CROSS-CUT POLYMER

Abstract

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

Description

Title of the invention: Cross-linked polymer

[0001] The invention relates to a water-soluble copolymer crosslinked by means of a crosslinking compound that is alkoxylated and associative. The invention also relates to the preparation of this polymer, its use for controlling the viscosity and the suspending properties of an aqueous composition, as well as the alkoxylated and associative crosslinking compound.

[0002] The crosslinking compound R according to the invention makes it possible to obtain a polymer that possesses numerous properties. In particular, this copolymer makes it possible to modify the rheology of an aqueous composition.

[0003] The polymer according to the invention also allows particles to be suspended and maintained in suspension within an aqueous composition. Generally, the suspension properties are evaluated by means of an application suspension test that determines the value of the elastic modulus G' and the value of Tan(φ) of the aqueous composition comprising a rheology-modifying agent. Homogeneous particle suspension is also desired. In general, the particles to be suspended in the continuous phase of the aqueous composition are solids, which may be solid or hollow.

[0004] The polymer according to the invention possesses 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 printing; drilling muds; plasterboard or plasterboard jointing compounds; hydraulic binders; ceramics; leather processing; the mining industry; and the agrochemical industry.

[0005] Advantageously, aqueous compositions comprising the polymer according to the invention possess properties and performance accessible for wide ranges of pH values, both at acidic pH values ​​and at neutral or basic pH values.

[0006] The polymerizable compound R according to the invention is multifunctional. It possesses specific properties due to its particular structure but also thanks to the different functional groups it comprises. Indeed, this compound is alkoxylated. It includes several olefinic unsaturations, making it polymerizable. And, it includes at least one hydrophobic group, which allows it to develop an associative character. These characteristics are thus uniquely combined within compound R according to The invention. Its use therefore allows easy and direct access to all these characteristics, particularly for preparing a copolymer, especially a HASE polymer (hydrophobically modified alkali-soluble emulsion or hydrophobically modified alkali-swellable emulsion). Reducing the number of reagents and simplifying the methods for preparing these polymers are always desirable.

[0007] Prior art rheology modifying agents, aqueous compositions comprising them and prior art compounds which enable their preparation do not always give satisfaction and lead to problems related to the many properties sought.

[0008] There is therefore a need for means of preparing rheology-modifying agents with improved properties, particularly properties present in aqueous compositions. The invention provides a solution to all or part of the problems encountered in the preparation of prior art rheology-modifying agents.

[0009] Thus, the invention provides a crosslinked water-soluble copolymer P, prepared by at least one polymerization reaction, in the presence of at least one initiating compound, • of at least one alkoxylated and polymerizable compound R of formula I:

[0010] [ChemI] in which:

[0011] - Q represents a multivalent hydrocarbon group comprising from 1 to 20 carbon atoms,

[0012] - q represents a number from 1 to 6,

[0013] - A represents a polymerizable group selected from acrylate, methacrylate, acrylurethane, methacrylurethane, allylurethane, 3-isopropenyl-α,α-dimethylbenzylurethane, vinyl, allylic, methallylic and iso-prenyl,

[0014] - B represents a hydrocarbon group comprising at least one unsaturation polymerizable olefinic,

[0015] - D represents at least one hydrocarbon group comprising at least 6 atoms of carbon,

[0016] - X independently represents a divalent group chosen from methylene, ethylene, propylene, butylene and their combinations,

[0017] - a represents a number from 1 to 100,

[0018] - b and d, independently represent 0 or a number less than 100; • of at least one compound Ml selected from methacrylic acid, a salt of methacrylic acid, an oligomer of methacrylic acid, a salt of a methacrylic acid oligomer, acrylic acid, a salt of acrylic acid, an oligomer of acrylic acid, a salt of an acrylic acid oligomer, maleic acid, itaconic acid, crotonic acid, their salts and combinations; and • of at least one compound M2 chosen from a CrC8 ester of a compound derived from an acid chosen from acrylic acid, methacrylic acid, maleic acid, itaconic acid and crotonic acid.

[0019] Essentially, according to the invention, compound R comprises at least two polymerizable unsaturated olefinic groups. Preferably, the polymerizable unsaturated olefinic groups of compound R have different reactivities.

[0020] Preferably according to the invention, group B is different from groups A and D.

[0021] Also preferably according to the invention, q represents 1, 2 or 3, more preferably 1 or 2.

[0022] Also preferably according to the invention, Q represents a multivalent hydrocarbon group comprising from 1 to 10 carbon atoms.

[0023] Also preferably for compound R according to the invention, Q represents

[0024] a multivalent hydrocarbon group comprising from 1 to 12 carbon atoms or from 1 to 10 carbon atoms. Also preferably for compound R according to the invention, Q represents a trivalent group, a tetravalent group, or a pentavalent group.

[0025] More preferably for 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 CrCi2-alkylene group, preferably a branched Ci-Cio-alkylene group or a branched Ci-C6-alkylene group, or a C5-C2o-arylene group, preferably a C5-Ci2-arylene group; most preferably a CH group or a phenylene group.

[0026] Also preferably for compound R according to the invention, group A is chosen from acrylate, methacrylate, acrylurethane, methacrylurethane, ally-lurethane and 3-isopropenyl-a,a-dimethylbenzylurethane; more preferably a methacrylate group.

[0027] Preferably according to the invention, the group X linked to the group A independently represents a divalent group selected 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.

[0028] Also preferably for compound R according to the invention, a represents a number from 1 to 80, preferably a number from 5 to 50 or from 5 to 30.

[0029] Also preferably for compound R according to the invention, B represents a hydrocarbon group comprising at least one group selected from a vinyl, allylic, methallylic, and isoprenyl group, in particular B represents a group selected from a vinyl, allylic, methallylic, and isoprenyl group, more preferably an allylic, methallylic, or isoprenyl group. Also preferably for compound R according to the invention, B represents a hydrocarbon group comprising a single polymerizable olefinic unsaturation.

[0030] Preferably according to the invention, the group X linked to the group B independently represents a divalent group selected 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.

[0031] Also preferably for compound R according to the invention, b represents 0 or 1 or a number from 1 to 100 or from 1 to 50, preferably a number 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.

[0032] Essentially, according to the invention, compound R comprises a hydrophobic group D. Preferably, compound R according to the invention comprises a group D comprising from 6 to 40 carbon atoms. More preferably, group D is a linear, branched, or cyclic hydrocarbon group, saturated, unsaturated, or aromatic. Much more preferably, group D is a linear, branched, or cyclic hydrocarbon group, saturated, unsaturated, or aromatic, 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. Much more preferably, group D is a linear or branched C8-C32-alkyl group or a C1O-C4O-aryl group.

[0033] Even more preferably, group D is a linear C8-C32-alkyl group or a linear C8-C24-alkyl group or a C6-C30-aryl group, for example a styryl group.

[0034] Preferably according to the invention, the group X linked to the group D independently represents a divalent group selected 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 a ratio mass oxyethylene / oxypropylene ranging from 90 / 10 to 70 / 30.

[0035] Also preferably for compound R according to the invention, d represents 0 or 1 or a number from 1 to 100 or from 1 to 50, preferably a number 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.

[0036] 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.

[0037] According to the invention, the molecular mass Mw can be calculated or determined by Size Exclusion Chromatography (SES), also known as Gel Permeation Chromatography (GPC). This technique uses a Waters brand liquid chromatography instrument equipped with a detector. This detector is a Waters brand refractometric concentration detector. This liquid chromatography instrument is equipped with a size exclusion column to separate the different molecular weights of the compounds being studied.

[0038] Preferably according to the invention, compound Ml is selected from methacrylic acid, a salt of methacrylic acid, acrylic acid, a salt of acrylic acid and their combinations.

[0039] According to the invention, compound Ml can be combined with at least one other anionic monomer, different from 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. More preferably according to the invention, compound Ml is methacrylic acid alone or combined with acrylic acid, preferably in a mass quantity of acrylic acid lower than the mass quantity of methacrylic acid.

[0040] More preferably according to the invention, compound M2 is a Ci-C7 ester, a Ci-C6 ester, or a Ci-C4 ester. Preferably, compound M2 is selected from Ci-C8-alkyl methacrylate, Ci-C8-alkyl acrylate, styrene, vinylcaprolactam, vinyl acetate, and combinations thereof. More preferably, compound M2 is selected 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 selected from ethyl acrylate, methyl acrylate, butyl acrylate, methyl methacrylate, and combinations thereof.

[0041] According to the invention, the polymer P can be prepared by carrying out a single polymerization reaction.

[0042] Preferably according to the invention, the polymer P is prepared by a polymerization reaction involving:

[0043] - from 0.2 to 10% by weight of compound R, or

[0044] - from 5 to 49.8% by weight of monomer Ml, or

[0045] - from 50 to 94.8% by weight of monomer M2,

[0046] with respect to the total weight quantity of compound R and monomers M1 and M2.

[0047] More preferably according to the invention, the polymer P is prepared by a polymerization reaction involving:

[0048] - from 0.5 to 5% by weight of compound R,

[0049] - from 10 to 44.5% by weight of monomer Ml, and

[0050] - from 55 to 89.5% by weight of monomer M2,

[0051] with respect to the total weight quantity of compound R and monomers M1 and M2.

[0052] According to the invention, the polymer P can 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 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.

[0053] According to the invention, the polymer P can be totally or partially acidic or totally or partially neutralized. Preferably, the polymer P is partially neutralized.

[0054] Also preferably, the polymer P can be neutralized by means of at least one compound selected from LiOH, NaOH, KOH, Zn(OH)2, Mg(OH)2, Ca(OH)2, ZnO, MgO, CaO, ammonium derivatives, ammonia, ammonia, amino bases, for example triethanolamine, aminomethylpropanol or 2-amino-2-methylpropanol (AMP) and their combinations, more preferably LiOH, NaOH, KOH, Mg(OH)2, Ca(OH)2, ammonia and their combinations.

[0055] Preferably, polymer P has a pKa less than 5 or a pKa ranging from 1.5 to 5.

[0056] Essentially, the water-soluble crosslinked copolymer P according to the invention is prepared using compound R and monomers M1 and M2. Other monomers may be used in the preparation of copolymer P.

[0057] Thus, the polymerization reaction can also utilize at least one compound M3 selected from hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethylhexyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, phosphated hydroxyethyl acrylate, phosphated hydroxypropyl acrylate, phosphated hydroxyethylhexyl acrylate, phosphated hydroxyethyl methacrylate, phosphated hydroxypropyl methacrylate, hydroxyethylhexyl methacrylate Phosphate, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), allylsulfonic acid, alkylenesulfonates, alkylenearylsulfonates, in particular styrenesulfonate, vinylsulfonate, methhallylsulfonate, allylsulfonate, methhallyl sulfate, allyl sulfate, 2-sulfoethyl methacrylate, 3-allyloxy-2-hydroxy-1-propanesulfonic acid, 3-sulfopropyl methacrylate, their salts and combinations. Preferably, compound M3 is used in an amount of less than 20% by weight, preferably from 0.2 to 20% by weight, in particular from 0.5 to 10% by weight, relative to the total weight of monomers.

[0058] The polymerization reaction may also involve at least one compound M4 of formula II:

[0059] [Chem 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, - R1 represents a group comprising at least one polymerizable olefinic unsaturation, preferably a group selected from acrylate, methacrylate, acrylurethane, methacrylurethane, vinyl, allylic, methallylic and isoprenyl; more preferably a methacrylate group, - R2 represents a linear, branched or cyclic, saturated, unsaturated or aromatic hydrocarbon group comprising 6 to 40 carbon atoms, preferably a linear or branched C6-C40-alkyl group, preferably a linear or branched C8-C30-alkyl group, a linear or branched C6-C4o-aryl group, preferably a C8-C30-aryl group, for example a tristyrylphenyl group.

[0060] Preferably, compound M4 is a compound of formula II in which:

[0061] - m represents an integer or decimal number from 20 to 40 and n is zero or

[0062] - m and n independently represent an integer or decimal number from 5 to 100 or

[0063] - the mass ratio m / n goes from 90 / 10 to 70 / 30.

[0064] The polymerization reaction may also utilize at least one compound M5 selected from:

[0065] - polyalkylene glycol acrylate, preferably polyethylene glycol acrylate and polyethylene polypropylene glycol acrylate,

[0066] - polyalkylene glycol methacrylate, preferably among polyethyl methacrylate lene glycol and polyethylene methacrylate / polypropylene glycol,

[0067] - allylpolyalkylene glycol, preferably between allylpolyethylene glycol and allylpoly- ethylenepolypropylene glycol,

[0068] - methylpolyalkylene glycol, preferably among methylpolyethylene glycol and methyl polyethylene polypropylene glycol,

[0069] - 3-methyl-3-buten-l-ylpolyalkylene glycol, preferably among 3-methyl-3-buten-1-ylpolyethylene glycol and 3-methyl-3-buten-1-ylpolyethylenepolypropylene glycol.

[0070] The polymerization reaction may optionally employ at least one other crosslinking compound M6 or at least one compound M6 comprising at least two olefinic unsaturations, different from compound R.

[0071] The invention also provides a method for preparing a copolymer P according to the invention, by a polymerization reaction involving at least one polymerizable compound, preferably compounds M1 and M2, and a compound R, defined according to the invention.

[0072] The properties of the copolymer P according to the invention allow it 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 suspending character of an aqueous composition, comprising adding to this composition at least one copolymer P according to the invention.

[0073] The amount of polymer P used in these methods may vary. Preferably, these methods implement 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.

[0074] 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:

[0075] [Chem I] A(XO):" .3 in which:

[0076] - Q represents a multivalent hydrocarbon group comprising from 1 to 20 carbon atoms,

[0077] - q represents a number from 1 to 6,

[0078] - A represents a polymerizable group selected from acrylate, methacrylate, acrylurethane, methacrylurethane, allylurethane, 3-isopropenyl-α,α-dimethylbenzylurethane, vinyl, allylic, methallylic and iso-prenyl,

[0079] - B represents a hydrocarbon group comprising at least one unsaturation polymerizable olefinic,

[0080] - D represents at least one hydrocarbon group comprising at least 6 atoms of carbon,

[0081] - X independently represents a divalent group chosen from methylene, ethylene, propylene, butylene and their combinations,

[0082] - a represents a number from 1 to 100,

[0083] - b and d, independently represent 0 or a number less than 100.

[0084] The invention also provides a method for preparing compound R according to the invention.

[0085] The compound R of formula I in which A represents a polymerizable group selected from acrylate and methacrylate, is prepared according to a preparation method which includes the reaction of an alkoxylated compound Ri of formula III:

[0086] [Chem III] in which:

[0087] - Q represents a multivalent hydrocarbon group comprising from 1 to 20 carbon atoms,

[0088] - q represents a number from 1 to 6,

[0089] - B represents a hydrocarbon group comprising at least one unsaturation polymerizable olefinic,

[0090] - D represents at least one hydrocarbon group comprising at least 6 atoms of carbon,

[0091] - X independently represents a divalent group chosen from methylene, ethylene, propylene, butylene and their combinations,

[0092] - a represents a number from 1 to 100,

[0093] - b and d, independently represent 0 or a number less than 100,

[0094] with at least one compound Rii selected from methacrylic acid, acrylic acid, maleic acid, methacrylic anhydride, maleic anhydride, their salts and their compounds combinations; preferably chosen from methacrylic anhydride.

[0095] The compound R of formula I in which A represents a polymerizable group selected from a vinyl, allylic, methallylic 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:

[0096] [Chem IV] A-T in which A represents a polymerizable group chosen from a vinyl, allylic, methallylic and isoprenyl group and T represents Br or I. Preferably, T represents Br.

[0097] The compound R according to the invention can be prepared by a reaction carried out without solvent, directly in liquid or molten reagents. It can also be prepared by a reaction that uses a solvent, preferably water, particularly when using a compound of formula III.

[0098] The compound R of formula I in which A represents a polymerizable group selected 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 (e.g. tolyl-diisocyanate, isophorone-diisocyanate, hexamethylene-diisocyanate) and at least one compound selected from ethylene glycol acrylate, ethylene glycol methacrylate, isoprenol, vinyl-ethylene glycol, allyl alcohol, methallyl alcohol, hydroxybutyl-vinyl ether and their combinations.

[0099] Preferably, the Riv compound is selected from 3-isopropenyl-α,α'-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 their combinations, much more preferably from 3-isopropenyl-α,α'-dimethylbenzyl isocyanate, 2-isocyanatoethyl methacrylate, a compound prepared by prior reaction of tolyl-diisocyanate or isophorone-diisocyanate and ethylene glycol methacrylate and their combinations.

[0100] During 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 compounds Riv are generally known as such, or they can be prepared from known compounds using methods known.

[0101] Preferred formula I compounds according to the invention define formula III compounds or formula IV compounds which are also preferred.

[0102] 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.

[0103] 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

[0104] Preparation and characterization of a compound R according to the invention

[0105] 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 at position 2 of group Q, relative to the OH group at position 1, and D represents a styryl group, are introduced, along with 0.822 g of alloocimene and 82.6 g of methacrylic anhydride (Rii). The mixture is heated to 80°C ± 2°C; the heating is maintained for 2 hours and 30 minutes. The compound RI according to the invention is obtained at 89.83% by weight.

[0106] Preparation and characterization of copolymers P according to the invention Copolymer PI

[0107] In a glass reactor, 520 g of deionized water and 3.17 g of sodium dodecyl sulfate are introduced.

[0108] In a first beaker, 108.24 g of methacrylic acid (compound Ml) is weighed,

[0109] 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 mixed in a second beaker. In a second beaker, 0.930 g of ammonium persulfate is dissolved in 10 g of deionized water. In a third beaker, 0.093 g of sodium metabisulfite is dissolved in 5 g of deionized water.

[0110] The contents of the reactor are heated to a temperature of 76°C ± 2°C, and for 2 hours, the reactants from the 3 beakers are introduced in parallel into the reactor. The mixture is then allowed to cool to room temperature. The PI copolymer according to the invention is obtained with 28.8% by weight of dry extract, the composition of which is detailed in Table 1. P2 Copolymer

[0111] In a glass reactor, 400 g of deionized water, 1.95 g of sodium dodecyl sulfate and 0.83 g of polyalkylene glycol (mono-butyl ether ethylene copolymer) are introduced oxide / propylene oxide - product B11 / 50).

[0112] In a first beaker, 114.0 g of methacrylic acid (compound Ml) is weighed,

[0113] 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 (Bll / 50), and 212.1 g of deionized water. In a second beaker, 0.456 g of ammonium persulfate dissolved in 8 g of deionized water is weighed out. In a third beaker, 0.046 g of sodium metabisulfite dissolved in 8 g of deionized water is weighed out.

[0114] 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. The mixture is then allowed to cool to room temperature. The copolymer P2 according to the invention is obtained with a dry extract content of 30.4% by weight, the composition of which is detailed in Table 1. P3 Copolymer

[0115] In a glass reactor, 400 g of deionized water, 1.95 g of sodium dodecyl sulfate and 0.83 g of polyalkylene glycol (Bll / 50) are introduced.

[0116] In a first beaker, 116.5 g of methacrylic acid (compound M1),

[0117] 203.1 g of ethyl acrylate (compound M2), 6.35 g of compound RI according to the invention are weighed out, 1.66 g of sodium dodecyl sulfate, 1.53 g of polyalkylene glycol (Bll / 50), and 212.1 g of deionized water. In a second beaker, 0.456 g of ammonium persulfate dissolved in 8 g of deionized water is weighed out. In a third beaker, 0.046 g of sodium metabisulfite dissolved in 8 g of deionized water is weighed out.

[0118] 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. The mixture is then allowed to cool to room temperature. The copolymer P3 according to the invention is obtained with a dry extract content of 30.1% by weight, the composition of which is detailed in Table 1.

[0119] [Tab 1] PI P2 P3 M2 60.57 61.69 62.31 Ml 37.45 35.3.1 35.94 RI 2.00 3.00 1.7'5

[0120] The rheology control properties and particle suspension capacity of the polymers according to the invention are evaluated by measuring the viscosity and yield stress of aqueous compositions prepared from these hydrophobic and crosslinked polymers.

[0121] To measure the viscosity, the prepared P3 copolymer is mixed with deionized water in a dry weight quantity of 2%, then an aqueous ammonia solution (28% by weight) is added to completely neutralize the composition up to a pH value of 8.5–9. Similar compositions are prepared by replacing polymer PI with polymers P2 and P3, respectively. The Brookfield viscosity of these compositions is then measured at 25°C and 100 rpm using a Brookfield DV1 viscometer equipped with a spindle adapted to the viscosity range of the composition. The results are presented in Table 2.

[0122] [Tab 2] Polymer PI P2 P3 Viscosity (mPa.s) 2600 3800 3500

[0123] A composition is then prepared by mixing the P3 polymer according to the invention in a dry weight quantity of 2.25% with 9% by dry weight of sodium lauryl ether sulfate and 3% by dry weight of cocamidopropyl betaine in deionized water (q.s. 100). The pH is adjusted to a value of 5 by adding an aqueous solution of citric acid.

[0124] 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.

[0125] 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 was measured 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 (60 mm diameter, 1° truncation angle) and then processed using RheoWin Data Manager software.

[0126] The yield stress at 25°C is 5.8 Pa and the yield stress at 50°C is 1.55 Pa.

[0127] It is observed that the copolymers according to the invention make it possible to thicken aqueous compositions significantly. They have a high yield strength 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 stress is applied to them (when the product is applied to the skin), these compositions become liquid, both at 25°C and at 50°C.

Claims

Demands

1. Crosslinked water-soluble copolymer P, prepared by at least one polymerization reaction, in the presence of at least one initiating compound, : of at least one alkoxylated and polymerizable compound R of formula I: [Chem I] (XOkB f A(XO)^Q"f(XO)dD 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, allyllurethane, 3-isopropenyl-α,α-dimethylbenzylurethane, vinyl, allylic, methallylic 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 their combinations, - a represents a number from 1 to 100, - b and d, independently represent 0 or a number less than 100; of at least one compound Ml selected from methacrylic acid, a salt of methacrylic acid, an oligomer of methacrylic acid, a salt of a methacrylic acid oligomer, acrylic acid, a salt of acrylic acid, an oligomer of acrylic acid, a salt of an acrylic acid oligomer, maleic acid, itaconic acid, crotonic acid, their salts and combinations; and of at least one compound M2 chosen from a CrC8 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 a C5-C20-arylene group, much more preferably a C5-Ci2-arylene group; most preferably a CH group or a phenylene group.

3. Polymer P according to any one of claims 1 or 2 wherein: - group A is selected from acrylate, methacrylate, acry-lurethane, methacrylurethane, allyllurethane and 3-isopropenyl-α,α-dimethylbenzylurethane; preferably a methacrylate group; or - group X bonded to group A independently represents a divalent group selected from methylene, ethylene, propylene, butylene and combinations thereof, preferably a methylene group or ethylene group alone or combined with a propylene group in an oxyethylene / oxypropylene mass ratio from 90 / 10 to 70 / 30; or - a represents a number from 1 to 80, preferably a number from 5 to 50 or from 5 to 30.

4. Polymer P according to any one of claims 1 to 3, wherein: - B represents a hydrocarbon group comprising at least one group selected from a vinyl, allylic, methallylic, and isoprenyl group, in particular B represents a group selected from a vinyl, allylic, methallylic, and isoprenyl group, more preferably an allylic, methallylic, or isoprenyl group; or - B represents a hydrocarbon group comprising a single in- polymerizable olefinic saturation; or - the group X linked to the group B independently represents a divalent group selected 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 from 90 / 10 to 70 / 30; or - b represents 0 or 1 or a number from 1 to 100 or from 1 to 50, preferably a number 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.

5. Polymer P according to any one of claims 1 to 4 wherein: - the group D is a linear, branched or cyclic hydrocarbon group, saturated, unsaturated or aromatic, more preferably, a linear, branched or cyclic hydrocarbon group, saturated, unsaturated or aromatic comprising from 6 to 40 carbon atoms, more preferably, a linear or branched Ce-C^-alkyl group or a Ce-C^-aryl group, much more preferably, a linear C8-C32-alkyl group or a linear C8-C24-alkyl group or a C6-C3o-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 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 - d represents 0 or 1 or a number from 1 to 100 or from 1 to 50, preferably a number 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.;

6. Polymer P according to any one of claims 1 to 5 of molecular weight 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 any one of claims 1 to 6 wherein: - compound M1 is selected from methacrylic acid, a salt of methacrylic acid, acrylic acid, a salt of acrylic acid and combinations thereof; or

8. - compound Ml is combined with at least one other anionic monomer, different from 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 a mass quantity of acrylic acid less than the mass quantity of methacrylic acid; or - Compound M2 is a C1-C7 ester or a Ci-C6 ester or a C1-C4 ester; preferably, compound M2 is selected from CrC8-alkyl methacrylate, CrC8-alkyl acrylate, styrene, vinylca-prolactam, vinylacetate and combinations thereof; more preferably, compound M2 is selected 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 selected from ethyl acrylate, methyl acrylate, butyl acrylate, methyl methacrylate and combinations thereof. Polymer P according to any one of claims 1 to 7, wherein: - a single polymerization reaction is involved; or which is prepared by a polymerization reaction involving: - 0.2 to 10% by weight, preferably 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 Ml monomer, or - 50 to 94.8% by weight, preferably 55 to 89.5% by weight, of M2 monomer, relative to the total weight quantity 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 selected from LiOH, NaOH, KOH, Zn(OH)2, Mg(OH)2, Ca(OH)2, ZnO, MgO, CaO, ammonium derivatives, ammonia, ammonia, amino bases, for example triethanolamine, aminomethylpropanol or 2-amino-2-methylpropanol (AMP) and their combinations, more preferably LiOH, NaOH, KOH, Mg(OH)2, Ca(OH)2, ammonia and their combinations; 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 M3 compound selected 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), allylsulfonic acid, alkylenesulfonates, alkylnearylsulfonates, including styrene sulfonate, vinyl sulfonate, methhallyl sulfonate, allyl sulfonate, methhallyl 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 weight of monomers; or - at least one compound M4 of formula II: [Chem 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, - R1 represents a group comprising at least one polymerizable olefinic unsaturation, preferably a group selected from acrylate, methacrylate, acrylurethane, methacrylurethane, vinyl, allylic, methallylic and isoprenyl; more preferably a methacrylate group, - R2 represents a linear, branched or cyclic hydrocarbon group, saturated, unsaturated or aromatic, comprising from 6 to 40 carbon atoms, preferably a Ce-Cw-alkyl group,

9. linear or branched, preferably a C8-C30-alkyl group, linear or branched, a Ce-C^-aryl group, preferably a C8-C30-aryl group, for example a tristy-rylphenyl group; preferably compound M4 is a compound of formula II in which: - m represents an integer or decimal number 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 M5 compound chosen from: - polyalkylene glycol acrylate, preferably between polyethylene glycol acrylate and polyethylene polypropylene glycol acrylate, - polyalkylene glycol methacrylate, preferably between polyethylene glycol methacrylate and polyethylene polypropylene glycol methacrylate, - allylpolyalkylene glycol, preferably between allylpolyethylene glycol and allylpolyethylenepolypropylene glycol, - methyllpolyalkylene glycol, preferably between methyll-polyethylene glycol and methyllpolyethylenepolypropylene glycol, - 3-methyl-3-buten-l-ylpolyalkylene glycol, preferably of 3-methyl-3-buten-l-ylpolyethylene glycol and 3-methyl-3-buten-l-ylpolyethylenepolypropylene glycol; or - at least one M6 crosslinking compound or at least one M6 compound comprising at least two olefinic unsaturations, different from compound R. Method for preparing a copolymer by a polymerization reaction involving at least one polymerizable compound and a compound R defined according to any one of claims 1 to 8; preferably, method for preparing a copolymer P according to any one of claims 1 to 8, by a polymerization reaction involving compounds M1 and M2 and a compound R, defined according to any one of the claims. Instructions 1 to 8.

10. Method of preparing an aqueous composition, preferably a method of controlling the viscosity of an aqueous composition or a method of improving the suspending character of an aqueous composition, comprising adding to this composition at least one copolymer P according to any one of claims 1 to 8.

11. Alkoxylated and polymerizable compound R of formula I: [Chem I] 1 A(XO) rfXO).DL Jq wherein: - 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 selected from acrylate, methacrylate, acrylurethane, methacrylurethane, allylurethane, 3-isopropenyl-α,α-dimethylbenzylurethane, vinylic, allylic, methallylic, 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 from 1 to 100, - b and d, independently represent 0 or a number less than 100.

12. Method of preparing a compound R according to claim 11 comprising the reaction of an alkoxylated compound Ri of formula III: [Chem III] (XO^BE v H(XO)fQ"'(XO)dD L Jq in which: - Q represents a multivalent hydrocarbon group comprising 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 chosen from methylene, ethylene, propylene, butylene and their combinations, - a represents a number from 1 to 100, - b and d independently represent 0 or a number less than 100, with: • at least one compound Rii selected 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, : [Chem IV] A-T in which A represents a polymerizable group selected from a vinyl, allylic, methallylic, and isoprenyl group, and T represents Br or I, preferably Br; or with: • a Riv compound prepared by prior reaction of a diisocyanate compound (e.g. tolyl-diisocyanate, isophorone-dii-socyanate, hexamethylene-diisocyanate) and at least one compound selected from ethylene glycol acrylate, ethylene glycol methacrylate, isoprenol, vinyl-ethylene glycol, allyl alcohol, methallyl alcohol, hydroxybutyl-vinyl ether and their combinations; preferably, with a Riv compound selected from 3-isopropenyl-a,a'-dimethylbenzyl isocyanate, 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, a compound prepared by prior reaction of tolyl-diisocyanate or isophorone-diisocyanate and ethylene glycol methacrylate and their combinations; much more preferably a Riv compound chosen from 3-isopropenyl-α,α'-dimethylbenzyl isocyanate, 2-isocyanatoethyl methacrylate, of a compound prepared by prior reaction of tolyl-diisocyanate or isophorone-diisocyanate and ethylene glycol methacrylate and their combinations.