WO1997047658A1

WO1997047658A1 - Association of a monomer, oligomer, polymer comprising at least one hydroxyl group, with a complexing amphiphilic compound

Info

Publication number: WO1997047658A1
Application number: PCT/FR1997/001035
Authority: WO
Inventors: Gilles Guerin; Ilias Ilioupoulos; Bruno Bavouzet; Paul-Joël DERIAN
Original assignee: Rhodia Chimie
Priority date: 1996-06-12
Filing date: 1997-06-11
Publication date: 1997-12-18
Also published as: FR2749853A1; FR2749853B1; AU3266497A

Abstract

The invention discloses the association of at least one monomer comprising at least one hydroxyl grouping, of at least one oligomer or of at least one polymer, of which at least one of the monomer units comprises at least one hydroxyl grouping, with at least one complexing amphiphilic compound of formulae: (I) Rn -X- (OH)3-n or (II) Rm - W - (OH)4-m, formulae in which X is a boron, phosphorus or aluminium atom, W is a titanium or zirconium atom. The invention also discloses the mixture of the said association, and more particularly of a polymer of which at least one of the monomer units comprises at least one hydroxyl grouping, with at least one surfactant.

Description

ASSOCIATION OF A MONOMER, OLIQOMER, POLYMER

INCLUDING AT LEAST ONE HYDROXYL GROUP,

WITH A COMPLEX AMPHIPHILIC COMPOUND

The present invention relates to the association of at least one monomer, oligomer or polymer comprising at least one hydroxyl group, with an amphiphilic complexing compound.

It also relates to the mixture of the abovementioned combination, and more particularly to at least one polymer of which at least one of the monomer units comprises at least one hydroxyl group, with at least one surfactant.

In many formulations, aqueous solutions of water-soluble polymers comprising hydroxy groups, and surfactants are used. Surfactants are used as dispersing agents, wetting ^émuls' rfiant and water-soluble polymers as thickeners, for example. The ranges of concentrations generally accessible are limited, and in most cases there are phenomena of incompatibility between the two compounds. Indeed, the increase in the latter leads to phase separations. These physical phenomena are known and described in the literature. As an example, the article by L PICULLEL et al. (Advances in Colloid Interface Sci., 41, p.149- 178, 1992) which classifies the different phase separations in aqueous solutions containing surfactants and polymers in terms of associative or segregative phase segregations, depending on the nature, more particularly the respective charges of the polymer and of the surfactant present.

To make the polymer and surfactant mixtures compatible, it is known to chemically graft hydrophobic groups onto the polymer. The polymer can then associate with a surfactant which induces an increase in viscosity of the mixtures in certain ranges of concentrations and concentration ratios between the polymer and the surfactant. This type of behavior is well known and described in the literature. By way of example, the articles by LOYEN et al. (Langmuir, 11, p. 1053-1056, 1995), of MAGNY et al. (Progr. Colloid polym. Sci, 89, p.118-121, 1992) by Me CORMICK et al. (Encyclopedia of polymer Science and Engineering, Eds Wiley-interscience, New-York, vol.17. P.730). We can also cite the behavior of commercial products derived from natural polysaccharides such as alkyl guars sold by Rhône-Poulenc. The object of the present invention is to propose an alternative solution to that known, described above.

Indeed, the present invention makes it possible to make compatible a polymer of which at least one of the monomer units comprises at least one hydroxyl group, with at least one surfactant for example, without having to use a chemical modification of the polymer in question, such as grafting. The solution proposed by the present invention consists in fact simply in bringing said polymer into contact with an appropriate complexing amphiphilic compound, the latter associating with the polymer by at least one chelating bond.

The present invention can also be implemented with a monomer or an oligomer. The association, with the amphiphilic complexing compound, of this type of low molecular weight compounds, makes it possible to modify the surfactant properties of the complexing agent. This can in particular be advantageous for stabilizing or destabilizing emulsions for example.

Thus, the subject of the present invention is a combination of at least one monomer comprising at least one hydroxyl group, at least one oligomer or at least one polymer, of which at least one of the monomer units comprises at least one hydroxyl group, with at least one amphiphilic complexing compound of the following formula:

(I) R _n - X - (OH) 3. _n or

(II) R _m - W - (OH) _4- m or their salts, formulas in which: - X is a boron, phosphorus or aluminum atom,

- W is a titanium or zirconium atom,

- n is equal to 1 or 2,

- m is equal to 1, 2 or 3,

- R, identical or different, correspond to the radical: R ¹ - E - L _y - Y _z -, with: - y and z, identical or different, equal to 0 or 1,

- R ¹ representing an aliphatic hydrocarbon chain, saturated or not, linear or branched, comprising 1 to 40 carbon atoms and which can be substituted by at least one perfluorinated and / or siloxane unit, or representing an aromatic radical substituted by at least one chain aliphatic hydrocarbon, saturated or unsaturated, linear or branched, comprising 1 to 40 carbon atoms and which can be substituted by at least one perfluorinated and / or siloxane unit,

- E representing the radical - [O - CH2 - C (R ² ) H] _p in which R ² corresponds to a hydrogen atom or to an alkyl radical comprising 1 to 4 carbon atoms and p is between 0 and 200 , - L corresponding to a bridging group comprising at least one heteroatom of the sulfur, nitrogen, oxygen type, - Y corresponding to a hydrocarbon chain, saturated or unsaturated, aliphatic or aromatic, comprising 1 to 12 carbon atoms, optionally substituted with at least one perfluorinated unit or one siloxane unit.

The invention therefore makes it possible to provide a simplified solution to the problem of compatibilization of such polymers with surfactants.

Thus, the compatibility of the modified polymer with another surfactant is improved, since the concentrations of the mixtures of modified polymer and of the surfactant can be increased without having phase separation.

Furthermore, it is possible to obtain a significant increase in the viscosity of mixtures of polymer modified by complexation and of a surfactant compared to mixtures of unmodified polymer and of a surfactant.

Furthermore, the surfactant properties of the complexing amphiphilic compound can be modified by adding an oligomer or a monosaccharide in particular.

Another advantage is that this mode of association can be modulated by the variation of a physico-chemical parameter such as temperature, pH or even by the addition of a third compound (de) stabilizing the complexation for example .

Furthermore, it has been found that the polymers thus treated can self-associate and give aqueous solutions having a viscosity greater than that of the same uncomplexed polymer. However, other characteristics and advantages of the invention will appear more clearly on reading the description and the examples which follow.

The amphiphilic complexing compound (or complexing compound), entering as a constituent element of the association according to the invention, can therefore correspond to one of the two formulas (I) and (II) below: (I) Rn - X - (OH) 3. _n or

(II) R _m - W - (OH) 4-m or their salts, formulas in which:

- X is a boron, phosphorus or aluminum atom, - W is a titanium or zirconium atom,

- n is equal to 1 or 2,

- m is equal to 1, 2 or 3,

- R, identical or different, correspond to the radical: R ¹ E - L _y - Y _z -, with:

- y and z, identical or different, equal to 0 or 1, - R ¹ representing an aliphatic hydrocarbon chain, saturated or not, linear or branched, comprising 1 to 40 carbon atoms and which can be substituted by at least one perfluorinated unit and / or siloxane, or representing an aromatic radical substituted by at least one aliphatic hydrocarbon chain, saturated or not, linear or branched, comprising 1 to 40 carbon atoms and which can be substituted by at least one perfluorinated and / or siloxane unit,

- E representing the radical - t O - CH2 - C (R ² ) H] _p in which R ² corresponds to a hydrogen atom or to an alkyl radical comprising 1 to 4 carbon atoms and p is between 0 and 200 ,

- L corresponding to a bridging group comprising at least one heteroatom of the sulfur, nitrogen, oxygen type, preferably nitrogen or oxygen.

- Y corresponding to a hydrocarbon chain, saturated or unsaturated, aliphatic or aromatic, comprising 1 to 12 carbon atoms, optionally substituted with at least one perfluorinated unit or one siloxane unit.

It should be noted that it would not be departing from the scope of the present invention if at least two of the abovementioned radicals R were linked together so as to form a ring.

According to a particular embodiment of the invention, R ¹ represents an aliphatic hydrocarbon chain, saturated or unsaturated, linear or branched, comprising 1 to 20 carbon atoms and which can be substituted by at least one perfluorinated and / or siloxane unit, or representing an aromatic radical substituted by at least one aliphatic hydrocarbon chain, saturated or unsaturated, linear or branched, comprising 1 to 20 carbon atoms and which can be substituted by at least one perfluorinated and / or siloxane unit. According to a preferred embodiment of the invention, R ¹ represents an aliphatic hydrocarbon chain, saturated or unsaturated, linear or branched, comprising 1 to 20 carbon atoms.

As regards the radical R ² , it preferably represents a hydrogen atom. In addition, p is more particularly between 0 and 20.

More particularly, the radical L is chosen from groups of the ketone, carbamate, amide, ether, ester, ammonium, urea, sulphide, sulphonamide type.

According to a particularly advantageous embodiment of the present invention, said complexing agent corresponds to formula (I). Preferably, X represents boron.

Another object of the present invention consists of an amphiphilic complexing compound of formula (I) in which X represents boron and in which p defined above is greater than or equal to 1.

All that has been indicated before concerning the preferred definitions of the various radicals and stoichiometric coefficients remains valid and will not be repeated now. The monomers, oligomers or polymers comprising at least one hydroxyl group, entering as the second constituent element of the association according to the invention, will now be described.

According to a first embodiment of the invention, a monomer or an oligomer comprising at least one hydroxyl group is used. It is specified here and for the whole description, that in the case of oiigomers, is meant compounds of which at least one of the monomer units comprises at least one hydroxyl group. Preferably, a monomer or an oligomer comprising at least two hydroxyl groups is used. As a compound of this type, mention may be made of compounds comprising a diol, triol, α-hydroxycarboxytic acid or else dicarboxylic acid function. By way of example of such compounds, and without intending to be limited thereto, mention may be made of pentane diol 1, 2 or 1, 3. benzene diol, 1,2,3-pentane triol, mannitol, oxalic acid, succinic acid, glycolic acid, lactic acid. It is also possible to use monomers or oligomers comprising at least one osidic function.

Thus, as suitable monomers and oligomers of sugar, there may be mentioned without intending to be limited to glucose, mannose, galactose, fructose, xγlose, as well as the monomers and oligomers described in the article by RJ FERRIER , Advances in Carbohydrate Chemistry, 1978. vol.35, p.31 -81, 1978.

It should be noted that all that has just been indicated concerning the monomers and oligomers comprising at least one hydroxyl group is particularly suitable when it is a combination with a compound of formula (I). Preferably, this association is particularly advantageous when X corresponds to boron.

According to a second embodiment of the invention, polymers are used comprising at least one hydroxyl group. More particularly, polymers are designated of which at least one of the monomer units comprises at least one hydroxyl group. According to a preferred embodiment of the invention, polymers are used, at least one of the monomer units of which comprises at least two hydroxyl groups.

It is further preferred to use polymers having a molecular weight greater than or equal to 2000 g / mole, preferably greater than or equal to 10 ⁵ g / mole. Among the suitable polymers, mention may be made of polymers comprising at least one osidic unit.

Mention may likewise be made of synthetic polymers such as vinyl alcohol, or also poly (glyceryl methacrylate) for example. With regard to polymers having at least one osidic unit, very particularly suitable are polysaccharides, natural or modified, of animal or vegetable origin, biogums.

As natural polysaccharides, there may be mentioned without limitation, alginates, guar gum, locust bean gum, Tara gum, cassia gum, Karaya gum, carrageenans, chitin derivatives, such as chitosan, starches, galactomannans, glucomannans, dextran.

As modified polysaccharides which may fall within the scope of the present invention, mention may in particular be made of cellulose derivatives such as cellulose hydroxyethers, methylceilulose and its derivatives, hydroxypropylmethylceilulose, hydroxybutylmethylcellulose, carboxymethylcellulose, ethylmethyl - cellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, as well as, in general, the other hydroxyalkylated derivatives of cellulose.

As biogums which can be used in the composition which is the subject of the present invention, there may be mentioned in particular the polysaccharides obtained by fermentation under the action of bacteria or fungi belonging for example to Xanthomonas, of the genus Arthrobacter, of the genus Azobacter, of the genus Agrobacter, in the genus Alcaligènes, in the genus Rhizobium, in the genus Sclerotium, in the genus Corticium, in the genus Sclerotinia. By way of example of biogums, there may be mentioned more particularly xanthan gum, scleroglucans, succinoglycans.

It should be noted that the polysaccharides mentioned above can be used in native form or chemically modified so as to give them an ionic or nonionic character different from the native form. Of course, it would not be departing from the scope of the present invention to use several of the monomers, oligomers or polymers mentioned, as well as their mixtures.

According to a particularly advantageous embodiment of the present invention, use is made of a polymer comprising at least one osidic group capable of forming a chelate with the boron atom present in the preferred complexing agent of the invention.

Among the osidic groups meeting this definition, mention may be made of those appearing in the article by RJ FERRIER, Advances in Carbohydrate Chemistry, 1978, vol.35, p.31-81, 1978. Among the nonlimiting examples of polymers corresponding to This definition includes polymers containing galactose and / or mannose units having diol groups in the cis position 1, 2 or 1, 3 such as hydrocolloids from fermentation or natural processes such as galactomannans (guar gums, locust bean gums , tara, cassia) or glucomannans such as konjac, derivatives of these polycarbohydrates modified to have a cationic character such as guar or carob derivatives such as their cationic derivatives (JAGUAR C13S, JAGUAR C162 marketed by RHONE-POULENC), nonionic derivatives such as hydroxypropylguars, anionic derivatives (carboxymethylguars) or mixed nonionic / anionic derivatives such as carboxyhydroxypropylguars or nonionic / cationic such as ammonium-hydroxypropyl-guars.

The same compounds can also be used, generally in the form of water-soluble polymers modified by hydrophobic groups covalently linked to the polymer backbone as described in patent EP 281 360.

Preferably, polysaccharides such as galactomannans or glucomannans and their derivatives will be used.

The synthesis of amphiphilic complexing compounds will now be described.

In the particular case of complexing compounds comprising boron, it is possible to use, for their synthesis, methods employing reagents of the organometallic or organolithium type. According to this method, the above reagent is brought into contact with, for example a trialkylborate, in an anhydrous solvent.

The product obtained can then be easily hydrolyzed to give the acid form.

Hydroboration reactions can also be carried out. According to this route, an olefin, and more particularly a compound having a terminal vinyic function, is brought into contact with a borane or a derivative. After the reaction, hydrolysis is carried out to obtain the acid form.

By borane or derivative is meant a compound having groups of type: (H) _n - B - (XR) 3- _n in which n is between 1 and 3. X represents sulfur or oxygen and R are identical or different may be alkyl, or alkylaryl radicals comprising 1 to 20 carbon atoms, optionally substituted by one or more halogen atoms. The R radicals can also be linked together so as to form a ring.

By way of example of compounds of the borane type, that is to say in which X represents oxygen, catecholborane is particularly suitable for this reaction.

As an example of compounds of the type derived from borane, that is to say in which X represents sulfur, mention may be made of dithiaborolane. It would not be departing from the scope of the present invention to use halogenated boranes and their complexes with monoalkyl- or dialkylsulfides. For example, the dibromoborane complex with dimethyl sulfide is a suitable compound of this type.

This reaction is carried out in a solvent which is for example of the type of cyclic ethers, saturated or not, such as tetrahydrofuran, or of the chlorinated type such as in particular dichloromethane.

The reaction takes place under an anhydrous atmosphere, and more particularly can take place under nitrogen or argon. The complexing agents used in the process according to the invention can also be prepared from aminoalkylboronic acids, aminoarylboronic acids or their salts. The reaction consists in bringing said boronic acid into contact with a compound having at least one carboxylic function, in acid form or in salt form.

More particularly, the reagent is an aminophéπylboronique acid. Furthermore, the amino function is preferably a primary amine function.

Preferably, the aminoarylboronic compound is reacted in the form of its salt. As regards the compound comprising at least one carboxylic acid function, use is made more particularly of acids comprising a carbon atom and up to 26 carbon atoms, saturated or unsaturated. Mention may in particular be made of butyric, capric, caproic, lauric, myristoleic and oleic acids.

One can likewise use surfactants comprising such functions such as alkylpotyoxyalkyienated acids, alkyiarylpolyoxyalkylenated acids comprising at least one terminal carboxylic acid function. More particularly, the number of carbon is between 1 and 40. In addition, the number of oxyalkylene units, such as oxyethylene, oxypropylene or their mixtures, is between 2 and 100.

It would not be departing from the scope of the present invention to use any surfactant compound of the type of alpha sulfonated derivatives of fatty acids, alkylbetaines, alkylaminobetaines, alkylimidopropionates, alkyiamphoacetates, aklkyldiamphoacetates for example.

According to a particular embodiment of the invention, the compound comprising at least one carboxylic function is used in the form of an alkali or alkaline-earth metal carboxylate.

According to a particularly advantageous variant, the reaction is carried out in the presence of a coupling agent.

The preferred agents are chosen from carbodiimides, of formula: R - N ≈ C = N -R, formula in which the radicals R, identical or different, are linear, branched or cyclic C1-C10 alkyl radicals, radicals C6-C14 aryls, or alkylaryls, said radicals R possibly being able to comprise a quaternary ammonium function. Among the particularly suitable agents, mention may be made of N.N'-dicyclohexyl carbodiimide, 1-ethyl-3 (3-dimethylaminopropyl) carbodiimide chloride, the latter being preferred. The reaction can take place in any suitable solvent, such as tetrahydrofuran or N-methylvinyipyrrolidone, and advantageously in water. By using a coupling agent, it is found quite advantageously that the reaction can take place at room temperature. In the absence of this agent, the reaction takes place at a temperature less than or equal to the boiling point of the solvent used. When the solvent used is water, the reaction is carried out at a pH more particularly between 5 and 11, preferably 6 and 10. It should be noted that this pH depends on the nature of the coupling agent used. in use and the solubility of the reagents in the reactive mixture.

The reaction can be carried out in air or under an inert atmosphere such as nitrogen or a rare gas such as argon.

As indicated previously, the subject of the present invention is the association of an amphiphilic complexing compound as just described with at least one monomer, an oligomer or a polymer comprising at least one hydroxyl group. With this association, a new amphiphilic species is obtained, more particularly having an increased hydrophilic character, the surfactant character of which is modified with respect to the behavior of the initial complexing agent.

This new character can be exploited to destabilize or stabilize gels, emulsions or suspensions in numerous fields of application, such as cosmetics, detergency, industrial cleaning, in particular metal treatment, agrochemistry, health. , preparation of paints and papers, petroleum development, construction, agrochemicals, etc.

As mentioned above, the present invention likewise relates to a mixture of at least one surfactant with the abovementioned combination, that is to say comprising the complexing amphiphilic compound and a monomer, oligomer or polymer comprising at least one hydroxyl group. With regard to the definition of the complexing agent and the mono-, oligo- and polymers, everything that has been said before remains valid and will therefore not be repeated in this part.

Anionic, nonionic, cationic, zwitterionic or amphoteric surfactants can be used. We can refer in particular to the book "Handbook of Industrial Surfactants", Gower Publishing Company, 1993 for more details in this regard. By way of nonlimiting examples, mention may especially be made of alkyl sulfates, alkyl ether sulfates, ethoxylated fatty alcohols, alkylamphoacetates, alkylamphodiacetates, alkylamphopropionates, alkylamphodipropionates, aikyisultaines, amphoteric derivatives of alkylpolyamines, in particular such as AMPHION XL® marketed by RHONE-POULENC. It should be noted that such a mixture makes it possible to obtain stable homogeneous solutions without phase separation. It also makes it possible to obtain solutions the rheology of which can be modulated by the relative concentration of the surfactant added in the solution comprising the combination according to the invention, that is to say the amphiphilic complexing compound and the mono-, oligo - Or polymer comprising at least one hydroxyl group. Among the possible and advantageous applications of the present invention, mention may be made of the exploitation of petroleum, with more particularly drilling muds and more precisely completion fluids or even better fracturing fluids. Quickly, it is recalled that the purpose of fracturing fluids is to open breaches in the rock of the deposit in order to allow the evacuation of hydrocarbons to the surface. For this, these fluids must be sufficiently viscous, even gelled, to infiltrate into the channels of the rock. They generally also include suspended particles which will promote fracturing and the opening of orifices. Subsequently, this gel is destabilized, which allows the hydrocarbons to be removed.

The mixture or combination according to the invention is introduced under concentration and pH conditions such that there is gelation. To destroy the gel, it suffices to modify, for example, the pH of the medium by adding an appropriate compound. It should be noted that this embodiment is particularly advantageous when the combination according to the invention comprises at least one amphiphilic compound complexing with at least one polymer as defined above, that is to say of which at least one monomeric units comprises at least one hydroxyl group.

Preferably, the complexing amphiphilic compound corresponds to formula (I) in which X represents boron.

In addition, this application is particularly suitable in the case where the complexing amphiphilic compound corresponds to formula (I) in which X represents boron and in which p is greater than or equal to 1.

The fracturing fluid according to the invention more particularly comprises 0.1 to 1.5% by weight of polymer, at least one of the monomer units of which comprises at least one hydroxyl group. Preferably, the polymer content in the fluid is between 0.2 and 0.8% by weight. As a particularly suitable polymer, mention may be made of guar and its derivatives. As regards the content of complexing amphiphilic compound, it is between 0.01 and 10% by weight relative to the polymer, and preferably between 0.1 and 10% by weight relative to the polymer. Preferably, the complexing amphiphilic compound corresponds to formula (I) and preferably X represents boron. In general, the fracturing fluid comprises the compounds as described in the book "Reservoir Stimulation", Ed. Mickael J. Economides and Kenneth G. Nolte, Schlumberger Educational Services, 1987.

Thus, the fluid according to ^the invention may further comprise conventional additives of this type of fluid. Thus, it may contain delaying and complexing agents, such as triethanolamine, α-hydroxy acids such as lactic acid, glycoiic acid and their salts.

The fluid can also include mineral fillers helping to maintain a high permeability of the rock, such as silica, sand. It can likewise include additives making it possible to reduce the swelling of clays such as sodium chloride, potassium chloride.

One of the possible applications of this combination or of the mixture according to the invention relates to stationery.

It is thus possible to use the combination according to the invention, or else its mixture with a surfactant, as charge retentive agent, which are generally calcium carbonate, titanium dioxide, during the manufacture of the paper sheet. They can also be used during the coating of paper as an agent modifying the rheology of the medium in order to obtain a homogeneous layer at the time of application and drying.

It should be noted that this embodiment is particularly advantageous when the combination according to the invention comprises at least one amphiphilic compound complexing with at least one polymer as defined above, that is to say of which at least one monomeric units comprises at least one hydroxyl group.

Preferably, the complexing amphiphilic compound corresponds to formula (!) In which X represents boron. In addition, this application is particularly suitable in the case where the complexing amphiphilic compound corresponds to formula (I) in which X represents boron and in which p is greater than or equal to 1.

According to another embodiment of the invention, the aforementioned association can find an application in the field of the manufacture of aqueous paints, as a thickening agent allowing an optimal distribution, and stable in storage, of the fillers and pigments in the formulation. It should be noted that the thickener also plays a role during the application of the paint, avoiding drips and weeping.

Finally, note that the association or the mixture according to the invention can also be used in the fields of cosmetics, detergency, pharmacy or agrochemistry, as an agent modifying the rheology of the medium.

With regard to these applications, all of the amphiphilic complexing agents described can be used, as previously. However, this is particularly suitable in cases where the complexing agent corresponds to your formula (I). Preferably. X in said formula represents boron.

A particularly advantageous embodiment corresponds to the use in the association of a complexing amphiphilic compound corresponding to formula (I) in which X represents boron and in which p is greater than or equal to 1.

Finally, it is again noted that ^the association or the mixture according to the invention may find applications in any field where a modifier surfactant properties is required.

In this case, it is preferred to use combinations or mixtures according to the invention, in which a monomer or an oligomer comprising at least one hydroxyl group is used.

Concrete but nonlimiting examples of the present invention will now be presented.

EXAMPLES 1 TO 3: Synthesis of complexing agents

FXEMPLE 1

This example relates to the synthesis of 3-octylamido phenylboronic acid formula: (HO) ₂ B - (Cβr-U) - NHCO-C ₈ H ₁₇

1 g of 3- (N-amino phenylboronic acid hemisutfate) is mixed with 200 g of water with 0.9 g of sodium octanoate. The mixing takes place under argon at 25 ° C.

1.02 g of 1-ethyl-3 (3-dimethylaminopropyl) carbodiimide chloride (Aldrich) is then added.

After 4 hours with stirring, the resulting product is filtered, washed with water and acetoitritrile. A pure product is obtained after recrystallization from a water / acetonitrile mixture.

EXAMPLE 2 The subject of this example is the synthesis of 3- (N-phenylacetamido) 1-dodecyl dodecaethylene glycolether boronic acid. of formula: (HO) 2B- (C ₆ H4) -NHCOCH2-0 (CH2CH2θ) i2-CH2 (CH2) ιoCH ₃ 1 g of 3-aminophenylboronic acid hemisurfate is mixed in 200 ml of water with 8.2 g of 1-dodecyl dodecaethylene glycol ether sodium ethanoate. The mixing takes place under argon at 60 ° C.

1.02 g of dimethylaminopropyl chloride 1, 3 - ethyl 3 carbodiimide (Aldrich) are then added.

After 15 hours with stirring, 50 ml of a 1M aqueous solution of sodium chloride are added.

The resulting product is extracted with dichloromethane.

After evaporation of the solvent, the product is purified by column chromatography.

After removal of the eluant, then Aceton ^'rtrile wherein the product has been diluted, there is obtained a viscous product.

EXAMPLE 3

This example relates to the synthesis of dodecylboronic acid, of formula: (HO) 2B-CH ₂ (CH2) ιoCH3.

6.38 g of 1-dodecene are mixed with 5 g of catecholborane under argon for 4 hours at 100 ° C.

The temperature of the medium is brought back to 25 ° C. Hydrolysis of the product obtained is then carried out by adding 50 ml of water. A brown precipitate is obtained which is filtered and which is recrystallized from hot water and then from hot heptane.

EXAMPLES 4 TO 7: Association of a Polymer and the Complexing Agent

In the examples which will be presented, we will use your following nomenclature: - product A: complexing agent,

- polymer B: polymer comprising at least one hydroxyl group.

- product C: surfactant with amphiphilic properties.

In addition, all the rheological characterizations were carried out on an RTS-lt rheometer from Rheometrics. When no precision is given in the operating mode on the geometry used, this is by default a cone-plane 50 mm. moreover, unless otherwise indicated, the measurements are made at a temperature of 25 ^β C. The guar used is a Meyproguar CSA 200/50 polymer.

The polyvinyl alcohol used is the product 25/140 Rhodoviol marketed by Rhône-Poulenc.

Sodium docecyl sulfate (SDS) and octaethylene glycol monododecyl ether (C12 (0E) 8) come from the company Fluka.

The sodium imide is from Merck.

EXAMPLES 4

In the following examples (4a and 4b), it is shown that the addition of complexing surfactant A improves the rheological properties of a polymer B in solution: increase in viscosity and elastic and viscous modules.

We note that there are different behaviors according to the relative concentration of A compared to that of B:

- viscoelasticity: significant increase in elastic and viscous modules as well as a modulation of the viscoelastic character of the medium (G '> G' or G '> G ") (Table 1a and 1 d);

- flow rheology: the known shear thinning behavior for guar alone (table 1b) can also be modified (rheo-thickening character - table 1c)

Example 4a: B = guar / A = Complexing agent according to Example 2

2.5 g of a 1% aqueous solution in guar and containing 400 ppm of NaN3

(Merck) is added to 2.5 ml of an aqueous solution containing a 2C concentration of complexing agent and a 2.2.C concentration of NaOH.

The guar concentration remains fixed and equal to 0.5% by mass. The sample is left under stirring for 24 hours and then its rheological characteristics have been measured.

Table 1 a: The elastic modulus (G ') and the loss modulus (G ") are given for each sample at frequencies of 0.1 and 1 Hz (0.1 Hz / 1 Hz) for a deformation of 10% .

Table 1b: A guar solution (0.5%) at a zero concentration of product C is subjected to increasing shear gradients. Each shear gradient is applied for 40 seconds and the viscosity measured at the end of this time is given.

Table 1c: A guar solution (0.5%) comprising the complexing agent A according to Example 2 (3.10-2 mol / l) is subjected to increasing shear gradients. Each shear gradient is applied for 60 seconds and the viscosity measured at the end of this time is given.

Example 4b: B = polyvinyl alcohol / A = complexing agent according to Example 2

Sample 1: 1 g of polyvinyl alcohol is dissolved in 20 ml of deionized water and left stirring for 24 hours. The sample is then characterized in rheology.

Sample II: 0.089 g of complexing agent and 0.02 ml of a sodium hydroxide solution (10 M) are added to 10 ml of sample I. The solution is stirred for 1 hour and then characterized in rheology. Table 1 d: The elastic modulus (G ') and the loss modulus (G ") are given for each sample (I and II) at frequencies of 1 Hz. The applied strain is 100% for sample I and 10% for sample II.

EXAMPLES 5

In the following examples (5a and 5b), it is shown that the addition of complexing surfactant A makes it possible to compatibilize mixed segregative polymer B / conventional surfactant C systems (table 2 a) and also to give rise to synergy at the rheological level of these systems (Tables 2b and 2c).

Example 5a: A = complexing agent according to Example 2 / B = guar / C = Ci2 (OE) 8 Samples, the compositions of which are given in Table 2a, are prepared by mixing the following constituents:

- an aqueous solution containing 1% of guar and containing 400 ppm of NaN3,

- an aqueous solution containing the complexing agent and the sodium hydroxide at the same concentration as the complexing agent, - the nonionic surfactant C.

The samples are left under stirring for 24 hours then are characterized in rheology.

Table 2a: State of the mixtures

An improvement in the compatibility of the guar complexed by the compound A with another surfactant is observed with respect to the mixture of the guar alone with this other surfactant.

Example 5b: A = complexing agent according to Example 1 / B = guar / C = SDS

The sample is prepared by mixing the following constituents:

- 2.5 g of a 1.5% guar aqueous solution containing 400 ppm of NaN3,

- 2.5 g of an aqueous solution containing: - a concentration of 2.Cs of SDS

- a 2R.Cs concentration of complexing agent

- a 2R.Cs concentration of NaOH.

R = (concentration of complexing agent / concentration of SDS). The sample is left under stirring for 24 hours then is characterized in rheology.

Table 2a: The elastic modulus (G ^* ) and the loss modulus (G ") are given for each sample at frequencies of 0.1 Hz for a deformation of 10%. Each sample is characterized by its concentration Cs in SDS and its ratio R = 0 or 0.1 The guar concentration remains fixed at 0.75% by mass.

An optimum of the viscoelastic properties of the complexed guar associated with another surfactant (SDS) is observed when Cs = 3.10 " ² mol / l and R = 0.1.

Table 2c: The elastic modulus (G ') and the loss modulus (G ") are given for each sample at frequencies of 1 Hz for a deformation of 10%. Each sample is characterized by its concentration Cs ≈ 1.6 10- ¹ mol / l in SDS and its ratio R. The guar concentration remains fixed at 0.75% by mass.

A significant increase in the viscoelastic properties of the guar and SDS surfactant solutions is observed by adding the complexing surfactant A.

EXAMPLE 6: A = complexing agent according to example 2 / B = guar

In the following example, it is shown that the properties of the systems described above have a variable and reversible nature as a function of the physico-chemical conditions of the pH of the medium.

2.5 g of a 1% aqueous solution in guar and containing 400 ppm of NaNβ are added to 2.5 g of an aqueous solution containing the complexing agent (5.10- * mol / l) and soda (variable concentration ).

The sample is left under stirring for 24 hours. Its pH is measured before each rheological measurement.

Table 3: The elastic modulus (G ") and the loss modulus (G") are given for each sample at frequencies of 0.09 and 0.9 Hz (0.1 Hz / 1 Hz) for a deformation of 10 %. Each sample is characterized by its pH.

The polymer and complexing concentrations remain fixed and equal to 0.5% by mass and 5 × 10 −4 mol / l, respectively.

EXAMPLES 7

This example illustrates the modification of the hydrophilicity of the complexing agent of Example 1 by the addition of an osidic monomer.

Example 7a:

The complexing agent of Example 1 is mixed with various amounts of mannitol and tensiometry measurements are carried out using a LAUDA® TVT1 tensiometer.

The results are collated in Table 4a below:

When mannitol is added to the complexing agent, a decrease in the surface-active power is observed, characterized by an increase in the surface tension of the water containing the complexing agent and the mannitol. The influence of mannitol is also found in the following example.

Example 7 t? ;

The critical micelle concentration (CMC) of the complexing agent according to Example 1 is measured alone or as a mixture with mannitol.

The measurement of the CMC is carried out according to the method described in the article by K. Kalyanasundaram and J.K. Thomas, Journal of the American Chemical Society, Vol. 99: 7, page 2039.

The measurements of the critical micelle concentration (CMC) are carried out by fluorescence using an SLM-Aminco SPF-500 Spectrofiuorometer device, the probe dissolved in the aqueous solution containing the complexing agent is pyrene

(concentration: 6.10- ⁷ M); excitation wavelength: 334 nm; line width: 5 nm; emission wavelength: 350 and 500 nm; line width: 0.5 nm. The results are collated in Table 4b below

The addition of mannitol causes an increase in the hydrophilicity of the complexing agent as indicated by the increase in CMC.

Claims

1 / Association of at least one monomer comprising at least one hydroxyl group, of at least one oligomer or of at least one polymer, of which at least one of the monomer units comprises at least one hydroxyl group, with at least one Amphiphilic complexing compound of the following formula:

(I) R _n - X - (OH) 3-n or

(II) R _m - W - (OHU-m formulas in which:

- X is a boron, phosphorus or aluminum atom,

- W is a titanium or zirconium atom,

- n is equal to 1 or 2,

- m is equal to 1, 2 or 3, - R, identical or different, correspond to the radical: R ¹ - E - L _y - Y _z -, with:

- y and z, identical or different, equal to 0 or 1,

- E representing the radical - [O - CH2 - CfR ^ H] _p in which R ² corresponds to a hydrogen atom or to an alkyl radical comprising 1 to 4 carbon atoms and p is between 0 and 200,

L corresponding to a bridging group comprising at least one heteroatom of the sulfur, nitrogen, oxygen type,

- Y corresponding to a hydrocarbon chain, saturated or not. aliphatic or aromatic, comprising 1 to 12 carbon atoms, optionally substituted by at least one perfluorinated unit or a siloxane unit.

21 Association according to the preceding claim, characterized in that the complexing amphiphilic compound corresponds to formula (I).

3 / Association according to the preceding claim, characterized in that the complexing amphiphilic compound is such that X represents boron. 4 / Association according to any one of the preceding claims, characterized in that the monomer comprises at least two hydroxyl groups, and in that the oligomer or the polymer are such that at least one of their monomer units comprises at at least two hydroxyl groups.

5 / Association according to the preceding claim, characterized in that the monomer and the oligomer are chosen from compounds comprising a diol, triol, α-hydroxycarboxylic acid or dicarboxylic acid function, or comprising at least one osidic function.

6 / Association according to any one of the preceding claims, characterized in that the polymer comprises at least one osidic unit, and preferably is chosen from polysaccharides, natural or modified, of animal, vegetable origin, biogums.

7 / Association according to any one of the preceding claims, characterized in that the polymer is chosen from synthetic polymers such as polyvinyl alcohol, or else poiy (glyceryl methacrylate).

8 / Mixture of an association according to any one of claims 1 to 7 and of at least one surfactant.

9 / mixture according to the preceding claim, characterized in that the surfactant is chosen from alkyisulphates, alkylethersulphates, ethoxylated fatty alcohols, alkylamphoacetates, alkyiamphodiacetates, alkyiamphopropionates, alkylamphodipropionates, aikyisultains, amphoteric derivatives of alkylpoly.

10 / Use of a combination or a mixture according to any one of the preceding claims, for petroleum exploitation, in particular in completion fluids, or even fracturing fluids.

11 / Use of a combination or a mixture according to the preceding claim, characterized in that the combination or the mixture comprises a polymer of which at least one of the monomer units comprises at least one hydroxyl group. 12 / Use of a combination or a mixture according to any one of claims 1 to 9, in the field of stationery, as a charge retaining agent or agent modifying the rheology of composition for coating paper.

13 / Use of a combination or a mixture according to the preceding claim, characterized in that the combination or the mixture comprises a polymer of which at least one of the monomer units comprises at least one hydroxyl group.

14 / Use of a combination or a mixture according to any one of claims 1 to 9, as an agent modifying the rheology of the medium in the field of cosmetics, detergency, pharmacy, agrochemistry, metal processing.

15 / Use of a combination or a mixture according to claim 14, characterized in that the combination or the mixture comprises at least one polymer of which at least one of the monomer units comprises at least one hydroxyl group.

16 / Use of a combination or a mixture according to any one of claims 1 to 9, as an agent modifying the surfactant properties of the medium.

17 / Use of a combination or a mixture according to the preceding claim, characterized in that the combination or the mixture comprises at least one monomer comprising at least one hydroxyl group, or at least one oligomer of which at least one monomeric units comprises at least one hydroxyl group.

18 / A complexing amphiphilic compound characterized in that it corresponds to formula (I) according to claim 1, in which X represents boron and in which p is greater than or equal to 1.

19 / Association according to any one of claims 1 to 7, characterized in that the complexing amphiphilic compound is according to claim 18.

20 / mixture according to any one of claims 8 to 9, characterized in that the complexing amphiphilic compound is according to claim 18.

21 / Use of a combination or a mixture according to any one of claims 10 to 17, characterized in that the complexing amphiphilic compound is according to claim 18.