Thickening alkylated copolymer

Abstract

The invention relates to a thickening (meth)acrylic copolymer prepared using a polyalkoxylated Guerbet alcohol comprising a double-branched alkyl group. The invention also relates to the process for preparing said copolymer and to the use thereof in aqueous compositions, in particular coating compositions.

Description

[0001] THICKENING ALKYLATED COPOLYMER

[0002] The invention relates to a thickening (meth)acrylic copolymer prepared using a polyalkoxylated Guerbet alcohol comprising a doubly branched alkyl group. The method for preparing this copolymer and its use in aqueous compositions, in particular in coating compositions, are also part of the invention.

[0003] Many technical fields require the use of aqueous compositions. In particular, aqueous hydraulic binder compositions, aqueous adhesive compositions, aqueous detergent compositions, aqueous cosmetic compositions, aqueous ink compositions, aqueous paper coating compositions, aqueous coating compositions, in particular aqueous varnish compositions or aqueous paint compositions, for example aqueous decorative paint compositions or aqueous industrial paint compositions, are known. In addition to their functional properties, these aqueous compositions must have a texture suitable for their use or storage. In particular, they must have a suitable viscosity. In addition, these aqueous compositions must be able to be used under conditions that can vary widely. In particular, the viscosity of these aqueous compositions may vary or degrade.The functional properties of these aqueous compositions may therefore be altered if their rheological behavior is not suitable, for example to prevent sedimentation or phase separation phenomena during storage time, which may also manifest themselves by viscosity variations. Such variations or degradations are particularly detrimental or damaging for aqueous hydraulic binder compositions, for aqueous adhesive compositions, for aqueous detergent compositions, for aqueous cosmetic compositions, for aqueous ink compositions, for aqueous paper coating compositions, for aqueous coating compositions, in particular for aqueous varnish or paint compositions.

[0004] There is therefore a need to be able to have aqueous compositions which do not have such disadvantages or aqueous compositions which do not lead to such problems.

[0005] In particular, it is particularly useful to be able to have available aqueous coating compositions, in particular aqueous varnish or paint compositions, whose viscosity is adapted to allow the maintenance of their homogeneity as well as the integrity of their functional properties. Maintaining the viscosity and limiting the loss of viscosity of these aqueous compositions should be possible for wide ranges of shear gradient.

[0006] Therefore, many aqueous coating compositions use rheology-modifying polymers. These polymers should make it possible to give aqueous compositions the desired rheological properties for wide shear rate ranges. These polymers should also improve the shear-thinning of these aqueous compositions by giving them sufficient pseudo-plasticity, ensuring their stability and homogeneity during their storage life, facilitating their transfer to application tools and helping to limit the appearance of drips once applied. The compatibility of the different constituents of an aqueous coating composition must also be taken into account. In particular, it is important that the thickening copolymer and the pigments and binders used have good compatibility.

[0007] Furthermore, it is also important to improve the pigment compatibility of aqueous coating compositions, especially paint compositions, and particularly with regard to the addition of pigment concentrates used for coloring. Without good pigment compatibility, the rheology of the composition can be significantly degraded. Insufficient pigment compatibility can also lead to a reduction in coloring strength and result in an uneven or washed-out shade, which may result in the use of a higher quantity of pigment or the presence of aesthetic defects in the final coating.

[0008] WO 2011119363 describes an adhesive based on Guerbet alcohol (meth)acrylate. US 2015329660 describes thickeners prepared in the presence of a non-polymerizable surfactant compound derived from a Guerbet alcohol. WO 2011130310 describes the use of a surfactant compound prepared with a Guerbet alcohol. WO 2011135039 describes the use of an associative vinyl copolymer. CA 2852651 describes a mixture of surfactant compounds prepared with Guerbet alcohols.

[0009] Polymers known as thickening agents do not always provide a satisfactory solution to these various problems. There is therefore a need for improved rheology-modifying copolymers. The copolymer according to the invention provides a solution to all or part of the problems of the polymers of the prior art. Thus, the invention provides a copolymer P prepared by at least one polymerization reaction:

[0010] • at least one anionic monomer (a) chosen from acrylic acid, an acrylic acid salt, methacrylic acid, a methacrylic acid salt and combinations thereof;

[0011] • at least one C1-C8 ester (b) of a compound derived from an acid chosen from acrylic acid, methacrylic acid, maleic acid, itaconic acid and crotonic acid;

[0012] • of at least one compound (c) prepared by reaction: o of at least one compound (d) obtained by:

[0013] ■ dimerization of two identical or different compounds of formula I by a Guerbet reaction:

[0014] R-CH[(CH2) m CH3]-(CH2) n -OH

[0015] (I) in which:

[0016] - R independently represents a linear C4-C9-alkyl group;

[0017] - m independently represents 0 or 1;

[0018] - n independently represents a number from 2 to 7; and

[0019] ■ polyalkoxylation of the dimer obtained, and o of at least one compound (e) comprising a polymerizable function and another function reactive with the hydroxyl group of compound (d).

[0020] Preferably for the copolymer P according to the invention, the anionic monomer (a) is chosen from acrylic acid, methacrylic acid and their combinations.

[0021] Also preferably for the copolymer P according to the invention, the ester (b) is a C1-C7 ester or a C1-C6 ester OR a C1-C4 ester, preferably a C1-C3 ester.

[0022] Also preferably for the copolymer P according to the invention, the ester (b) is an acrylic acid ester or a methacrylic acid ester, preferably an acrylic acid ester. In particular, the ester (b) 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. More preferably, the ester (b) is chosen from ethyl acrylate, methyl acrylate, butyl acrylate, methyl methacrylate and combinations thereof.

[0023] Essentially according to the invention, compound (d) is obtained by a dimerization reaction of two compounds of formula I. This dimerization is a Guerbet reaction carried out with these two alcohols of formula I. The dimerization reaction and its conditions of implementation are known as such. The Guerbet reaction is generally carried out at high temperature and pressure, in a basic medium and in the presence of a catalyst. Compound (d) can be prepared from the same compound of formula I or from two different compounds of formula I. The dimer obtained is treated in order to obtain the polyalkoxylated compound (d).

[0024] Preferably according to the invention, the dimerization of two identical compounds of formula I leads to a homodimer (dl). Also preferably according to the invention, compound (d) is a homodimer (dl) obtained by dimerization of two identical compounds of formula I in which:

[0025] - R represents a linear Cs-Cv-alkyl group;

[0026] - m represents 0 or 1, preferably 0;

[0027] - n represents a number ranging from 2 to 7.

[0028] More preferably according to the invention, compound (d) is a homodimer (dl) obtained by dimerization of two identical compounds of formula I in which:

[0029] - R represents a linear C4-C9-alkyl group, preferably a linear C5-C7-alkyl group;

[0030] - m represents 0 or 1, preferably 0;

[0031] - n represents a number ranging from 5 to 7, preferably from 4 to 6, more preferably 4 or 5.

[0032] Particularly preferably according to the invention, the dimerization is carried out from two different compounds (d) of formula I and results in a mixture comprising 2 different homodimers (dl) and one heterodimer (d2). Preferably, it is a mixture consisting of 2 different homodimers (dl) and one heterodimer (d2). Also preferably, a mixture of compounds (d) can be obtained by dimerization of two different compounds of formula I in which:

[0033] - R independently represents a linear Cs-Cv-alkyl group;

[0034] - m independently represents 0 or 1, preferably 0;

[0035] - n independently represents a number ranging from 2 to 7. Preferably according to the invention, a mixture of compounds (d) can be obtained by dimerization of two different compounds of formula I in which:

[0036] - R independently represents a linear C4-C9-alkyl group, preferably a linear Cs-Cv-alkyl group;

[0037] - m independently represents 0 or 1, preferably 0;

[0038] - n independently represents a number ranging from 5 to 7, preferably from 4 to 6, more preferably 4 or 5.

[0039] A preferred mixture of compounds (d) comprises a heterodimeric compound (d2) obtained by dimerization of a first compound of formula I in which R represents a linear Cs-alkyl group, m represents 0 and n represents 5 and a second different compound of formula I in which R represents a linear C?-alkyl group, m represents 0 and n represents 4.

[0040] A particularly preferred mixture of compounds (d) comprises:

[0041] - a heterodimeric compound (d2) obtained by dimerization of a first compound of formula I in which R represents a linear Cs-alkyl group, m represents 0 and n represents 5 and of a second different compound of formula I in which R represents a linear Cv-alkyl group, m represents 0 and n represents 4,

[0042] - a first homodimer (dl) obtained by dimerization of a compound of formula I in which R represents a linear Cs-alkyl group, m represents 0 and n represents 5,

[0043] - a second homodimer (dl) obtained by dimerization of a different compound of formula I in which R represents a linear C?-alkyl group, m represents 0 and n represents 4.

[0044] According to the invention, the dimerization carried out from two different compounds of formula I can lead to a mixture consisting of two different homodimers (dl) and one heterodimer (d2).

[0045] According to the invention, compound (d) is prepared by dimerization of two compounds of formula I and polyalkoxylation of the dimer obtained. The polyalkoxylation reaction and its conditions of implementation are known as such. Preferably for the copolymer P according to the invention, compound (d) comprises from 10 to 150 alkoxylations. More preferably, compound (d) comprises from 20 to 100 alkoxylations or from 10 to 70 alkoxylations, more preferably from 20 to 60 alkoxylations. Also preferably, compound (d) is polyethoxylated or is polyethoxylated-polypropoxylated or is polyethoxylated-polybutoxylated, preferably compound (d) is polyethoxylated. More preferably compound (d) is polyethoxylated. Particularly preferably, compound (d) comprises from 10 to 150 ethoxylations, more preferably from 20 to 100 ethoxylations or from 10 to 70 ethoxylations, much more preferably from 20 to 60 ethoxylations.

[0046] According to the invention, compound (e) comprises a polymerizable function, preferably a terminal ethylenic group, which is capable of reacting with the polymerizable groups of compounds (a) and (b). Preferably according to the invention, the polymerizable function of compound (e) is chosen from vinyl, allyl, methallyl, isoprenyl, styrylyl, acrylate, methacrylate, itaconate, maleate, crotonate.

[0047] Preferably according to the invention, compound (e) may be chosen from acrylic acid, methacrylic acid, maleic acid, itaconic acid, crotonic acid, acrylic anhydride, methacrylic anhydride, maleic anhydride, itaconic anhydride, styrylyl isocyanates (e.g. 3-isopropenyl-a, a'-dimethylbenzyl isocyanate or TMI, CAS number 2094-99-7), acrylate-alkylene isocyanates (e.g. 2-isocyanatoethyl acrylate, CAS number 13641-96-8), methacrylate-alkylene isocyanates (e.g. 2-isocyanatoethyl methacrylate, CAS number 30674-80-7) and combinations thereof.

[0048] Also preferably according to the invention, compound (e) can be prepared by prior reaction of a diisocyanate compound (for example tolyl diisocyanate, isophorone 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.

[0049] More preferably according to the invention, compound (e) is chosen from acrylic anhydride, methacrylic anhydride, 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 combinations thereof.

[0050] For the preparation of the copolymer P according to the invention, the quantities of compounds (a), (b) and (c) can vary. Preferably for the copolymer P, the polymerization reaction involves:

[0051] - from 20 to 74.9% by weight or from 25 to 69.5% by weight, preferably from 30 to 68% by weight or from 35 to 60% by weight, of monomer (a) or

[0052] - from 25 to 79.9% by weight or from 30 to 74.5% by weight, preferably from 30 to 68% by weight or from 35 to 64.5% by weight, of monomer (b), or - from 0.1 to 55% by weight or from 0.5 to 45% by weight, preferably from 2 to 40% by weight or from 5 to 30% by weight, of monomer (c), relative to the total quantity by weight of monomers (a), (b) and (c).

[0053] Also preferably according to the invention, the polymerization reaction can implement:

[0054] - from 20 to 74.9% by weight of monomer (a),

[0055] - from 25 to 79.9% by weight of monomer (b), and

[0056] - from 0.1 to 55% by weight of monomer (c), relative to the total quantity by weight of monomers (a), (b) and (c).

[0057] Also preferably according to the invention, the polymerization reaction can implement:

[0058] - from 25 to 69.5% by weight of monomer (a),

[0059] - from 30 to 74.5% by weight of monomer (b), and

[0060] - from 0.5 to 45% by weight of monomer (c), relative to the total quantity by weight of monomers (a), (b) and (c).

[0061] Also preferably according to the invention, the polymerization reaction can implement:

[0062] - from 30 to 68% by weight of monomer (a),

[0063] - from 30 to 68% by weight of monomer (b), and

[0064] - from 2 to 40% by weight of monomer (c), relative to the total quantity by weight of monomers (a), (b) and (c).

[0065] Also preferably according to the invention, the polymerization reaction can implement:

[0066] - from 35 to 60% by weight of monomer (a),

[0067] - from 35 to 64.5% by weight of monomer (b), and

[0068] - from 5 to 30% by weight of monomer (c), relative to the total quantity by weight of monomers (a), (b) and (c).

[0069] Also preferably for copolymer P, the polymerization reaction involves:

[0070] - from 20 to 70% by weight or from 25 to 65% by weight, preferably from 30 to 65% by weight or from 35 to 60% by weight, of monomer (a) or

[0071] - from 25 to 75% by weight or from 30 to 70% by weight, preferably from 30 to 65% by weight or from 35 to 60% by weight, of monomer (b), or - from 5 to 55% by weight or from 5 to 45% by weight, preferably from 5 to 40% by weight or

[0072] 5 to 30% by weight of monomer (c), relative to the total amount by weight of monomers (a), (b) and (c).

[0073] More preferably for copolymer P, the polymerization reaction involves:

[0074] - from 20 to 70% by weight or from 25 to 65% by weight, preferably from 30 to 65% by weight or from 35 to 60% by weight, of monomer (a),

[0075] - from less than 25 to less than 75% by weight or from less than 30 to less than 70% by weight, preferably from less than 30 to less than 65% by weight or from less than 35 to less than 60% by weight, of monomer (b),

[0076] - more than 5 to 55% by weight or more than 5 to 45% by weight, preferably more than 5 to 40% by weight or more than 5 to 30% by weight, of monomer (c), relative to the total amount by weight of monomers (a), (b) and (c).

[0077] Also more preferably for copolymer P, the polymerization reaction involves:

[0078] - from 20 to 70% by weight or from 25 to 65% by weight, preferably from 30 to 65% by weight or from 35 to 60% by weight, of monomer (a),

[0079] - from 24 to 74% by weight or from 29 to 69% by weight, preferably from 29 to 64% by weight or from 34 to 59% by weight, of monomer (b),

[0080] - from 6 to 55% by weight or from 6 to 45% by weight, preferably from 6 to 40% by weight or

[0081] 6 to 30% by weight of monomer (c), relative to the total amount by weight of monomers (a), (b) and (c).

[0082] Particularly preferably for copolymer P, the polymerization reaction involves:

[0083] - from 50 to 70% by weight or from 05 to 65% by weight of monomer (a),

[0084] - from less than 25 to less than 45% by weight or from less than 30 to less than 40% by weight of monomer (b),

[0085] - more than 5 to 55% by weight or more than 5 to 45% by weight of monomer (c), relative to the total quantity by weight of monomers (a), (b) and (c).

[0086] Also particularly preferably for copolymer P, the polymerization reaction involves:

[0087] - from 50 to 70% by weight or from 50 to 65% by weight of monomer (a),

[0088] - from 24 to 44% by weight or from 29 to 39% by weight of monomer (b),

[0089] - from 6 to 55% by weight or from 6 to 45% by weight of monomer (c), relative to the total quantity by weight of monomers (a), (b) and (c).

[0090] Particularly preferably for copolymer P, the polymerization reaction uses more than 5% by weight, preferably more than 6% by weight or more than 8% by weight, of monomer (c) relative to the total amount by weight of monomers (a), (b) and (c). Also particularly preferably for copolymer P, the polymerization reaction uses more than 50% by weight or more than 55% by weight of monomer (a) relative to the total amount by weight of monomers (a), (b) and (c).

[0091] According to the invention, the polymerization reaction can use only compounds (a), (b) and (c) or use one or more other additional compounds. Then, the polymerization reaction can also use at least one crosslinking monomer (f) or at least one monomer (f) comprising at least two olefinic unsaturations, preferably less than 5% by weight, preferably from 0.01 to 4% by weight, in particular from 0.02 to 4% by weight or from 0.02 to 2% by weight, in particular from 0.02 to 1% by weight, of monomer (f) relative to the total quantity by weight of monomers.

[0092] According to the invention, the polymerization reaction can also use at least one hydrophobic monomer (g) different from compound (c), preferably chosen from a compound of formula (II):

[0093] R 1 -(OE) m -(OP) p -R 2

[0094] (II) in which:

[0095] - m and p, identical or different, independently represent 0 or an integer or decimal number less than 150, m or p is different from 0,

[0096] - OE independently represents a CH2CH2O group,

[0097] - OP independently represents a group chosen from CH(CH3)CH2O and CH2CH(CH3)O,

[0098] - R 1 independently represents a group comprising at least one polymerizable olefinic unsaturation, preferably an acrylate group or a methacrylate group and

[0099] - R 2independently represents a linear or branched C6-C4o-alkyl group, a phenyl group, a polyphenyl group, preferably a linear or branched C10-C30-alkyl group, more preferably a linear or branched C12-C22-alkyl group, or a group comprising 2 to 5 phenyls or a tristyrylphenyl group or a pentastyrylcumylphenyl group, preferably less than 20% by weight, preferably from 0.05 to 20% by weight, in particular from 0.1 to 10% by weight, of monomer (g) relative to the total quantity by weight of monomers.

[0100] More preferably, the polymerization reaction may use at least one compound (h) chosen from 2-acrylamido-2-methylpropane sulfonic acid, ethoxymethacrylate sulfonic acid, sodium methallyl sulfonate, styrene sulfonate hydroxyethyl-acrylate phosphate, hydroxypropyl-acrylate phosphate, hydroxyethylhexyl-acrylate phosphate, hydroxyethyl-methacrylate phosphate, hydroxypropyl-methacrylate phosphate, hydroxyethylhexyl-methacrylate phosphate, their salts and their combinations, 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 (h) relative to the total amount by weight of monomers.

[0101] Also preferably, the polymerization reaction may use at least one compound (i) chosen from hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethylhexyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethylhexyl methacrylate, 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 (i) relative to the total quantity by weight of monomers.

[0102] Advantageously according to the invention, the polymerization reaction does not use an amide or an amide derivative or does not use hydroxyethyl(meth)acrylate or hydroxypropyl(meth)acrylate,

[0103] According to the invention, the copolymer P can be used as such, in an acid form, or it can be totally or partially neutralized or coacervated. Preferably, the copolymer P can be totally or partially neutralized, preferably by means of at least one compound chosen from NaOH, KOH, ammonium derivatives, ammonia, amine bases, for example triethanolamine, aminomethylpropanol or 2-amino-2-methyl-propanol (AMP) and combinations thereof. Also preferably, the copolymer P can be totally or partially coacervated, preferably by reducing the pH, for example by reducing the pH to a value below 6.5, or by increasing the ionic strength.The reduction of the pH can be carried out by means of an acidic compound, in particular by means of at least one organic or mineral acidic compound, in particular an acidic compound chosen from phosphoric acid, citric acid, glucono-lactone, lactic acid, salicylic acid, glycolic acid, ascorbic acid, glutamic acid, hydrochloric acid, acetic acid, D-gluconic acid, sulfonic acid, methanesulfonic acid, benzimidazole-sulfonic acid, tartaric acid, 4-aminobenzoic acid, benzoic acid, sorbic acid, phenylbenzimidazole sulfonic acid, benzylidene camphor sulfonic acid, terephthalylidene dicamphor sulfonic acid, kojic acid, hyaluronic acid.The increase in ionic strength can be achieved by adding at least one ionized compound or at least one salt, in particular NaCl, KC1, MgCh, CaCh, MgSCU, CaSÛ4, or by adding phenylbenzimidazole sulfonic acid (PB SA) or sodium salt of pyroglutamic acid (NaPCA) or by adding at least one ionized organic sunscreen.

[0104] Generally according to the invention, the copolymer P in solution in water has a pH greater than 4, preferably greater than 5, more preferably greater than 6 or 6.5. The copolymer P generally has a pH less than 13, preferably less than 12, more preferably less than 11. In particular, the copolymer P has a pH ranging from 4 to 13 or from 4 to 12 or from 4 to 11, preferably ranging from 5 to 13 or from 5 to 12 or from 5 to 11, more preferably ranging from 6 to 13 or from 6 to 12 or from 6 to 11, also more preferably ranging from 6.5 to 13 or from 6.5 to 12 or from 6.5 to 11.

[0105] The copolymer P according to the invention can be used in many technical fields, in particular as a rheology control agent. It can be incorporated into different compositions. Thus, the invention provides a rheological control composition comprising at least one copolymer P according to the invention and water.

[0106] The rheological control composition according to the invention is particularly suitable for facilitating the implementation of pigments in aqueous medium, in particular organic or mineral pigments. It can be incorporated into a particular pigmented formulation. Thus, the invention provides an aqueous formulation comprising:

[0107] - at least one rheological control composition according to the invention; optionally

[0108] - 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

[0109] - at least one agent selected from a particle spacing agent, a dispersing agent, a steric stabilizing agent, an electrostatic stabilizing agent, an opacifying agent, a coloring agent, a solvent, a coalescing agent, an anti-foaming agent, a preservative, a biocidal agent, a spreading agent, a thickening agent, a film-forming copolymer and mixtures thereof.

[0110] Preferably, the formulation according to the invention is a coating formulation, in particular an ink formulation, a varnish formulation, an adhesive formulation, a paint formulation, for example decorative paint or industrial paint. The copolymer P according to the invention can also be used in the field of printing, in particular textile printing. Thus, the invention provides a concentrated aqueous pigment paste comprising at least one copolymer P according to the invention and at least one organic or mineral colored pigment.

[0111] The invention also provides a method for controlling the viscosity of an aqueous composition which comprises the addition of at least one copolymer P according to the invention to this composition. The method for controlling the viscosity according to the invention is implemented for an aqueous composition which is an aqueous formulation according to the invention.

[0112] The advantageous, particular or preferred characteristics of the copolymer P according to the invention define rheological control compositions, aqueous formulations, pigment pastes as well as viscosity control methods according to the invention which are also advantageous, particular or preferred.

[0113] The following examples illustrate the various aspects of the invention.

[0114] EXAMPLES of copolymers PI, P2, P3 according to the invention according to the invention

[0115] In the first step, the following are weighed into an Erlenmeyer flask: 17.8g of toluene diisocyanate (TDI), 0.098g of alloocimene, 0.255g of titanium diisopropoxide bis(acetylacetonate) (Tyzor AA 105) and 39.1g of ethyl acrylate (monomer b).

[0116] Then, 13.3g of ethylene glycol methacrylate (MAEG) and 7.1g of ethyl acrylate (monomer b) are weighed into a dropping funnel. The contents of this funnel are poured into the Erlenmeyer flask over 20 minutes at a temperature below 35°C and left to react for 30 minutes. Compound (el) (MAEG-TDI) is obtained.

[0117] In a second step, 250 g of compound (d2a) (prepared by Guerbet reaction dimerization of a compound of formula I in which R represents a linear Cs-alkyl group, m represents 0 and n represents 5 and of a compound of formula I in which R represents a linear C?-alkyl group, m represents 0 and n represents 4, ethoxylated 50 times - Isofol 2426S-50OE) are weighed into a 1000 ml reactor which is kept in the molten state at 65°C. Compound (el) is then poured over 20 minutes at 65°C onto this compound (d2a) and heating is maintained for 1 hour and 30 minutes. Finally, the mixture is diluted with 57.98 g of monomer b (ethyl acrylate) and 167.98 g of deionized water to obtain a liquid at room temperature. Monomer (cl) is obtained from compounds (d2a) and (el) in ethyl acrylate (monomer b). according to the invention

[0118] In a glass reactor, 200.0 g of compound (d2a) (Isofol2426S-50OE), 0.126 g of alloocimene and 12.02 g of methacrylic anhydride (compound e) are introduced. The mixture is heated at 82°C ± 2°C for 2 hours and 30 minutes. At room temperature, the monomer (c2) obtained is then diluted with 133.38 g of monomer (a) (methacrylic acid) and 59.96 g of deionized water.

[0119] Preparation and characterization of the (PI) according to the invention

[0120] 269 ​​g of deionized water and 2.37 g of sodium dodecyl sulfate are introduced into a glass reactor.

[0121] In a first glass beaker, weigh 120.6 g of monomer (a) (methacrylic acid), 148.5 g of monomer (b) (ethyl acrylate), 23.9 g of compound (cl), 2.43 g of sodium dodecyl sulfate and 258.7 g of deionized water.

[0122] In a second glass beaker, weigh 0.318g of ammonium persulfate and dissolve it in 5.6g of deionized water.

[0123] In a third container, of the disposable syringe type, 10.42 g of monomer (h) (sodium salt of 2-acrylamido-2-methylpropane sulfonic acid) at 50% by weight in water are weighed.

[0124] The contents of the reactor are heated to a temperature of 85°C ± 2°C. Within 2 hours, the reactants from the 3 containers are introduced into the polymerization reactor at a temperature of 85°C ± 2°C.

[0125] 0.224 g of ammonium persulfate dissolved in 22.4 g of deionized water are then added over 1 hour, maintaining the temperature at 85°C ± 2°C. Heating is continued for 1 hour before the medium is allowed to cool to room temperature.

[0126] The copolymer (PI) is obtained at 30.4% by weight of dry extract, the composition of which is detailed in Table 1.

[0127] Preparation and characterization of the copolymer (P2) according to the invention

[0128] 269 ​​g of deionized water and 2.37 g of sodium dodecyl sulfate are introduced into a glass reactor.

[0129] In a first glass beaker, weigh 120.6 g of monomer (a) (methacrylic acid), 148.5 g of monomer (b) (ethyl acrylate), 23.9 g of monomer (cl), 2.43 g of sodium dodecyl sulfate, 258.7 g of deionized water and 1.0 g of n-dodecyl mercaptan.

[0130] In a second glass beaker, weigh 0.318 g of ammonium persulfate and dissolve it in 5.6 g of deionized water.

[0131] In a third container, of the disposable syringe type, 10.42 g of monomer (h) (sodium salt of 2-acrylamido-2-methylpropane sulfonic acid) at 50% by weight in water are weighed.

[0132] The contents of the reactor are heated to a temperature of 85°C ± 2°C.

[0133] For 2 hours, the reagents from the 3 containers are introduced into the polymerization reactor at a temperature of 85°C ± 2°C.

[0134] 0.224 g of ammonium persulfate dissolved in 22.4 g of deionized water are then added over 1 hour, maintaining the temperature at 85°C ± 2°C. Heating is continued for 1 hour before the medium is allowed to cool to room temperature.

[0135] A copolymer (P2) is obtained with 30.0% by weight of dry extract, the composition of which is detailed in Table 1.

[0136] Preparation and characterization of the copolymer (P3) according to the invention

[0137] 269 ​​g of deionized water and 2.37 g of sodium dodecyl sulfate are introduced into a glass reactor.

[0138] In a first glass beaker, weigh 120.6 g of monomer (a) (methacrylic acid), 148.5 g of monomer (b) (ethyl acrylate), 23.9 g of monomer (cl), 2.43 g of sodium dodecyl sulfate, 258.7 g of deionized water and 0.5 g of n-dodecyl mercaptan.

[0139] In a second glass beaker, weigh 0.318 g of ammonium persulfate and dissolve it in 5.6 g of deionized water.

[0140] In a third container, of the disposable syringe type, 10.42 g of monomer (h) (sodium salt of 2-acrylamido-2-methylpropane sulfonic acid) at 50% by weight in water are weighed.

[0141] The contents of the reactor are heated to a temperature of 85°C ± 2°C.

[0142] Within 2 hours, the reactants from the 3 containers are introduced into the polymerization reactor at a temperature of 85°C ± 2°C.

[0143] 0.224 g of ammonium persulfate dissolved in 22.4 g of deionized water are then added over 1 hour, maintaining the temperature at 85°C ± 2°C. Heating is continued for 1 hour before the medium is allowed to cool to room temperature.

[0144] A copolymer (P3) is obtained with 30.2% by weight of dry extract, the composition of which is detailed in Table 1.

[0145] Preparation and characterization of the copolymer (P4) according to the invention

[0146] 260.7 g of deionized water and 2.49 g of sodium dodecyl sulfate are introduced into a glass reactor.

[0147] In a first glass beaker, weigh 110.18 g of monomer a (methacrylic acid), 162.11 g of monomer b (ethyl acrylate), 30.3 g of compound (c2), 2.49 g of sodium dodecyl sulfate and 325 g of deionized water.

[0148] In a second glass beaker, weigh 0.329 g of ammonium persulfate and dissolve it in 4 g of deionized water.

[0149] The contents of the reactor are heated to a temperature of 85°C ± 2°C.

[0150] In 2 hours, the reactants from the 2 containers are introduced into the polymerization reactor at a temperature of 85°C ± 2°C.

[0151] 0.256 g of ammonium persulfate dissolved in 59 g of deionized water are then added over 1 hour, maintaining the temperature at 85°C ± 2°C. Heating is continued for 1 hour before the medium is allowed to cool to room temperature.

[0152] A copolymer (P4) is obtained with 30.0% by weight of dry extract, the composition of which is detailed in Table 1.

[0153] Table 1

[0154] Examples 2: preparation and characterization of aqueous paint formulations according to the invention

[0155] By mixing the different ingredients under agitation, a matt paint formulation according to the invention is prepared. The compounds and quantities (g) used are detailed in Table 2.

[0156] Table 2

[0157] Then, the paint formulation is colored by adding 5% by weight of a black pigment

[0158] (Colanyl N500 black Clariant) to obtain the formulation F1 according to the invention. In a similar manner, the aqueous formulations F2 and F3 according to the invention are prepared by replacing the copolymer composition PI respectively with the copolymer compositions P2 and P3 according to the invention.

[0159] Then, for each formulation Fl, F2 and F3, we measure, at 25°C:

[0160] • Brookfield viscosity at 10 rpm (pB 10, mPa.s);

[0161] • Brookfield viscosity at 100 rpm (pBlOO, mPa.s);

[0162] • Cone Plan viscosity or ICI viscosity measured at high velocity gradient (pi, mPa.s);

[0163] • Stormer viscosity measured using the standard module, at medium velocity gradient (pS, Krebs Units or KU).

[0164] The results are measured immediately after the addition of the black pigment (T=0) and measured 24 hours after this addition (T=24H). They are presented in Table 3.

[0165] The pigment compatibility of the Fl, F2 and F3 formulations is evaluated on a dry film of paint. The coloring of the initially white paint is obtained by adding 5% of black pigment-based colorant (Colanyl N500 Clariant black), a percentage calculated in relation to the weight of the white paint formulation.

[0166] The test, known as such, of finger rubbing of colored paint applied at a wet thickness of 150 micrometers on a contrast card (rub ouf test) makes it possible to subject a small part of the surface of the freshly applied colored paint film to a shearing effect generated by a circular movement of the finger. The shearing effect can modify the stability and distribution of the colored pigment in the matrix that constitutes the colored paint film and consequently, the intensity of the coloring at the location of the sheared area.

[0167] Once the colored paint film is dry, the difference in color between the initially sheared area of ​​the colored paint film and the unsheared area of ​​colored paint is measured using a spectro-guide sphere gloss spectrophotometer marketed by the company Byk.

[0168] The color difference is quantified by the AE value calculated from the measurement parameters corresponding to the known L*a*b* color space. A low AE value means a reduced color difference between the sheared and unsheared areas, and therefore an improvement in pigment compatibility.

[0169] The unsheared colored paint area is also measured according to one of the parameters of the L*a*b* color space. The L* parameter quantifies the intensity of the coloring. A low value for the L* parameter means reduced lightness and therefore a greater black intensity corresponding to an improvement in the pigment compatibility of the evaluated paint formulation in which the copolymer according to the invention is implemented. The results are presented in Table 3.

[0170] Table 3 For formulations F1, F2 and F3 according to the invention, the copolymers according to the invention allow good control of the different components of viscosity, both after preparation and over time. The copolymers according to the invention provide good pigment compatibility to these paint formulations.

Claims

CLAIMS Copolymer P prepared by at least one polymerization reaction: • of at least one anionic monomer (a) selected from acrylic acid, a salt of acrylic acid, methacrylic acid, a salt of methacrylic acid and their combinations; • of at least one Ci-Cs ester (b) of a compound derived from an acid selected from acrylic acid, methacrylic acid, maleic acid, itaconic acid and crotonic acid; • of at least one compound (c) prepared by reaction: o of at least one compound (d) obtained by: ■ Dimerization of two identical or different compounds of formula I by a Guerbet reaction: R-CH[(CH2) m CH3]-(CH2) n -OH (I) in which: - R independently represents a linear C4-C9-alkyl group; - m represents independently 0 or 1; - n independently represents a number from 2 to 7; and ■ polyalkoxylation of the resulting dimer, and o of at least one compound (e) comprising a polymerizable function and another reactive function with the hydroxyl group of compound (d). Copolymer P according to claim 1, wherein the anionic monomer (a) is selected from acrylic acid, methacrylic acid, and combinations thereof. Copolymer P according to claim 1 or 2, wherein: • ester (b) is a C1-C7 ester or a C1-C4 ester OR a C1-C4 ester, preferably a C1-C3 ester, • ester (b) is an acrylic acid ester or a methacrylic acid ester, preferably an acrylic acid ester, • the ester (b) is selected from methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, ethylhexyl methacrylate and their combinations, more preferably • The ester (b) is selected from ethyl acrylate, methyl acrylate, butyl acrylate, methyl methacrylate, and combinations thereof. Polypolymer P according to any one of claims 1 to 3, wherein: • Dimerization of two identical compounds of formula I leads to a homodimer (dl); or • Compound (d) is a homodimer (dl) obtained by dimerization of two identical compounds of formula I in which: - R represents a linear Cs-Cv-alkyl group; - m represents 0 or 1, preferably 0; - n represents a number from 2 to 7; or • Compound (d) is a homodimer (dl) obtained by dimerization of two identical compounds of formula I in which: - R represents a linear C4-C9-alkyl group, preferably a linear Cs-Cv-alkyl group; - m represents 0 or 1, preferably 0; - n represents a number from 5 to 7, preferably from 4 to 6, more preferably 4 or 5. Polymer P according to any one of claims 1 to 4, wherein: • Dimerization of two different compounds (d) of formula I leads to a mixture comprising two different homodimers (dl) and one heterodimer (d2); or • a mixture of compounds (d) is obtained by dimerization of two different compounds of formula I in which: - R independently represents a linear Cs-Cv-alkyl group; - m represents independently 0 or 1, preferably 0; - n independently represents a number from 2 to 7; or • a mixture of compounds (d) is obtained by dimerization of two different compounds of formula I in which: - R independently represents a linear C4-C9-alkyl group, preferably a linear Cs-Cv-alkyl group; - m represents independently 0 or 1, preferably 0; - n independently represents a number from 5 to 7, preferably from 4 to 6, more preferably 4 or 5; or • a mixture of compounds (d) comprising a heterodimeric compound (d2) obtained by dimerization of a first compound of formula I in which R represents a linear Cs-alkyl group, m represents 0 and n represents 5 and a second different compound of formula I in which R represents a linear C7-alkyl group, m represents 0 and n represents 4; or • a mixture of compounds (d) comprising: o a heterodimeric compound (d2) obtained by dimerization of a first compound of formula I in which R represents a linear Cs-alkyl group, m represents 0 and n represents 5 and a second different compound of formula I in which R represents a linear Cα-alkyl group, m represents 0 and n represents 4, o a first homodimer (dl) obtained by dimerization of a compound of formula I in which R represents a linear Cs-alkyl group, m represents 0 and n represents 5, o a second homodimer (dl) obtained by dimerization of a different compound of formula I in which R represents a linear Cα-alkyl group, m represents 0 and n represents 4. Copolymer P according to any one of claims 1 to 5 wherein: • Compound (d) comprises from 10 to 150 alkoxylations, preferably from 20 to 100 alkoxylations, or from 10 to 70 alkoxylations, more preferably from 20 to 60 alkoxylations, or • compound (d) is polyethoxylated or is polyethoxylated-polypropoxylated or is polyethoxylated-polybutoxylated, preferably compound (d) is polyethoxylated, or • Compound (d) comprises from 10 to 150 ethoxylations, preferably from 20 to 100 ethoxylations, or from 10 to 70 ethoxylations, more preferably from 20 to 60 ethoxylations. Copolymer P according to any one of claims 1 to 6, wherein: • the polymerizable function of compound (e) is a terminal ethylenic group, preferably selected from vinyl, allyl, methallyl, isoprenyl, styrylyl, acrylate, methacrylate, itaconate, maleate, crotonate, or • Compound (e) is selected from acrylic acid, methacrylic acid, maleic acid, itaconic acid, crotonic acid, acrylic anhydride, methacrylic anhydride, maleic anhydride, itaconic anhydride, styrylyl isocyanates (e.g., 3-isopropenyl-α,α'-dimethylbenzyl isocyanate or TMI, CAS No. 2094-99-7), acrylate alkylene isocyanates (e.g., 2-isocyanatoethyl acrylate, CAS No. 13641-96-8), methacrylate alkylene isocyanates (e.g., 2-isocyanatoethyl methacrylate, CAS No. 30674-80-7) and combinations thereof, or • Compound (e) is prepared by pre-reaction of a diisocyanate compound (e.g. tolyl-diisocyanate, isophorone-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.

8. Copolymer P according to any one of claims 1 to 7, wherein the polymerization reaction involves: - from 20 to 74.9% by weight or from 25 to 69.5% by weight, preferably from 30 to 68% by weight or from 35 to 60% by weight, of monomer (a) or - from 25 to 79.9% by weight or from 30 to 74.5% by weight, preferably from 30 to 68% by weight or from 35 to 64.5% by weight, of monomer (b), or - from 0.1 to 55% by weight or from 0.5 to 45% by weight, preferably from 2 to 40% by weight or from 5 to 30% by weight, of monomer (c), relative to the total weight quantity of monomers (a), (b) and (c).

9. Copolymer P according to any one of claims 1 to 8, wherein the polymerization reaction also involves: • at least one crosslinking monomer (f) or at least one monomer (f) comprising at least two olefinic unsaturations, preferably less than 5% by weight, preferably from 0.01 to 4% by weight, in particular from 0.02 to 4% by weight or from 0.02 to 2% by weight, in particular from 0.02 to 1% by weight, of monomer (f) relative to the total weight of monomers, or • at least one hydrophobic monomer (g) different from compound (c), preferably chosen from a compound of formula (II): R 1 -(OE) m -(OP) p -R 2 (II) in which: - m and p, whether identical or different, independently represent 0 or an integer or decimal number less than 150, where m or p is different from 0. - OE independently represents a CH2CH2O group, - OP independently represents a group chosen from CH(CH3)CH2O and CH2CH(CH3)O, - R 1independently represents a group comprising at least one polymerizable olefinic unsaturation, preferably an acrylate group or a methacrylate group and - R 2 independently represents a linear or branched C0-C4o-alkyl group, a phenyl group, a polyphenyl group, preferably a linear or branched C10-C5o-alkyl group, more preferably a linear or branched C12-C22-alkyl group, or a group comprising 2 to 5 phenyl groups, or a tristyrylphenyl group, or a pentastyrylcumylphenyl group, preferably less than 20% by weight, preferably from 0.05 to 20% by weight, in particular from 0.1 to 10% by weight, of monomer (g) relative to the total weight of monomers, or • at least one compound (h) selected from 2-acrylamido-2-methylpropane sulfonic acid, ethoxymethacrylate sulfonic acid, sodium methallyl sulfonate, styrene sulfonate, hydroxyethyl acrylate phosphate, hydroxypropyl acrylate phosphate, hydroxyethylhexyl acrylate phosphate, hydroxyethyl methacrylate phosphate, hydroxypropyl methacrylate phosphate, hydroxyethylhexyl methacrylate phosphate, 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 (h) relative to the total weight of monomers, or • at least one compound (i) selected from hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethylhexyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethylhexyl methacrylate, preferably less than 20% in weight, preferably from 0.2 to 20% by weight, in particular from 0.5 to 10% by weight, of monomer (i) relative to the total weight of monomers. Copolymer P according to any one of claims 1 to 9: • totally or partially neutralized, preferably by means of at least one compound selected from NaOH, KOH, ammonium derivatives, ammonia, amino bases, for example triethanolamine, aminomethylpropanol or 2-amino-2-methylpropanol (AMP) and their combinations, or • fully or partially coacerbated, preferably: - by reducing the pH, for example by reducing the pH to a value below 6.5, in particular by means of an acidic compound, in particular by means of at least one organic or mineral acidic compound, in particular an acidic compound selected from phosphoric acid, citric acid, gluconolactone, lactic acid, salicylic acid, glycolic acid, ascorbic acid, glutamic acid, hydrochloric acid, acetic acid, D-gluconic acid, sulfonic acid, methanesulfonic acid, benzimidazolesulfonic acid, tartaric acid, 4-aminobenzoic acid, benzoic acid, sorbic acid, phenylbenzimidazolesulfonic acid, benzylidene camphorsulfonic acid, terephthalylidene dicamphorsulfonic acid, kojic acid, hyaluronic acid or - by increasing the ionic strength, for example by adding at least one ionized compound or at least one salt, in particular NaCl, KCl, MgCh, CaCh, MgSU4, CaSU4, or by adding phenylbenzimidazolesulfonic acid (PBSA) or sodium pyroglutamic acid (NaPCA), or by adding at least one ionized organic sunscreen. Copolymer P according to any one of claims 1 to 10, in aqueous solution, • having a pH greater than 4, preferably greater than 5, more preferably greater than 6 or 6.5 or • having a pH below 13, preferably below 12, more preferably below 11 or • having a pH ranging from 4 to 13 or from 4 to 12 or from 4 to 11, preferably ranging from 5 to 13 or from 5 to 12 or from 5 to 11, more preferably ranging from 6 to 13 or from 6 to 12 or from 6 to 11, also more preferentially ranging from 6.5 to 13 or from 6.5 to 12 or from 6.5 to 11.

12. Rheological control composition comprising at least one copolymer P according to any one of claims 1 to 11 and water.

13. Aqueous formulation comprising: - at least one composition according to claim 12; 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 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.

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

15. Concentrated aqueous pigment paste comprising at least one copolymer P according to any one of claims 1 to 11 and at least one organic or mineral colored pigment.

16. Method for controlling the viscosity of an aqueous composition comprising the addition of at least one copolymer P according to any one of claims 1 to 11 in this composition.

17. Method according to claim 16 wherein the aqueous composition is an aqueous formulation defined according to one of claims 13 or 14.

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