Voc-free urethane copolymer

Abstract

The invention relates to a process for preparing a urethane copolymer using a polyalkoxylated and polyhydroxylated compound which does not contain any volatile residue of alkanes, aromatic hydrocarbon compounds or alkenes. The copolymer according to the invention is useful as an agent for controlling rheology in an aqueous medium, in particular for paint compositions, for paper coating slips or for cosmetic compositions.

Description

[0001] VOC-FREE URETHANE COPOLYMER

[0002] The invention relates to a method for preparing a urethane copolymer using a polyalkoxylated and polyhydroxylated compound which does not comprise a volatile residue of alkanes, a volatile residue of aromatic hydrocarbon compounds or a volatile residue of alkenes. The copolymer according to the invention is useful as a rheology control agent in aqueous medium, in particular for paint compositions, for paper coating colors or for cosmetic compositions.

[0003] Generally speaking, for aqueous coating compositions, and in particular for aqueous paint or varnish compositions, it is necessary to control the viscosity for both low or medium shear rates and high shear rates. Indeed, during its preparation, storage, application or drying, a paint formulation undergoes numerous constraints requiring particularly complex rheological properties. A high viscosity of the paint formulation must be sought at high shear rates. A reduced viscosity at low or medium shear rates will also allow a good taut appearance to be obtained after application of the paint. In addition, in order not to form drips, it is necessary for the paint formulation to have a high viscosity at low and medium shear rates.In order for the paint to have a high levelling capacity after being deposited on a surface, a reduced viscosity at low and medium shear gradients of the paint formulation is required.

[0004] Furthermore, when preparing paper coating colors, it is also necessary to improve the viscosity under low shear gradient, while improving the 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 gradient, that is well suited to effective application.

[0005] Also, when preparing aqueous cosmetic compositions, rheology control is an essential property. Indeed, the viscosity of these cosmetic compositions must be controlled at the time of their preparation, transport or storage, but also at the time of their application. The use of these aqueous cosmetic compositions, particularly on the skin or hair, requires properties that are often very specific from a rheological point of view as well as from a safety point of view.

[0006] The compatibility of the various constituents of an aqueous composition with controlled rheology 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, in particular alkanes, aromatic hydrocarbon compounds or alkenes. These compounds should not be present in the ingredients used for the preparation of paint or varnish compositions or used for the preparation of paper coating colors. In particular, rheological control agents and the compounds used for their preparation should contain only negligible or minor amounts of alkane residue, aromatic hydrocarbon compound residue or alkene residue.In particular, the presence of such compounds must be absolutely controlled in order to avoid their release during the implementation of paint or varnish compositions or during the manufacture of paper or packaging, and in particular during the manufacture of paper or packaging for food products.

[0007] Controlling the possible presence of such compounds is therefore essential to ensure the final quality of the aqueous compositions used. This control should therefore be effective while being simple to carry out, using widely accessible techniques.

[0008] EP 0889100 discloses a thickening associative polyurethane compound. WO 2007048766A2 describes compositions comprising an associative polyurethane thickener and ethoxylated mono- or diglycerides of carboxylic acids. WO 2019091819 describes a composition comprising a polyurethane prepared using a particular Guerbet alcohol which is combined with a particular surfactant compound. WO 2018073545 describes a rheological control agent comprising a polyurethane prepared in the absence of a diisocyanate compound. There is therefore a need for a method for 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.

[0009] The invention therefore provides a method for preparing a copolymer P comprising the polymerization reaction: a) of at least one isocyanate compound (a) independently chosen from a diisocyanate compound (a1), a polyisocyanate compound (a2) and combinations thereof; b) of at least one compound (b) of formula I:

[0010] R-(X) m -OH (I) in which:

[0011] - R independently represents a group chosen from a linear C4-C40-alkyl group, a branched C4-C40-alkyl group, a Cs-C40-cycloalkyl group, a Cs-C40-aryl group and combinations thereof,

[0012] - m represents 0 or a number ranging from 1 to 200,

[0013] - X independently represents an alkoxylated group chosen from oxyethylene, oxypropylene, oxybutylene and combinations thereof; c) at least one polyalkoxylated polyhydroxylated compound (c) comprising an amount of at least one compound chosen from alkanes, aromatic hydrocarbon compounds, alkenes and combinations thereof, measured by GC-MS, which is less than 0.5 ppm by weight of compound (c).

[0014] The method according to the invention comprises the use of compound (a) during 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).

[0015] Preferably according to the invention, the compound (a) is a diisocyanate compound (al) chosen from:

[0016] - symmetrical aromatic diisocyanate compounds, preferably:

[0017] . 2,2'-diphenylmethylene diisocyanate (2,2'-MDI) and 4,4'-diphenylmethylene diisocyanate (4,4'-MDI);

[0018] . 4,4'-dibenzyl diisocyanate (4,4'-DBDI);

[0019] . toluene 2,6-diisocyanate (2,6-TDI);

[0020] . m-xylylene diisocyanate (m-XDI); - symmetrical alicyclic diisocyanate compounds, preferably methylene bis(4-cyclohexylisocyanate) (H12MDI);

[0021] - symmetrical aliphatic diisocyanate compounds, preferably hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI);

[0022] - asymmetric aromatic diisocyanate compounds, preferably:

[0023] . 2,4'-diphenylmethylene diisocyanate (2,4'-MDI);

[0024] . 2,4'-dibenzyl diisocyanate (2,4'-DBDI);

[0025] . toluene 2,4-diisocyanate (2,4-TDI);

[0026] - asymmetric alicyclic diisocyanate compounds, preferably isophorone diisocyanate (IPDI).

[0027] More preferably according to the invention, the compound (al) is chosen from IPDI, HDI, H12MDI and their combinations.

[0028] Also preferably according to the invention, the compound (a) is a polyisocyanate compound (a2) strictly comprising more than 2 isocyanate functions or more than 2.2 isocyanate functions or even more than 2.5 isocyanate functions. More preferably, the polyisocyanate compound (a2) comprises more than 2.6 isocyanate functions or more than 2.7 isocyanate functions or more than 3 isocyanate functions; more preferably, the polyisocyanate compound (a2) comprises from 2.2 to 6 isocyanate functions, from 2.2 to 4 isocyanate functions, from 2.2 to 3.5 isocyanate functions, from 2.5 to 6 isocyanate functions, from 2.2 to 5 isocyanate functions, from 2.5 to 4 isocyanate functions, from 2.5 to 3.5 isocyanate functions, in particular from 2.6 to 3.3 isocyanate functions.

[0029] Also preferably according to the invention, compound (a) is a polyisocyanate (a2) chosen from:

[0030] . triphenylmethane-4,4',4”-triisocyanate or l,l',l”-methylidynetris (4-isocyanatobenzene); Or

[0031] * an isocyanurate compound, in particular an isocyanurate compound of a compound chosen from:

[0032] * symmetrical aromatic diisocyanate compounds, preferably:

[0033] . 2,2'-diphenylmethylene diisocyanate (2,2'-MDI) and 4,4'-diphenylmethylene diisocyanate (4,4'-MDI);

[0034] . 4,4'-dibenzyl diisocyanate (4,4'-DBDI);

[0035] . toluene 2,6-diisocyanate (2,6-TDI); . m-xylylene diisocyanate (m-XDI);

[0036] * symmetrical alicyclic diisocyanate compounds, preferably methylene bis(4-cyclohexylisocyanate) (H12MDI);

[0037] * symmetrical aliphatic diisocyanate compounds, preferably hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI);

[0038] * asymmetric aromatic diisocyanate compounds, preferably:

[0039] . 2,4'-diphenylmethylene diisocyanate (2,4'-MDI);

[0040] . 2,4'-dibenzyl diisocyanate (2,4'-DBDI);

[0041] . toluene 2,4-diisocyanate (2,4-TDI);

[0042] . a trimeric biurea compound, in particular a trimeric biurea compound of a compound chosen from:

[0043] * symmetrical aromatic diisocyanate compounds, preferably:

[0044] . 2,2'-diphenylmethylene diisocyanate (2,2'-MDI) and 4,4'-diphenylmethylene diisocyanate (4,4'-MDI);

[0045] . 4,4'-dibenzyl diisocyanate (4,4'-DBDI);

[0046] . toluene 2,6-diisocyanate (2,6-TDI);

[0047] . m-xylylene diisocyanate (m-XDI);

[0048] * symmetrical alicyclic diisocyanate compounds, preferably methylene bis(4-cyclohexylisocyanate) (H12MDI);

[0049] * symmetrical aliphatic diisocyanate compounds, preferably hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI);

[0050] * asymmetric aromatic diisocyanate compounds, preferably:

[0051] . 2,4'-diphenylmethylene diisocyanate (2,4'-MDI);

[0052] . 2,4'-dibenzyl diisocyanate (2,4'-DBDI);

[0053] . toluene 2,4-diisocyanate (2,4-TDI);

[0054] * asymmetric alicyclic diisocyanate compounds, preferably isophorone diisocyanate (IPDI).

[0055] More preferably, compound (a2) is selected from triphenylmethane-4,4',4”- triisocyanate, 1,1',1”-methylidynetris (4-isocyanatobenzene), HDI isocyanurate, IPDI isocyanurate, PDI isocyanurate, HDI biurea trimer and IPDI biurea trimer, PDI biurea trimer.

[0056] Preferably according to the invention, compound (b) is a compound of formula I in which R 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 combinations thereof.

[0057] Preferably according to the invention, compound (b) is a compound of formula I in which R independently represents a linear C4-C36-alkyl group, a branched C4-C36-alkyl group or a Cs-Cs6-aryl group; preferably a linear C6-Cs6-alkyl group, a branched C6-Cs6-alkyl group or a C6-Cs6-aryl group; more preferably a linear C6-C24-alkyl group, a branched C6-C24-alkyl group or a C6-C24-aryl group.

[0058] Also preferably according to the invention, compound (b) is a compound of formula I in which X independently represents an ethoxylated group or a combination of ethoxylated groups and propoxylated groups, more preferably X represents an ethoxylated group.

[0059] Also preferably according to the invention, compound (b) is a compound of formula I in which m represents 0 or a number ranging from 1 to 150, preferably from 1 to 100 or from 1 to 50, more preferably from 2 to 50 or from 2 to 25.

[0060] More preferably according to the invention, compound (b) is a compound of formula I in which:

[0061] - R independently represents a linear C4-C36-alkyl group, a branched C4-C36-alkyl group or a Cs-Cs6-aryl group; preferably a linear C6-C36-alkyl group, a branched C6-Cs6-alkyl group or a C6-Cs6-aryl group; more preferably a linear C6-C24-alkyl group, a branched C6-C24-alkyl group or a C6-C24-aryl group;

[0062] - X independently represents an ethoxylated group or a combination of ethoxylated groups and propoxylated groups, more preferably X represents an ethoxylated group; and

[0063] - m represents 0 or a number ranging from 1 to 150, preferably from 1 to 100 or from 1 to 50, more preferably from 2 to 50 or from 2 to 25.

[0064] Preferably according to the invention, compound (c) is a compound (cl) of formula II: HO-La-OH in which:

[0065] - L independently represents an oxyalkylene residue;

[0066] - n independently represents a number ranging from 30 to 1000. Preferably according to the invention, compound (c) is a compound (cl) of formula II in which L independently represents an oxyethylene residue or in which n independently represents a number ranging from 50 to 400, preferably from 100 to 300.

[0067] More preferably according to the invention, compound (c) is a compound (cl) of formula II in which L independently represents an oxyethylene residue and n independently represents a number ranging from 50 to 400, preferably from 100 to 300.

[0068] Compound (c1) may be used alone or it may be combined with one or more other compounds. In this case, compound (c1) of formula II may be combined with a non-alkoxylated compound (c2) comprising at least three hydroxyl groups. Preferably according to the invention, compound (c2) comprises three hydroxyl groups, more preferably, compound (c2) is chosen from glycerol, pentaerythritol and combinations thereof.

[0069] According to the invention, compound (c) may also be associated with a polyalkoxylated compound (c3) comprising at least three hydroxyl groups. According to the invention, the polyalkoxylated compound (c3) is different from compound (c2).

[0070] Preferably according to the invention, the polyalkoxylated compound (c3) is polyethoxylated pentaerythritol or else comprises three hydroxyl groups, more preferably the compound (c3) is polyethoxylated glycerol.

[0071] The method according to the invention can implement one or more combinations of compounds (c1), (c2) and (c3).

[0072] Essentially according to the invention, the polyhydroxylated compound (c) is polyalkoxylated. It therefore comprises alkoxylated groups. Preferably, the method according to the invention uses a compound (c) comprising from 10 to 150 alkoxylations, more preferably from 20 to 100 alkoxylations or from 10 to 70 alkoxylations. More preferably, the compound (c) comprises from 20 to 60 alkoxylations.

[0073] Also preferably, the method according to the invention uses a compound (c) which is polyethoxylated or which is polyethoxylated-polypropoxylated or which is polyethoxylated-polybutoxylated. More preferably, the compound (c) is polyethoxylated. Particularly preferably, the compound (c) comprises from 10 to 150 ethoxylations, more preferably from 20 to 100 ethoxylations or from 10 to 70 ethoxylations. Even more preferably, the compound (c) comprises from 20 to 60 ethoxylations.

[0074] The preparation method according to the invention can use polyalkoxylated compounds (c), (cl) and (c3) whose molar mass (Mw) measured by CES can vary in significant proportions. Preferably according to the invention, compounds (c), (cl) or (c3) independently have a molar mass (Mw) measured by CES ranging from 1,500 to 40,000 g / mol, preferably from 2,000 to 20,000 g / mol. More preferably according to the invention, the molar mass (Mw) of compounds (c), (cl) or (c3) ranges, independently, from 2,000 to 15,000 g / mol or from 2,000 to 12,000 g / mol.

[0075] According to the invention, the molar mass of compounds (c), (cl) or (c3) is determined by Size Exclusion Chromatography (CES) or in English “Gel Permeation Chromatography” (GPC). This technique uses a “Waters” brand liquid chromatography device equipped with a detector. This detector is a “Waters” 2414 type refractometric concentration detector. This liquid chromatography device is equipped with two size exclusion columns in order 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, non-stabilized).

[0076] In a first step, approximately 25 mg of compound is solubilized in 5 mL of THF, to which 0.1 mol% of water is added as an internal flow marker. The solution is then filtered at 0.2 pm. 50 pL is then injected into the chromatography apparatus (eluent: THF, HPLC grade, non-stabilized).

[0077] The liquid chromatography apparatus contains an isocratic pump (Waters 515) with a flow rate set at 0.3 mL / min. The chromatography apparatus also includes an oven which includes a column system in series: an Agilent PLgel MiniMIX-A column of 250 mm length and 4.6 mm diameter followed by an Agilent PLgel MiniMIX-B column of 250 mm length and 4.6 mm diameter. The detection system consists of a Waters RI 2414 refractometric detector. The columns are maintained at a temperature of 35°C and the refractometer is brought to a temperature of 35°C. The chromatography apparatus is calibrated using polymethyl methacrylate standards certified by the supplier Agilent (EasiVial PMMA).

[0078] According to the invention, compound (c) can be used in various liquid or solid forms, preferably solid at a temperature above 25°C. In solid form, compound (c) can take various forms, for example in a form chosen from pellet, flake, ground material, chip, powder and combinations thereof.

[0079] Essentially according to the invention, compound (c) has a very high degree of purity, in particular with regard to the presence of volatile organic compounds, in particular residual volatile organic compounds originating from the processes used for its preparation. Thus, compound (c) used according to the invention comprises a zero or particularly low quantity of alkanes, aromatic hydrocarbon compounds or alkenes.

[0080] According to the invention, the quantities of residual compounds are measured using widely available and easy-to-implement techniques. Indeed, 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 measurement by GC-MS comprises the injection into the chromatograph, at a regulated temperature, of the compound (c) to be analyzed, then the separation of the different volatile compounds by means of a capillary column, then the detection of any volatile residual compounds by means of a mass spectrometer and the analytical treatment of the detection peaks.

[0081] Thus, the compound (c) used according to the invention comprises an amount of at least one compound chosen from alkanes, aromatic hydrocarbon compounds, alkenes and their combinations, measured by GC-MS, which is less than 0.5 ppm by weight of compound (c). Preferably according to the invention, the compound (c) comprises an amount of alkanes which is less than 0.5 ppm by weight of compound (c). Also preferably according to the invention, the compound (c) comprises an amount of aromatic hydrocarbon compounds, which is less than 0.5 ppm by weight of compound (c). Also preferably according to the invention, the compound (c) comprises an amount of alkenes, which is less than 0.5 ppm by weight of compound (c). More preferably according to the invention, compound (c) comprises a quantity of alkanes of less than 0.2 ppm by weight, preferably a quantity of less than 0.1 ppm by weight or even zero, measured by GC-MS.

[0082] Preferably, the alkanes according to the invention are chosen from C3-C20-alkanes, in particular Cv-Cu-alkanes.

[0083] Also more preferably according to the invention, compound (c) comprises an amount of aromatic hydrocarbon compounds of less than 0.2 ppm by weight, preferably an amount of less than 0.1 ppm by weight or even zero, measured by GC-MS.

[0084] Also preferably, the aromatic hydrocarbon compounds according to the invention are chosen from toluene, benzene, xylene, naphthalene and their combinations.

[0085] Also more preferably according to the invention, compound (c) comprises an amount of alkenes of less than 0.2 ppm by weight, preferably an amount of less than 0.1 ppm by weight or even zero, measured by GC-MS.

[0086] Also preferably, the alkenes according to the invention are chosen from C7-C14 alkenes and their combinations.

[0087] Particularly preferably according to the invention, compound (c) therefore does not comprise any alkane or does not comprise any aromatic hydrocarbon compound or does not comprise any alkene. More preferably according to the invention, compound (c) does not comprise any alkane, aromatic hydrocarbon compound or alkene.

[0088] According to the invention, a zero quantity of a compound, in particular of a compound chosen from alkanes, aromatic hydrocarbon compounds or alkenes, characterizes both the total absence of this compound and its presence in a quantity that is not significant from an analytical point of view. The quantification limits generally accepted by means of the analysis techniques for this compound therefore characterize its absence within the compound (c) used according to the invention.

[0089] When preparing the copolymer P according to the invention, the amounts of compounds (a), (b) and (c) can vary. Preferably, the method according to the invention comprises a polymerization reaction which uses from 20 to 74.9 mol%, preferably from 25 to 60 mol%, of compound (a) relative to the total molar amount of compounds (a), (b) and (c).

[0090] Also preferably, the method according to the invention comprises a polymerization reaction which uses from 25 to 79.9 mol%, preferably from 35 to 70 mol%, of compound (b) relative to the total molar quantity of compounds (a), (b) and (c). Also preferably, the method according to the invention comprises a polymerization reaction which uses from 0.1 to 55 mol%, preferably from 5 to 40 mol%, of compound (c) relative to the total molar quantity of compounds (a), (b) and (c).

[0091] Preferably, the method according to the invention comprises a polymerization reaction which implements:

[0092] - from 20 to 74.9 mol% or from 25 to 60 mol% of compound (a) or

[0093] - from 25 to 79.9 mol% or from 35 to 70 mol% of compound (b), or

[0094] - from 0.1 to 55 mol% or from 5 to 40 mol% of compound (c), relative to the total molar quantity of compounds (a), (b) and (c).

[0095] More preferably, the method according to the invention comprises a polymerization reaction which implements:

[0096] - from 20 to 74.9 mol%, preferably from 25 to 60 mol%, of compound (a),

[0097] - from 25 to 79.9 mol%, preferably from 35 to 70 mol%, of compound (b), and

[0098] - from 0.1 to 55 mol%, preferably from 5 to 40 mol%, of compound (c), relative to the total molar quantity of compounds (a), (b) and (c).

[0099] In addition to compounds (a), (b) and (c), the preparation method according to the invention also includes the possibility of using other compounds during the polymerization reaction.

[0100] Thus, the preparation method according to the invention can also comprise a polymerization reaction which also uses at least one hydrophobic compound (d) of formula III:

[0101] R^OE) q -(OP) r -OH

[0102] (III) 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,

[0103] - OE independently represents a CH2CH2O group,

[0104] - OP independently represents a group chosen from CH(CH3)CH2O and CH2CH(CH3)O,

[0105] - R 1independently represents a group selected from a linear C4-C40-alkyl group, a branched C4-C40-alkyl group, a Cs-C40-cycloalkyl group, a C5-C40-aryl group and combinations thereof.

[0106] The invention also relates to a method for preparing a Pc copolymer comprising the polymerization reaction of at least one compound (a), at least one compound (b) and at least one compound (d).

[0107] Preferably according to the invention, compound (d) is a compound of formula III in which:

[0108] - r represents 0; or

[0109] - R 1represents a linear or branched C6-C40-alkyl group, a phenyl group, a polyphenyl group, preferably a linear or branched C w-Cso-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 pentastyry leumy Iphény 1 group.

[0110] 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 (d) relative to the total molar quantity of monomers.

[0111] The preparation method according to the invention makes it possible to obtain the copolymer P. During the preparation of this copolymer, the compound (c) used comprises a small or zero quantity of alkanes, aromatic hydrocarbon compounds or alkenes. Prior to the polymerization reaction, the invention makes it possible to select the compound (c) according to the quantity of alkanes, aromatic hydrocarbon compounds or alkenes that it may optionally comprise. Thus, the invention provides a method for preparing a copolymer P according to the invention which also comprises the selection prior to the polymerization reaction of the polyhydroxylated compound (c) comprising the measurement by GC-MS of the quantity Q of at least one compound chosen from alkanes, aromatic hydrocarbon compounds, alkenes and their combinations, then: - the use of the compound (c) if the quantity Q is zero or

[0112] - the elimination of compound (c) if the quantity Q is non-zero or if it is greater than 0.5 ppm by weight of compound (c).

[0113] 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 the compound (c). The invention provides a method for selecting a polyhydroxylated compound (c) comprising measuring by GC-MS the quantity Q of at least one compound chosen from alkanes, aromatic hydrocarbon compounds, alkenes and their combinations, then:

[0114] - the implementation of the compound (c) if the quantity Q is zero or

[0115] - the elimination of compound (c) if the quantity Q is non-zero.

[0116] The selection method according to the invention comprises an elimination step which may be total or partial, in particular depending on the quantity present within compound (c) of the possible compound chosen from alkanes, aromatic hydrocarbon compounds, alkenes and their combinations.

[0117] The preparation method according to the invention is particularly effective for obtaining a copolymer P comprising a reduced or zero level of alkanes, aromatic hydrocarbon compounds or alkenes. The invention also provides a copolymer P prepared according to the preparation method according to the invention. Preferably, the copolymer P according to the invention comprises an amount of at least one compound chosen from alkanes, aromatic hydrocarbon compounds, alkenes and their combinations, measured by GC-MS, which is less than 0.5 ppm by weight of compound (c), more preferably an amount of less than 0.1 ppm by weight of compound (c) or even a zero amount of compound chosen from alkanes, aromatic hydrocarbon compounds, alkenes and their combinations.

[0118] 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 chosen from a solvent, in particular water or a coalescence solvent, for example glycol, butyl glycol, butyl diglycol, monopropylene glycol, ethylene glycol, ethylene diglycol, “Dowanol” products with CAS number 34590-94-8), “Texanol” products with CAS number 25265-77-4).

[0119] In particular within the rheology modifying agent, the copolymer P may be combined with at least one additive chosen 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.

[0120] 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 chosen from a hydroxylated surfactant compound of natural origin, for example alkyl-polyalkylene glycol of natural origin, in particular alkyl-polyethylene glycol of natural origin; a polysaccharide derivative of natural origin, for example cyclodextrin of natural origin, cyclodextrin derivative of natural origin, polyethers, alkyl-glucosides of natural origin and combinations thereof.

[0121] The invention also relates to an aqueous formulation comprising:

[0122] - at least one copolymer P or at least one rheology modifying agent according to the invention and, optionally,

[0123] - 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

[0124] - 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.

[0125] Preferably, the aqueous 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.

[0126] 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.

[0127] 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 paint or varnish, or a paper coating composition or a cosmetic composition or a detergent composition or an adhesive composition.

[0128] The copolymer P prepared according to the invention has particularly effective rheological control properties for aqueous compositions. The invention provides a method for controlling the viscosity of an aqueous composition comprising the addition to this composition of at least one copolymer P according to the invention.

[0129] 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.

[0130] The following examples illustrate the various aspects of the invention.

[0131] EXAMPLES:

[0132] Example 1: preparation and characterization of copolymers PI to P6 according to the invention:

[0133] The compounds used are chosen from:

[0134] - diisocyanate compound (a): isophorone diisocyanate (IPDI), compound (ala),

[0135] - diisocyanate compound (a): 4,4'-diisocyanato dicyclohexylmethane (H12MDI), compound (alb),

[0136] - compound (b): compound (ba) of formula I in which R represents a cardanyl group, ethoxylated 4 times, - compound (b): compound (bb) of formula I in which R represents a 1-hexanyl group,

[0137] - compound (b): compound (bc) of formula I in which R represents a 1-ethylhexanyl group,

[0138] - compound (b): compound (bd) of formula I in which R represents a 1-octanyl group,

[0139] - compound (b): compound (be) of formula I in which R represents a 1-dodecanyl group,

[0140] - compound (c): compound (cia) of formula II in which in which L represents an oxyethylene residue and n represents approximately 225 (Polyglycol 10000 SG “Vita Clariant”).

[0141] Compound (cia) is analyzed by GC-MS using a gas chromatograph ('Agilent' 7890B) including a headspace injector ('Agilent' 7967 A) and a mass spectrometer ('Agilent' 5977B) as detector.

[0142] A 2 g sample of compound is placed in a vial (screw cap, 2 mL headspace) and injected into the chromatograph. After detection and processing of the peaks of the compounds present in the sample, in addition to the compound (cia), the presence of the compounds detailed in Table 1 is characterized.

[0143] Table 1 In a 2L reactor, 261.9g of compound (cia) and 24.8g of compound (ba) are introduced. Heating is carried out at 90°C under vacuum for 30 min, then 12.8g of compound (ala) are introduced and the heating is increased and maintained at a temperature of 100°C for 45 min. The PI polymer according to the invention is obtained.

[0144] In a similar manner, polymers P2 to P5 are prepared according to the invention. The compounds and quantities (g) used are presented in Table 2.

[0145] Table 2

[0146] Example 2: preparation and characterization of rheology modifying agents MRI to MR5 according to the invention:

[0147] The PI polymer of Example 1 is cooled to 60°C and then mixed with 266.4g of a surfactant compound (“Simulsol” SL7G “Seppic”) and 432.9g of water to obtain the MRI rheology modifying agent according to the invention.

[0148] Similarly, the rheology modifying agent MR2 according to the invention is prepared by mixing the polymer P2 with 799.2 g of water.

[0149] The rheology modifying agent MR3 according to the invention is prepared by mixing the polymer P3 with 749.2 g of water.

[0150] The rheology modifying agent MR4 according to the invention is prepared by mixing the polymer P4 with 749.4 g of water.

[0151] The rheology modifying agent MR5 according to the invention is prepared by mixing the polymer P5 with 266.4 g of surfactant compound (“Simulsol” SL7G “Seppic”) and 432.9 g of water. For each rheology modifying agent, the resulting low gradient viscosity is determined: Brookfield viscosity at 100 rpm (spindle no. 6) noted VB (mPa.s). These measurements are made 24 hours after preparation of the agent. The agents are thermostated at 25 ± 0.5 °C. The results are presented in Table 3.

[0152] Table 3

[0153] Example 3: Preparation and characterization of aqueous coating compositions CRI to CR5 according to the invention: Each composition is prepared by mixing the different ingredients. The ingredients and quantities (in g) are detailed in Table 4.

[0154] Table 4 For each composition, the resulting viscosities are determined at different speed gradients: - at low gradient: Brookfield viscosities at 10 rpm and 100 rpm, respectively noted VB 10 and VB 100 (mPa.s),

[0155] - medium gradient: Stormer viscosity (Krebs Unit, KU),

[0156] - high gradient: ICI viscosity (mPa.s). 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 5.

[0157] Table 5 The copolymers according to the invention make it possible to effectively thicken a solvent-free matte paint at different shear gradients.

[0158] In the field of water-based paints, a high viscosity at a low or medium shear rate reflects good static behavior. This ensures good stability during storage while avoiding sedimentation and limiting the tendency to run on vertical surfaces.

[0159] These paint compositions do not include VOCs originating from the polyhydroxylated compound used during the preparation of the copolymer according to the invention.

Claims

DEMANDS 1. Method for preparing a copolymer P comprising the polymerization reaction of: a) at least one isocyanate compound (a) selected independently from a diisocyanate compound (a1), a polyisocyanate compound (a2) and their combinations; b) at least one compound (b) of formula I: R-(X) m -OH (I) in which: - R independently represents a group chosen from a linear C4-C40-alkyl group, a branched C4-C40-alkyl group, a Cs-C40-cycloalkyl group, a C5-C40-aryl group and their combinations, - m represents 0 or a number from 1 to 200, - X independently represents an alkoxy group selected from oxyethylene, oxypropylene, oxybutylene and their combinations; c) of at least one polyalkoxy polyhydroxy compound (c) 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 (c).

2. Method according to claim 1 wherein: * The diisocyanate compound (al) is chosen from: - symmetrical aromatic diisocyanate compounds, preferably: ** 2,2'-diphenylmethylene diisocyanate (2,2'-MDI) and 4,4'-diphenylmethylene diisocyanate (4,4'-MDI); **4,4'-dibenzyl diisocyanate (4,4'-DBDI); **Toluene 2,6-diisocyanate (2,6-TDI); ** m-xylylene diisocyanate (m-XDI); - symmetrical alicyclic diisocyanate compounds, preferably methylene bis(4-cyclohexylisocyanate) (H12MDI); - symmetrical aliphatic diisocyanate compounds, preferably hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI); - preferably dissymmetric aromatic diisocyanate compounds: ** 2,4'-diphenylmethylene diisocyanate (2,4'-MDI); ** 2,4'-dibenzyl diisocyanate (2,4'-DBDI); **Toluene 2,4-diisocyanate (2,4-TDI); - asymmetrical alicyclic diisocyanate compounds, preferably isophorone diisocyanate (IPDI), preferably according to the invention, the compound Al being selected from IPDI, HDI, H12MDI and their combinations; or * The polyisocyanate compound (A2) comprises strictly more than 2 isocyanate functions or more than 2.2 isocyanate functions or more than 2.5 isocyanate functions; preferably, the polyisocyanate compound A2 comprises more than 2.6 isocyanate functions or more than 2.7 isocyanate functions or more than 3 isocyanate functions; more preferably, the polyisocyanate compound A2 comprises from 2.2 to 6 isocyanate functions, from 2.2 to 4 isocyanate functions, from 2.2 to 3.5 isocyanate functions, from 2.5 to 6 isocyanate functions, from 2.2 to 5 isocyanate functions, from 2.5 to 4 isocyanate functions, from 2.5 to 3.5 isocyanate functions, in particular from 2.6 to 3.3 isocyanate functions; or * The polyisocyanate compound (a2) is chosen from: ** triphenylmethane-4,4',4”-triisocyanate or l,r,l”-methylidynetris (4-isocyanatobenzene); Or *** an isocyanurate compound, in particular an isocyanurate compound of a compound selected from: *** symmetrical aromatic diisocyanate compounds, preferably: ** 2,2'-diphenylmethylene diisocyanate (2,2'-MDI) and 4,4'-diphenylmethylene diisocyanate (4,4'-MDI); **4,4'-dibenzyl diisocyanate (4,4'-DBDI); **Toluene 2,6-diisocyanate (2,6-TDI); ** m-xylylene diisocyanate (m-XDI); *** symmetrical alicyclic diisocyanate compounds, preferably methylene bis(4-cyclohexylisocyanate) (H12MDI); *** symmetrical aliphatic diisocyanate compounds, preferably hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI); *** asymmetric aromatic diisocyanate compounds, preferably: ** 2,4'-diphenylmethylene diisocyanate (2,4'-MDI); ** 2,4'-dibenzyl diisocyanate (2,4'-DBDI); **Toluene 2,4-diisocyanate (2,4-TDI); ** a biurea trimer compound, in particular a biurea trimer compound of a compound selected from: *** symmetrical aromatic diisocyanate compounds, preferably: ** 2,2'-diphenylmethylene diisocyanate (2,2'-MDI) and 4,4'-diphenylmethylene diisocyanate (4,4'-MDI); **4,4'-dibenzyl diisocyanate (4,4'-DBDI); **Toluene 2,6-diisocyanate (2,6-TDI); ** m-xylylene diisocyanate (m-XDI); *** symmetrical alicyclic diisocyanate compounds, preferably methylene bis(4-cyclohexylisocyanate) (H12MDI); *** symmetrical aliphatic diisocyanate compounds, preferably hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI); *** asymmetric aromatic diisocyanate compounds, preferably: ** 2,4'-diphenylmethylene diisocyanate (2,4'-MDI); ** 2,4'-dibenzyl diisocyanate (2,4'-DBDI); **Toluene 2,4-diisocyanate (2,4-TDI); *** dissymmetric alicyclic diisocyanate compounds, preferably isophorone diisocyanate (IPDI), preferably compound (a2) is selected from triphenylmethane- 4,4',4”-triisocyanate, l,l',l”-methylidynetris (4-isocyanatobenzene), an HDI isocyanurate, an IPDI isocyanurate, a PDI isocyanurate, an HDI biurea trimer and an IPDI biurea trimer, a PDI biurea trimer.

3. A method according to claim 1 or 2, wherein compound (b) is a compound of formula I in which: - R independently represents a linear C4-C36-alkyl group, a branched C4-C36-alkyl group, or a Cs-Csô-aryl group; preferably a linear C6-C36-alkyl group, a branched Cô-Csô-alkyl group, or a Cô-Csô-aryl group; more preferably a linear Cô-C24-alkyl group, a branched Cô-C24-alkyl group, or a Cô-C24-aryl group; or - X independently represents an ethoxylated group or a combination of ethoxylated and propoxylated groups, more preferably X represents an ethoxylated group; or - m represents 0 or a number from 1 to 150, preferably from 1 to 100 or from 1 to 50, more preferably from 2 to 50 or from 2 to 25.

4. A method according to any one of claims 1 to 3, wherein compound (c) is selected from: * a compound (cl) of formula II: HO-L a -OH (II) in which: - L independently represents an oxyalkylene residue; - n independently represents a number ranging from 30 to 1000; * a compound (cl) of formula II associated with a non-alkoxylated compound (c2) comprising at least three hydroxyl groups; * a polyalkoxylated compound (c3) comprising at least three hydroxyl groups; * their combinations.

5. A method according to any one of claims 1 to 4, wherein compound (c) is selected from: * a compound (cl) of formula II: -L n -OH in which: - L independently represents an oxyethylene residue; or - n independently represents a number from 50 to 400, preferably from 100 to 300; or in which L independently represents an oxyethylene residue and n independently represents a number from 50 to 400, preferably from 100 to 300; * a compound (c2) comprising three hydroxyl groups, preferably selected from glycerol, pentaerythritol and their combinations; * of polyethoxylated pentaerythritol or a polyalkoxylated compound (c3) different from compound (c2) and comprising three hydroxyl groups, preferably a compound (c3) which is polyethoxylated glycerol.

6. A method according to any one of claims 1 to 5, wherein: * Compound (c) 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 (c) is polyethoxylated or is polyethoxylated-polypropoxylated or is polyethoxylated-polybutoxylated, preferably compound (c) is polyethoxylated, or * Compound (c) 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.

7. Method according to any one of claims 1 to 6 wherein the compounds (c), (cl) or (c3) independently have a molar mass (Mw) measured by CES ranging from 1,500 to 40,000 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.

8. A method according to any one of claims 1 to 7, wherein compound (c) comprises * 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 alkanes, in particular alkanes selected from C3-C20 alkanes 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 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 an amount less than 0.1 ppm by weight or even zero, measured by GC-MS, of alkenes, in particular alkenes selected from Cv-Cu-alkenes and their combinations.

9. A method according to any one of claims 1 to 8, wherein the polymerization reaction involves: - from 20 to 74.9 mol%, preferably from 25 to 60 mol%, of monomer (a) or - from 25 to 79.9 mol%, preferably from 35 to 70 mol%, of compound (b), or - from 0.1 to 55 mol%, preferably from 5 to 40 mol%, of monomer (c), relative to the total molar amount of compounds (a), (b) and (c).

10. A method according to any one of claims 1 to 9, wherein the polymerization reaction also employs at least one hydrophobic compound (d) different from compound (b), preferably a compound of formula III: R 1 -(OE) q -(OP) r -OH (III) in which: - q and r, whether identical or different, independently represent 0 or an integer or decimal number less than 150; 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 1represents a C-C40-alkyl group, linear or branched, a phenyl group, a polyphenyl group, preferably a C-w-Cso-alkyl group, linear or branched, more preferably a Ci2-C22-alkyl group, linear or branched, or a group comprising 2 to 5 phenyls or a tristyrylphenyl group or a pentastyrylcumylphenyl group, preferably less than 20 mol%, preferably from 0.05 to 20 mol%, in particular from 0.1 to 10 mol%, of monomer (d) relative to the total molar amount of monomers.

11. Method for selecting a polyhydroxylated compound (c) comprising measuring by GC-MS the amount Q of at least one compound selected from alkanes, aromatic hydrocarbon compounds, alkenes and their combinations, then - the implementation of compound (c) if the quantity Q is zero or - the elimination of compound (c) if the quantity Q is non-zero or greater than 0.5 ppm by weight of compound (c).

12. Copolymer P prepared according to the preparation method according to any one of claims 1 to 10.

13. Method for preparing a rheology-modifying agent comprising: - the preparation of a copolymer P according to any one of claims 1 to 10, - the mixing of copolymer P with at least one compound selected from a solvent, including water or a coalescing solvent, for example glycol, butyl glycol, butyldiglycol, monopropylene glycol, ethylene glycol, ethylenediglycol, "Dowanol" products (CAS number 34590-94-8), "Texanol" products (CAS number 34590-94-8) CAS is 25265-77-4) or with at least one additive selected from an amphiphilic compound, including a surfactant compound, preferably a hydroxylated surfactant compound, for example alkyl-polyalkyleneglycol, including 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.

14. Rheology modifying agent comprising a copolymer P defined according to any one of claims 1 to 10 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 of natural origin, in particular alkyl-polyethylene glycol of natural origin; a polysaccharide derivative of natural origin, for example cyclodextrin of natural origin, cyclodextrin derivative of natural origin, polyethers, alkyl-glucosides of natural origin and combinations thereof.

15. Aqueous composition comprising at least one copolymer P defined according to any one of claims 1 to 10 or 11 or comprising at least one rheology modifying agent according to claim 14.

16. Composition according to claim 15 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.

17. Method for controlling the viscosity of an aqueous composition comprising the addition of at least one copolymer P defined according to one of claims 1 to 10 or 11.

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