VOC-FREE COPOLYMER

Abstract

The invention relates to a method for preparing a copolymer using a polyalkoxylated and polyhydroxylated compound that does not contain volatile residues of alkanes, aromatic hydrocarbons, or alkenes. The copolymer according to the invention is useful as a rheology control agent in aqueous media, particularly for paint compositions, paper coating slurries, or cosmetic compositions.

Description

Title of the invention: VOC-FREE COPOLYMER

[0001] The invention relates to a method for preparing a copolymer using a polyalkoxylated and polyhydroxylated compound that does not contain volatile residues of alkanes, volatile residues of aromatic hydrocarbon compounds, or volatile residues of alkenes. The copolymer according to the invention is useful as a rheology control agent in aqueous media, particularly for paint compositions, paper coating slurries, or cosmetic compositions.

[0002] Generally, for aqueous coating compositions, and particularly for aqueous paint or varnish compositions, it is necessary to control the viscosity at both low and medium shear rates as well as at high shear rates. Indeed, during its preparation, storage, application, or drying, a paint formulation is subjected to numerous stresses requiring particularly complex rheological properties. A high viscosity of the paint formulation must be achieved at high shear rates. A lower viscosity at low and medium shear rates will also result in a good, smooth finish after application. Furthermore, to prevent runs, the paint formulation must have a high viscosity at low and medium shear rates.For the paint to have a high leveling capacity after being applied to a surface, a reduced viscosity at low and medium shear gradients is required for the paint formulation.

[0003] Furthermore, when preparing paper coating slurries, it is also necessary to improve viscosity under low shear gradients, while simultaneously improving water retention within the aqueous composition used. These compositions must have viscosities under different shear gradients that allow them to be used effectively, particularly when applied to the surface of a sheet of paper. These compositions must have an apparent viscosity, therefore under low shear gradients, that is well-suited to efficient application.

[0004] Also, when preparing aqueous cosmetic compositions, rheological control is an essential property. Indeed, the viscosity of these cosmetic compositions must be controlled during their preparation, transport, and storage, as well as during their application. The use of these aqueous cosmetic compositions, particularly on the skin or hair, often requires very specific properties from both a rheological and a safety perspective.

[0005] The compatibility of the various constituents of a rheologically controlled aqueous composition is also an important property, as is the presence in small quantities, or even the absence, of certain harmful or prohibited compounds within these compositions. In particular, these aqueous compositions, or the compounds used in their preparation, should not contain volatile organic compounds, especially alkanes, aromatic hydrocarbons, or alkenes. These compounds should not be present in the ingredients used for the preparation of paint or varnish compositions or used in the preparation of paper coating slurries. In particular, rheological control agents, as well as the compounds used in their preparation, should contain only negligible or zero amounts of residual alkanes, residual aromatic hydrocarbons, or residual alkenes.In particular, the presence of such compounds must be strictly controlled to prevent their release during the application of paint or varnish compositions, or during the manufacture of paper or packaging, and especially during the manufacture of paper or packaging for food products.

[0006] Monitoring for the possible presence of such compounds is therefore essential to ensure the final quality of the aqueous compositions used. This monitoring should therefore be effective while also being easily achievable using widely available techniques.

[0007] There is therefore a need for a method of preparing rheological control agents which makes it possible to provide a solution to all or part of the problems encountered during the preparation of known copolymers.

[0008] The invention therefore provides a method for preparing a copolymer P comprising the polymerization reaction: a) of at least one dihalogenated compound (a) of formula I: [Chem I] (CH2)-R2 (I) in which R independently represents Cl, Br or I; b) of at least one compound (b) polyalkoxylated, polyhydroxylated and comprising an amount of at least one compound selected from alkanes, aromatic hydrocarbon compounds, alkenes and their combinations, measured by GC-MS, which is less than 0.5 ppm by weight of compound (b).

[0009] For the effectiveness of the method according to the invention, the reaction of the polyhydroxylated compound (b) with the dihalogenated compound (a) can be carried out in the presence of a base. Preferably according to the invention, the base is used in a molar excess relative to the molar amount of OH groups of compound (b). Preferably, the base is used in a molar quantity of 1.05 to 10, preferably 1.1 to 7, molar equivalents relative to the molar quantity of OH groups in compound (b). The use of the base leads to an increase in pH during the implementation of the method according to the invention. Preferably, the polymerization is carried out at a pH greater than 10 or greater than 12.

[0010] According to the invention, numerous bases can be used. Preferably, according to the invention, the base is a strong mineral base or a strong organic base. More preferably, the base is selected from sodium hydride, potassium hydride, NaOH, KOH, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium tert-butanolate, and potassium tert-butanolate. Sodium hydroxide is the preferred base.

[0011] Generally, according to the invention, the base allows the alkoxide derivative of compound (b) to be obtained. Advantageously, the treatment, total or partial, of compound (b) with the base, prior to the polymerization reaction, can allow the direct introduction of this alkoxide derivative of compound (b). The alkoxide derivative of compound (b) can optionally be stored separately and then introduced during polymerization in the presence of compound (a).

[0012] The method according to the invention comprises using compound (a) in the polymerization reaction. Preferably, the polymerization reaction uses a single compound (a) or two or three different compounds (a). More preferably, the polymerization reaction uses a single compound (a).

[0013] According to the invention, compound (a) comprises two halides. Preferably, compound (a) is a compound of formula I in which R represents either Br or Cl, preferably Br. More preferably, compound (a) is selected from dibromomethane, diiodomethane, and combinations thereof. Dibromomethane is particularly preferred.

[0014] Preferably according to the invention, compound (b) is a compound (bl) of formula II: [Chem II] HO-Ln-OH (II) in which: - L independently represents an oxyalkylene residue; - n independently represents a number ranging from 30 to 1000.

[0015] Preferably according to the invention, compound (b) is a compound (bl) of formula II in which L independently represents an oxyethylene residue or in which n independently represents a number from 50 to 400, preferably from 100 to 300. More preferably according to the invention, compound (b) is a compound (bl) of formula II in which L independently represents an oxyethylene residue and n independently represents a number from 50 to 400, preferably from 100 to 300.

[0016] The compound (bl) can be used alone or it can be combined with one or more other compounds. In this case, the compound (bl) of formula II can be combined with a non-alkoxy compound (b2) comprising at least 3 hydroxyl groups. Preferably according to the invention, the compound (b2) comprises 3 hydroxyl groups; more preferably, the compound (b2) is selected from glycerol, pentaerythritol, and combinations thereof.

[0017] According to the invention, compound (b) can also be associated with a polyalkoxylated compound (b3) comprising at least 3 hydroxyl groups. According to the invention, the polyalkoxylated compound (b3) is different from compound (b2).

[0018] Preferably according to the invention, the polyalkoxylated compound (b3) is polyethoxylated pentaerythritol or comprises 3 hydroxyl groups, more preferably the compound (b3) is polyethoxylated glycerol.

[0019] The method according to the invention can implement one or more combinations of compounds (bl), (b2) and (b3).

[0020] Essentially, according to the invention, the polyhydroxylated compound (b) is polyalkoxylated. It therefore comprises alkoxylated groups. Preferably, the method according to the invention uses a compound (b) comprising from 70 to 500 alkoxylations, more preferably from 80 to 400 alkoxylations or from 100 to 300 alkoxylations. More preferably, the compound (b) comprises from 100 to 250 alkoxylations.

[0021] Preferably, the method according to the invention also employs a compound (b) that is polyethoxylated, or that is polyethoxylated-polypropoxylated, or that is polyethoxylated-polybutoxylated. More preferably, compound (b) is polyethoxylated.

[0022] In a particularly preferred manner, compound (b) comprises from 70 to 500 ethoxylations, more preferably from 80 to 400 ethoxylations or from 100 to 300 ethoxylations. Much more preferably, compound (b) comprises from 100 to 250 ethoxylations.

[0023] The preparation method according to the invention can utilize polyalkylated compounds (b), (bl), and (b3) whose molar mass (Mw) measured by CES can vary significantly. Preferably according to the invention, compounds (b), (bl), or (b3) independently have a molar mass (Mw) measured by CES ranging from 1,500 to 80,000 g / mol, preferably from 2,000 to 20,000 g / mol. More preferably according to the invention, the molar mass (Mw) of compounds (b), (bl), or (b3) independently ranges from 2,000 to 15,000 g / mol or from 2,000 to 12,000 g / mol.

[0024] According to the invention, the molar mass of compounds (b), (bl), or (b3) is determined by Size Exclusion Chromatography (SEC), also known as Gel Permeation Chromatography (GPC). This technique employs a Waters liquid chromatography system equipped with a detector. This detector is a Waters 2414 type refractometric concentration detector. This liquid chromatography system is equipped with two size exclusion columns to separate the different molecular weights of the polymers or compounds studied. The elution liquid phase is an organic phase composed of THF (HPLC grade, unstabilized).

[0025] In a first step, approximately 25 mg of the compound is solubilized in 5 mL of THF, to which 0.1 mol% water is added as an internal flow marker. The solution is then filtered to 0.2 µm. 50 pL is then injected into the chromatography apparatus (eluent: THF, HPLC grade, unstabilized).

[0026] The liquid chromatography apparatus includes an isocratic pump (Waters 515) with a flow rate set at 0.3 mL / min. The chromatography apparatus also includes a furnace comprising a series column system: a 250 mm long and 4.6 mm diameter Agilent PLgel MiniMIX-A column followed by a 250 mm long and 4.6 mm diameter Agilent PLgel MiniMIX-B column. The detection system consists of a Waters 2414 RI refractometer detector. The columns are maintained at 35°C and the refractometer is also heated to 35°C.

[0027] The chromatography apparatus is calibrated using polymethyl methacrylate standards certified by the supplier “Agilent” (“EasiVial” PMMA).

[0028] According to the invention, the compound (b) can be used in various forms, liquid or solid, preferably solid at a temperature above 25°C. In solid form, the compound (b) can take various forms, for example in a form selected from pellet, flake, crushed, chip, powder and combinations thereof.

[0029] Essentially, according to the invention, compound (b) has a very high degree of purity, particularly with regard to the presence of volatile organic compounds, notably residual volatile organic compounds from the processes used in its preparation. Thus, compound (b) produced according to the invention comprises zero or a particularly low amount of alkanes, aromatic hydrocarbon compounds, or alkenes.

[0030] According to the invention, the quantities of residual compounds are measured using widely available and easy-to-implement techniques. In fact, particularly advantageously according to the invention, the quantities of residual compounds are measured by gas chromatography coupled with mass spectrometry (GC-MS). The chromatograph used is equipped with a mass spectrometer as a detector. According to the invention, the GC-MS measurement comprises the injection into the chromatograph, at a regulated temperature, of the compound (b) to be analyzed then the separation of the different volatile compounds by means of a capillary column then the detection of possible residual volatile compounds by means of a mass spectrometer and the analytical processing of the detection peaks.

[0031] Thus, the compound (b) implemented according to the invention comprises an amount of at least one compound selected from alkanes, aromatic hydrocarbon compounds, alkenes and their combinations, measured by GC-MS, which is less than 0.5 ppm by weight of compound (b).

[0032] Preferably according to the invention, compound (b) comprises an amount of alkanes that is less than 0.5 ppm by weight of compound (b). Also preferably according to the invention, compound (b) comprises an amount of aromatic hydrocarbon compounds that is less than 0.5 ppm by weight of compound (b). Also preferably according to the invention, compound (b) comprises an amount of alkenes that is less than 0.5 ppm by weight of compound (b).

[0033] More preferably according to the invention, the compound (b) comprises an amount of alkanes less than 0.2 ppm by weight, preferably an amount less than 0.1 ppm by weight or even zero, measured by GC-MS.

[0034] Preferably, the alkanes according to the invention are chosen from among the C3-C2o-alkanes, in particular the C7-Ci4-alkanes.

[0035] Also more preferably according to the invention, the compound (b) comprises an amount of aromatic hydrocarbon compounds less than 0.2 ppm by weight, preferably an amount less than 0.1 ppm by weight or even a zero amount, measured by GC-MS.

[0036] Also preferably, the aromatic hydrocarbon compounds according to the invention are chosen from toluene, benzene, xylene, naphthalene and their combinations.

[0037] Also more preferably according to the invention, the compound (b) comprises

[0038] an amount of alkenes less than 0.2 ppm by weight, preferably an amount less than 0.1 ppm by weight or even zero, measured by GC-MS.

[0039] Also preferably, the alkenes according to the invention are chosen from among the C7-Ci 4-alkenes and their combinations.

[0040] In a particularly preferred manner according to the invention, compound (b) therefore comprises no alkane, no aromatic hydrocarbon compound, or no alkene. More preferably according to the invention, compound (b) comprises neither an alkane, nor an aromatic hydrocarbon compound, nor an alkene.

[0041] According to the invention, a zero quantity of a compound, in particular a compound selected from alkanes, aromatic hydrocarbon compounds or alkenes, characterizes both The total absence of this compound is equivalent to its presence in an analytically insignificant quantity. The limits of quantification generally accepted by analytical techniques for this compound therefore characterize its absence within compound (c) implemented according to the invention.

[0042] During the preparation of the copolymer P according to the invention, the amounts of compounds (a) and (b) may vary. Preferably, the method according to the invention comprises a polymerization reaction that uses 20 to 75 mol%, preferably 35 to 75 mol%, of compound (a) relative to the total mol% of compounds (a) and (b). Also preferably, the method according to the invention comprises a polymerization reaction that uses 25 to 80 mol%, preferably 25 to 65 mol, of compound (b) relative to the total mol% of compounds (a) and (b).

[0043] More preferably, the method according to the invention comprises a polymerization reaction which implements: - 20 to 75 mol% of compound (a) and - 25 to 80 mol% of compound (b), relative to the total molar amount of compounds (a) and (b).

[0044] More preferably, the method according to the invention comprises a polymerization reaction which implements: - 35 to 75 mol% of compound (a) and - 25 to 65 mol% of compound (b), relative to the total molar amount of compounds (a) and (b).

[0045] In addition to compounds (a) and (b), the preparation method according to the invention also includes the possibility of using other compounds during the polymerization reaction.

[0046] Thus, the preparation method according to the invention may also include a polymerization reaction which also uses at least one compound (c) of formula III: [Chem III] HO-Q1 (III) in which Q1 independently represents a group chosen from a linear C4-C40-alkyl group, a branched C4-C40-alkyl group, a C5-C40-cycloalkyl group, a C5-C40-aryl group and their combinations.

[0047] The invention also relates to a method of preparing a copolymer Pa comprising the polymerization reaction of at least one compound (a), at least one compound (b) and at least one compound (c).

[0048] Preferably according to the invention, compound (c) is a compound of formula III in which Q1 independently represents a linear C4-C36-alkyl group, a branched C4-C36-alkyl group or a C5-C36-aryl group; preferably a linear C6-C36-alkyl group, a branched C6-C36-alkyl group or a C6-C36-aryl group; more preferably a linear C6-C24-alkyl group, a branched C6-C24-alkyl group or a C6-C24-aryl group.

[0049] Also preferably according to the invention, the polymerization reaction uses less than 40 mol%, preferably from 0.1 to 40 mol%, in particular from 0.5 to 35 mol%, of compound (c) relative to the total mol amount of monomers.

[0050] Preferably according to the invention, during the preparation of the Pa copolymer, the polyalkoxyl polyhydroxyl compound (b) is used in a molar quantity providing a number of hydroxyl groups (OH) less than the number of halides provided by the compound (a).

[0051] The use of a base during the implementation of the preparation method according to the invention can allow the alkoxide derivative of the monoalcohol (c) to be obtained. Prior preparation of the alkoxide derivative of compound (c) can also allow its direct introduction. It can therefore also be stored separately and then introduced during the implementation of the preparation method according to the invention. The preparation method according to the invention may also include a polymerization reaction that also uses at least one compound selected from a compound (d) of formula IV: [Chem IV]XT (IV) in which: - X independently represents Cl, Br or I - T independently represents a group chosen from a linear C4-C40-alkyl group, a branched C4-C40-alkyl group, a C5-C40-cycloalkyl group, a C5-C40-aryl group and their combinations.

[0052] The invention also relates to a method of preparing a Pb copolymer comprising the polymerization reaction of at least one compound (a), at least one compound (b) and at least one compound (d).

[0053] Preferably according to the invention, compound (d) is a compound of formula IV in which: - X represents Br or Cl, preferably Br, or - T independently represents a linear C4-C36-alkyl group, a branched C4-C36-alkyl group or a C5-C36-aryl group; preferably a linear C6-C36-alkyl group, a branched C6-C36-alkyl group or a C6-C36-aryl group; more preferably a linear C6-C24-alkyl group, a branched C6-C24-alkyl group or a C6-C24-aryl group.

[0054] Also preferably according to the invention, the polymerization reaction uses less than 60 mol%, preferably from 0.1 to 60 mol%, in particular from 0.5 to 55 mol%, of compound (d) relative to the total mol amount of monomers.

[0055] Preferably according to the invention, during the preparation of the Pb copolymer, the polyalkoxy polyhydroxy compound (b) is used in a molar quantity providing a number of hydroxyl groups (OH) greater than the number of halides provided by the compound (a).

[0056] The preparation method according to the invention may also include a polymerization reaction which also employs at least one compound selected from a hydrophobic compound (e) of formula V: [Chem V] R1-(OE)q-(OP)r-OH (V) in which: - q and r, whether identical or different, independently represent 0 or an integer or decimal number less than 150; q is not equal to 0. - OE independently represents a CH2CH2O group, - OP independently represents a group chosen from CH(CH3)CH2O and CH2CH(CH3)O, - R1 independently represents a group chosen from a linear C4-C40-alkyl group, a branched C4-C40-alkyl group, a C5-C40-cycloalkyl group, a C5-C40-aryl group and their combinations.

[0057] The invention also relates to a method of preparing a Pc copolymer comprising the polymerization reaction of at least one compound (a), at least one compound (b) and at least one compound (e).

[0058] Preferably according to the invention, compound (e) is a compound of formula V in which: - r represents 0; or - R1 represents a linear or branched C6-C40-alkyl group, a phenyl group, a polyphenyl group, preferably a linear or branched Ci0-C30-alkyl group, more preferably a linear or branched Ci2-C22-alkyl group, or a group comprising 2 to 5 phenyls or a tristyrylphenyl group or a pentastyrylcumylphenyl group.

[0059] Also preferably according to the invention, the polymerization reaction uses less than 20 mol%, preferably from 0.05 to 20 mol%, in particular from 0.1 to 10 mol%, of compound (e) relative to the total mol amount of monomers.

[0060] During the preparation of the copolymer P according to the invention from at least one compound (c), (d) and (e), the quantities of these compounds may vary.

[0061] Preferably, the method according to the invention comprises a polymerization reaction which implements: - from 20 to 74.9 mol% or from 25 to 69.5 mol% of compound (a) or - from 25 to 79.9 mol% or from 30 to 74.5 mol% of compound (b), or - from 0.1 to 55 mol% or from 0.5 to 45 mol% of a compound selected from compound (c), compound (d), compound (e) and their combinations,

[0062] with respect to the total molar quantity of compounds (a), (b), (c), (d) and (e).

[0063] More preferably, the method according to the invention comprises a polymerization reaction which implements: - 30 to 68 mol% or 35 to 60 mol% of compound (a) or - 30 to 68 mol% or 35 to 60 mol% of compound (b), or - from 2 to 40 mol% or from 5 to 30 mol%, of a compound chosen from compound (c), compound (d), compound (e) and their combinations, compared to the total molar quantity of compounds (a), (b), (c), (d) and (e).

[0064] More preferably, the method according to the invention comprises a polymerization reaction which implements: - from 20 to 74.9 mol% or from 25 to 69.5 mol%, preferably from 30 to 68 mol% or from 35 to 60 mol%, of compound (a), - from 25 to 79.9 mol% or from 30 to 74.5 mol%, preferably from 30 to 68 mol% or from 35 to 60 mol%, of compound (b), and - from 0.1 to 55 mol% or from 0.5 to 45 mol%, preferably from 2 to 40 mol% or from 5 to 30 mol%, of a compound selected from compound (c), compound (d), compound (e) and their combinations, compared to the total molar quantity of compounds (a), (b), (c), (d) and (e).

[0065] The preparation method according to the invention makes it possible to obtain the copolymer P or the copolymers Pa, Pb, and Pc. During the preparation of these copolymers, the compound (b) used comprises a small or zero amount of alkanes, aromatic hydrocarbon compounds, or alkenes. Prior to the polymerization reaction, the invention makes it possible to select the compound (b) according to the amount of alkanes, aromatic hydrocarbon compounds, or alkenes that it can possibly understand. Thus, the invention provides a method for preparing a copolymer according to the invention which also includes the pre-polymerization reaction selection of the polyhydroxylated compound (b) comprising the measurement by GC-MS of the amount Q of at least one compound selected from alkanes, aromatic hydrocarbon compounds, alkenes and their combinations, then: - the implementation of compound (b) if the quantity Q is zero or - the elimination of compound (b) if the quantity Q is non-zero or if it is greater than 0.5 ppm by weight of compound (b).

[0066] The implementation of the GC-MS measurement makes it possible to determine the quantity of at least one compound chosen from alkanes, aromatic hydrocarbon compounds, alkenes and their combinations, which may be present in compound (b). The invention provides a method for selecting a polyhydroxylated compound (b) comprising measuring by GC-MS the quantity Q of at least one compound chosen from alkanes, aromatic hydrocarbon compounds, alkenes and their combinations, then: - implementing compound (b) if the quantity Q is zero or - eliminating compound (b) if the quantity Q is non-zero.

[0067] The selection method according to the invention includes an elimination step which may be total or partial, in particular depending on the quantity present within the compound (b) of the eventual compound chosen from alkanes, aromatic hydrocarbon compounds, alkenes and their combinations.

[0068] The preparation method according to the invention is particularly effective for obtaining a copolymer P comprising a reduced or zero amount of alkanes, aromatic hydrocarbon compounds, or alkenes. The invention also provides a copolymer P prepared according to the preparation method of the invention. Preferably, the copolymer P according to the invention comprises an amount of at least one compound selected from alkanes, aromatic hydrocarbon compounds, alkenes, and their combinations, measured by GC-MS, which is less than 0.5 ppm by weight of compound (b), more preferably an amount less than 0.1 ppm by weight of compound (b), or even zero of the compound selected from alkanes, aromatic hydrocarbon compounds, alkenes, and their combinations.

[0069] The invention also provides a Pa, Pb or Pc copolymer prepared according to the preparation method of the invention. Preferably, the Pa, Pb or Pc copolymer according to the invention comprises an amount of at least one compound selected from alkanes, aromatic hydrocarbon compounds, alkenes and their combinations, measured by GC-MS, which is less than 0.5 ppm by weight of compound (b), more preferably an amount less than 0.1 ppm by weight of compound (b) or even a zero amount of compound selected from alkanes, aromatic hydrocarbon compounds, alkenes and their combinations.

[0070] The copolymer P according to the invention is particularly useful for controlling the rheology of aqueous compositions. The invention provides a method for preparing a rheology-modifying agent comprising preparing a copolymer P according to the invention and mixing the copolymer P with at least one compound selected from a solvent, in particular water or a coalescing solvent, for example glycol, butyl glycol, butyldiglycol, monopropylene glycol, ethylene glycol, ethylenediglycol, "Dowanol" products of which CAS number is 34590-94-8, "Texanol" products of which CAS number is 25265-77-4.

[0071] In particular within the rheology modifying agent, the copolymer P can be combined with at least one additive selected from an amphiphilic compound, in particular a surfactant compound, preferably a hydroxylated surfactant compound, for example alkyl-polyalkyleneglycol, in particular alkyl-polyethyleneglycol and alkyl-polypropyleneglycol; a polysaccharide derivative, for example cyclodextrin, cyclodextrin derivative, polyethers, alkyl-glucosides; a hydrotropic compound, an antifoaming agent, a biocidal agent and combinations thereof.

[0072] Preferably according to the invention, the rheology modifying agent comprises a copolymer P according to the invention and at least one substance of natural origin, in particular a substance selected from a naturally sourced hydroxylated surfactant compound, for example alkyl-polyalkyleneglycol, in particular alkyl-polyethylene glycol; a polysaccharide derivative, for example cyclodextrin, cyclodextrin derivative, polyethers, alkyl-glucosides and their combinations.

[0073] The invention also relates to an aqueous formulation comprising: - at least one copolymer P or at least one rheology-modifying agent according to the invention and, optionally, - 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 stabilizing agent, an electrostatic stabilizing agent, 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. Preferably, the aqueous formulation according to the invention is a coating formulation, in particular an ink formulation, a varnish formulation, an adhesive formulation, or a paint formulation, for example, decorative or industrial paint.

[0074] The invention also 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.

[0075] Particularly advantageously, the rheology-modifying agent according to the invention can be used in aqueous media. The invention thus provides an aqueous composition comprising at least one copolymer P according to the invention and at least one rheology-modifying agent according to the invention. Preferably, according to the invention, this composition is a coating composition, in particular a paint or varnish, or a paper coating composition, or a cosmetic composition, or a detergent composition, or an adhesive composition.

[0076] The copolymer P prepared according to the invention possesses particularly effective rheological control properties for aqueous compositions. The invention provides a method for controlling the viscosity of an aqueous composition comprising adding to this composition at least one copolymer P according to the invention.

[0077] The advantageous, particular or preferred characteristics of the preparation method according to the invention define copolymers P, aqueous compositions, formulations, pigment pastes as well as selection methods and viscosity control methods according to the invention which are also advantageous, particular or preferred.

[0078] The following examples illustrate the different aspects of the invention. EXAMPLES

[0079] Example 1: Preparation and characterization of PI to P3 copolymers according to the invention

[0080] The compounds used are chosen from: - dihalogenated compound (a): dibromomethane, compound (aa), - compound (b): compound (bla) of formula II in which L represents an oxyethylene residue and n represents approximately 225 (Polyglycol 10,000 SG Vita "Clariant"), - compound (c): compound (ca) of formula III in which Q1 represents an n-dodecanyl group, - compound (d): compound (da) of formula IV in which X represents a bromide and T represents an n-dodecanyl group.

[0081] The compound (bla) is analyzed by GC-MS using a gas chromatograph (“Agilent” 7890B) comprising a headspace injector (“Agilent” 7967A) and a mass spectrometer (“Agilent” 5977B) as detector.

[0082] A 2 g sample of compound is placed in a 2 mL vial (with headspace) and injected into the chromatograph. After detection and processing of the compound peaks in the sample, besides compound (cia), the presence of the compounds detailed in Table 1 is characterized.

[0083] [Table 1] | pti's V'CXS compounds. i acetic acid Md 6 ” y op O?: | L3-dmoLme V 4 OQ J UR'kî' -.w ethanol 109-86-4 * 2 84 2 - uuthy Uimolme 497-26-7 l 44X *55 5'6 441 'acetone 5^78-1^-3 I2o 229 momd- a mate « dycol t: f: 5 lo 091 eth\ km?

[0084] In a 2 L reactor, 391.3 g of compound (bla), 9.3 g of sodium hydroxide, and 0.6 g of water are mixed for 60 min at 60°C. Then, 5.1 g of compound (aa) are added. The temperature is increased to 100°C, and stirring is continued for 120 min. The PI polymer according to the invention is obtained.

[0085] In a 2L reactor, 187.5g of compound (bla), 4.4g of sodium hydroxide, and 0.12g of water are mixed for 60 min at 60°C. Then, 2.45g of compound (aa) are added. The temperature is increased to 100°C and stirring is continued for 120 min. Next, 9.34g of compound (da) are added, with stirring maintained for 120 min at 110°C. The polymer P2 according to the invention is obtained.

[0086] In a 2L reactor, 182.3g of compound (bla), 6.2g of compound (ca), 8.6g of sodium hydroxide, and 1.0g of water are mixed for 90 min at 75°C. Then, 8.1g of compound (aa) are added while maintaining stirring for 120 min at 110°C. The P3 polymer according to the invention is obtained.

[0087] Example 2: Preparation and characterization of rheology modifying agents MRI to MR3 according to the invention

[0088] The PI polymer of Example 1 is cooled to 60°C and then mixed with 594g of water to obtain the rheology modifying agent MRI according to the invention.

[0089] Similarly, the rheology modifying agent MR2 according to the invention is prepared by mixing the polymer P2 with 796.2g of water and acetic acid to achieve a pH of 7 + / - 0.5.

[0090] Similarly, the rheology modifying agent MR3 according to the invention is prepared by mixing the P3 polymer with 785g of water and acetic acid to achieve a pH of 7 + / - 0.5.

[0091] For each rheology-modifying agent, the resulting low-gradient viscosity is determined: Brookfield viscosity at 100 rpm (mobile #6), denoted VB (mPa·s). These measurements are taken 24 hours after preparation of the agent. The agents are thermostated at 25 ± 0.5°C. The results are presented in Table 2.

[0092] [Table 2] Agent Vh f mP.î Q i [liltZ............ i. 1.520 'J ' i no MR3............................................... 2,236........................]

[0093] Example 3: Preparation and characterization of aqueous coating compositions from CRI to CR3 according to the invention

[0094] Each composition is prepared by mixing the different ingredients. The ingredients and quantities (in g) are detailed in Table 3.

[0095] [Table 3] Ingredients of the waterborne paint formulation Quantity (g) Ecodis P50 (dispersant Coatex) 2.00 Tego 810 (antifoam Tego) 0.51 Acticide MBS (bactericide Thor) 1.00 TiONa 568 (TiO2 Tronox) 40.01 Omyacoat 850 OG (CaCO3 Omya) 110.00 Durcal 2 AV (CaCO3 Omya) 150.29 Acronal S790 (binder BASF) 65.00 Monopropylene glycol 5.06 Texanol (coalescing agent Eastman) 5.02 NaOH (20 wt% in water) 0.41 MRI to MR3 agent (40 wt% PI or 20 wt% P2 and P3) 4.70 Water 116.00 Total 500.00

[0096] For each composition, the resulting viscosities are determined at different velocity gradients: - at low gradient: Brookfield viscosities at 10 rpm and 100 rpm, respectively denoted VB10 and VB100 (mPa.s), - at medium gradient: Stormer viscosity (Krebs Unit, KU), HERE (mPa.s) 210 110 - at high gradient: viscosity HERE (mPas.s).

[0097] These measurements are taken 24 hours after preparation of the formulation. The formulations are thermostated at 25 ± 0.5°C. The results are presented in Table 4.

[0098] [Table 4] (on'pOMhonx Viscosities) § ><ix aàu m XB'Ounra-} \ R b»1’ v'd'a Si> m u kl s « R? I''"! t ■ î oun ; xï "R t J 44o : : 7,t

[0099] The copolymers according to the invention make it possible to effectively thicken a solvent-free matte paint at different shear gradients.

[0100] In the field of water-based paints, a high viscosity at a low or medium shear gradient indicates good static behavior. This ensures good stability during storage while preventing sedimentation and limiting the tendency to run on vertical surfaces.

[0101] These paint compositions do not include VOCs from the polyhydroxylated compound used in the preparation of the copolymer according to the invention.

Claims

Demands

1. Method of preparing a copolymer P comprising the polymerization reaction of: a) at least one dihalogenated compound (a) of formula I: [Chem I] (CH2)-R2 (I) in which R independently represents Cl, Br or I; b) at least one polyalkoxylated, polyhydroxylated compound (b) comprising an amount of at least one compound selected from alkanes, aromatic hydrocarbon compounds, alkenes and their combinations, measured by GC-MS, which is less than 0.5 ppm by weight of compound (b).

2. Method according to claim 1 wherein: * the polymerization reaction uses a single compound (a) or 2 or 3 different compounds (a); or * compound (a) is a compound of formula I in which R independently represents Br or Cl, preferably Br; or * compound (a) is selected from dibromomethane, diiodomethane and their combinations.

3. A method according to any one of claims 1 or 2 wherein compound (b) is selected from: * a compound (bl) of formula II: [Chem II] HO-Ln-OH (II) in which: - L independently represents an oxyalkylene residue; - n independently represents a number from 30 to 1000; * a compound (bl) of formula II associated with a non-alkoxy compound (b2) comprising at least 3 hydroxyl groups; * a polyalkoxy compound (b3) comprising at least 3 hydroxyl groups; * combinations thereof.

4. A method according to any one of claims 1 to 3 wherein compound (b) is selected from: * a compound (bl) of formula II: [Chem II] HO-Ln-OH (II) wherein: - L independently represents an oxyethylene residue; or - n independently represents a number from 50 to 400, preferably from 100 to 300; preferably L independently represents an oxyethylene residue and n independently represents a number from 50 to 400, preferably from 100 to 300; * a compound (b2) comprising 3 hydroxyl groups, preferably a compound (b2) selected from glycerol, pentaerythritol and their combinations; * polyethoxylated pentaerythritol or a polyalkoxylated compound (b3) different from compound (b2) and comprising 3 hydroxyl groups, preferably a compound (b3) which is polyethoxylated glycerol, .

5. A method according to any one of claims 1 to 4 wherein: * compound (b) comprises from 70 to 500 alkoxylations, preferably from 80 to 400 alkoxylations or from 100 to 300 alkoxylations, more preferably from 100 to 250 alkoxylations, or * compound (b) is polyethoxylated or is polyethoxylated-polypropoxylated or is polyethoxylated-polybutoxylated, preferably compound (b) is polyethoxylated, or * compound (b) comprises from 70 to 500 ethoxylations, preferably from 80 to 400 ethoxylations or from 100 to 300 ethoxylations, more preferably from 100 to 250 ethoxylations.

6. Method according to any one of claims 1 to 5 wherein compounds (b), (bl) or (b3) independently have a molar mass (Mw) measured by CES ranging from 1,500 to 80,000 g / mol, preferably from 2,000 to 20,000 g / mol, more preferably from 2,000 to 15,000 g / mol or from 2,000 to 12,000 g / mol.

7. A method according to any one of claims 1 to 6, wherein compound (b) comprises: * an amount less than 0.2 ppm by weight, preferably an amount less than 0.1 ppm by weight or even zero, measured by GC-MS, of alkanes, in particular C3-C2o-alkanes, or * an amount less than 0.2 ppm by weight, preferably less than 0.1 ppm by weight or even zero, measured by GC-MS, of aromatic hydrocarbon compounds, in particular aromatic hydrocarbon compounds selected from toluene, benzene, xylene, naphthalene and their combinations, or * an amount less than 0.2 ppm by weight, preferably less than 0.1 ppm by weight or even zero, measured by GC-MS, of alkenes, in particular C7-Ci4-alkenes.

8. Method according to any one of claims 1 to 7 wherein the polymerization reaction employs: - 20 to 75 mol%, preferably 35 to 75 mol%, of compound (a) or - 25 to 80 mol%, preferably 25 to 65 mol%, of compound (b), relative to the total molar amount of compounds (a) and (b).

9. A method according to any one of claims 1 to 8, wherein the polymerization reaction also incorporates at least one compound selected from: a) a compound (c) of formula III: [Chem III]HO-Q1(III) in which Q1 independently represents a group selected from a linear C4-C40-alkyl group, a branched C4-C40-alkyl group, a C5-C40-cycloalkyl group, a C5-C40-aryl group, and combinations thereof; b) a compound (d) of formula IV: [Chem IV]XT(IV) in which: - X independently represents Cl, Br, or I, - T independently represents a group selected from a linear C4-C40-alkyl group, a branched C4-C40-alkyl group, a C5-C40-cycloalkyl group, a C5-C40-aryl group, and combinations thereof; or (c) a hydrophobic compound (e) of formula V: [Chem V] R1-(OE)q-(OP)r-OH (V) in which: - q and r, identical or different, independently represent 0 or an integer or decimal number less than 150, q is different from 0, - OE independently represents a CH2CH2O group, - OP independently represents a group chosen from CH(CH3)CH2O and CH2CH(CH3)O, - R1 independently represents a group chosen from a linear C4-C40-alkyl group, a branched C4-C40-alkyl group, a C5-C40-cycloalkyl group, a C5-C40-aryl group and their combinations.

10. Method according to claim 9 wherein: * compound (c) is a compound of formula III in which Q1 independently represents a linear C4-C36-alkyl group, a branched C4-C36-alkyl group or a C5-C36-aryl group; preferably a linear C6-C36-alkyl group, a branched C6-C36-alkyl group or a C6-C36-aryl group; more preferably a linear C6-C24-alkyl group, a branched C6-C24-alkyl group or a C6-C24-aryl group; or * the polymerization reaction involves less than 40 mol%, preferably from 0.1 to 40 mol%, in particular from 0.5 to 35 mol%, of compound (c) relative to the total mol% of monomers; or * compound (d) is a compound of formula IV in which: - X represents Br or Cl, preferably Br, or - T independently represents a linear C4-C36-alkyl group, a branched C4-C36-alkyl group or a C5-C36-aryl group;preferably a linear C6-C36-alkyl group, a branched C6-C36-alkyl group or a C6-C36-aryl group; more preferably a linear C6-C24-alkyl group, a branched C6-C24-alkyl group or a C6-C24-aryl group; or * the polymerization reaction involves less than 60 mol%, preferably from 0.1 to 60 mol%, in particular from 0.5 to 55%; molar, of compound (d) relative to the total molar amount of monomers; or * compound (e) is a compound of formula V in which: - r represents 0; or - R1 represents a linear or branched C6-C40-alkyl group, a phenyl group, a polyphenyl group, preferably a linear or branched Cio-C3O-alkyl group, more preferably a linear or branched Ci2-C22-alkyl group, or a group comprising 2 to 5 phenyls or a tristyrylphenyl group or a pentastyrylcumylphenyl group; or * the polymerization reaction involves less than 20 mol%, preferably from 0.05 to 20 mol%, in particular from 0.1 to 10 mol%, of compound (e) relative to the total molar amount of monomers.

11. A method according to any one of claims 9 or 10 wherein the polymerization reaction involves: - 20 to 74.9 mol% or 25 to 69.5 mol%, preferably 30 to 68 mol% or 35 to 60 mol%, of compound (a) or - 25 to 79.9 mol% or 30 to 74.5 mol%, preferably 30 to 68 mol% or 35 to 60 mol%, of compound (b), or - 0.1 to 55 mol% or 0.5 to 45 mol%, preferably 2 to 40 mol% or 5 to 30 mol%, of a compound selected from compound (c), compound (d), compound (e) and combinations thereof, relative to the total mol% of compounds (a), (b), (c), (d) and (e).

12. Method according to any one of claims 1 to 11 comprising the pre-reaction selection of the polyhydroxylated compound (b) comprising the measurement by GC-MS of the quantity Q of at least one compound selected from alkanes, aromatic hydrocarbon compounds, alkenes and their combinations, then: - the implementation of the compound (b) if the quantity Q is zero or - the elimination of the compound (b) if the quantity Q is non-zero or if it is greater than 0.5 ppm by weight of compound (b).

13. Copolymer P prepared according to the preparation method of any one of claims 1 to 12, preferably a copolymer P comprising an amount of at least one compound selected from alkanes, aromatic hydrocarbon compounds, alkenes and their combinations, measured by GC-MS, which is less than 0.5 ppm by weight of compound (b), more preferably an amount less than 0.1 ppm by weight of compound (b) or even a zero amount of compound chosen from alkanes, aromatic hydrocarbon compounds, alkenes and their combinations.

14. Method of preparing a rheology modifying agent comprising: * the preparation of a copolymer P defined according to any one of claims 1 to 13, * the mixing of the copolymer P with at least one compound selected from a solvent, in particular water or a coalescing solvent, for example glycol, butyl glycol, butyldiglycol, monopropylene glycol, ethylene glycol, ethylenediglycol, Dowanol products of which CAS number 34590-94-8, Texanol products of which CAS number 25265-77-4 or with at least one additive selected from an amphiphilic compound, in particular a surfactant compound, preferably a hydroxylated surfactant compound, for example alkyl-polyalkylene glycol, in particular alkyl-polyethylene glycol and alkyl-polypropylene glycol; a polysaccharide derivative, for example cyclodextrin, cyclodextrin derivative, polyethers, alkyl-glucosides; a hydrotropic compound, an antifoaming agent, a biocidal agent and combinations thereof.

15. Rheology modifying agent comprising a copolymer P defined according to any one of claims 1 to 13 and at least one substance of natural origin, in particular a substance selected from a hydroxylated surfactant compound of natural origin, for example alkyl-polyalkyleneglycol, in particular alkyl-polyethylene glycol; a polysaccharide derivative, for example cyclodextrin, cyclodextrin derivative, polyethers, alkyl-glucosides and combinations thereof.

16. Aqueous composition comprising at least one copolymer P defined according to any one of claims 1 to 13 and at least one rheology modifying agent according to claim 15.

17. Composition according to claim 16 which is a coating composition, in particular of paint or varnish, or a paper coating composition or a cosmetic composition or a detergent composition or an adhesive composition.

18. Method for controlling the viscosity of an aqueous composition comprising adding to this composition at least one copolymer P defined according to any one of claims 1 to 13.

19. Method for selecting a polyhydroxylated compound (b) comprising measuring by GC-MS the quantity Q of at least one compound selected from alkanes, aromatic hydrocarbon compounds, alkenes and their combinations, then: - implementing the compound (b) in the method according to any one of claims 1 to 11 if the quantity Q is zero or - eliminating the compound (b) if the quantity Q is non-zero.