any fuel obtained from vegetable or animal oil (including used cooking oil) converted by transesterification with an alcohol (mainly methanol or ethanol) to obtain an ester Vegetable Oil Methyl (VOME) or Vegetable Oil Ethyl Ester (EEHV);
• Bossi-urea relates to a chemical molecule having two urea functions; the urea function being defined as the -NH-CO-NH- functional group;
• Fuel refers to a fuel for an engine that converts chemical energy into mechanical energy.
• Conventional fuels are liquids essentially derived from petroleum and supplying several types of products (gasolines, diesel fuel, jet fuel, etc.) intended to supply a heat engine. Fuels can be used in very different vehicles (cars, planes, ships, etc.). Fuels also include fuels derived from biomass (biofuels), the Fischer-Tropsch process using coal as feedstock or the modified Fischer-Tropsch process (or GTL "Gas to Liquids” method) using natural gas coal as a raw material.
• biomass biomass
• Fischer-Tropsch process using coal as feedstock
• GTL "Gas to Liquids” method modified Fischer-Tropsch process
• Macromolecular chain relates to a molecule of high molecular molar mass, consisting of the repetition of a basic pattern.
• the macromolecular chains may be of organic or mineral origin; preferably organic.
• the macromolecular chains may be of natural or synthetic origin; preferably, these chains are of synthetic origin and are chosen from the family comprising poly (acrylate), poly (methacrylate), polyolefins, polycarbonates, polyethers, poly (diene), poly (vinyl acetate ), polycarbonates, polysiloxanes, polyesters, polynorbornenes, polycyclooctenes and polystyrenes.
• the macromolecular chains are poly (isobutene) and poly (butyl acrylate);
• “Combustible” refers to a material capable of burning on contact with oxygen or an oxygen-containing gas, producing a usable amount of heat
• "Little Clogged” refers to the spacer of a bis-urea substituted in positions 1 and 3 by urea functions; said spacer being optionally substituted with one or two groups, each independently selected from halogens, alkyls, alkenes, alkynes, heteroalkyls, heteroalkenes or heteroalkynes; preferably the spacer of a "light-free" bis-urea is a phenyl group substituted at the 1-position and 3-position by urea functions and optionally substituted at the 4-position or the 4-and 6-position;
• Clogged refers to the spacer of a bis-urea substituted in positions 1 and 3 by urea functions and substituted by three or four groups, each independently selected from halogens, alkyls, alkenes, alkynes, heteroalkyls, heteroalkenes or heteroalkynes; preferably, the spacer is a phenyl group substituted in position 1 and 3 by urea functions and substituted by at least three groups chosen from alkyl chains containing 1 to 4 carbon atoms and halogens chosen from Cl or Br;
• Spacer refers to the chemical group separating the two urea functions within a bis-urea molecule; according to the invention, the spacer relates to an aryl or heteroaryl group substituted in particular by two urea functions respectively in position 1 and 3 of the aryl or heteroaryl group;
• a mixture of bis-ureas provides complementary spacers when it comprises bis-ureas with a sparse spacer and bis-ureas with a congested spacer;
• Gel or “physical gel” relates to a solid three-dimensional network formed by physical interactions between chemical entities diluted in a fluid.
• a gel can exhibit properties ranging from soft and ductile to hard and brittle. In particular, a gel is considered stable when it has no flow.
• gel or “physical gel” refers to any solid three-dimensional architecture obtained by self-assembly by hydrogen bonds intermolecular bis-ureas conventional or functionalized by macromolecular chains;
• Halogen refers to a chemical element selected from I7 th column of the periodic table; preferably Cl or Br;
• Heteroalkene relates to an alkene chain having at least one atom different from a carbon atom or hydrogen atom; preferably, said atom being selected from N, S, P or O;
• Heteroalkyne refers to an alkyne chain having at least one atom other than a carbon or hydrogen atom; preferably, said atom being selected from N, S, P or O;
• Heteroalkyl refers to an alkyl group having at least one atom different from a carbon atom or hydrogen atom; preferably, said atom being selected from N, S, P or O;
• Heteroaryl refers to an aryl group having at least one atom different from a carbon or hydrogen atom; preferably, said atom being selected from N, S, P or O;
• Oil refers to a fatty substance, liquid at room temperature and insoluble in water. It can be of synthetic, vegetable, animal or mineral origin;
• Long alkyl chains refers to apolar solvents having alkyl chains comprising at least 10 carbons; preferably comprising 12 to 40 carbon atoms;
• Lubricant relates to a fatty substance comprising a compound or a mixture of compounds, intended to reduce the phenomena of friction or abrasion when it is introduced between two solid bodies.
• lubricant includes all lubricants for mechanical or anatomical use;
• Polar is a molecule or a solvent having a non-zero resulting dipole moment
• Protic refers to a chemical entity capable of providing an H + ion to its environment
• Reversible or “thermoreversible”: according to the invention, the composition has a reversible (or thermoreversible) gel / liquid behavior depending on whether its temperature is below (gel) or above (liquid) its gel temperature / liquid
• a reversible composition within the meaning of the invention is a composition which can pass indefinitely from the gel state to a liquid state or from a liquid state to a gel state depending on its temperature;
• Ambient temperature refers to the temperature of the surrounding environment. According to the invention, the ambient temperature is 20 ° C ⁇ 5 ° C;
• Gel / liquid transition temperature refers to the particular phase change temperature of a compound or a mixture of compounds, characterizing the transition from a gel state to a liquid state.
• the present invention relates to a mixture or a composition
• a mixture or a composition comprising a mixture of conventional bis-ureas and bis-ureas functionalized with macromolecular chains, in which: the conventional bis-ureas are of general formula (I),
• X represents a group selected from aryl or heteroaryl groups; optionally substituted with one or more groups selected from halogens, alkyls, alkenes, alkynes, heteroalkyls, heteroalkenes or heteroalkynes; preferably, X represents a phenyl group substituted with at least one alkyl chain comprising 1 to 4 carbon atoms and / or at least one halogen selected from Cl or Br; R 1 and R 2 each independently represent a linear or branched group selected from alkyl, alkene, alkyne, aryl, arylalkyl, heteroaryl, heteroalkyl, heteroalkene or heteroalkyne; said linear or branched group being optionally substituted by a halogen, alkyl, alkene, alkyne, heteroalkyl, heteroalkene or heteroalkyne group; the bis-ureas functionalized by macromolecular chains are of general formula (II),
• Y represents a group selected from aryl or heteroaryl groups; optionally substituted with one or more groups selected from halogens, alkyls, alkenes, alkynes, heteroalkyls, heteroalkenes or heteroalkynes; preferably, Y represents a phenyl group substituted with at least one alkyl chain comprising 1 to 4 carbon atoms or at least one halogen chosen from Cl or Br;
• R 3 and R 4 represents a macromolecular chain, preferably chosen from the family comprising poly (acrylate), poly (methacrylate), polyolefins, polycarbonates, polyethers, poly (diene), poly (vinyl acetate), polycarbonate, polysiloxanes, polyesters, polynorbornenes, polycyclooctenes and polystyrenes; and the other of R 3 and R 4 represents a linear or branched group selected from alkyl, alkene, alkyne, aryl, arylalkyl, heteroaryl, heteroalkyl, heteroalkene or heteroalkyne; said linear or branched group being optionally substituted by a halogen, alkyl, alkene, alkyne, heteroalkyl, heteroalkene or heteroalkyne group, or a macromolecular chain, preferably selected from the family comprising poly (acrylate), poly (methacrylate), polyolefins and polyst
• X and Y are complementary spacers.
• the invention relates to a mixture or a composition consisting of a mixture of conventional bis-ureas, of bis-ureas functionalized by macromolecular chains and of a solvent, in which: the conventional bis-ureas are of general formula (I),
• X and Y are complementary spacers.
• said conventional bisurea of formula (I) are chosen from ethylhexylureido toluene (EHUT), ethylhexylureidotrimethylbenzene (EHUTMB) and ethylhexylureidoxylene (EHUX).
• ethylhexylureido toluene is ethylhexylureido-4-methylbenzene of formula
• ethylhexylureidotrimethylbenzene is ethylehexylureido-2,4,6-trimethylbenzene of formula
• ethylhexylureidoxylene is ethylhexylureido-4,6-dimethylbenzene of formula
• the bis-ureas functionalized with macromolecular chains of formula (II) are selected from oligomers, polymers or copolymers chosen from the family comprising poly (acrylate), poly (methacrylate), polyolefins polycarbonates, polyethers, poly (diene), polyvinyl acetate, polycarbonate, polysiloxanes, polyesters, polynorbornenes, polycyclooctenes and polystyrenes.
• said macromolecular chains are chosen according to the nature of the solvent.
• the macromolecular chains functionalizing the bisureas of formula (II) are chosen so as to facilitate the solubilization of bis-ureas conventional compounds of formula (I) in solvents in which these bis-ureas are not or only slightly soluble.
• the macromolecular chains functionalizing the bisureas of formula (II) are chosen so as to stabilize the self-assemblies of bisureas in solvents in which the conventional bisureas of formula (I) do not form no gel; preferably in solvents in which the bis-ureas do not form a gel that is stable in time or stable in temperature.
• the macromolecular chains are chosen from poly (isobutene) chains when the solvent is selected from apolar solvents, in particular chosen from apolar solvents comprising long alkyl chains; in particular comprising dodecane, tridecane, tetradecane, pentadecane, cetane, heptadecane, octadecane, nonadecane, eicosane, heneicosane, docosan, tricosane tetracosane, pentacosane, hexacosane, heptacosane, octacosan, nonacosane, triacontane , untriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane, heptatriacon
• the macromolecular chains are poly (butyl acrylate) chains when the solvent is selected from polar solvents; preferably when the solvent is chosen in particular from tetrahydrofuran (THF) or ethyl acetate.
• solvent is selected from polar solvents; preferably when the solvent is chosen in particular from tetrahydrofuran (THF) or ethyl acetate.
• the macromolecular chains are poly (ethylene oxide) (POE) chains when the solvent is selected from water, alcohols or acetonitrile.
• the macromolecular chains have a number-average molar mass, M n , ranging from 300 to 100,000 g / mol.
• the macromolecular chains have a degree of polymerization in number, DP n , ranging from 2 to 1000; preferably from 90 to 200; more preferably from 13 to 35.
• the degree of number polymerization, DP n is equal to the ratio of the number-average molar mass of the macromolecular chains, M n , to the molar mass of the monomer unit (also called repeat unit) Mo.
• said bis-ureas functionalized by macromolecular chains, of formula (II) are poly (isobutene) ureidotoluene (PIBUT); preferably the functionalized bis-ureas are poly (isobutene) ureido-4-methylbenzene of formula
• n represents an integer from 2 to 1000; preferably n is an integer of 5 to 50.
• said bis-ureas functionalized with macromolecular chains, of formula (II) are poly (isobutene) ureidotrimethylbenzene (PIBUTMB); preferably, said functionalized bis-ureas are poly (isobutene) ureido-2,4,6-trimethylbenzene of formula
• n represents an integer from 2 to 1000; preferably n is an integer of 5 to 50.
• said bis-ureas functionalized by macromolecular chains, of formula (II) are poly (isobutene) ureidoxylene (PIBUX); preferably, said functionalized bis-ureas are poly (isobutene) ureido-4,6-dimethylbenzene of formula where n represents an integer from 2 to 1000; preferably n is an integer of 5 to 50.
• said bis-ureas functionalized by macromolecular chains, of formula (II) are poly (butyl acrylate) ureidoxylene (PABUX); preferably, said functionalized bis-ureas are poly (butyl acrylate) ureido-4,6-dimethylbenzene of formula
• n represents an integer from 2 to 1000; preferably n is an integer of 5 to 50.
• said bis-ureas functionalized by macromolecular chains, of formula (II) are poly (butyl acrylate) ureidoxylene (PABUX); preferably, said functionalized bis-ureas are poly (butyl acrylate) ureido-4,6-dimethylbenzene of formula
• n represents an integer from 2 to 1000; preferably n is an integer of 5 to 50.
• said bis-ureas functionalized with macromolecular chains of formula (II), are poly (ethylene oxide) ureidoxylene (POEUX); preferably, said functionalized bis-ureas are poly (ethylene oxide) ureido-4,6-dimethylbenzene of formula where neither and n 2 each independently represent an integer from 2 to 1000; preferably ni and n 2 each independently represent an integer from 2 to 50.
• ni represents an integer from 2 to 20.
• n 2 represents an integer of 2 to 20.
• the mixture or the composition comprising the mixture comprises a low-space X spacer and a crowded Y spacer.
• the mixture or the composition comprising the mixture comprises a crowded X spacer and a slightly congested Y spacer.
• a space-constrained spacer is a phenyl group substituted at the 1-position and 3-position by urea functions; said phenyl group being optionally further substituted with one or two groups, each independently selected from halogens, alkyls, alkenes, alkynes, heteroalkyls, heteroalkenes or heteroalkynes; preferably chosen from an alkyl chain comprising 1 to 4 carbon atoms and / or a halogen selected from Cl or Br.
• the lightly spaced spacer is a phenyl group substituted in position 1 and 3 by urea and unsubstituted functions. on other positions.
• the space-less spacer is a phenyl group substituted at the 1-position and 3-position by urea functions and unsubstituted at the 2-position.
• the unshielded spacer is a phenyl group substituted at the 1-position and 3-position. urea functions, and substituted in the 4-position by Cl, Br or a methyl group.
• the unencumbered spacer is a phenyl group substituted in the 1-position and 3-position by urea functions, and substituted in the 4-position by Cl.
• the unencumbered spacer is a phenyl group substituted in position. 1 and 3 by urea functions, and substituted in the 4-position by Br. In one embodiment, the unencumbered spacer is a phenyl group substituted in position 1 and 3 by urea functions, and substituted in position 4 by a group. methyl. In a mode of realization, the space-less spacer is a phenyl group substituted in position 1 and 3 by urea functions, and substituted in position 4 and 6 by Cl, Br or a methyl group. In one embodiment, the unencumbered spacer is a phenyl group substituted at the 1-position and 3-position by urea functions, and substituted at position 4 and 6 with Cl.
• the unencumbered spacer is a group. phenyl substituted at the 1-position and 3-position by urea functions, and substituted at position 4 and 6 with Br. In one embodiment, the unencumbered spacer is a phenyl group substituted in the 1-position and 3-position by urea functions, and substituted in position 4 and 6 with a methyl group.
• a hindered spacer is a phenyl group substituted at the 1 and 3 positions by urea functions and substituted with three or four groups, each independently selected from halogens, alkyls, alkenes, alkynes, heteroalkyls, heteroalkenes or heteroalkynes; preferentially selected from alkyl chains having 1 to 4 carbon atoms and halogens selected from Cl or Br.
• the hindered spacer is a phenyl group substituted in the 1 and 3 position by urea functions and substituted on all the other positions.
• the hindered spacer is a phenyl group substituted at the 1-position and 3-position by urea functions and substituted at the 2, 4 and 6 position with Cl, Br or a methyl group.
• the hindered spacer is a phenyl group substituted at the 1 and 3 positions with urea functions and substituted at the 2, 4 and 6 positions with Cl.
• the hindered spacer is a phenyl group. substituted in positions 1 and 3 by urea functions and substituted in position 2, 4 and 6 by Br.
• the congested spacer is a phenyl group substituted in position 1 and 3 by urea functions and substituted in position 2, 4 and 6 with a methyl group.
• the spacer is selected from benzyl, tolyl, xylyl or trimethylbenzyl groups; optionally substituted with one or more halogen groups, preferably with one or more Cl or Br atoms.
• the present invention also relates to bis-ureas functionalized with macromolecular chains of general formula (III):
• A-, A or -CH3
• Y represents a group selected from aryl or heteroaryl groups; optionally substituted with one or more groups selected from halogens, alkyls, alkenes, alkynes, heteroalkyls, heteroalkenes or heteroalkynes; preferably, Y represents a phenyl group substituted with at least one alkyl chain comprising 1 to 4 carbon atoms or at least one halogen chosen from Cl or Br;
• R 3 represents a linear or branched group selected from alkyl, alkene, alkyne, aryl, arylalkyl, heteroaryl, heteroalkyl, heteroalkene or heteroalkyne; said linear or branched group being optionally substituted by a halogen, alkyl, alkene, alkyne, heteroalkyl, heteroalkene or heteroalkyne group, or a macromolecular chain, preferably selected from the family comprising poly (acrylate), poly (methacrylate), polyolefins and polystyrenes; preferentially R 3 is a phenyl group substituted with an alkyl chain; more preferably R 3 is butylbenzyl;
• p represents an integer of 1 to 1000; preferably p is an integer of 2 to 50; more preferably, p is 3; n 'represents an integer of 1 to 1000; preferably is an integer of 2 to 500;
• m ' represents an integer from 0 to 1000. According to one embodiment, m' represents an integer equal to 0. According to one embodiment, said bis-ureas functionalized with macromolecular chains of formula (III), are polydimethylsiloxaneeuridotoluene (PDMSUT), preferably polydimethylsiloxaneeuridotoluene of formula:
• n ' is an integer from 1 to 1000; preferably is an integer of 2 to 500.
• the present invention also relates to a mixture or a composition comprising a mixture of conventional bis-ureas and bis-ureas functionalized with macromolecular chains, in which: the conventional bis-ureas are of general formula (I),
• A-, A or -CH 3
• Y, R 3 , p, n 'and m' are defined as above; and X and Y are complementary spacers.
• the macromolecular chains functionalizing the bisureas of formula (III) are chosen so as to stabilize the self-assemblies of the bisureas in solvents in which the conventional bisureas of formula (I) do not form no gel; preferably in solvents in which the bis-ureas do not form a gel that is stable in time or stable in temperature.
• the invention relates to a mixture or a composition consisting of a mixture of conventional bis-ureas, of bis-ureas functionalized by macromolecular chains and of a solvent, in which: the conventional bis-ureas are of general formula (I),
• A-, A or -CH3
• mixtures or compositions comprising the mixtures of bis-ureas having complementary spacers X and Y are described in the following table:
• the mixture of the invention comprises conventional bis-ureas of general formula (I),
• X represents a crowded spacer; preferentially a trimethylbenzene group;
• Ri and R 2 are defined as before; and bis-ureas functionalized with macromolecular chains, of general formula (II),
• Y represents a slightly congested spacer: preferably a toluene or xylene group; R 3 and R 4 are defined as above.
• the mixture of the invention comprises: conventional bis-ureas of general formula (I),
• X represents a space-free spacer; preferably a toluene or xylene group;
• Ri and R 2 are defined as before; of bis-ureas functionalized with macromolecular chains, of general formula (II),
• Y represents a crowded spacer; preferentially a trimethylbenzene group; R 3 and R 4 are defined as above.
• the mixture or the composition comprising the mixture, conventional bis-ureas of formula (I) and functionalized bis-ureas of formula (II) results in a stable gel whose gel / liquid transition temperature is greater than that of a solution obtained from said conventional bis-ureas, alone.
• the mixture or the composition comprising the mixture, conventional bis-ureas of formula (I) and functionalized bis-ureas of formula (III) leads to a stable gel whose gel / liquid transition temperature is greater than that of a solution obtained from said conventional bis-ureas, alone.
• the blend of the invention comprises from 1% to 99mol. functionalized bis-ureas of formula (II) or formula (III) relative to the total molar amount of bis-ureas; preferably 10 mol. at 90 mol. relative to the total molar amount of bis-ureas; more preferably 50 mol. relative to the total molar amount of bis-ureas.
• the preferred mixtures correspond to the molar compositions of the conventional bis-ureas of formula (I) / functionalized bis-ureas of formula (II) below (% mol /% mol.): 10/90; 20/80; 30/70; 40/60; 50/50; 60/40; 70/30; 80/20 and 90/10.
• the preferred mixtures correspond to the molar compositions of the conventional bis-ureas of formula (I) / functionalized bis-ureas of formula (III) below (% mol /% mol.): 10/90; 20/80; 30/70; 40/60; 50/50; 60/40; 70/30; 80/20 and 90/10.
• the mixture of the invention comprises an equimolar mixture of conventional bis-ureas of formula (I) and functionalized bis-ureas of formula (II).
• the mixture of the invention comprises an equimolar mixture of conventional bis-ureas of formula (I) and functionalized bis-ureas of formula (III).
• the mass content of bis-ureas in the mixture or the composition comprising the mixture is 0.1 to 10% by weight relative to the total mass of the composition; preferentially, the mass ratio of bis-ureas is less than or equal to 10%; more preferably the mass content of bis-ureas is about 0.4%; 0.5% or 1% by weight relative to the total mass of the composition.
• the molar concentration of bis-ureas in the mixture of the invention is from 0.001 to 0.1 mol / L; preferably from 0.002 to 0.008 mol / L: more preferably the molar concentration of bis-ureas in the composition is about 5 mmol / L.
• the mixture or composition comprising the mixture is capable of forming a physical gel when said mixing is carried out at a temperature below the gel / liquid transition temperature characterizing said mixture of bisureas. Said gel / liquid transition temperature varies for each mixture of bis-ureas depending on its composition and / or the presence of solvent.
• the mixture of the invention has a gel / liquid transition temperature greater than ambient temperature; preferably, said gel / liquid transition temperature is greater than 40 ° C; preferentially the temperature of gel / liquid transition is greater than 70 ° C; more preferably the gel / liquid transition temperature is about 100 ° C.
• said gel / liquid transition temperature is below ambient temperature; preferably, said gel / liquid transition temperature is less than 15 ° C.
• the mixture of the invention is capable of forming a physical gel when mixing is carried out at ambient temperature.
• the mixture of the invention is capable of forming a liquid when the mixture is heated to a temperature above its gel / liquid transition temperature.
• the mixture or the composition comprising the mixture has a reversible behavior between a physical gel state and a liquid state; more particularly the composition is thermoreversible.
• the Applicant believes that the possibility of obtaining a gel at room temperature, with or without heating, from the mixture of conventional bis-ureas and of bis-ureas functionalized with macromolecular chains results from both an improved solubilization by the introduction of bis-ureas having macromolecular chains in the medium, and a synergistic effect between the different spacers of bis-ureas to stabilize the assemblies of bis-ureas in solution.
• the present invention also relates to a composition
• a composition comprising: a mixture of conventional bis-ureas of formula (I) and of bis-ureas functionalized with macromolecular chains of formula (II) or of formula (III) as previously described, and at least a solvent.
• the solvent of the composition is selected from polar polar, aprotic polar and apolar polar aprotic liquids.
• the solvent is selected from apolar solvents, preferentially apolar solvents containing long alkyl chains or an oil; more preferably, apolar solvents containing long alkyl chains.
• the solvent of the composition is chosen from solvents comprising long alkyl chains such as dodecyl, tridecyl, tetradecyl, pentadecyl, cetyl, heptadecyl, octadecyl, nonadecyl, eicosyl, henicosyl, docosyl, tricosyl, tetracosyl and pentacosyl.
• hexacosyl, heptacosyl, octacosyl, nonacosyl triacontyl, untriacontyl, dotriacontyl, tritriacontyl, tetracyclonyl, pentatriacontyl, hexatriacontyl, heptatriacontyl, octatriacontyl, nonatriacontyl and tetracontyl.
• the solvent is selected from polar solvents, preferentially water, acetonitrile, chloroform, 1,2-dimethoxyethane, N, N-dimethylacetamide, ⁇ , ⁇ -dimethylformamide, tetrahydrofuran or ethyl acetate.
• the solvent is an oil or a mixture of oils selected from vegetable, animal, mineral or synthetic oils; preferentially among liquid hydrocarbon fuels, fuels or lubricants; more preferably the solvent is PAO6 oil.
• the solvent is a silicone oil; preferably, decamethylcyclopentasiloxane (D5).
• the invention also relates to a process for preparing a composition comprising a mixture with gentle stirring, and optionally in the presence of heating: conventional bis-ureas of general formula (I),
• the present invention relates to a method for obtaining, with stirring, and optionally in the presence of heating, a composition
• a composition comprising the following steps: the preparation of a mother solution Si comprising conventional bisureas of formula (I) and a solvent in which said conventional bis-ureas are soluble, the preparation of a stock solution S 2 comprising functionalized bis-ureas of formula (II) and at least one solvent in which said functionalized bis-ureas are soluble, identical or different from that of the solution Si, a mixing step of the solutions Si and S 2 .
• the invention also relates to a process for preparing a composition comprising a mixture with gentle stirring, and optionally in the presence of heating: conventional bis-ureas of general formula (I),
• A-, A or -CH3
• the present invention relates to a process for obtaining, with stirring, and optionally in the presence of heating, a composition
• a composition comprising the following steps: preparing a mother solution Si comprising conventional bis-ureas of formula (I) and a solvent in which said conventional bis-ureas are soluble, the preparation of a stock solution S 2 comprising functionalized bis-ureas of formula ( III) and at least one solvent in which said functionalized bis-ureas are soluble, identical or different from that of the Si solution, a step of mixing the Si and S 2 solutions .
• the mother solutions S 1 and S 2 do not individually form a gel that is stable in time or stable in temperature.
• only the mixing step of the stock solutions Si and S 2 leads to a physical gel; preferentially to a stable gel over time at a temperature below the gel / liquid transition temperature.
• only the step of mixing the stock solutions Si and S 2 leads to the formation of a gel by a tubular self-assembly of bis-ureas by intermolecular hydrogen bonds.
• the mass concentration of conventional bis-ureas of formula (I) in the stock solution Si is between 0 and 150 g / L; preferably, the mass concentration is from 1 to 110 g / l. According to one embodiment, the mass concentration of conventional bis-ureas of formula (I) in the mother solution Si is approximately equal to 2, 4, 40, 50 or 100 g / l.
• the mass concentration of functionalized bis-ureas of formula (II) in the stock solution S 2 is between 0 to 150 g / L; preferably, the mass concentration is from 1 to 110 g / l. According to one embodiment, the mass concentration of functionalized bis-ureas of formula (II) in the stock solution S 2 is approximately equal to 2, 4, 40, 50 or 100 g / L.
• the mass concentration of functionalized bis-ureas of formula (III) in the stock solution S 2 is between 0 to 150 g / L; preferably, the mass concentration is from 1 to 110 g / l. According to one embodiment, the mass concentration of functionalized bis-ureas of formula (III) in the parent solution S 2 is approximately equal to 2, 4, 40, 50 or 100 g / l.
• the composition of the process of the invention comprises a mixture of bis-ureas comprising from 1% to 99 mol. functionalized bis-ureas of formula (II) with respect to the total molar amount of bis-ureas; preferably 10 mol. at 90 mol. relative to the total molar amount of bis-ureas; more preferably about 50 mol. relative to the total molar amount of bis-ureas.
• the composition of the process of the invention comprises a mixture of bis-ureas comprising from 1% to 99 mol. functionalized bis-ureas of formula (III) with respect to the total molar amount of bis-ureas; preferably 10 mol. at 90 mol. relative to the total molar amount of bis-ureas; more preferably about 50 mol. relative to the total molar amount of bis-ureas.
• the preferred compositions of the process of the invention correspond to mixtures comprising molar compositions of the following conventional bis-ureas of formula (I) / functionalized bis-ureas of formula (II) (% mol /% mol.) : 10/90; 20/80; 30/70; 40/60; 50/50; 60/40; 70/30; 80/20 and 90/10.
• the preferred compositions of the process of the invention correspond to the mixtures comprising molar compositions of the following conventional bis-ureas of formula (I) / functionalized bis-ureas of formula (III) (% mol /% mol.) : 10/90; 20/80; 30/70; 40/60; 50/50; 60/40; 70/30; 80/20 and 90/10.
• the solvent of the composition is selected from polar polar, aprotic polar and apolar polar aprotic liquids.
• the solvent of the mother solution Si is identical to the solvent of the solution S 2 . According to one embodiment, the solvent of the mother solution Si is different from the solvent of the solution S 2 .
• the solvent is selected from apolar solvents, preferably toluene or very apolar solvents containing long alkyl chains (C12-C40) including decane, undecane, dodecane, tridecane, tetradecane, pentadecane, cetane, heptadecane, octadecane, nonadecane, eicosane, henicosane, docosan, tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, untriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane, heptatriacontane
• the solvent of the process is selected from polar solvents, preferentially water, acetonitrile, chloroform, 1,2-dimethoxyethane, ⁇ , ⁇ -dimethylacetamide, ⁇ , ⁇ -dimethylformamide, tetrahydrofuran or ethyl acetate.
• the solvent is an oil or a mixture of oils selected from vegetable, animal, mineral or synthetic oils, liquid hydrocarbon fuels, fuels or lubricants such as gas oils, bio-diesel fuels and fuels.
• the solvent is PAO6 oil.
• the solvent is a silicone oil; preferably, decamethylcyclopentasiloxane (D5).
• the invention also relates to the use of the mixture of the invention as described above, for texturing or thickening a product, in particular an oil, a fuel or a lubricant; preferentially for the manufacture of gels from oils.
• the mixture of the invention is used as an additive in a cosmetic composition, or an ink, in a fuel or in a lubricant, especially automotive.
• the mixture of the invention is used as an organogelator, alone or in a cosmetic preparation, an ink, a fuel or a lubricant, especially automobile.
• FIG. 1 is a photograph showing solutions of EHUTMB (left), PIBUX (right) and EHUTMB / PIBUX mixture (90 mol./10 mol.) (In the middle) in solution in dodecane ( 4 g / L).
• Figure 2A is a photograph showing solutions of EHUTMB (right), PABUX (left) and equimolar mixture EHUTMB / PABUX (middle) in ethyl acetate solution (50 g / L). L).
• Figure 2B is a photograph showing solutions of EHUTMB (right), PABUX (left) and an EHUTMB / PABUX equimolar mixture (in the middle) in solution in THF (100 g / L).
• Figure 3 is a graph showing the evolution of relative viscosities for various solutions in toluene (40 g / L) comprising conventional bis-ureas having a trimethylbenzene spacer (EHUTMB), alone or in combination with functionalized bis-ureas.
• EHUTMB trimethylbenzene spacer
• FIG. 4 shows the infrared spectra of two mixtures PIBUX / EHUTMB (top, equimolar composition, bottom composition PIBUX / EHUTMB 10% mol / 90% mol in solution in toluene at 4g / L, taken at different temperatures between 20 ° C and 80 ° C.
• FIG. 5 is a graph showing the evolution of the ratio of the absorption bands of the NH bond of the bis-ureas (3333 cm -1 and 3300 cm -1 ) as a function of the temperature of the mixture for an equimolar composition PIBUX / EHUTMB in the toluene.
• Figure 6 shows the infrared spectra of two mixtures EHUTMB / PIBUX (% mol ./ mol) 70/30 (6A) and 90/10 (6B) in dodecane at 4g / L taken at different temperatures between 20 ° C and 110 ° C.
• FIG. 7 is a graph showing the evolution of the ratio of the absorption bands of the NH bond of the bis-ureas (3333 cm -1 and 3300 cm -1 ) as a function of the temperature of the mixture for EHUTMB / PIBUX mixtures (mol% ./mol.) 30/70 (7A); 40/60 (7B); 60/40 (7C); 70/30 (7D) and 90/10 (7E), in dodecane.
• Figure 8 is a graph showing the evolution of the relative viscosities of EHUTMB / PIBUX solutions in toluene (2 g / L) at different temperatures.
• Figure 9 shows the evolution of the elastic moduli G 'and G "of a mixture EHUTMB / PIBUX (90 mol./10 mol.) In dodecane (4g / L)
• Figure 10 is a photograph showing solutions of EHUTMB (left), PDMSUT (right) and an EHUTMB / PDMSUT equimolar mixture (in the middle) dissolved in decamethylcyclopentasiloxane (25 g / L).
• EXAMPLE 1 Preparation of gels from an equimolar mixture of conventional bis-ureas and functionalized in the presence of an apolar solvent - Influence of the spacer.
• Table 1 presents the results obtained for these various solutions.
• the Applicant believes that the functionalized bis-ureas could not form gels because of the steric hindrance of the macromolecular chains which prevents tubular self-assembly of functionalized bis-ureas; the equimolar mixture of conventional and functionalized bis-ureas containing identical spacers, that is to say mixtures EHUT / PIBUT (with a toluene spacer) and EHUTMB / PIBUTMB (with a trimethylbenzene spacer) does not form gels ; the equimolar mixture of conventional and functionalized bis-ureas containing different spacers, that is to say mixtures EHUT / PIBUX, EHUT / GDPUTMB, EHUTMB / PIBUT, EHUTMB / PIBUX, EHUX / PIBUT and EHUX / PIBUTMB, makes it possible to form stable gels.
• Figure 1 shows a photograph showing a solution of EHUTMB (left), PIBUX (right) and EHUTMB / PIBUX mixture (90% mol / 10 mol%) (in the middle) in dodecane (4g / Room temperature.
• FIG. 1 shows that the classic bis-urea EHUTMB is not soluble in dodecane (white precipitate) unlike PIBUX functionalized bis-urea which provides a homogeneous solution.
• the photograph also shows that the EHUTMB / PIBUX mixture (90 mol% / 10 mol%) of these bis-ureas containing complementary spacers (trimethylbenzene spacer for EHUTMB and xylene spacer for PIBUX) makes it possible to obtain 1) good solubilization.
• Gel formation is obtained by tubular self-assembly of bis-ureas in solution by means of intermolecular hydrogen bonds. However, depending on the polarity of the solvent, there may be competition between the formation of hydrogen bonds between the bis-ureas and the formation of hydrogen bonds between the bis-ureas and the solvent.
• the EHUTMB bis-urea ( Figure 2B, right) and PABUX ( Figure 2B, left) are each soluble in THF at a concentration of 100 g / L. However, these bis-urea solutions do not form a gel at room temperature; these solutions are liquid.
• the functionalized bis-urea PABUX, has made it possible to promote the solubilization of the conventional bis-urea EHUTMB in solvents which are unfavorable for the formation of gel by hydrogen bonds.
• the conventional bisurea EHTUMB is not soluble in apolar solvents having long alkyl chains such as dodecane.
• Functional bis-urea PIBUX is soluble in dodecane.
• PIBUX / EHUTMB solutions at a concentration of 4 g / L in dodecane were prepared and a macroscopic observation of the resulting compositions was performed.
• Table 2 shows the results obtained for the various mixtures made as a function of the molar amount of functionalized bis-ureas (PIBUX) relative to the total molar amount of bis-ureas introduced into the mixture.
• PIBUX functionalized bis-ureas
• PIBUX improves the solubilization of EHUTMB in dodecane; in fact, when the composition mainly comprises PIBUX functionalised bis-ureas (> 70 mol in PIBUX in the mixture), a homogeneous liquid solution is obtained: the conventional and functionalized bis-ureas are solubilized in the medium.
• EXAMPLE 4 Demonstration by viscometry of the effect of complementary spacers for an EHUTMB / PIBUX mixture in toluene.
• This experiment aims to confirm by viscometry the effect of complementary spacers on gel formation in toluene.
• Example 5 Detection by FTIR spectrometry of the effect of complementary spacers for EHUTMB / PIBUX mixtures - temperature stability of the gels.
• This experiment aims to evaluate by FTIR spectroscopy the temperature stability of various compositions comprising the mixture of conventional bis-ureas having a trimethylbenzene spacer (EHUTMB) and functionalized bis-ureas having a xylene spacer (PIBUX).
• EHUTMB trimethylbenzene spacer
• PIBUX functionalized bis-ureas having a xylene spacer
• the IRFT analysis makes it possible to observe the absorption bands of the NHs of the urea functions.
• the NH bond resonates at different frequencies depending on whether it is bonded ( ⁇ 3400cm ⁇ 1 ) or not (> 3400cm ⁇ 1 ) by hydrogen bonding to another urea function.
• value of the ratio of the absorbances at 3330 and 3300cm is characteristic of their assembly structure: this ratio is of the order of 1.1 for the filamentary structure and the order of 1.3 for the tubular structure.
• the results presented in FIG. 4 show that for an EHUTMB / PIBUX mixture (50 ⁇ mol / 50 ⁇ mol), the NH absorption bands change shape when the temperature of the mixture is greater than or equal to approximately 70.degree.
• the gel / liquid transition temperature of the mixture EHUTMB / PIBUX (50% mol / 50 mol%) in toluene is thus about 70 ° C.
• the gel obtained by EHUTMB / PIBUX (50 mol / 50 mol) in toluene therefore remains stable when heated to temperatures not exceeding 70 ° C.
• the NH absorption bands change shape when the temperature of the mixture is greater than or equal to about 50 ° C.
• the gel / liquid transition temperature of the EHUTMB / PIBUX mixture (90 ⁇ mol / 10 mol) in toluene is therefore about 50.degree.
• the gel obtained with EHUTMB / PIBUX (90% mol / 10 mol%) in toluene therefore remains stable when heated at temperatures not exceeding 50 ° C.
• Figure 5 shows the evolution of the ratio of the absorbances at 3330 and 3300cm -1 as a function of the temperature of a mixture EHUTMB / PIBUX (90 ⁇ mol / 10 moL) This representation confirms that the gel / liquid transition temperature for this mixture is about 50 ° C. 5.2 in dodecane
• EHUTMB / PIBUX compositions (% .mol /% mol.): 90/10; 30/70; 40/60; 60/40 and 70/30.
• Figures 7A-7E show that the gel / liquid transition in the dodecane is greater than 50 ° C.
• the compositions comprising mixtures of 30 to 70 mol. conventional bis-ureas and functionalized bis-ureas provide temperature-stable gels up to about 100 ° C.
• the mixture of conventional bis-ureas having a trimethylbenzene spacer (EHUTMB) and functionalized bis-ureas having a xylene spacer (PIBUX) was studied in toluene, solvent in which these two bisureas are soluble, at a total concentration of bis-ureas in toluene of 2 g / L.
• the aim is to evaluate the temperature range over which the EHUTMB / PIBUX mixture provides a stable gel. For this, the relative viscosity of various EHUTMB / PIBUX compositions was measured at 20 ° C, 40 ° C, 60 ° C and 80 ° C.
• a solution comprising only EHUTMB is very viscous whatever the temperature (20, 40, 60 or 80 ° C); a solution comprising only PIBUX is moderately viscous at 20 ° C and becomes less and less viscous when the temperature is increased to 80 ° C; a solution comprising a mixture PIBUX / EHUTMB has high viscosities for temperatures up to 60 ° C, in particular an equimolar mixture PIBUX / EHUTMB is stable up to a temperature of 67 ° C.
• Example 7 Rheological analysis of EHUTMB / PIBUX mixtures in dodecane.
• the mixture EHUTMB / PIBUX (90/10) is dissolved in dodecane at a total mass concentration of bis-ureas of 4 g / l.
• FIG. 9 shows the elastic modulus G 'and the viscous modulus G "of the EHUTMB / PIBUX mixture (90/10) as a function of the scanning frequency for a stress of 3 Pa at a temperature of 25 ° C.
• Figure 9 also shows the same analysis done after 7 months.
• Example 8 Obtaining gels in oils.
• an equimolar POEUX / EHUTMB mixture makes it possible firstly to solubilize each EHUTMB and POEUX bis-urea in acetonitrile and, in a second step, to obtain a gel.
• PIBUX Thesis of Cécile Fonteneau, "Synthesis and properties of supramolecular polymers associated by hydrogen bonds with urea motifs, Pierre and Marie Curie University: Paris, France, 2013); PABUX (Fonteneau, C. et al., Polym Chem 2014, 5 (7), 2496); POEUX (Obert, E. et al., J. Am Chem Soc 2007, 129 (50), 15601) and PDMSUT (Colombani et al., Macromolecules 2005, 38, 1752).
• PIBUTMB PolylsoButyleneUreidoTrimethylbenzene
• the solutions for the viscometric analysis were prepared in anhydrous toluene, previously filtered with 0.45 ⁇ m porosity filters.
• Functionalized bis-urea solutions were prepared at 80 g / L and conventional bis-urea solutions were prepared at concentrations of 5 mM.
• the solutions were stirred on a vibrating tray for 10 days.
• the EHUX solutions are then heated at 80 ° C. with constant stirring for 12 hours to obtain complete dissolution of the bisphenols. ureas in solution.
• Solutions comprising conventional bis-ureas were mixed with polymer-functionalized bis-ureas and supplemented with a filtered solvent to obtain compositions comprising 1 mole, 5 moles. and 10 mol.
• the solutions were prepared by separately dissolving the conventional bis-ureas and functionalized with polymers in toluene (2 g / L). These solutions were then stirred on a vibrating tray for 10 days. These two solutions were then mixed according to the following functionalized bis-urea / bis-urea (mol / mol) compositions: 10/90; 20/80; 30/70; 40/60; 50/50; 60/40; 70/30; 80/20 and 90/10. The mixtures obtained were then stirred overnight in order to homogenize the compositions before the FTIR analysis.
• the spectra were recorded using a Nicolet IslO spectrometer equipped with a SPECAC supplied VTC21525 heater in 2 mm optical path vessels equipped with CaF 2 windows.
• the rheological analysis was carried out on a HAAKE Rheostress (RS) 600 rheometer, with a plane cone type geometry, diameter 4 cm, angle 2 °, titanium C35 2 ° Ti L04026.
• the sample is set up in terms of the rheometer. Then the geometry of the apparatus is adjusted. The sample is heated at 80 ° C for 15 min and then allowed to stand at 25 ° C for 2h before the stress and frequency sweep.
• the number-average molar masses, M n and mass average, M w , of the macromolecular chains were determined by steric exclusion chromatography (Size exclusion chromatography, SEC) in THF at a flow rate of ImL / min.

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