EP3204449A1

EP3204449A1 - Composition containing bis-ureas for forming stable gels

Info

Publication number: EP3204449A1
Application number: EP15788164.0A
Authority: EP
Inventors: Laurent Bouteiller; Emilie RESSOUCHE; Sandrine PENSEC; Benjamin Isare
Original assignee: Centre National de la Recherche Scientifique CNRS; Universite Pierre et Marie Curie Paris 6
Current assignee: Centre National de la Recherche Scientifique CNRS; Sorbonne Universite
Priority date: 2014-10-10
Filing date: 2015-10-09
Publication date: 2017-08-16
Also published as: WO2016055751A1; US20170335071A1; FR3027029A1; FR3027029B1

Abstract

The invention relates to a composition comprising classic bis-ureas and bis-ureas functionalised by macromolecular chains, said bis-ureas including complementary spacers of the aryl type, the mixture of said bis-ureas in a solvent leading to a stable physical gel. The invention also relates to a method for producing said composition and to the use of said composition as an organogelator, alone or in a cosmetic preparation, an ink, a fuel or a lubricant, especially of a motor vehicle.

Description

COMPOSITION BASED ON BIS-UREES TO TRAIN

STABLE GELS

FIELD OF THE INVENTION 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.

STATE OF THE ART

Since the 1980s, the interest aroused by organogellators has grown steadily as evidenced by the exponential number of publications on the subject.

These small molecules have the capacity to structure all kinds of organic solvents even at relatively low mass concentrations (less than 1% by weight) and to give them the desired texture or viscosity, which is of particular interest to scientists and scientists. because of the many possible applications.

This particular property is the consequence of intermolecular interactions sufficiently stabilizing to compensate for the loss of entropy linked to the decrease of their degree of freedom when these molecules are placed in contact with solvents. These interactions can be of various kinds: dipolar interactions, Van der Waals forces, π interactions or intra- or intermolecular hydrogen bonds. The vast majority of organogellators provide thermoreversible gels and use intermolecular interactions such as hydrogen bonds as a driving force for their self-assembly in solution.

Among this group, the family of urea, and more particularly of bisurea, has been widely studied.

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:

in which 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.

According to the nature of the solvent used, the concentration of bis-urea and the temperature, these bis-ureas self-associate by hydrogen bonds in filamentary (a) or tubular (b) assemblies: b}

tubular filamentary

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. In order to overcome the problem of solubility of conventional bisureas in this type of solvent, ie in the solvents in which these bis-ureas are not soluble, one of the tracks pursued in the prior art is to functionalize the bisureas by means of macromolecular chains.

Thus, Pensée et al. (Macromolecules 2010) have reported the synthesis of a bis-urea functionalized by chains of poly (isobutene) having a toluene spacer (PIBUT):

PIBUT These functionalized bis-ureas are capable of self-assembly by hydrogen bonds in different types of solvents. However, the steric hindrance of these bis-ureas due to the functionalization of the poly (isobutene) chains leads systematically to a filament self-assembly irrespective of the nature of the solvent; the composition remains liquid.

An equimolar mixture of conventional bis-ureas of ethylhexylureido toluene (EHUT)

and bis-ureas functionalized by PIBUT macromolecular chains, has been studied in heptane, solvent in which the EHUT bis-ureas and the PIBUT bis-ureas are each soluble. The results of this study have shown that it is possible to combine in heptane conventional EHUT bisurea with bis-urea functionalized with PIBUT macromolecular chains to form gels, but the gels obtained have transition temperatures. lower than that of classical bisurea.

Isare et al. ("Engineering the cavity of self-assembled dynamic nanotubes, J. Phys Chem B, Vol 113, 2009, pp 3360-3364) have shown that the spacers of the bis-ureas can influence the gel / liquid transition temperature; especially when the mixture comprises bis-ureas having complementary spacers, i.e., bis-ureas having a hindered spacer and bis-ureas having a low-space spacer. The mixture of the conventional ethylhexylureidotoluene bis-urea (EHUT) having a toluene spacer with the conventional ethylhexylureidotrimethylbenzene bis-urea (EHUTMB) having a trimethylbenzene spacer, solubilized in toluene, solvent in which the EHUT bis-ureas and the EHUTMB bis-ureas are each soluble, makes it possible to obtain a gel which has a transition temperature of around 65 ° C. whereas 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.

All of these experiments have been carried out on conventional bis-ureas and in solvents in which these bis-ureas are soluble. To the knowledge of the Applicant, no information is given in the prior art on the behavior that functionalized bis-ureas could have by macromolecular chains having a chosen spacer, mixed with conventional bis-ureas having a complementary spacer. of the chosen spacer.

On the other hand, there is a need to develop novel bisurea systems which provide chemically stable gels in all kinds of solvents, including solvents in which conventional bis-ureas are not soluble. or do not form a gel; more particularly, in solvents useful in industry, for example solvents containing long alkyl chains or in polar solvents. Finally, there is also a need for systems that make it possible to make gels whose transition temperature is adapted to the desired use.

Surprisingly, the Applicant has demonstrated that the mixture of conventional bis-ureas and bis-ureas functionalized by macromolecular chains, having complementary spacers was not only possible, but that it led to thermally stable gels, which it allowed to improve the solubilization of conventional bis-ureas and to promote the formation of gels having transition temperatures of interest.

SUMMARY The invention thus relates to 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),

Formula I in which

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),

Formula II in which

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;

at least one of 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, polyethers, poly (diene), polyvinyl acetate, polycarbonate, polysiloxanes, polyesters, polynorbornenes, polycyclooctenes and polystyrenes; preferentially R ₃ and R 1 are identical; more preferably R ₃ and R 4 are identical and each represents a macromolecular chain of poly (isobutene) or poly (butyl acrylate);

and

X and Y are complementary spacers.

According to one embodiment, 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.

According to one embodiment, 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.

According to one embodiment, 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. According to one embodiment, the solvent is an apolar solvent having long alkyl chains or an oil.

According to one embodiment, said oil comprises vegetable, animal, mineral or synthetic oils; liquid hydrocarbon fuels; fuels; lubricants; more preferably PA06 oil. According to one embodiment, 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.

According to one embodiment, 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.

DEFINITIONS

In the present invention, the terms below are defined as follows: "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. According to the invention, 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. According to the invention, the term "assembly" is intended to mean the association by weak bonds, preferably by hydrogen bonds, of bis-ureas in solution. According to the invention, 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);

"Bis-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. first;

"Macromolecular chain" relates to a molecule of high molecular molar mass, consisting of the repetition of a basic pattern. In the present invention, the macromolecular chains may be of organic or mineral origin; preferably organic. According to the invention, 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. Preferably, 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;

"Complementary Spacers" Within the meaning of the invention, a mixture of bis-ureas provides complementary spacers when it comprises bis-ureas with a sparse spacer and bis-ureas with a congested spacer;

"About": placed before a number, this term means plus or minus 10% of the nominal value of this number;

"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. In the present invention, the term "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. In particular, the term 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.

DETAILED DESCRIPTION

The present invention 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),

Formula I in which

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),

Formula II in which

at least one of 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 polystyrenes; preferentially R ₃ and R ₄ are identical; more preferably R ₃ and R 1 are identical and represent each a macromolecular chain of poly (isobutene) or poly (butyl acrylate);

and

X and Y are complementary spacers.

According to one embodiment, 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),

Formula I wherein X, R 1 and R ₂ are defined as above; and the bis-ureas functionalized by macromolecular chains are of general formula (II),

Formula II wherein Y, R ₃ and R ₄ are defined as above;

and X and Y are complementary spacers.

According to one embodiment, said conventional bisurea of formula (I) are chosen from ethylhexylureido toluene (EHUT), ethylhexylureidotrimethylbenzene (EHUTMB) and ethylhexylureidoxylene (EHUX).

According to a preferred embodiment, ethylhexylureido toluene (EHUT) is ethylhexylureido-4-methylbenzene of formula

According to a preferred embodiment, ethylhexylureidotrimethylbenzene (EHUTMB) is ethylehexylureido-2,4,6-trimethylbenzene of formula

According to a preferred embodiment, ethylhexylureidoxylene (EHUX) is ethylhexylureido-4,6-dimethylbenzene of formula

According to one embodiment, 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.

In one embodiment, said macromolecular chains are chosen according to the nature of the solvent.

According to one embodiment, 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.

According to one embodiment, 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.

According to one embodiment, 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, heptatriacontane, octatriacontane, nanotriacontane, tetracontane; preferentially when the solvent chosen is dodecane.

According to one embodiment, 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.

According to one embodiment, the macromolecular chains are poly (ethylene oxide) (POE) chains when the solvent is selected from water, alcohols or acetonitrile. According to one embodiment, the macromolecular chains have a number-average molar mass, M _n , ranging from 300 to 100,000 g / mol. According to one embodiment, 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.

According to one embodiment, 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

where n represents an integer from 2 to 1000; preferably n is an integer of 5 to 50.

According to one embodiment, 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

According to one embodiment, 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.

According to one embodiment, 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

According to one embodiment, 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.

According to one embodiment, ni represents an integer from 2 to 20. According to one embodiment, n ₂ represents an integer of 2 to 20.

According to one embodiment, the mixture or the composition comprising the mixture comprises a low-space X spacer and a crowded Y spacer.

According to one embodiment, the mixture or the composition comprising the mixture comprises a crowded X spacer and a slightly congested Y spacer. According to one embodiment, 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. In one embodiment, the lightly spaced spacer is a phenyl group substituted in position 1 and 3 by urea and unsubstituted functions. on other positions. In one embodiment, 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. In one embodiment, 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. In one embodiment, 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. In one embodiment, 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. In one embodiment, 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. According to one embodiment, 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. In one embodiment, the hindered spacer is a phenyl group substituted in the 1 and 3 position by urea functions and substituted on all the other positions. In one embodiment, 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. In one embodiment, 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. In one embodiment, 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. In one embodiment, 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. According to one embodiment, 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

ITT formula in which

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:

wherein 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),

Formula I wherein X, R 1 and R ₂ are defined as above; the bis-ureas functionalized by macromolecular chains are of general formula (III),

A-, = A or -CH ₃

Formula 111

wherein Y, R ₃ , p, n 'and m' are defined as above; and X and Y are complementary spacers.

According to one embodiment, 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.

Formula I wherein X, R 1 and R ₂ are defined as above; and the bis-ureas functionalized by macromolecular chains are of general formula (III),

A-, = A or -CH3

Formula ITT wherein Y, R ₃ , p, n 'and m' are defined as above; and X and Y are complementary spacers.

According to one embodiment, the mixtures or compositions comprising the mixtures of bis-ureas having complementary spacers X and Y are described in the following table:

Spacer X Blend of Spacer Y of bis-ureas

No. Conventional Formula (I) functionalized formula (II) or

formula (III)

1

^ position of urea functions

According to one embodiment, the mixture of the invention comprises conventional bis-ureas of general formula (I),

Formula I

in which 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),

Formula II in which

Y represents a slightly congested spacer: preferably a toluene or xylene group; R ₃ and R 4 are defined as above.

According to one embodiment, the mixture of the invention comprises: conventional bis-ureas of general formula (I),

Formula I wherein 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),

Formula II in which

Y represents a crowded spacer; preferentially a trimethylbenzene group; R ₃ and R 4 are defined as above.

According to one embodiment, 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. According to one embodiment, 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.

In one embodiment, 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.

According to the present invention, 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. According to the present invention, 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. According to one embodiment, the mixture of the invention comprises an equimolar mixture of conventional bis-ureas of formula (I) and functionalized bis-ureas of formula (II).

According to one embodiment, the mixture of the invention comprises an equimolar mixture of conventional bis-ureas of formula (I) and functionalized bis-ureas of formula (III).

In one embodiment, 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.

In one embodiment, 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. In one embodiment, 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. According to one embodiment, 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.

According to one embodiment, said gel / liquid transition temperature is below ambient temperature; preferably, said gel / liquid transition temperature is less than 15 ° C.

According to one embodiment, the mixture of the invention is capable of forming a physical gel when mixing is carried out at ambient temperature.

According to one embodiment, 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.

According to one embodiment, 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.

Without wishing to be bound by a particular theory, 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 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.

In one embodiment, the solvent of the composition is selected from polar polar, aprotic polar and apolar polar aprotic liquids. According to one embodiment, 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. According to one embodiment, 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.

According to one embodiment, the solvent is selected from polar solvents, preferentially water, acetonitrile, chloroform, 1,2-dimethoxyethane, N, N-dimethylacetamide, Ν, Ν-dimethylformamide, tetrahydrofuran or ethyl acetate.

According to one embodiment, 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. According to one embodiment, 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),

Formula I wherein X, R 1 and R ₂ are defined as above; of bis-ureas functionalized with macromolecular chains, of general formula (II)

Formula II wherein Y, R ₃ and R ₄ are defined as above; and a solvent.

More particularly, the present invention relates to a method for obtaining, with stirring, and optionally in the presence of heating, 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),

Formula I wherein X, R 1 and R ₂ are defined as above; of bis-ureas functionalized with macromolecular chains, of general formula (III)

A-, = A or -CH3

Formula 111 wherein Y, R ₃ , p, n 'and m' are defined as above; and a solvent.

More particularly, the present invention relates to a process for obtaining, with stirring, and optionally in the presence of heating, 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} .

According to one embodiment, the mother solutions S ₁ and S ₂ do not individually form a gel that is stable in time or stable in temperature.

According to one embodiment, 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. According to one embodiment, 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.

In one embodiment, 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.

In one embodiment, 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.

In one embodiment, 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.

In one embodiment, 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.

In one embodiment, 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.

According to the present invention, 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.

According to the present invention, 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.

In one embodiment, the solvent of the composition is selected from polar polar, aprotic polar and apolar polar aprotic liquids.

According to one embodiment, 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 .

According to one embodiment, 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, octatriacontane, nonatriacontane and tetracontane. According to one embodiment, the solvent is dodecane.

According to one embodiment, the solvent of the process is selected from polar solvents, preferentially water, acetonitrile, chloroform, 1,2-dimethoxyethane, Ν, Ν-dimethylacetamide, Ν, Ν-dimethylformamide, tetrahydrofuran or ethyl acetate.

According to one embodiment, 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.

According to a preferred embodiment, the solvent is PAO6 oil.

According to one embodiment, 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. According to one embodiment, 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.

According to one embodiment, 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.

BRIEF DESCRIPTION OF THE FIGURES

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. macromolecular chains having either a xylene spacer (PIBUX) or a trimethylbenzene spacer (PIBUTMB).

Figure 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).

EXAMPLES The present invention will be better understood on reading the following examples which illustrate the invention in a nonlimiting manner.

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. These experiments show that under certain conditions it is possible to form stable gels in solvents in which conventional bis-ureas do not permit to obtain stable gels in time or to obtain gels having a gel / liquid transition temperature greater than ambient temperature.

Various solutions of bis-ureas have been studied in toluene (5 mM): solutions of classical bis-ureas selected from EHUT, EHUTMB or EHUX;

functionalized bis-urea solutions with poly (isobutene) chains selected from PIBUT, PIBUTMB or PIBUX;

equimolar mixtures of conventional and functionalized bis-urea solutions. 1.1. Macroscopic assessment of solutions

Table 1 presents the results obtained for these various solutions.

Table 1. Rheological behavior of various bis-urea solutions.

Surprisingly, the Applicant has found that: only the conventional bisureas EHUT, EHUTMB and EHUX do not make it possible to form gels in toluene; only bis-ureas functionalized with poly (isobutene) chains (PIBUT, PIBUTMB and PIBUX) do not make it possible to form gels. Without wishing to be bound by theory, 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.

Comparable results were obtained in dodecane. 1.2. Example of the EHUTMB / PIBUX mixture in dodecane

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.

Figure 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. EHUTMB bisureas in dodecane (absence of precipitate), and 2) gel formation. 1.3. conclusions

The mixture at ambient temperature of conventional bis-ureas and functionalized with poly (isobutene) chains having complementary spacers allows 1) to improve the solubilization of conventional bis-ureas and 2) to provide gels in a solvent in which, alone, conventional bis-ureas are not soluble or form no gel (here in the dodecane). Example 2 Obtaining Gels from an Equimolar Mixture of Conventional Bisurea and Functionalized in the Presence of a Polar Solvent - Influence of the Spacer

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.

This study therefore aims to evaluate the effect of the complementary spacers of the bis-urea mixture on the formation of gel in polar solvents, unfavorable to the combination of bis-ureas in solution. Since the poly (isobutene) chains are insoluble in polar solvents, macromolecular chains of poly (butyl acrylate) have been used to functionalize the bis-urea having a xylyl spacer. The bis-urea obtained is polybutyl acrylate ureidoxylene (PABUX). The classic bisurea EHUTMB has a trimethylbenzene spacer. 2.1. in ethyl acetate

The classic bisurea EHUTMB (Figure 2A, right) is not soluble in ethyl acetate at a concentration of 50 g / L, unlike functionalized bis-urea PABUX for the same concentration, which leads to a clear liquid (Figure 2A, left). However, it is found that equimolar mixture EHUTMB / PABUX, at a concentration of 50 g / L, provides a translucent gel that does not flow, even when the sample is returned (Figure 2A, in the middle). 2.2. in THF

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 equimolar mixture EHUTMB / PABUX, in THF at a concentration of 100 g / L, provided a gel that does not flow, even when the sample is returned (Figure 2B, in the middle).

2.3. Conclusion

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.

This result can be compared with that observed for the mixture PIBUX / EHUTMB in dodecane (and when the macromolecular chains are chains of poly (isobutene)) where the hydrogen bonds between bis-ureas were stronger. It is thus demonstrated here that the invention covers a wide variety of possibilities, where one can select the nature of the macromolecular chain suitable for solubilizing and stabilizing the assemblies of bis-ureas in the chosen solvent: here, poly chains (butyl acrylate) for polar solvents. The solubilization of these assemblies could be carried out at room temperature, which is a definite advantage, and allowed the formation of gels.

It has also been shown that the competition between the formation of hydrogen bonds between the solvent and bis-ureas on the one hand, and self-association of bisurea on the other hand, can be counterbalanced by the preferential interaction between complementary spacers, here between xylene and trimethylbenzene spacers. Example 3 Effect of the Composition of EHUTMB / PIBUX Mixtures on Gel Formation in Dodecane

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.

Table 2. Macroscopic appearance of solutions comprising PIBUX and EHUTMB bis-ureas for different compositions.

The results show that 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.

On the other hand, these results show that intermediate compositions of a mixture EHUTMB / PIBUX (that is to say the amount of EHUTMB and PIBUX is between 30 and 70 mol relative to the total amount of bis-ureas in the medium) allow to obtain elastic gels at room temperature without heating. When the composition mainly comprises conventional EHUTMB bis-ureas (<30 mol in PIBUX), the composition does not make it possible to obtain stable homogeneous gels.

In conclusion, these results show that stable gels are obtained for compositions comprising 30 to 70 mol. in PIBUX functionalised bis-ureas relative to the total molar amount of bis-ureas 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.

In order to evaluate the influence of the spacers on the viscosity of the mixture, the experiments were carried out in a solvent in which the conventional bis-ureas and the functionalized bis-ureas are each individually soluble.

Several solutions of bis-ureas were produced in toluene, at a total mass concentration of bis-ureas equal to 40 g / l and at a mass ratio of between 13 and 16% of bis-ureas relative to the total amount of solid. : solutions comprising conventional bis-ureas having a trimethylbenzene spacer (EHUTMB), alone; solutions comprising a mixture of conventional bis-ureas having a trimethylbenzene spacer (EHUTMB) and functionalized bis-ureas having a trimethylbenzene spacer (PIBUTMB); solutions comprising a mixture of conventional bis-ureas having a trimethylbenzene spacer (EHUTMB) and functionalized bis-ureas having a xylene spacer (PIBUX). Figure 3 shows the evolution of the relative viscosities for these various solutions as a function of the molar concentration of conventional bisurea EHUTMB in the medium. The results show that: solutions comprising only conventional bis-ureas having a trimethylbenzene spacer (EHUTMB) are low viscosity, the solutions remain liquid; the mixture of conventional EHUTMB bis-ureas and PIBUTMB functionalized bis-ureas, having identical spacers (trimethylbenzene), leads to solutions having a viscosity comparable to that of solutions comprising conventional EHUTMB bisureas alone; the mixture of conventional EHUTMB bis-ureas and of PIBUX functionalized bis-ureas, having different and complementary spacers (respectively trimethylbenzene and xylene), leads to solutions having a higher viscosity than solutions comprising conventional EHUTMB bisureas alone. .

In conclusion, these results confirm the importance of the pair of spacers chosen when mixing conventional bis-ureas and functionalized bis-ureas, for the gel formulation. In particular, it has been shown that the mixture of functionalized bis-ureas having a xylene spacer (PIBUX), with conventional bis-ureas having a trimethylbenzene spacer (EHUTMB) leads to increases in relative viscosity; translating a good self-association of these compounds into the mixture.

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).

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. On the other hand, 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.

5.1. in toluene An analysis was carried out at different temperatures on an EHUTMB / PIBUX mixture in solution in toluene at a total mass concentration of 4g / L of bis-ureas, for EHUTMB / PIBUX compositions (% .mol /% mol. ): 50/50 and 90/10.

The results presented in FIG. 4 show that for an EHUTMB / PIBUX mixture (50 μmol / 50 μmol), 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. For an EHUTMB / PIBUX mixture (90% mol / 10 mol%) 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 μmol / 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 μmol / 10 moL) This representation confirms that the gel / liquid transition temperature for this mixture is about 50 ° C. 5.2 in dodecane

An analysis was carried out at different temperatures on an EHUTMB / PIBUX mixture in solution in dodecane at a total mass concentration of 4g / L of bis-ureas. for EHUTMB / PIBUX compositions (% .mol /% mol.): 90/10; 30/70; 40/60; 60/40 and 70/30.

The results are shown in Figures 6 and 7.

In a manner similar to the experiments carried out in toluene, these results show that the NH absorption bands change shape when the temperature of the mixture increases (Examples for the EHUTMB / PIBUX (.mol / mol.) 90/10 and 70 compositions. / 30, Figures 6A and 6B).

Figures 7A-7E show that the gel / liquid transition in the dodecane is greater than 50 ° C. In particular, 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.

5.3. conclusions

In conclusion, these results show that it is possible by FTIR spectroscopy 1) to evaluate the transition temperature from a gel state to a liquid state, and 2) to evaluate the temperature stability of the bis-urea mixtures. . These results also show that the mixture of conventional bis-ureas and of functionalized bis-ureas having complementary spacers according to the invention (here EHUTMB / PIBUX) makes it possible to obtain gels having improved temperature stability (the mixtures remain stable for temperatures much higher than the ambient temperature). Example 6 Influence of the Temperature on the Relative Viscosity of EHUTMB / PIBUX Mixtures

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.

The results (FIG. 8) show that the EHUTMB / PIBUX composition (50 μmol / 50 μmol) has a very high relative viscosity (> 18) when this mixture is heated to a temperature below 80 ° C .; however, the viscosity is minimal when the mixture is heated to 80 ° C.

In addition, these results show that: 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.

Therefore, these results show that an equimolar mixture of conventional bis-ureas having a trimethylbenzene spacer and functionalized bis-ureas having a xylene spacer, provides a stable gel to a temperature of 67 ° C.

Example 7: Rheological analysis of EHUTMB / PIBUX mixtures in dodecane.

A mixture of EHUTMB classic bis-ureas and PIBUX functionalised bis-ureas with a molar composition EHUTMB / PIBUX 90/10, has been studied in rheology.

The mixture EHUTMB / PIBUX (90/10) is dissolved in dodecane at a total mass concentration of bis-ureas of 4 g / l.

The rheological analysis, in particular the study of the elastic modulus G 'and the module The viscous G "of a sample makes it possible to evaluate the rheological behavior of a material, since a material is considered to be an elastic gel if G '>G".

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.

These results show: on the one hand, that G '> G ", that is to say that the gel is elastic, on the other hand, after 7 months, the sample has comparable modules G' and G" to those obtained at t = 0.

In conclusion, the EHUTMB / PIBUX mixture in dodecane, with a 90/10 molar composition, exhibits a stable elastic gel behavior over time.

Example 8: Obtaining gels in oils.

8.1. From a mixture of EHUTMB / PDMSUT in a silicone oil The mixture of conventional bis-ureas having a trimethylbenzene spacer (EHUTMB) and functionalized bis-ureas of formula (III) having a toluene spacer (PDMSUT) was studied in a silicone oil, decamethylcyclopentasiloxane (D5), at a concentration of 25 g / l.

The results (FIG. 10) show that: a solution comprising only EHUTMB is insoluble in the silicone oil; a solution comprising only PDMSUT is viscous but does not form a gel; a PDMSUT / EHUTMB [1: 2 molar ratio] mixture makes it possible firstly to solubilize each EHUTMB bis-urea and PDMSUT in the silicone oil, and in a second step, to obtain a stable gel.

Therefore, these results show that a mixture of conventional bis-ureas having a trimethylbenzene spacer and functionalized bis-ureas having a toluene spacer makes it possible to obtain a stable gel in solvents in which the conventional bis-ureas are not soluble, such as silicone oil.

8.2. From an EHUTMB / PIBUX mixture in PA06 mineral oil

The mixture of conventional bis-ureas having a trimethylbenzene spacer (EHUTMB) and functionalized bis-ureas of formula (II) having a xylene spacer (PIBUX) was studied in mineral oil PA06 at a concentration of 10 g / l.

The results show that: a solution comprising only EHUTMB is insoluble in PA06 (formation of a white precipitate); a solution comprising only PIBUX is viscous but does not form a gel;

an equimolar mixture PIBUX / EHUTMB makes it possible initially to solubilize each bis-urea EHUTMB and PIBUX in PA06 and in a second time, makes it possible to obtain a gel. Therefore, these results show that a mixture of conventional bis-ureas possessing a trimethylbenzene spacer and functionalized bis-ureas having a xylene spacer, makes it possible to obtain a stable gel in solvents in which the conventional bis-ureas are not soluble, such as PA06.

EXAMPLE 9 Preparation of Gels from an EHUTMB / POEUX Mixture in Acetonitrile

The mixture of conventional bis-ureas having a trimethylbenzene spacer (EHUTMB) and Functionalized bis-urea chains of poly (ethylene oxide) of formula (II) having a xylene spacer (POEUX) was studied in acetonitrile at a concentration of 25 g / L.

The results show that: a solution comprising only EHUTMB is insoluble in acetonitrile (formation of a white precipitate); a solution comprising only POEUX is viscous but does not form a gel;

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.

Therefore, these results show that a mixture of conventional bis-ureas possessing a trimethylbenzene spacer and functionalized bis-ureas having a xylene spacer, makes it possible to obtain a stable gel in solvents in which the conventional bis-ureas are not soluble, such as acetonitrile.

Material and methods

Equipment

The conventional bis-ureas and functionalized bis-ureas employed in the present invention have previously been synthesized according to the protocols described in the literature: EHUT (Lortie, F. et al., Langmuir 2002, 18, 7218); EHUTMB (Isare, B. et al., J. Phys Chem B 2009, 113, 3360); EHUX (Isare, B. et al Langmuir 2012, 28 (19), 7535); PIBUT (Thought, S. et al., Macromolecules 2010, 43 (5), 2529); 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). The synthesis of PIBUTMB (PolylsoButyleneUreidoTrimethylbenzene) was carried out according to the following protocol:

1 eq. of 2,4,6-trimethyl-1,3-phenylene diisocyanate was dissolved in anhydrous dichloromethane under an inert atmosphere, and the mixture was transferred via cannula into a stirred solution of Kerocom® PolylsoButylene Amine (Kerocom® PIBA, 60). % in solution in hydrocarbon, BASF, about 2 eq.) at room temperature under an inert atmosphere. The reaction was allowed to stand overnight with stirring at room temperature under an inert atmosphere. A colorless viscous liquid was obtained and then the liquid was precipitated dropwise twice in ethyl acetate with stirring. A clear colorless oil was obtained after decantation, and extracted with ethyl acetate. This oil was dried under vacuum (1.10 ^" mbar) at 60 ^° C. A colorless viscous oil was obtained (75%) The product obtained was characterized by steric exclusion chromatography in THF, at a concentration of 5 mg.mL ^-1 (results given in polystyrene equivalent) and by 1 H NMR.

1H NMR (500 MHz, CDCl ₃ -DMSO-d ₆ , 50 ° C) δ (ppm): 0.89-1.36 (m, 297H, CH ₃ - (CH ₂ -C (CH ₃ ) 2) _n CH ₂ -CH (CH ₃ ) -CH ₂ ); 2.04-2.09 (m, 9H, CH ₃ -Ph); 3.08 (m, 4H, CH ₂ -NH); 5.25 (s, 2H, CH ₂ -NH); 6.68 (s, 2H, Ph-NH); 6.80 (s, 1H, Ph-H).

DP = 32.82; M _n = 2330 g.mol ^-1 Viscosimetry

The solutions for the viscometric analysis were prepared in anhydrous toluene, previously filtered with 0.45 μm 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. in conventional bis-ureas in the mixture, for an overall solid concentration of 40 g / L. The resulting mixtures were stirred overnight to homogenize the compositions prior to the viscometric analysis at 20 ° C, 40 ° C, 60 ° C and 80 ° C. The solvents used were also analyzed to determine the relative viscosity of the samples. The apparatus used for these analyzes is a Anton Paar AMVN micro balloon viscometer. Fourier Transform Infrared Spectroscopy (FTIR)

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.

In order to obtain a thermal equilibrium during the analyzes for each temperature studied, the measurements were carried out after 30 min of equilibration at the target temperature. The spectra of the solvent alone were conducted at each temperature under the same conditions as those used for the bis-urea solutions and then these measurements were subtracted from those of the samples.

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.

rheology

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.

Measurement of the number-average molar masses, M _n and mass average, M _w 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. The apparatus used is the Viscotek Detector Array Model TDA 302 equipped with a light scattering detector (LALS: θ = 7 °, RALS: θ = 90 °, laser: λ = 670 nm), a detector of refractive index (λ ^ 670 nm), a viscometric detector and three columns Polymer Laboratories Miced C, thermostated at 40 ° C.

Claims

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),

Formula I in which

Formula II in which

at least one of 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, polyethers, poly (diene), polyvinyl acetate, polycarbonate, polysiloxanes, polyesters, polynorbornenes, polycyclooctenes and polystyrenes; preferably R ₃ and R 4 are identical; more preferably R ₃ and R 4 are identical and each represents a macromolecular chain of poly (isobutene) or poly (butyl acrylate);

and

X and Y are complementary spacers.

2. Composition according to claim 1, in which the conventional bis-ureas of formula (I) are chosen from ethylhexylureidotoluene (EHUT), ethylhexylureidotrimethylbenzene (EHUTMB) and ethylhexylureidoxylene (EHUX), preferably the bis-ureas of formula (I) are EHUTMB molecules.

3. Composition according to any one of claims 1 to 2, wherein the bis-ureas functionalized with macromolecular chains of formula (II) are chosen from poly (isobutene) ureido toluene (PIB UT), 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.

4. Composition comprising the mixture described according to any one of claims 1 to 3, and at least one solvent, preferably selected from apolar solvents having long alkyl chains or polar solvents.

5. Process for the preparation of the composition according to claim 4, 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 with presence of heating.

The process of claim 5 wherein the solvent is an apolar solvent having long alkyl chains or an oil.

The method of any one of claims 5 and 6, wherein said oil comprises vegetable, animal, mineral or synthetic oils; liquid hydrocarbon fuels; fuels; lubricants; more preferably PA06 oil.

The process of claim 5 wherein the solvent is a polar solvent.

9. Use of the composition according to any one of claims 1 to 4, as an additive in a cosmetic composition, or an ink, in a fuel or in a lubricant, especially automotive.

10. Use of the composition according to claim 4, as an organogelator, alone or in a cosmetic preparation, an ink, a fuel or a lubricant, especially automotive.