WO2025056838A1 - Cross-linked polymer - Google Patents

Abstract

The invention relates to a water-soluble copolymer which is cross-linked by means of an alkoxylated and associative cross-linking compound. The invention also relates to the preparation of said polymer, its use for controlling the viscosity and suspending nature of an aqueous composition, as well as to the alkoxylated and associative cross-linking compound.

Description

CROSSLINKED POLYMER

The invention relates to a water-soluble copolymer crosslinked by means of a crosslinking compound which is alkoxylated and associative. The invention also relates to the preparation of this polymer, its use for controlling the viscosity and the suspensive character of an aqueous composition as well as the alkoxylated and associative crosslinking compound.

The crosslinking compound R according to the invention makes it possible to obtain a polymer which has numerous properties. In particular, this copolymer makes it possible to modify the rheology of an aqueous composition.

The polymer according to the invention also makes it possible to suspend and maintain in suspension particles within an aqueous composition. Generally, the suspensive properties are evaluated by means of a suspension application test which makes it possible to determine the value of the modulus of elasticity G' and the value of Tan (δ) of the aqueous composition comprising a rheology modifying agent. The homogeneous suspension of particles is also sought. Generally, the particles to be suspended in the continuous phase of the aqueous composition are solid bodies, which may in particular be solid or hollow.

The polymer according to the invention has properties that are particularly sought after in many technical fields. Indeed, many fields use aqueous compositions whose properties must be controlled by means of such polymers, in particular aqueous compositions useful in the fields of cosmetics; personal, domestic or industrial hygiene; detergents; paints and varnishes; paper coatings; textile dyes; textile prints; drilling muds; plasterboards or joint pastes for plasterboards; hydraulic binders; ceramics; leather treatment; the mining industry; the agrochemical industry.

Advantageously, the aqueous compositions comprising the polymer according to the invention have properties and performances accessible for wide ranges of pH values, both at acidic pH values and at neutral or basic pH values.

The polymerizable compound R according to the invention is polyfunctional. It has specific properties due to its particular structure but also thanks to the different functions it contains. Indeed, this compound is alkoxylated. It comprises several olefinic unsaturations making it polymerizable. And, it comprises at least one hydrophobic group which allows it to develop an associative character. These characteristics are thus grouped in a unique way within the compound R according to the invention. Its use therefore allows easy and direct access to all these characteristics, in particular to prepare a copolymer, in particular a HASE polymer (hydrophobically modified alkali-swellable emulsion, Hydrophobically modified Alkali-Soluble Emulsion or Hydrophobically modified Alkali-Swellable Emulsion). The reduction of the number of reagents and the simplification of the methods for preparing these polymers are always sought.

Document WO2023065802 describes resins crosslinked using a crosslinking compound which is derived from magnolol and which comprises allylic ether groups. Documents WO2017207945 and WO2014096709 describe polymers crosslinked using divalent unsaturated compounds, in particular di(meth)acrylate compounds.

State-of-the-art rheology modifying agents, aqueous compositions comprising them and state-of-the-art compounds which enable them to be prepared are not always satisfactory and lead to problems linked to the numerous properties sought.

There is therefore a need for means of preparing rheology modifying agents having improved properties, in particular properties present in aqueous compositions. The invention makes it possible to provide a solution to all or part of the problems encountered during the preparation of rheology modifying agents of the state of the art.

dans laquelle : Thus, the invention provides a crosslinked water-soluble copolymer P, prepared by at least one polymerization reaction, in the presence of at least one initiator compound,: of at least one alkoxylated and polymerizable compound R of formula I:

in which:

- Q represents a multivalent hydrocarbon group comprising from 1 to 20 carbon atoms,

- q represents a number from 1 to 6,

- A represents a polymerizable group chosen from acrylate, methacrylate, acrylurethane, methacrylurethane, allylurethane, 3-isopropenyl-a,a- dimethylbenzylurethane, vinyl, allyl, methallyl and isoprenyl,

- B represents a hydrocarbon group comprising at least one polymerizable olefinic unsaturation,

- D represents at least one hydrocarbon group comprising at least 6 carbon atoms,

- X independently represents a divalent group chosen from methylene, ethylene, propylene, butylene and combinations thereof,

- a represents a number ranging from 1 to 100,

- b and d, independently represent 0 or a number less than 100;

• at least one compound Ml chosen from methacrylic acid, a salt of methacrylic acid, an oligomer of methacrylic acid, a salt of oligomer of methacrylic acid, acrylic acid, a salt of acrylic acid, an oligomer of acrylic acid, a salt of oligomer of acrylic acid, maleic acid, itaconic acid, crotonic acid, their salts and their combinations; and

• at least one compound M2 chosen from a C1-C8 ester of a compound derived from an acid chosen from acrylic acid, methacrylic acid, maleic acid, itaconic acid and crotonic acid.

Essentially according to the invention, the compound R comprises at least 2 unsaturated olefinic groups which are polymerizable. Preferably, the polymerizable unsaturated olefinic groups of the compound R have different reactivities.

Preferably according to the invention, group B is different from groups A and D. Also preferably according to the invention, q represents 1, 2 or 3, more preferably 1 or 2.

Also preferably according to the invention, Q represents a multivalent hydrocarbon group comprising from 1 to 10 carbon atoms.

Also preferably for the compound R according to the invention, Q represents a multivalent hydrocarbon group comprising from 1 to 12 carbon atoms or from 1 to 10 carbon atoms. Also preferably for the compound R according to the invention, Q represents a trivalent group, a tetravalent group or a pentavalent group.

More preferably for the compound R according to the invention, Q represents a linear Ci-Ci2-alkylene group, preferably a linear Ci-Cio-alkylene group or a linear Ci-C6-alkylene group, or a branched Ci-Ci2-alkylene group, of preferably a branched C1-C10-alkylene group or a branched C1-C6-alkylene group, or even a C5-C2o-arylene group, preferably a Cs-C12-arylene group; most preferably a CH group or a phenylene group. Also preferably for the compound R according to the invention, the group A is chosen from acrylate, methacrylate, acrylurethane, methacrylurethane, allylurethane and 3-isopropenyl-a,a-dimethylbenzylurethane; more preferably a methacrylate group.

Preferably according to the invention, the group X linked to the group A independently represents a divalent group chosen from methylene, ethylene, propylene, butylene and their combinations, more preferably a methylene group or an ethylene group alone or combined with a propylene group in an oxyethylene/oxypropylene mass ratio ranging from 90/10 to 70/30.

Also preferably for the compound R according to the invention, a represents a number ranging from 1 to 80, preferably a number ranging from 5 to 50 or from 5 to 30.

Also preferably for the compound R according to the invention, B represents a hydrocarbon group comprising at least one group chosen from a vinyl, allylic, methallyl and isoprenyl group, in particular B represents a group chosen from a vinyl, allylic, methallyl and isoprenyl group, more preferably an allylic, methallyl or isoprenyl group. Also preferably for the compound R according to the invention, B represents a hydrocarbon group comprising a single polymerizable olefinic unsaturation.

Preferably according to the invention, the group X linked to the group B independently represents a divalent group chosen from methylene, ethylene, propylene, butylene and their combinations; more preferably, a methylene group or an ethylene group alone or combined with a propylene group in an oxyethylene/oxypropylene mass ratio ranging from 90/10 to 70/30.

Also preferably for the compound R according to the invention, b represents 0 or 1 or a number ranging from 1 to 100 or from 1 to 50, preferably a number ranging from 2 to 100 or from 2 to 50, more preferably from 5 to 100 or from 5 to 50, much more preferably from 5 to 40 or from 5 to 30.

Essentially according to the invention, the compound R comprises a hydrophobic group D. Preferably, the compound R according to the invention comprises a group D comprising from 6 to 40 carbon atoms. More preferably, the group D is a linear, branched or cyclic, saturated, unsaturated or aromatic hydrocarbon group. More preferably, group D is a linear, branched or cyclic, saturated, unsaturated or aromatic hydrocarbon group comprising from 6 to 40 carbon atoms. Most preferably, group D is a linear or branched C6-C4o-alkyl group or a C6-C4o-aryl group. More preferably, group D is a linear or branched Cs-C32-alkyl group or a C10-C4o-aryl group.

Even more preferably, the group D is a linear Cs-C32-alkyl group or a linear Cs-C24-alkyl group or a C6-Cso-aryl group, for example a styryl group.

According to the invention, group D is a hydrocarbon group. It does not contain any heteroatom. In particular, it does not contain any oxygen.

Preferably according to the invention, the group X linked to the group D independently represents a divalent group chosen from methylene, ethylene, propylene, butylene and their combinations, more preferably, a methylene group or an ethylene group alone or combined with a propylene group in an oxyethylene/oxypropylene mass ratio ranging from 90/10 to 70/30.

Also preferably for the compound R according to the invention, d represents 0 or 1 or a number ranging from 1 to 100 or from 1 to 50, preferably a number ranging from 2 to 100 or from 2 to 50, more preferably from 5 to 100 or from 5 to 50, even more preferably from 5 to 40 or from 5 to 30.

The compound R according to the invention is polymerizable. Its molecular mass can vary. Preferably, the compound R according to the invention has a molecular mass Mw, measured by CES, ranging from 100 g/mol to 10,000 g/mol. More preferably, its mass ranges from 200 g/mol to 8,000 g/mol or from 200 g/mol to 5,000 g/mol, more preferably from 200 g/mol to 4,000 g/mol or from 500 g/mol to 4,000 g/mol, much more preferably from 500 g/mol to 3,000 g/mol or from 500 g/mol to 2,000 g/mol.

According to the invention, the molecular mass Mw can be calculated or determined by Size Exclusion Chromatography (SEC) or in English "Gel Permeation Chromatography" (GPC). This technique uses a "Waters" brand liquid chromatography device equipped with a detector. This detector is a "Waters" brand refractometric concentration detector. This liquid chromatography device is equipped with a size exclusion column in order to separate the different molecular weights of the compounds studied. Preferably according to the invention, the compound Ml is chosen from methacrylic acid, a methacrylic acid salt, acrylic acid, an acrylic acid salt and combinations thereof.

According to the invention, compound Ml may be combined with at least one other anionic monomer, different from compound Ml, and chosen from acrylic acid, methacrylic acid, an acrylic acid salt, a methacrylic acid salt, maleic acid, a maleic acid salt, itaconic acid, an itaconic acid salt, crotonic acid, a crotonic acid salt, an acrylic acid oligomer and combinations thereof. More preferably according to the invention, compound Ml is methacrylic acid alone or combined with acrylic acid, preferably in an amount by mass of acrylic acid less than the amount by mass of methacrylic acid.

More preferably according to the invention, compound M2 is a C1-C7 ester or a C1-C6 ester or a C1-C4 ester. Preferably, compound M2 is chosen from C1-C8-alkyl methacrylate, C1-C8-alkyl acrylate, styrene, vinylcaprolactam, vinyl acetate and combinations thereof. More preferably, compound M2 is chosen from methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, ethylhexyl methacrylate and combinations thereof. Even more preferably, compound M2 is chosen from ethyl acrylate, methyl acrylate, butyl acrylate, methyl methacrylate and combinations thereof.

According to the invention, the polymer P can be prepared by involving a single polymerization reaction.

Preferably according to the invention, the polymer P is prepared by a polymerization reaction using: from 0.2 to 10% by weight of compound R, or from 5 to 49.8% by weight of monomer M1, or from 50 to 94.8% by weight of monomer M2, relative to the total quantity by weight of compound R and monomers M1 and M2.

More preferably according to the invention, the polymer P is prepared by a polymerization reaction using: from 0.5 to 5% by weight of compound R, from 10 to 44.5% by weight of monomer M1, and from 55 to 89.5% by weight of monomer M2, relative to the total quantity by weight of compound R and of monomers M1 and M2. According to the invention, the polymer P may have a molecular mass Mw, measured by CES, ranging from 20,000 g/mol to 800,000 g/mol or from 20,000 g/mol to 500,000 g/mol. More preferably, the molecular mass Mw of the polymer P, measured by CES, ranges from 20,000 g/mol to 400,000 g/mol or from 20,000 g/mol to 300,000 g/mol.

According to the invention, the polymer P may be totally or partially acidic or totally or partially neutralized. Preferably, the polymer P is partially neutralized.

Also preferably, the polymer P can be neutralized by means of at least one compound chosen from LiOH, NaOH, KOH, Zn(OH)2, Mg(OH)2, Ca(OH)2, ZnO, MgO, CaO, ammonium derivatives, ammonia, aqueous ammonia, amine bases, for example triethanolamine, aminomethylpropanol or 2-amino-2-methyl-propanol (AMP) and their combinations, more preferably LiOH, NaOH, KOH, Mg(OH)2, Ca(OH)2, aqueous ammonia and their combinations.

Preferably, the polymer P has a pKa of less than 5 or a pKa ranging from 1.5 to 5.

Essentially, the crosslinked water-soluble copolymer P according to the invention is prepared by means of the compound R and the monomers M1 and M2. In the preparation of the copolymer P, other monomers can be used.

Then, the polymerization reaction can also implement at least one compound M3 chosen from hydroxyethyl-acrylate, hydroxypropyl-acrylate, hydroxyethylhexyl-acrylate, hydroxyethyl-methacrylate, hydroxypropyl-methacrylate, hydroxyethylhexyl-methacrylate, phosphated hydroxyethyl-acrylate, phosphated hydroxypropyl-acrylate, phosphated hydroxyethylhexyl-acrylate, phosphated hydroxyethyl-methacrylate, phosphated hydroxypropyl-methacrylate, phosphated hydroxyethylhexyl-methacrylate, 2-acrylamido-2-methylpropane sulfonic acid (AMPS), allyl-sulfonic acid, alkylenesulfonates, alkylenearylsulfonates in particular styrene-sulfonate, vinyl-sulfonate, methallyl-sulfonate, allyl-sulfonate, methallyl-sulfate, allyl-sulfate, 2-sulfoethyl methacrylate, acid 3-allyloxy-2-hydroxy-l-propanesulfonic acid, 3-sulfopropyl methacrylate, their salts and their combinations. Preferably, compound M3 is used in an amount of less than 20% by weight, preferably 0.2 to 20% by weight, in particular 0.5 to 10% by weight, relative to the total amount by weight of monomers.

dans laquelle : The polymerization reaction can also use at least one compound M4 of formula II:

in which:

- m or n is different from 0,

- m independently represents 0 or a number less than 150,

- n independently represents 0 or a number less than 150,

- OE represents an oxyethylene group,

- OP independently represents an oxypropylene group,

- R ¹ represents a group comprising at least one polymerizable olefinic unsaturation, preferably a group chosen from acrylate, methacrylate, acrylurethane, methacrylurethane, vinyl, allyl, methallyl and isoprenyl; more preferably a methacrylate group,

- R ² represents a linear, branched or cyclic, saturated, unsaturated or aromatic hydrocarbon group comprising from 6 to 40 carbon atoms, preferably a linear or branched C6-C4o-alkyl group, preferably a linear or branched Cs-Cso-alkyl group, a C6-C4o-aryl group, preferably a Cs-Cso-aryl group, for example a tristyrylphenyl group.

Preferably, compound M4 is a compound of formula II in which: m represents an integer or decimal number ranging from 20 to 40 and n is zero or m and n independently represent an integer or decimal number ranging from 5 to 100 or the mass ratio m/n ranges from 90/10 to 70/30.

The polymerization reaction may also use at least one compound M5 chosen from: polyalkylene glycol acrylate, preferably from polyethylene glycol acrylate and polyethylenepolypropylene glycol acrylate, polyalkylene glycol methacrylate, preferably from polyethylene glycol methacrylate and polyethylenepolypropylene glycol methacrylate, allylpolyalkylene glycol, preferably from allylpolyethylene glycol and allylpolyethylenepolypropylene glycol, methallylpolyalkylene glycol, preferably from methallylpolyethylene glycol and methallylpolyethylenepolypropylene glycol, 3-methyl-3-buten-l-ylpolyalkylene glycol, preferably from 3-methyl-3-buten-l-ylpolyethylene glycol and 3-methyl-3-buten-l-ylpolyethylenepolypropylene glycol.

The polymerization reaction may optionally use at least one other crosslinking compound M6 or at least one compound M6 comprising at least two olefinic unsaturations, different from compound R.

The invention also provides a method for preparing a copolymer P according to the invention, by a polymerization reaction using at least one polymerizable compound and a compound R defined according to the invention; preferably a method for preparing a copolymer P according to the invention, by a polymerization reaction using compounds M1 and M2 and a compound R, defined according to the invention.

The properties of the copolymer P according to the invention make it possible to act particularly effectively on the viscosity of an aqueous composition. Thus, the invention also provides a method for preparing an aqueous composition, preferably a method for controlling the viscosity of an aqueous composition or a method for improving the suspensive nature of an aqueous composition, comprising the addition to this composition of at least one copolymer P according to the invention.

The amount of polymer P used in these methods may vary. Preferably, these methods use from 0.2% by weight to 10% by weight, preferably from 0.5% by weight to 8% by weight or from 0.5% by weight to 5% by weight, of polymer P relative to the composition.

dans laquelle : The compound R according to the invention makes it possible in particular to prepare the copolymer P according to the invention. Thus, the invention also provides an alkoxylated and polymerizable compound R of formula I:

in which:

Q represents a multivalent hydrocarbon group comprising from 1 to 20 carbon atoms, q represents a number ranging from 1 to 6,

A represents a polymerizable group chosen from acrylate, methacrylate, acrylurethane, methacrylurethane, allylurethane, 3-isopropenyl-a,a-dimethylbenzylurethane, vinyl, allyl, methallyl and isoprenyl,

- B represents a hydrocarbon group comprising at least one polymerizable olefinic unsaturation,

- D represents at least one hydrocarbon group comprising at least 6 carbon atoms,

X independently represents a divalent group selected from methylene, ethylene, propylene, butylene and combinations thereof, a represents a number ranging from 1 to 100,

- b and d, independently represent 0 or a number less than 100.

The invention also provides a method for preparing compound R according to the invention.

dans laquelle : The compound R of formula I in which A represents a polymerizable group chosen from acrylate and methacrylate, is prepared according to a preparation method which comprises the reaction of an alkoxylated compound Ri of formula III:

in which:

Q represents a multivalent hydrocarbon group comprising from 1 to

20 carbon atoms, q represents a number from 1 to 6,

- B represents a hydrocarbon group comprising at least one polymerizable olefinic unsaturation,

- D represents at least one hydrocarbon group comprising at least 6 carbon atoms,

X independently represents a divalent group selected from methylene, ethylene, propylene, butylene and combinations thereof, a represents a number ranging from 1 to 100,

- b and d, independently represent 0 or a number less than 100, with at least one compound Rii chosen from methacrylic acid, acrylic acid, maleic acid, methacrylic anhydride, maleic anhydride, their salts and their combinations; preferably chosen from methacrylic anhydride. The compound R of formula I in which A represents a polymerizable group chosen from a vinyl, allylic, methallyl and isoprenyl group, is prepared according to a preparation method which comprises the reaction of an alkoxylated compound Ri of formula II in the presence of a strong base and with a compound Riii of formula IV:

A-T (IV) in which A represents a polymerizable group chosen from a vinyl, allylic, methallyl and isoprenyl group and T represents Br or I. Preferably, T represents Br.

The compound R according to the invention can be prepared according to a reaction carried out without solvent, directly in the liquid or molten reactants. It can also be prepared according to a reaction which uses a solvent, preferably water, in particular when using a compound of formula III.

The compound R of formula I in which A represents a polymerizable group chosen from acrylurethane, methacrylurethane, allylurethane, methallylurethane and 3-isopropenyl-a,a-dimethylbenzylurethane, is prepared according to a preparation method which comprises the reaction of an alkoxylated compound Ri of formula III with 3-isopropenyl-a,a'-dimethylbenzyl isocyanate (CAS No. 2094-99-7) or with a compound Riv prepared by prior reaction of a diisocyanate compound (for example tolyl diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate) and at least one compound chosen from ethylene glycol acrylate, ethylene glycol methacrylate, isoprenol, vinyl ethylene glycol, allyl alcohol, methallyl alcohol, hydroxybutyl vinyl ether and combinations thereof.

Preferably, the compound Riv is chosen from 3-isopropenyl-a,a'-dimethylbenzyl isocyanate (CAS No. 2094-99-7), 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, a compound prepared by prior reaction of tolyl-diisocyanate or isophorone-diisocyanate and ethylene glycol methacrylate and combinations thereof, much more preferably from 3-isopropenyl-a,a'-dimethylbenzyl isocyanate, 2-isocyanatoethyl methacrylate, a compound prepared by prior reaction of tolyl-diisocyanate or isophorone-diisocyanate and ethylene glycol methacrylate and combinations thereof.

In the preparation of compound R, compounds of formula III, compounds Rii, compounds of formula IV and compounds Riv are generally used in stoichiometric amounts. Compounds of formula III, compounds Rii, compounds of Formula IV and Riv compounds are generally known as such or they can be prepared from known compounds by known methods.

Preferred compounds of formula I according to the invention define compounds of formula III or compounds of formula IV which are also preferred.

The particular, advantageous or preferred characteristics of the copolymer P according to the invention define compounds R and methods of preparation or use according to the invention which are also particular, advantageous or preferred.

The following examples illustrate the different aspects of the invention, in particular the preparation and characterization of paper coating compositions according to the invention.

EXAMPLES

Preparation and characterization of a compound R according to the invention

In a glass reactor, 370.0 g of compound Ri of formula II in which Q represents a phenylene group, q represents 1-3, a represents 10, X represents an ethylene group, b and d represent 0, B represents a CH=CH-CH3 group in position 2 of the group Q, relative to the OH group in position 1, and D represents a styryl group, 0.822 g of alloocimene and 82.6 g of methacrylic anhydride (Rii) are introduced. The mixture is heated to 80°C ± 2°C; heating is maintained for 2 hours and 30 minutes. The compound RI according to the invention is obtained at 89.83% by weight.

Preparation and characterization of P copolymers according to the invention

PI copolymer

520 g of deionized water and 3.17 g of sodium dodecyl sulfate are introduced into a glass reactor.

In a first beaker, 108.24 g of methacrylic acid (compound M1), 176.22 g of ethyl acrylate (compound M2), 6.48 g of compound RI according to the invention, 1.06 g of sodium dodecyl sulfate and 120 g of deionized water are weighed. In a second beaker, 0.930 g of ammonium persulfate dissolved in 10 g of deionized water are weighed. In a third beaker, 0.093 g of sodium metabisulfite dissolved in 5 g of deionized water are weighed.

The contents of the reactor are heated to a temperature of 76°C ± 2°C and for 2 hours, the reagents from the 3 beakers are introduced in parallel into the reactor. Then, the medium is allowed to cool to room temperature. The PI copolymer according to the invention is obtained at 28.8% by weight of dry extract, the composition of which is detailed in Table 1. P2 copolymer

400 g of deionized water, 1.95 g of sodium dodecyl sulfate and 0.83 g of polyalkylene glycol (mono-butyl ether ethylene oxide/propylene oxide copolymer - product B 11/50) are introduced into a glass reactor.

In a first beaker, 114.0 g of methacrylic acid (compound M1), 201.07 g of ethyl acrylate (compound M2), 10.89 g of compound RI according to the invention, 1.66 g of sodium dodecyl sulfate, 1.53 g of polyalkylene glycol (B1 l/50) and 212.1 g of deionized water are weighed. In a second beaker, 0.456 g of ammonium persulfate dissolved in 8 g of deionized water are weighed. In a third beaker, 0.046 g of sodium metabisulfite dissolved in 8 g of deionized water is weighed.

The contents of the reactor are heated to a temperature of 76°C ± 2°C and for 2 hours, the reagents from the 3 beakers are introduced in parallel into the reactor. Then, the medium is allowed to cool to room temperature. The copolymer P2 according to the invention is obtained at 30.4% by weight of dry extract, the composition of which is detailed in Table 1.

P 3 copolymer

400 g of deionized water, 1.95 g of sodium dodecyl sulfate and 0.83 g of polyalkylene glycol (Bl l/50) are introduced into a glass reactor.

In a first beaker, 116.5 g of methacrylic acid (compound M1), 203.1 g of ethyl acrylate (compound M2), 6.35 g of compound RI according to the invention, 1.66 g of sodium dodecyl sulfate, 1.53 g of polyalkylene glycol (B1 l/50) and 212.1 g of deionized water are weighed. In a second beaker, 0.456 g of ammonium persulfate dissolved in 8 g of deionized water are weighed. In a third beaker, 0.046 g of sodium metabisulfite dissolved in 8 g of deionized water is weighed.

The contents of the reactor are heated to a temperature of 76°C ± 2°C and for 2 hours, the reagents from the 3 beakers are introduced in parallel into the reactor. Then, the medium is allowed to cool to room temperature. The copolymer P3 according to the invention is obtained at 30.1% by weight of dry extract, the composition of which is detailed in Table 1.

Table 1

The rheology control properties and the particle suspensive capacity of the polymers according to the invention are evaluated by measuring the viscosity and the flow threshold. of aqueous compositions prepared from these hydrophobic and crosslinked polymers.

To measure the viscosity, the prepared copolymer PI is mixed with deionized water in an amount of 2% by dry weight and then an aqueous ammonia solution (28% by weight) is added to completely neutralize the composition to a pH value of 8.5-9. Analogous compositions are prepared by replacing the polymer PI with polymers P2 and P3, respectively. The Brookfield viscosity at 25°C and 100 rpm of these compositions is then measured using a Brookfield DV1 viscometer equipped with a spindle adapted to the viscosity range of the composition. The results are shown in Table 2.

Table 2

A composition is then prepared by mixing the polymer P3 according to the invention in a quantity by dry weight of 2.25% with 9% by dry weight of sodium lauryl ether sulfate and 3% by dry weight of cocamidopropyl betaine in deionized water (qsp 100). The pH is adjusted to a value of 5 by adding an aqueous solution of citric acid.

The Brookfield viscosity measured at 25°C and 100 rpm using a Brookfield DV1 viscometer equipped with a spindle adapted to the viscosity range is 10,300 mPa.s.

The yield stress is the applied stress that causes the aqueous composition comprising the polymer according to the invention to flow. A stress ramp varying from 0.01 Pa to 100 Pa is used over a period of 300 seconds. The yield stress measurement was carried out at 25°C and then at 50°C using a “Haake Mars III” imposed stress rheometer (“ThermoFisher Scientific”) equipped with a CP60-1/S cone-plate geometry (diameter of 60 mm, truncation angle of 1°) and then using the “RheoWin Data Manager” software processing.

The flow threshold at 25°C is 5.8 Pa and the flow threshold at 50°C is 1.55 Pa. It is found that the copolymers according to the invention make it possible to thicken aqueous compositions significantly. They have a high flow threshold and they make it possible to obtain shear-thinning compositions: at rest, their character is solid and they do not flow under their own weight (for example, in the cosmetic bottle) while when a certain constraint is applied to them (when applying the product to the skin), these compositions become liquid, both at 25°C and at 50°C.

Claims

1. Crosslinked water-soluble P copolymer, prepared by at least one polymerization reaction, in the presence of at least one initiator compound: • at least one alkoxylated and polymerizable compound R of formula I:

in which: Q represents a multivalent hydrocarbon group comprising from 1 to 20 carbon atoms, q represents a number ranging from 1 to 6, A represents a polymerizable group chosen from acrylate, methacrylate, acrylurethane, methacrylurethane, allylurethane, 3-isopropenyl-a,a-dimethylbenzylurethane, vinyl, allyl, methallyl and isoprenyl, - B represents a hydrocarbon group comprising at least one polymerizable olefinic unsaturation, - D represents at least one hydrocarbon group comprising at least 6 carbon atoms, X independently represents a divalent group selected from methylene, ethylene, propylene, butylene and combinations thereof, a represents a number ranging from 1 to 100, - b and d, independently represent 0 or a number less than 100; • at least one compound Ml chosen from methacrylic acid, a salt of methacrylic acid, an oligomer of methacrylic acid, a salt of oligomer of methacrylic acid, acrylic acid, a salt of acrylic acid, an oligomer of acrylic acid, a salt of oligomer of acrylic acid, maleic acid, itaconic acid, crotonic acid, their salts and their combinations; and • at least one compound M2 chosen from a C1-C8 ester of a compound derived from an acid chosen from acrylic acid, methacrylic acid, maleic acid, itaconic acid and crotonic acid. 2. Polymer P according to claim 1 for which: q represents 1, 2 or 3, preferably 1 or 2; or Q represents a multivalent hydrocarbon group comprising from 1 to 12 carbon atoms or from 1 to 10 carbon atoms, preferably a trivalent group, a tetravalent group or a pentavalent group, more preferably a linear Ci-Ci2-alkylene group, much more preferably a linear Ci-Cio-alkylene group or a linear Ci-C6-alkylene group, or a branched Ci-Ci2-alkylene group, much more preferably a branched Ci-Cio-alkylene group or a branched Ci-C6-alkylene group, or even a Cs-C2o-arylene group, much more preferably a Cs-C -arylene group; most preferably a CH group or a phenylene group. 3. Polymer P according to one of claims 1 or 2 for which: the group A is chosen from acrylate, methacrylate, acrylurethane, methacrylurethane, allylurethane and 3-isopropenyl-a,a-dimethylbenzylurethane; preferably a methacrylate group; or the group X linked to the group A independently represents a divalent group chosen from methylene, ethylene, propylene, butylene and their combinations, preferably a methylene group or an ethylene group alone or combined with a propylene group in an oxyethylene/oxypropylene mass ratio ranging from 90/10 to 70/30; or a represents a number ranging from 1 to 80, preferably a number ranging from 5 to 50 or from 5 to 30. 4. Polymer P according to one of claims 1 to 3 for which: - B represents a hydrocarbon group comprising at least one group chosen from a vinyl, allylic, methallyl and isoprenyl group, in particular B represents a group chosen from a vinyl, allylic, methallyl and isoprenyl group, more preferably an allylic, methallyl or isoprenyl group; or - B represents a hydrocarbon group comprising a single polymerizable olefinic unsaturation; or the group X linked to the group B independently represents a group divalent chosen from methylene, ethylene, propylene, butylene and their combinations, preferably a methylene group or an ethylene group alone or combined with a propylene group in an oxyethylene/oxypropylene mass ratio ranging from 90/10 to 70/30; or - b represents 0 or 1 or a number ranging from 1 to 100 or from 1 to 50, preferably a number ranging from 2 to 100 or from 2 to 50, more preferably from 5 to 100 or from 5 to 50, even more preferably from 5 to 40 or from 5 to 30. 5. Polymer P according to one of claims 1 to 4 for which: the group D is a linear, branched or cyclic, saturated, unsaturated or aromatic hydrocarbon group, more preferably, a linear, branched or cyclic, saturated, unsaturated or aromatic hydrocarbon group comprising from 6 to 40 carbon atoms, more preferably, a linear or branched C6-C40-alkyl group or a C6-C40-aryl group, much more preferably, a linear Cs-C32-alkyl group or a linear Cs-C24-alkyl group or a C6-Cso-aryl group, for example a styryl group; or the group X linked to the group D independently represents a divalent group chosen from methylene, ethylene, propylene, butylene and combinations thereof, preferably a methylene group or an ethylene group alone or combined with a propylene group in an oxyethylene/oxypropylene mass ratio ranging from 90/10 to 70/30; or d represents 0 or 1 or a number ranging from 1 to 100 or from 1 to 50, preferably a number ranging from 2 to 100 or from 2 to 50, more preferably from 5 to 100 or from 5 to 50, even more preferably from 5 to 40 or from 5 to 30. 6. Polymer P according to one of claims 1 to 5 with a molecular mass Mw, measured by CES, ranging from 20,000 g/mol to 800,000 g/mol or from 20,000 g/mol to 500,000 g/mol, preferably from 20,000 g/mol to 400,000 g/mol or from 20,000 g/mol to 300,000 g/mol. 7. Polymer P according to one of claims 1 to 6 for which: the compound Ml is chosen from methacrylic acid, a salt of methacrylic acid, acrylic acid, a salt of acrylic acid and their combinations; or the compound Ml is combined with at least one other anionic monomer, different from the compound Ml, and selected from acrylic acid, methacrylic acid, an acrylic acid salt, a methacrylic acid salt, maleic acid, a maleic acid salt, itaconic acid, an itaconic acid salt, crotonic acid, a crotonic acid salt, an acrylic acid oligomer and combinations thereof; or compound Ml is methacrylic acid alone or combined with acrylic acid, preferably in an amount by mass of acrylic acid less than the amount by mass of methacrylic acid; or compound M2 is a C1-C7 ester or a C1-C6 ester or a C1-C4 ester; preferably, compound M2 is selected from C1-C8-alkyl methacrylate, C1-C8-alkyl acrylate, styrene, vinylcaprolactam, vinyl acetate and combinations thereof; more preferably, compound M2 is chosen from methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, ethylhexyl methacrylate and combinations thereof; even more preferably, compound M2 is chosen from ethyl acrylate, methyl acrylate, butyl acrylate, methyl methacrylate and combinations thereof. 8. Polymer P according to one of claims 1 to 7 for which: - a single polymerization reaction is involved; or which is prepared by a polymerization reaction using: from 0.2 to 10% by weight, preferably from 0.5 to 5% by weight, of compound R, or from 5 to 49.8% by weight, preferably from 10 to 44.5% by weight, of monomer M1, or from 50 to 94.8% by weight, preferably from 55 to 89.5% by weight, of monomer M2, relative to the total quantity by weight of compound R and monomers M1 and M2; or which is: - totally or partially acidic or totally or partially neutralized; preferably, partially neutralized, preferably by means of at least one compound chosen from LiOH, NaOH, KOH, Zn(OH)2, Mg(OH)2, Ca(OH)2, ZnO, MgO, CaO, ammonium derivatives, ammonia, aqueous ammonia, amine bases, for example triethanolamine, aminomethylpropanol or 2-amino-2-methyl-propanol (AMP) and combinations thereof, more preferably LiOH, NaOH, KOH, Mg(OH)2, Ca(OH)2, aqueous ammonia and combinations thereof; or having: - a pKa less than 5 or a pKa ranging from 1.5 to 5; or for which: the polymerization reaction also involves: • at least one compound M3 chosen from hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethylhexyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethylhexyl methacrylate, phosphated hydroxyethyl acrylate, phosphated hydroxypropyl acrylate, phosphated hydroxyethylhexyl acrylate, phosphated hydroxyethyl methacrylate, phosphated hydroxypropyl methacrylate, phosphated hydroxyethylhexyl methacrylate, acid 2-acrylamido-2-methylpropane sulfonic (AMPS), allyl-sulfonic acid, alkylenesulfonates, alkylenearylsulfonates in particular styrene-sulfonate, vinyl-sulfonate, methallyl-sulfonate, allyl-sulfonate, methallyl-sulfate, allyl-sulfate, 2-sulfoethyl methacrylate, acid 3-allyloxy-2-hydroxy-l-propanesulfonic acid, 3-sulfopropyl methacrylate, their salts and combinations thereof; preferably less than 20% by weight, preferably from 0.2 to 20% by weight, in particular from 0.5 to 10% by weight, of monomer M3 relative to the total amount by weight of monomers; or • at least one compound M4 of formula II:

in which: m or n is different from 0, m independently represents 0 or a number less than 150, n independently represents 0 or a number less than 150, OE represents an oxyethylene group, OP independently represents an oxypropylene group, - R ¹ represents a group comprising at least one polymerizable olefinic unsaturation, preferably a group chosen from acrylate, methacrylate, acrylurethane, methacrylurethane, vinyl, allyl, methallyl and isoprenyl; more preferably a methacrylate group, - R ² represents a linear, branched or cyclic, saturated, unsaturated or aromatic hydrocarbon group comprising from 6 to 40 carbon atoms, preferably a linear or branched C6-C4o-alkyl group, preferably a linear or branched Cs-Cso-alkyl group, a C6-C4o-aryl group, preferably a Cs-Cso-aryl group, for example a tristyrylphenyl group; preferably the compound M4 is a compound of formula II in which: m represents an integer or decimal number ranging from 20 to 40 and n is zero or m and n independently represent an integer or decimal number ranging from 5 to 100 or the mass ratio m/n ranges from 90/10 to 70/30; or • at least one compound M5 chosen from: polyalkylene glycol acrylate, preferably from polyethylene glycol acrylate and polyethylenepolypropylene glycol acrylate, polyalkylene glycol methacrylate, preferably from polyethylene glycol methacrylate and polyethylenepolypropylene glycol methacrylate, allylpolyalkylene glycol, preferably from allylpolyethylene glycol and allylpolyethylenepolypropylene glycol, methallylpolyalkylene glycol, preferably from methallylpolyethylene glycol and methallylpolyethylenepolypropylene glycol, 3-methyl-3-buten-1-ylpolyalkylene glycol, preferably from 3-methyl-3-buten-1-ylpolyethylene glycol and 3-methyl-3-buten-1-ylpolyethylenepolypropylene glycol; or at least one crosslinking compound M6 or at least one compound M6 comprising at least two olefinic unsaturations, different from compound R. 9. Method for preparing a copolymer by a polymerization reaction using at least one polymerizable compound and a compound R defined according to one of claims 1 to 8; preferably method for preparing a copolymer P according to one of claims 1 to 8, by a polymerization reaction using compounds M1 and M2 and a compound R, defined according to one of claims 1 to 8. 10. Method of preparing an aqueous composition, preferably a method of control of the viscosity of an aqueous composition or method of improving the suspensive character of an aqueous composition, comprising the addition to this composition of at least one copolymer P according to one of claims 1 to 8. 11. Alkoxylated and polymerizable compound R of formula I:

in which: Q represents a multivalent hydrocarbon group comprising from 1 to 20 carbon atoms, q represents a number from 1 to 6, A represents a polymerizable group chosen from acrylate, methacrylate, acrylurethane, methacrylurethane, allylurethane, 3-isopropenyl-a,a-dimethylbenzylurethane, vinyl, allyl, methallyl and isoprenyl, - B represents a hydrocarbon group comprising at least one polymerizable olefinic unsaturation, - D represents at least one hydrocarbon group comprising at least 6 carbon atoms, X independently represents a divalent group selected from methylene, ethylene, propylene, butylene and combinations thereof, a represents a number ranging from 1 to 100, - b and d, independently represent 0 or a number less than 100; preferably compound R defined according to one of claims 1 to 8. 12. A method of preparing a compound R according to claim 11 comprising reacting an alkoxylated compound Ri of formula III:

in which: Q represents a multivalent hydrocarbon group comprising from 1 to 20 carbon atoms, q represents a number ranging from 1 to 6, - B represents a hydrocarbon group comprising at least one polymerizable olefinic unsaturation, - D represents at least one hydrocarbon group comprising at least 6 carbon atoms, X independently represents a divalent group selected from methylene, ethylene, propylene, butylene and combinations thereof, a represents a number ranging from 1 to 100, - b and d, independently represent 0 or a number less than 100, with: • at least one compound Rii chosen from methacrylic acid, acrylic acid, maleic acid, methacrylic anhydride, maleic anhydride, their salts and their combinations; or with: • a compound Riii of formula IV, in the presence of a strong base,: A-T (IV) in which A represents a polymerizable group chosen from a vinyl, allylic, methallyl and isoprenyl group and T represents Br or I, preferably Br; or with: • a Riv compound prepared by prior reaction of a diisocyanate compound (for example tolyl diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate) and at least one compound chosen from ethylene glycol acrylate, ethylene glycol methacrylate, isoprenol, vinyl ethylene glycol, allyl alcohol, methallyl alcohol, hydroxybutyl vinyl ether and combinations thereof; preferably, with a Riv compound chosen from 3-isopropenyl-a,a'-dimethylbenzyl isocyanate, 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, of a compound prepared by prior reaction of tolyl diisocyanate or isophorone diisocyanate and ethylene glycol methacrylate and combinations thereof; more preferably a Riv compound chosen from 3-isopropenyl-a,a'-dimethylbenzyl isocyanate, 2-isocyanatoethyl methacrylate, of a compound prepared by prior reaction of tolyl diisocyanate or isophorone diisocyanate and ethylene glycol methacrylate and combinations thereof.