PREPARATION OF HYDROPHOBIC POLYETHER COMPOUND

Abstract

The invention relates to a thickening copolymer and its batch preparation method. The preparation method first comprises a polymerization reaction of a dihalogenated compound and a polyhydroxylated monomer, followed by a reaction with a hydrophobic monoalcohol. This copolymer allows for viscosity control of an aqueous composition.

Description

Description Title of the invention: PREPARATION OF COMPOUND Hydrophobic polyether The invention relates to a thickening copolymer and its continuous preparation method. The preparation method first comprises a polymerization reaction of a dihalogenated compound and a polyhydroxylated monomer, followed by a reaction with a hydrophobic monoalcohol. This copolymer allows for viscosity control of an aqueous composition. Many technical fields require controlling the rheology of the compounds used, particularly the rheology of aqueous compositions. Having a variety of effective thickening agents is therefore very useful. Among thickening agents, a distinction is made between associative thickeners, which are generally water-soluble polymers containing hydrophobic groups that are often insoluble in water. Such macromolecules exhibit associative properties: once introduced into water, the hydrophobic groups can assemble into micellar aggregates. These aggregates are linked together by the hydrophilic parts of the polymers. This results in the formation of a three-dimensional network that increases the viscosity of the medium. Within compositions also comprising a latex-type binder, thickening agents generally interact with the particles of these binders. Such interactions typically enhance the thickening effect. Generally, methods for preparing thickening compositions comprising a hydrophilic polymer that is advantageously water-soluble, flexible, and reproducible are sought. Improving the thickening efficiency of the resulting thickening agent is also a priority. According to the invention, a water-soluble polymer is defined as a polymer that is completely miscible with water at a temperature above its melting point. In general, for aqueous coating compositions, and particularly for aqueous paint or varnish compositions, it is necessary to control viscosity at both low and medium shear rates as well as high shear rates. Indeed, during its preparation, storage, application, and drying, a paint formulation undergoes numerous stresses requiring particularly complex rheological properties. During paint storage, pigment particles tend to settle due to gravity. Stabilizing the dispersion of these pigment particles then requires the use of of a paint formulation with high viscosity at very low shear gradients corresponding to the limiting velocity of the particles. Paint pick-up is the amount of paint carried by an application tool, such as a brush, roller, or paint roller. A tool that picks up a large amount of paint when dipped and then withdrawn from the paint pot will prevent the need for more frequent refills. Paint pick-up is an increasing function of viscosity. The calculation of the equivalent shear gradient depends on the paint flow rate for a given thickness of paint on the tool. Therefore, the paint formulation should also have high viscosity at low to medium shear gradients. Furthermore, a high filling power of the paint must be sought so that, when applied to a substrate, a significant amount of paint is deposited with each pass. High filling power then allows for a thicker wet film with each application of the tool. A high viscosity of the paint formulation is therefore necessary at high shear gradients. High viscosity at high shear gradients will also reduce or eliminate the risk of splashing or droplet formation during paint application. Hydrophobic compounds, particularly hydrophobically modified compounds such as associative nonionic thickening agents, are known as rheology modifiers. However, existing compounds do not always provide satisfactory solutions. Therefore, there is a need for improved rheology modifiers. Furthermore, it is also important to have access to improved copolymer preparation methods. Indeed, existing methods can generate numerous problems that make them difficult to implement. It can prove impossible to effectively implement certain thickening agent preparation methods due to the significant challenges encountered, particularly viscosity drift issues in the reaction medium used to prepare thickening agents. It is also important to have flexible preparation methods available, particularly methods that allow for varying the reagents introduced (nature, quantity) into the reaction zones during synthesis. Improving the reproducibility of copolymer preparation methods should also be a priority. Therefore, there is a need for a method of preparing thickening copolymer that can provide a solution to all or part of the problems of known methods. Thus, the invention provides a batch preparation method for a copolymer P including: * The polymerization reaction in the presence of a base: a) of at least one dihalogenated compound a; b) of at least one polyhydroxylated monomer b used in a molar quantity contributing a number of hydroxyl groups (OH) less than the number of halides contributed by compound a and * the reaction with at least one hydrophobic monoalcohol c. For the method according to the invention to be effective, the presence of a base is essential to allow the reaction of the polyhydroxylated monomer b and the monoalcohol c with the dihalogenated compound a. Preferably according to the invention, the base is used in a molar excess relative to the molar amount of OH groups of the monomer b and the monoalcohol c. More preferably, the base is used in a molar amount of 1.05 to 15, preferably 2 to 13, molar equivalents relative to the molar amount of OH groups of the monomer b and the monoalcohol c. The base used leads to an increase in pH during the implementation of the method according to the invention. Preferably, the polymerization is carried out at a pH greater than 10 or greater than 12. According to the invention, numerous bases can be used. Preferably, according to the invention, the base is a strong mineral base or a strong organic base. More preferably, the base is selected from sodium hydride, potassium hydride, NaOH, KOH, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium tert-butanolate, and potassium tert-butanolate. Sodium hydroxide is the preferred base. Generally, according to the invention, the base allows the alkoxide derivative of compound b or the alkoxide derivative of monoalcohol c to be obtained. Advantageously, the treatment, total or partial, with the base of compound b or monoalcohol c, prior to carrying out the reaction, can allow the direct introduction of this alkoxide derivative of compound b or this alkoxide derivative of monoalcohol c. The alkoxide derivative of compound b or the alkoxide derivative of monoalcohol c can optionally be stored separately and then introduced during the implementation of the reaction in the presence of compound a. The method according to the invention comprises the polymerization of the poly-hydroxylated monomer b and the dihalogenated compound a. Preferably, the method according to the invention employs a single dihalogenated compound a or 2 or 3 different dihalogenated compounds a. Preferably according to the invention, the dihalogenated compound a is a compound al of formula I: [Chem I] LX!, (D in which: - L independently represents a divalent hydrocarbon group, preferably a C,-C;p-alkylene group, more preferably a C,-C-alkylene group, much more preferably CH, ; - X! independently represents Br, Cl or I, preferably Br. Preferably, the method according to the invention uses a single polyhydroxyl compound b or two or three different polyhydroxyl compounds b. More preferably according to the invention, the polyhydroxyl compound b is a compound comprising two, three, or four hydroxyl groups. More preferably, the polyhydroxylated compound b is a compound bl of formula 11: [Chem IT] HO-Q,-OH (wIm in which: - Q independently represents an oxyalkylene group, preferably chosen from oxyethylene, oxyethylene-oxypropylene comprising at most 40 mol% oxypropylene, oxyethylene-oxybutylene comprising at most 20 mol% oxybutylene, and their combinations, - n independently represents a number ranging from 20 to 800. To ensure that the oxyethylene-oxypropylene copolymer retains its water-soluble character, its oxypropylene content is less than 40 mol%, advantageously less than 35 mol%. To ensure that the oxyethylene-oxybutylene copolymer retains its water-soluble character, its oxybutylene content is less than 20 mol%, advantageously less than 15 mol%. The preferred polyhydroxylated compound b1 of formula II comprises oxyethylene Q groups. Preferably according to the invention, the polyhydroxylated compound b1 has a molar mass (Mw) ranging from 800 to 40,000 g / mol, preferably from 2,000 to 20,000 g / mol, and more preferably from 2,000 to 15,000 g / mol. According to the invention, the molar mass of compound b1 is determined by Size Exclusion Chromatography (SEC). Also preferably, the method according to the invention uses a single hydrophobic monoalcohol c or 2 or 3 different hydrophobic monoalcohols c. More preferably, the hydrophobic monoalcohol is a compound cl of formula II: [Chem II] R- X,-OH (Im in which: - R independently represents a hydrophobic hydrocarbon group, preferably a linear, branched or cyclic hydrocarbon group, saturated, unsaturated or aromatic, or comprising from 6 to 40 carbon atoms, - n represents 0 or a number from 1 to 500, - X independently represents an alkoxy group, preferably an alkoxy group chosen from an ethoxy group, a propoxy group, a butoxy group and their combinations. According to the invention, the hydrocarbon group R advantageously represents an alkyl or alkenyl group, linear, branched or cyclic, advantageously linear or branched, comprising from 6 to 40 carbon atoms, preferably from 6 to 32 carbon atoms. According to the invention, the hydrocarbon group R can also include an aromatic group comprising from 6 to 40 carbon atoms, preferably from 7 to 32 carbon atoms. According to the invention, the hydrocarbon group R may comprise a radical of formula (IV): [Chem IV] VAI (IV) in which R” represents a hydrocarbon group of formula C;sHz,, in which x = 0, 2, 4, 6; thus potentially comprising 0, 1, 2 or 3 ethylenic unsaturations (double bonds). Such a radical of formula (IV) is advantageously derived from cardanol, and thus of bio-sourced and non-polluting origin. According to the invention, the hydrocarbon group R may also comprise a tristyrylphenyl (TSP) group of formula: ne AA AR VU C CF CA XX a or a distyrylphenyl (DSP) group with the formula: ne È my ane + ne / SN tr ph “ A Ï ] J f > [, & af OU a LU Æ Preferably according to the invention, n can represent 0. The compound is then a non-alkoxylated monoalcohol. Also preferably according to the invention, n can represent a number from 2 to 100, preferably a number from 2 to 50 or from 5 to 25. Preferably according to the invention, X represents an ethoxylated group or a propoxylated group or a combination of ethoxylated and propoxylated groups. Preferably according to the invention, n represents a number from 2 to 100, preferably a number from 2 to 50 or from 5 to 25, and X represents an ethoxylated group. Also preferably according to the invention, n represents a number from 2 to 100, preferably a number from 2 to 50 or from 5 to 25, and X represents a propoxylated group. According to the invention, the copolymer P is advantageously prepared, with respect to the total weight amount of compounds a, b and c, by means of: # 10 mol% to 80 mol% of dihalogenated compound a; #5 molar % to 75 molar % of polyhydroxylated monomer b; #15 molar to 85 molar hydrophobic monoalcohol c. Copolymer P can also be prepared by reactive extrusion, relative to the total molar amount of compounds a, b, and c, using: # 15 mol% to 70 mol% of dihalogenated compound a; # 10 molar % to 65 molar % of polyhydroxylated monomer b; #20 molar to 75 molar hydrophobic monoalcohol c. A particular example of copolymer P can be prepared by reactive extrusion, with respect to the total molar amount of compounds a, b and c, using 50 mol% of dihalogenated compound a, 20 mol% of polyhydroxylated monomer b and 30 mol% of hydrophobic monoalcohol c. A particularly advantageous feature of the invention is that the method can be carried out with or without a solvent, for example, in a solvent chosen from water, an organic solvent, and combinations thereof, preferably water. Preferably, according to the invention, the preparation method can be carried out in the absence of a solvent. Advantageously, the preparation method according to the invention may also include a final acid treatment of the copolymer P leading to a pH below 8, preferably above 6, for example by means of an acid, in particular a carboxylic acid such as acetic acid or lactic acid. According to the invention, the reactants are generally reacted at a temperature between 70°C and 120°C. Hot water or steam can be used as a heat transfer fluid to control the reactor temperature within the range of 70°C to 120°C. The residence time in the reactor can be controlled, for example, from less than one hour to more than six hours. A twin-screw extruder can be fitted to the end of the reactor. The preparation method according to the invention is particularly advantageous both in itself and for enabling the production of a specific copolymer P. Thus, the invention also relates to a copolymer P obtained according to the batch preparation method defined in the invention. Surprisingly, the preparation method according to the invention also improves the viscosifying properties of the P copolymer according to the invention. Also, the method according to the invention makes it possible to obtain P copolymers having high molar masses (Mw). Preferably according to the invention, the molar mass (Mw) of the copolymer P may be up to 500,000 g / mol, advantageously it may vary from 8,000 to 500,000 g / mol, preferably from 20,000 to 500,000 g / mol. The method according to the invention makes it possible to obtain P polymers with a high molar mass (Mw), advantageously ranging from 120,000 to 500,000 g / mol, preferably from 150,000 to 500,000 g / mol, and more preferably from 150,000 to 300,000 g / mol. The method according to the invention also makes it possible to prepare P copolymers with a lower molar mass (Mw), advantageously ranging from 10,000 to 150,000 g / mol, preferably from 20,000 to 150,000 g / mol, and more preferably from 20,000 to 120,000 g / mol. According to the invention, the molar mass of copolymer P or compound b is determined by Size Exclusion Chromatography (SEC), also known as Gel Permeation Chromatography (GPC). This technique employs a Waters liquid chromatography system equipped with a detector. This detector is a Waters 2414 refractometric concentration detector. This liquid chromatography system has two size exclusion columns to separate the different molecular weights of the polymers or compounds being studied. The elution liquid phase is an organic phase composed of THF (HPLC grade, unstabilized). In a first step, approximately 25 mg of the copolymer or compound is solubilized in 5 mL of THF, with the addition of 0.1 mol% water used as Internal flow marker. Then, the solution is filtered at 0.2 µm. 50 µL are then injected into the chromatography instrument (eluent: THF, HPLC grade, unstabilized). The liquid chromatography apparatus contains an isocratic pump (Waters 515) with a flow rate set at 0.3 mL / min. The apparatus also includes a furnace with a series column system: a 250 mm long, 4.6 mm diameter Agilent PLgel MiniMIX-A column followed by a 250 mm long, 4.6 mm diameter Agilent PLgel MiniMIX-B column. The detection system consists of a Waters 2414 RI refractometer. The columns and the refractometer are maintained at 35°C. The chromatography apparatus is calibrated using polymethyl methacrylate standards certified by the supplier "Agilent" ("Easivial" PMMA). The copolymer P according to the invention can be used directly or it can be associated with other substances in a composition. The invention also provides a rheological control composition comprising at least one copolymer P according to the invention. The composition according to the invention can optionally be acidified, leading to a pH below 8, preferably above 6, for example by means of an acid, in particular a carboxylic acid such as acetic acid or lactic acid. Preferably, in the rheological control composition according to the invention, the copolymer P according to the invention is combined with at least one solvent, in particular water or a coalescing solvent, for example glycol, butyl glycol, butyldiglycol, monopropylene glycol, ethylene glycol, ethylenediglycol, "Dowanol" products of which CAS number 34590-94-8, "Texanol" products of which CAS number 25265-77-4; or combined with at least one additive selected from an amphiphilic compound, in particular a surfactant compound, preferably a hydroxylated surfactant compound, for example alkyl-polyalkylene glycol, in particular alkyl-polyethylene glycol and alkyl-polypropylene glycol; a polysaccharide derivative, for example cyclodextrin, cyclodextrin derivative, polyethers, alkyl-glucosides; a hydrotropic compound, an anti-foaming agent, a biocidal agent and their combinations. The invention also provides an aqueous formulation that can be used in many technical fields. The aqueous formulation according to the invention comprises: - at least one composition according to the invention; possibly - at least one organic or mineral pigment or organic, organometallic or mineral particles, for example calcium carbonate, talc, kaolin, mica, silicates, silica, metal oxides, in particular titanium dioxide, iron oxides; and possibly: - at least one agent chosen from among a particle spacer agent, an agent dispersant, steric stabilizer, electrostatic stabilizer, opacifier, colorant, solvent, coalescing agent, antifoaming agent, preservative, biocide, spreading agent, thickening agent, film-forming copolymer and mixtures thereof. Depending on the specific copolymer P or the additives it comprises, the formulation according to the invention can be implemented in numerous technical fields. Thus, the formulation according to the invention can be a coating formulation. Preferably, the formulation according to the invention is an ink formulation, an adhesive formulation, a varnish formulation, or a paint formulation, for example, decorative or industrial paint. The invention also provides a concentrated aqueous pigment paste comprising at least one copolymer P and at least one organic or mineral colored pigment. The copolymer P and the formulation according to the invention possess properties that allow them to be used to modify or control the rheology of the medium containing them. Thus, the invention also provides a method for controlling the viscosity of an aqueous composition. This viscosity control method according to the invention comprises the addition of at least one copolymer P, obtained according to the invention, to an aqueous composition. Preferably, the viscosity control method according to the invention is implemented for an aqueous composition that is a formulation according to the invention. The advantageous, particular or preferred characteristics of the preparation method according to the invention define copolymers P, aqueous compositions, formulations, pigment pastes as well as viscosity control methods according to the invention which are also advantageous, particular or preferred. The following examples illustrate the different aspects of the invention. EXAMPLES The following compounds a, b and c are used for the preparation of copolymers: - compound al: dibromomethane, - compound bl: polyethylene glycol with a molecular mass of 8,000 g / mol, - compound cl: hydrophobic monoalcohol of formula III in which R represents an octyldodecanyl (C.9-alkyl branched) group, - compound c2: hydrophobic monoalcohol of formula III in which R represents a cardanyl group (linear C,,-aromatic alkyl) ethoxylated 4 times, - compound c3: hydrophobic monoalcohol of formula III in which R represents a cardanyl group (linear C,,-aromatic alky), - compound c4: hydrophobic monoalcohol of formula III in which R represents a 2-hexyldecanyl (C,5-alkyl branched) group. In a 2 L reactor, compounds bl and cl are introduced, along with sodium hydroxide (20% in water). The reaction mixture is stirred for 90 min at 75°C. Compound al is added, and the temperature is increased to 100°C. Heating is continued for 60 min. After cooling, a rheological control composition (RCC) according to the invention is prepared, comprising the copolymer P1, which is introduced directly after preparation into an aqueous composition whose final pH is adjusted to approximately 7 using an aqueous solution of acetic acid. The composition also includes a surfactant (ethoxylate alcohol - Emulan HE 51 from BASF). The RCC composition comprises 20 wt% of copolymer P1, 13.3 wt% of the surfactant, and 66.7 wt% of the aqueous solution comprising the acetic acid.In a manner analogous to the preparation of the copolymer P1 and the composition CRI, the copolymers P2, P3 and P4 are prepared and characterized, as well as the rheological control compositions CR2, CR3 and CR4 according to the invention comprising respectively the copolymer P2, P3 and P4. The compositions CR2, CR3 and CR4 comprise respectively: . - 30% by weight, 30% by weight and 20% by weight of P2, P3 or P4 copolymer, - 20% by weight, 20% by weight and 13.3% by weight of surfactant compound and - 50% by weight, 50% by weight and 66.7% by weight of aqueous solution comprising acetic acid. The compounds and molar quantities of the compounds used are presented in Table 1. [Table 1] | COMPOSITIONS... movapomeenpemmnnçnns CÜREOSE,ommmnnnmnnçnnenans depolymers Lai …i el 9216364 soda Example 2: Preparation and characterization of aqueous paint formulations comprising copolymers P1 and P2 according to the invention The CRI and CR2 compositions of Pl and P2 copolymers according to the invention are used as thickening agents in a solvent-free matte paint formulation. The CR1 and CR2 compositions, comprising the thickening copolymers P1 and P2 respectively, have a dry extract of 30% by weight of active ingredient. Each paint formulation is prepared by mixing the different ingredients. The ingredients and quantities (in g) of the paint formulations are detailed in Table 2. [Table 2] Ingredients of the aqueous paint formulation Quantity (g) |“Ecodis” P50 (“Coatex” dispersant) |“Tego” 810 (“Tego” anti-foam) |“Acticide” MBS (bactericide “Thor”) |“TiONa” 568 (TIO; “Tronox”) |“Omyacoat” 850 OG (CaCO; “Omya”) |“Durcal” 2 AV (CaCO; “Omya”) |“Acronal” S790 (“Basf” binder) [Monopropylene glycol | Texanol » (Eastman coalescing agent) NaOH (20 wt% in water) Composition CRI or CR2 (30 wt% of P1 or P2) fs pu For each paint formulation, the resulting viscosities are determined at different speed gradients: - at low gradient: Brookfield viscosities at 10 and 100 rpm, respectively denoted VB10 and VB100 (mPa.s), - at medium gradient: Stormer viscosity (Krebs Unit, KU). These measurements were taken 24 hours after preparation of the formulation. The formulations were thermostated at 25 ± 0.5°C. The results are presented in Table 3. [Table 3] Confusions 1 Wiisvosités F Compositions nee Misosities riens :.copolymers) … VBIO (mPas) | VRI0O (mPa.s) | Stormer viscosity (RU). The copolymers according to the invention allow for the efficient thickening of a solvent-free matte paint at various shear gradients. These copolymers can be used effectively as pseudoplastic additives. In the field of water-based paints, high viscosity at low or medium shear gradients indicates good static behavior. This ensures good stability during storage while preventing sedimentation and limiting the tendency to run on vertical surfaces.

Claims

Demands

1. Batch preparation method of a copolymer P comprising: * the polymerization reaction in the presence of a base: a) of at least one dihalogenated compound a of formula I: [Chem I] lx*2 (I) in which: - L independently represents a divalent hydrocarbon group; - X1 independently represents Br or I; b) of at least one polyhydroxylated monomer b used in a molar quantity providing a number of hydroxyl groups (OH) less than the number of halides provided by compound a; and * the reaction with at least one hydrophobic monoalcohol c.

2. A preparation method according to claim 1 wherein: * the base is used in a molar excess relative to the molar amount of OH groups of monomer b and monoalcohol c, preferably used in a molar amount of 1.05 to 15, preferably 2 to 13, molar equivalents relative to the molar amount of OH groups of monomer b and monoalcohol c; or * the polymerization is carried out at a pH greater than 10 or greater than 12; or * the base is a strong mineral base or a strong organic base, preferably a base selected from sodium hydride, potassium hydride, NaOH, KOH, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium tert-butanolate, potassium tert-butanolate.

3. A preparation method according to any one of claims 1 or 2 wherein: * a single dihalogenated compound a is used or wherein 2 or 3 different dihalogenated compounds a are used; or * the dihalogenated compound a is a compound al of formula I in which: - L independently represents a Ci-Cio-alkylene group, more preferably a Ci-C2-alkylene group, much more preferably CH2; - X1 independently represents Br or I, preferably Br.

4. A preparation method according to any one of claims 1 to 3 wherein: * a single polyhydroxylated compound b is used or wherein 2 or 3 different polyhydroxylated compounds b are used; or * the polyhydroxylated compound b is a compound comprising 2, 3 or 4 hydroxyl groups; or * the polyhydroxylated compound b is a compound bl of formula II: [Chem II] HO-Qn-OH (II) wherein: - Q independently represents an oxyalkylene group, preferably selected from oxyethylene, oxyethylene-oxypropylene comprising at most 40 mol% oxypropylene, oxyethylene-oxybutylene comprising at most 20 mol% oxybutylene, and combinations thereof; - n independently represents a number from 20 to 800; or * the polyhydroxylated compound has a mass molar mass (Mw) ranging from 800 to 40,000 g / mol, preferably from 2,000 to 20,000 g / mol, more preferably from 2,000 to 15,000 g / mol.

5. A preparation method according to any one of claims 1 to 4 wherein: * a single hydrophobic monoalcohol c is used or wherein 2 or 3 different hydrophobic monoalcohols c are used; or * the hydrophobic monoalcohol c is a compound cl of formula III: [Chem III] R-Xn-OH (HD in which: - R independently represents a hydrophobic hydrocarbon group, preferably a linear, branched or cyclic hydrocarbon group, saturated, unsaturated or aromatic, or comprising from 6 to 40 carbon atoms, - n represents 0 or a number from 1 to 500, - X independently represents an alkoxy group, preferably an alkoxy group selected from an ethoxy group, a propoxy group, a butoxy group and combinations thereof.

6. A preparation method according to any one of claims 1 to 5 wherein the copolymer P is prepared, relative to the total weight amount of compounds a, b and c, using: * 10 mol% to 80 mol%, or 15 mol% to 70 mol%, for example 50 mol%, of dihalogenated compound a; * 5 mol% to 75 mol%, or 10 mol% to 65 mol%, for example 20 mol%, of polyhydroxylated monomer b; * 15 mol% to 85 mol%, or 20 mol% to 75 mol%, for example 30 mol%, of hydrophobic monoalcohol c.

7. A preparation method according to any one of claims 1 to 6 carried out in the absence of solvent or in a solvent selected from water, an organic solvent and combinations thereof, preferably water.

8. A preparation method according to any one of claims 1 to 7 also comprising a final acid treatment of the copolymer P leading to a pH below 8, preferably above 6, for example by means of an acid, in particular a carboxylic acid such as acetic acid or lactic acid.

9. Copolymer P obtained according to the preparation method defined according to any one of claims 1 to 8.

10. Rheological control composition comprising at least one copolymer P as defined in claim 9, optionally acid-treated leading to a pH below 8, preferably above 6, for example by means of an acid, in particular a carboxylic acid such as acetic acid or lactic acid.

11. Rheological control composition comprising at least one copolymer P as defined in claim 9 combined with at least one solvent, in particular water or a coalescing solvent, for example glycol, butyl glycol, butyldiglycol, monopropylene glycol, ethylene glycol, ethylenediglycol, "Dowanol" products of CAS number 34590-94-8, "Texanol" products of CAS number 25265-77-4; or combined with at least one additive selected from an amphiphilic compound, in particular a surfactant compound, preferably a hydroxylated surfactant compound, for example alkyl-polyalkylene glycol, in particular alkyl-polyethylene glycol and alkyl-polypropylene glycol; a polysaccharide derivative, for example cyclodextrin, cyclodextrin derivative, polyethers, alkyl-glucosides; a hydrotropic compound, an antifoaming agent, a biocidal agent and their combinations.

12. Aqueous formulation comprising: - at least one composition according to one of claims 10 or 11; optionally - at least one organic or mineral pigment or organic, organo-metallic or mineral particles, for example calcium carbonate, talc, kaolin, mica, silicates, silica, metal oxides, in particular titanium dioxide, iron oxides; and optionally - at least one agent selected from a particle spacer, a dispersing agent, a steric stabilizer, an electrostatic stabilizer, an opacifying agent, a coloring agent, a solvent, a coalescing agent, an antifoaming agent, a preservative, a biocidal agent, a spreading agent, a thickening agent, a film-forming copolymer and mixtures thereof.

13. Formulation according to claim 12 of coating, in particular an ink formulation, a varnish formulation, an adhesive formulation, a paint formulation, for example decorative paint or industrial paint.

14. Concentrated aqueous pigment paste comprising at least one copolymer P as defined in claim 9 and at least one organic or mineral colour pigment.

15. Method for controlling the viscosity of an aqueous composition comprising the addition of at least one copolymer P defined according to claim 9, in an aqueous composition.

16. Method according to claim 15 wherein the aqueous composition is a formulation defined according to one of claims 12 or 13.