Thixotropic compositions based on diurea-diurethanes

Abstract

The present invention relates to a thixotropic composition comprising a diurea-diurethane compound and an aprotic solvent, a process for its preparation, and its use as a rheological agent, especially a thixotropic agent, especially in binder compositions.

Description

[Technical Field]

[0001] The present invention relates to thixotropic compositions comprising one or more diurea-diurethane compounds and an aprotic solvent, to a process for their preparation, and to their use as rheological agents, especially thixotropic agents, especially in binder compositions.

[0002] Diurea-diurethane compounds are already known as organic gelators, i.e. small organic molecules capable of gelling any kind of organic solvent even at relatively low weight concentrations (less than 1% by weight), or as rheological additives, i.e. additives that make it possible to modify the rheology of the applied formulation, for example by obtaining thixotropic or pseudoplastic effects.

[0003] Liquid thixotropic agents are particularly valuable because they can be easily incorporated into formulations, especially water-based coating formulations.

[0004] U.S. Patent No. 4,314,924 describes a thixotropic composition containing a diurea-diurethane solution in an aprotic solvent and 0.1 to 2 moles of LiCl per urea group. LiCl is used to stabilize the composition. However, the presence of this lithium salt can cause corrosion problems when the composition is applied to metal substrates and can lead to uncontrolled formation of materials due to its Lewis acidity. Furthermore, lithium salts, especially LiCl, are toxic compounds, and formulations containing them are subject to current regulations regarding chemical classification, labeling, and packaging. The composition is prepared by reacting one mole of a monoalcohol with one mole of a diisocyanate to form a monoisocyanate adduct, which is then introduced into an aprotic solvent containing 0.5 moles of a polyamine and 0.1 to 2 moles of LiCl. However, as a result of using a stoichiometric ratio between the monoalcohol and the diisocyanate, the structure of the diurea-diurethane compound is not fully controlled. This can result in the formation of unreactive or insoluble materials that tend to precipitate.

[0005] U.S. Patent No. 6,420,466 describes a method for preparing thixotropic agents, including diurea-diurethane compounds, by reacting a monoalcohol with excess toluene diisocyanate to form a monoisocyanate adduct. The excess toluene diisocyanate is subsequently removed by vacuum distillation, and the monoisocyanate adduct is then reacted with a diamine in an aprotic solvent in the presence of LiCl. This method also uses corrosive lithium salts, and the distillation step of the excess diisocyanate is expensive and requires specialized plant on an industrial scale.

[0006] Therefore, there is a need for new liquid thixotropic additives based on diurea-diurethanes that are stable in the absence of lithium salts, can be easily prepared without a distillation step of residual diisocyanate, and have rheological performance qualities that are at least equivalent to, and in fact superior to, those of comparable additives of the prior art.

[0007] After much research and study, the applicant company has developed a thixotropic composition that meets this need. Summary of the Invention

[0008] The present invention relates to a compound of formula (I) [ka] wherein R', R2 and R3 are as defined below, or a mixture of compounds of formula (I) and an aprotic solvent; The composition contains less than 0.1 moles of salt per urea group in the composition, excluding the aprotic solvent.

[0009] Another subject of the present invention is a process for preparing a thixotropic composition comprising the following steps: a) reacting at least one diisocyanate of formula OCN-R2-NCO with at least one alcohol of formula R'-OH to form at least one monoisocyanate adduct of formula R'-OC(=O)-NH-R2-NCO, wherein the molar ratio of the total amount of alcohol to the total amount of diisocyanate is in the range of 1.10 to 1.80, particularly 1.20 to 1.60, more particularly 1.25 to 1.45, and even more particularly 1.30 to 1.40; b) Formula (I) [ka] (wherein R', R2 and R3 are as described below) reacting at least one monoisocyanate adduct obtained in step a) with at least one diamine of formula H2N-R3-NH2 in the presence of less than 0.2 moles of a metal salt per mole of diamine used to form at least one compound of formula

[0010] Another subject of the invention is a binder composition comprising a binder and a thixotropic composition according to the invention or prepared according to the method of the invention.

[0011] Another subject of the present invention is the use of the thixotropic composition according to the invention or prepared according to the method of the present invention as a rheological agent, in particular a thixotropic agent. DETAILED DESCRIPTION OF THE INVENTION

[0012] [Definition] In this patent application, the terms "including a" and "including an" mean "including one or more."

[0013] Unless otherwise specified, weight percentages in a compound or composition are expressed relative to the weight of the compound or composition.

[0014] The term "diurea-diurethane compound" means a compound having two urea functional groups and two urethane functional groups.

[0015] The term "diurethane compound" means a compound having two urethane functional groups and no urea functional groups.

[0016] The term "polyurea-diurethane compound" means a compound having two urethane functional groups and at least four urea functional groups.

[0017] The term "urea functional group" or "urea group" refers to the sequence --NH--C(.dbd.O)--NH--.

[0018] The term "urethane functional group" or "urethane group" refers to the sequence --NH--C(.dbd.O)--O-- or --OC(.dbd.O)--NH--.

[0019] The term "solvent" means a liquid that has the property of dissolving, diluting, or reducing the viscosity of other substances without chemically altering them or being altered itself.

[0020] "Aprotic solvent" means a solvent that does not have an acidic hydrogen atom. In particular, an aprotic solvent does not contain a hydrogen atom bonded to a heteroatom (O, N, or S).

[0021] The term "salt" means an ionic compound. The salt may be an inorganic or organic salt, although inorganic salts are preferred. In the sense of the present invention, the term "salt" does not include ionic surfactants.

[0022] The term "surfactant" refers to a compound capable of modifying the surface tension between two surfaces. Surfactants may in particular be amphiphilic compounds, i.e., exhibiting two parts of different polarity, where the lipophilic part (which holds the fatty substances) is non-polar, and the other hydrophilic part (which is water-miscible) is polar.

[0023] The term "alkyl" refers to a group of the formula -C n H 2n+1 Alkyl may be linear or branched. C1-C 30 Alkyl means alkyl having 1 to 30 carbon atoms.

[0024] The term "alkenyl" means a monovalent acyclic hydrocarbon group having one or more C=C double bonds. Alkenyl may be linear or branched. C-C 30 Alkenyl means an alkenyl having from 2 to 30 carbon atoms.

[0025] The term "cycloalkyl" means a monovalent cyclic hydrocarbon group. Cycloalkyl can be saturated or unsaturated. Cycloalkyl is non-aromatic. C5-C 12 Cycloalkyl means a cycloalkyl having from 5 to 12 carbon atoms.

[0026] The term "aryl" means a monovalent aromatic hydrocarbon radical. C-C 12 Aryl means an aryl having 6 to 12 carbon atoms.

[0027] The term "arylalkyl" refers to an alkyl group substituted with an aryl group.

[0028] The term "aliphatic" means a non-aromatic acyclic compound or group. It can be linear or branched, saturated or unsaturated, and substituted or unsubstituted. It can contain one or more linkages / functional groups selected from, for example, ethers, esters, amines, and mixtures thereof.

[0029] The term "alicyclic" refers to a non-aromatic compound or group that contains a ring having only carbon atoms as ring atoms, which may be substituted or unsubstituted.

[0030] The term "aromatic" refers to a compound or group containing an aromatic ring, i.e., a compound that obeys Hückel's rule of aromaticity, especially a compound containing a phenyl group. It may be substituted or unsubstituted. It may contain one or more bonds / functional groups as defined for the term "aliphatic."

[0031] The term "araliphatic" refers to a compound or group that contains an aliphatic portion and an aromatic portion.

[0032] The term "heterocyclic" means a compound or group containing a ring having at least one heteroatom selected from N, O and / or S as a ring atom. It may be substituted or unsubstituted. It may be aromatic or non-aromatic.

[0033] [Thixotropic composition] The thixotropic compositions of the present invention comprise a diurea-diurethane compound or a mixture of diurea-diurethane compounds and an aprotic solvent, as described below.

[0034] The compositions of the present invention are stable despite containing little or no salt. The thixotropic compositions of the present invention contain less than 0.1 moles of salt per urea group in the composition, excluding aprotic solvents. The number of urea groups is determined based on the total number of compounds contained in the composition, excluding aprotic solvents. The compound of formula (I) contains two urea groups. When a composition contains 1 mole of the compound of formula (I) and no other compounds having at least one urea group are present in the composition, the composition contains less than 0.2 moles of salt.

[0035] In particular, the thixotropic composition may comprise from 0 to less than 0.1 moles, or from 0 to 0.09 moles, or from 0 to 0.07 moles, or from 0 to 0.05 moles, or from 0 to 0.03 moles, or from 0 to 0.01 moles, or from 0 to 0.001 moles of salt per urea group in the composition, excluding aprotic solvents.

[0036] More particularly, the thixotropic composition may contain less than 1%, or between 0% and 0.9%, or between 0% and 0.7%, or between 0% and 0.5%, or between 0% and 0.25%, or between 0% and 0.2%, or between 0% and 0.15%, or between 0% and 0.09%, or between 0% and 0.03% LiCl by weight, based on the weight of the composition excluding aprotic solvents.

[0037] More particularly, the thixotropic composition may contain less than 1.6%, or 0% to 1.4%, or 0% to 1.1%, or 0% to 0.8%, or 0% to 0.4%, or 0% to 0.3%, or 0% to 0.25%, or 0% to 0.15%, or 0% to 0.05% LiNO by weight, based on the weight of the composition excluding aprotic solvents.

[0038] The salt may be selected from metal salts, ionic liquids, and ammonium salts. In particular, the salt may be a metal salt selected from halides, acetates, formates, or nitrates. More particularly, the salt may be a lithium salt. Even more particularly, the salt may be a lithium salt selected from LiCl, LiNO, LiBr, and mixtures thereof.

[0039] The compositions of the present invention can be particularly stable without the addition of stabilizers, especially surfactants. According to certain embodiments, the thixotropic compositions of the present invention contain less than 0.1 moles of surfactant per urea group in the composition.

[0040] In particular, the thixotropic composition may comprise from 0 to 0.1 moles, or from 0 to 0.08 moles, or from 0 to 0.06 moles, or from 0 to 0.04 moles, or from 0 to 0.02 moles, or from 0 to 0.01 moles, or from 0 to 0.001 moles of surfactant per urea group in the composition, excluding the aprotic solvent.

[0041] More particularly, the thixotropic composition may comprise less than 3%, or 0% to 2.8%, or 0% to 2.4%, or 0% to 2%, or 0% to 1.6%, or 0% to 1.2%, or 0% to 1%, or 0% to 0.5%, or 0% to 0.1%, or 0% to 0.01% surfactant by weight, based on the weight of the composition, excluding aprotic solvents.

[0042] The surfactant may be chosen in particular from anionic surfactants, cationic surfactants, nonionic surfactants, zwitterionic surfactants and mixtures thereof. The surfactant may in particular have an HLB of 8 to 12.

[0043] Examples of anionic surfactants are sulfonates, sulfates, sulfosuccinates, phosphates, and carboxylates. Examples of cationic surfactants are quaternary ammonium salts (especially tetraalkylammonium salts and quaternary ammonium esters or ester quats). Examples of nonionic surfactants are alkoxylated (especially ethoxylated and / or propoxylated) fatty alcohols, alkyl glycosides, esters of fatty acids (especially glycol esters, glycerol esters, sorbitan esters, or sucrose esters of fatty acids), and alkoxylated (especially ethoxylated and / or propoxylated) esters of fatty acids. Examples of zwitterionic surfactants are betaines, imidazolines, sultaines, phospholipids, and amine oxides.

[0044] The composition according to the invention may have an NCO value of less than 0.5 mg KOH / g, in particular less than 0.2 mg KOH / g, more particularly less than 0.1 mg KOH / g, and even more particularly 0 mg KOH / g. The NCO value may be measured according to the method described below.

[0045] [Compound of formula (I)] The thixotropic composition according to the present invention has the formula (I): [ka] wherein R', R2 and R3 are as described below, or a mixture of compounds of formula (I).

[0046] Preferably, the compound of formula (I) does not contain a tertiary amine or quaternary ammonium functional group.

[0047] The compounds of formula (I) may in particular correspond to the reaction product of at least one alcohol of formula R'-OH, at least one diisocyanate of formula OCN-R2-NCO and at least one diamine of formula H2N-R3-NH2.

[0048] The thixotropic composition may contain, by molar ratio, in particular from 5% to 80%, in particular from 15% to 75%, more particularly from 25% to 65% of compounds of formula (I) relative to the total molar amount of compounds having one or more functional groups selected from urea, urethane and mixtures thereof, excluding the aprotic solvent.

[0049] [R' group] A compound of formula (I) contains two R' groups. The R' groups of one and the same compound of formula (I) may be the same or different. A composition of the present invention may contain a mixture of compounds of formula (I) having the same R' group. A composition of the present invention may contain a mixture of compounds of formula (I) having different R' groups. For example, some compounds of the mixture may have the same R' group and some compounds of the mixture may have different R' groups.

[0050] Each R' group may result from the use of an alcohol of formula R'-OH to form the diurea-diurethane compound of formula (I). The R' group may correspond to the residue of the alcohol of formula R'-OH, excluding the OH group. The R' groups and corresponding alcohols of formula R'-OH described below also apply to the method of the present invention.

[0051] Each R' is an alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, -[(CR a R b ) n -O] m-Y and ·-[(CR c R d ) p -C(=O)O] q - independently selected from Z; The symbol · represents the point of attachment to the urethane group of formula (I); Y and Z are independently selected from alkyl, alkenyl, cycloalkyl, aryl, and arylalkyl; R a , R b , R c and R d is independently selected from H and methyl, in particular H; each n is independently equal to 2, 3, or 4, particularly n is 2; m is in the range of 1 to 30, particularly m is in the range of 2 to 25; p ranges from 3 to 5, and in particular p is 5; q ranges from 1 to 20, and in particular q ranges from 2 to 10.

[0052] The R' group is alkyl, particularly C1 to C 30 Examples of suitable alkyl groups are methyl, propyl, 1-methylethyl, butyl, X 1-2 -methylpropyl, pentyl, X 1-3 -Methylbutyl, Hexyl, X 1-4 -Methylpentyl, Heptyl, X 1-5 -Methylhexyl, Octyl, X 1-6 -Methylheptyl, 2-ethylhexyl, nonyl, X 1-7 -Methyloctyl, Decyl, X 1-8 -Methylnonyl, undecyl, X 1-9 -Methyldecyl, dodecyl, X 1-10 -Methylundecyl, Tridecyl, X 1-11 -methyldodecyl, 2,5,9-trimethyldecyl, tetradecyl, X 1-12 -Methyltridecyl, Pentadecyl, X 1-13 -methyltetradecyl, hexadecyl, X 1-14 -methylpentadecyl, heptadecyl, X 1-15 -Methylhexadecyl, octadecyl, X 1-16-Methylheptadecyl, Nonadecyl, X 1-17 -Methyloctadecyl, icosyl, X 1-18 -methylnonadecyl, henicosyl, X 1-19 -Methylicosyl, docosyl, X 1-20 -methylhenicosyl, 2-propylheptyl, 2-propylnonyl, 2-pentylnonyl, 2-butyloctyl, 2-butyldecyl, 2-hexyloctyl, 2-hexyldecyl, 2-octyldecyl, 2-hexyldodecyl, 2-octyldodecyl, 2-decyltetradecyl, 6-methyldodecyl and isomers thereof, wherein X a-b represents an integer that can take any value between a and b, and X a-b indicates the position of the substituent in the alkyl group. 1-11 The 2,5,9-trimethyldecyl group is a dodecyl group substituted with a methyl group at the 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11 position, such as 11-methyldodecyl or 2-methyldodecyl. The term "isomer" is understood to mean an alkyl group containing the same number of carbon atoms but with a different substitution scheme, for example, an ethyl group instead of a methyl or more methyl group. Thus, the 2,5,9-trimethyldecyl group is an isomer of the 11-methyldodecyl or 2-methyldodecyl group. The above alkyl group may be bonded to a urethane group, particularly at the 1-position. Thus, the 2,5,9-trimethyldecyl group has the following formula: [ka] (where the wavy line represents the point of attachment of the compound of formula (I) to the urethane group) It can be expressed by:

[0053] The R' group is alkenyl, especially C2 to C 30 An example of a suitable alkenyl group is hexa-Y 2-5 -enyl, hepta-Y 2-6 -Enil, Octa-Y 2-7 -Enil, Nona-Y 2-8 -Enil, Deca-Y 2-9 -Enil, Undeca-Y 2-10 -enil, dodeca-Y 2-11-enyl, trideca-Y 2-12 -enyl, tetradeca-Y 2-13 -enil, hexadeca-Y 2-15 -enil, octadeca-Y 2-17 -Enil, Icosa-Y 2-19 -Enil, Docosa-Y 2-21 -enyl, heptadeca-8,11-dienyl, octadeca-9,12-dienyl, nonadeca-10,13-dienyl, icosa-11,14-dienyl, docosa-13,16-dienyl, octadeca-5,9,12-trienyl, octadeca-6,9,12-trienyl, octadeca-9,12,15-trienyl, octadeca-9,11,13-trienyl, icosa-8,11,14-trienyl and icosa-11,14,17-trienyl, wherein Y a-b represents an integer that can take any value between a and b, and Y a-b indicates the position of the double bond in the alkenyl group. Hexa-Y 2-5 The -enyl group is a hexenyl group in which the double bond can be in the 2-, 3-, 4- or 5-position, corresponding to the hex-2-enyl, hex-3-enyl, hex-4-enyl and hex-5-enyl groups. The above alkenyl groups can be bonded to the urethane group in particular in the 1-position. Thus, the hex-2-enyl group has the following formula: [ka] (where the wavy line represents the point of attachment of the compound of formula (I) to the urethane group) It can be expressed by:

[0054] The R' group is cycloalkyl, particularly C5 to C 12 Examples of suitable cycloalkyl groups are cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl.

[0055] The R' group is an aryl, particularly C6 to C 12It may be aryl. Examples of suitable aryl groups are phenyl, naphthyl, biphenyl, ortho-, meta- or para-tolyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-xylyl and mesityl.

[0056] The R' group is an arylalkyl, particularly C7 to C 12 It may be arylalkyl. Examples of suitable arylalkyl groups are benzyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl and 2-phenylbutyl.

[0057] The R' group is -[(CR a R b ) n -O] m may be a -Y group, where Y is selected from alkyl, alkenyl, cycloalkyl, aryl, and arylalkyl; R a and R b is independently selected from H and methyl, in particular H; each n is independently equal to 2, 3, or 4, particularly n is 2; m is in the range of 1 to 30, particularly m is in the range of 2 to 25.

[0058] ·-[(CR a R b ) n -O] m Examples of -Y groups are alkoxylated derivatives of the above-mentioned alkyl, alkenyl, cycloalkyl, aryl, and alkylaryl groups. Particularly suitable are polyethylene glycols, polypropylene glycols, copoly(ethylene glycol / propylene glycol), and polytetramethylene glycols containing terminal groups selected from the above-mentioned alkyl, alkenyl, cycloalkyl, aryl, and arylalkyl groups. These groups can be obtained, in particular, by reacting alcohols R'OH having the above-mentioned R' groups with cyclic compounds selected from ethylene oxide, propylene oxide, tetrahydrofuran, and mixtures thereof.

[0059] The R' group is -[(CR c R d ) p -C(=O)O] q may be a -Z group, where Z is selected from alkyl, alkenyl, cycloalkyl, aryl, and arylalkyl; R c and R d is independently selected from H and methyl, in particular H; p ranges from 3 to 5, and in particular p is 5; q is in the range of 1 to 20, particularly q is in the range of 2 to 10.

[0060] ·-[(CR c R d ) p -C(=O)O] q Examples of -Z groups are esterified derivatives of the above-mentioned alkyl, alkenyl, cycloalkyl, aryl, and arylalkyl groups. Particularly suitable polyesters contain end groups selected from the above-mentioned alkyl, alkenyl, cycloalkyl, aryl, and arylalkyl groups. These groups can be obtained, in particular, by reacting an alcohol R'OH having the above-mentioned R' group with a lactone selected from γ-butyrolactone, δ-valerolactone, ε-caprolactone, and mixtures thereof.

[0061] According to one embodiment, each R' is selected from the group consisting of alkyl and -[(CR a R b ) n -O] m In particular, each R' is independently selected from linear or branched C-C 30 Alkyl and -[CH2-CH2-O] m -Y, where Y is C-C 24 alkyl, and m ranges from 1 to 25. More particularly, each R' is a branched C-C 20 Alkyl and -[CH2-CH2-O] m-Y, where Y is C1-C6 alkyl and m ranges from 1 to 20.

[0062] Even more particularly, each R' is octyl, X 1-6 -Methylheptyl, 2-ethylhexyl, nonyl, X 1-7 -Methyloctyl, Decyl, X 1-8 -Methylnonyl, undecyl, X 1-9 -Methyldecyl, dodecyl, X 1-10 -Methylundecyl, Tridecyl, X 1-11 -methyldodecyl, 2,5,9-trimethyldecyl, tetradecyl, X 1-12 -Methyltridecyl, Pentadecyl, X 1-13 -methyltetradecyl, hexadecyl, X 1-14 -methylpentadecyl, heptadecyl, X 1-15 -Methylhexadecyl, octadecyl, X 1-16 -Methylheptadecyl, Nonadecyl, X 1-17 -Methyloctadecyl, icosyl, X 1-18 -methylnonadecyl, henicosyl, X 1-19 -Methylicosyl, docosyl, X 1-20 -methylhenicosyl, 2-propylheptyl, 2-propylnonyl, 2-pentylnonyl, 2-butyloctyl, 2-butyldecyl, 2-hexyloctyl, 2-hexyldecyl, 2-octyldecyl, 2-hexyldodecyl, 2-octyldodecyl, 2-decyltetradecyl, 6-methyldodecyl and their isomers, ·-[CH2-CH2-O]3-(CH2)3-CH3 and ·-[CH2-CH2-O] m -CH3 (wherein m=2 to 20).

[0063] The compounds of formula (I) may have the same or different R' groups. The compounds of formula (I) may have R' groups with different molecular weights. The compounds of formula (I) may have R' groups with different chemical properties, particularly hydrophilicity.

[0064] The composition of the present invention may include compounds of formula (I) with the same R' group. The composition of the present invention may include compounds of formula (I) with different R' groups. The composition of the present invention may include compounds of formula (I) with the same R' group and compounds of formula (I) with different R' groups.

[0065] The compositions according to the invention may in particular comprise compounds of formula (I) in which the R' groups are identical. The R' groups may be identical and correspond to R1, which may be linear or branched C1-C1, as described above. 30 Alkyl, especially linear or branched C8-C 20 Alkyl, more particularly branched C8-C 20 It is alkyl.

[0066] The composition according to the invention may in particular comprise a mixture of compounds of formula (I), said mixture comprising at least one compound of formula (I) in which the R' groups are different. The mixture may comprise at least one compound of formula (I) in which the R' groups have different molecular weights. The mixture may comprise at least one compound of formula (I) in which the R' groups have different chemical properties, in particular hydrophilicity.

[0067] Compositions comprising compounds of formula (I) with different R' groups can in particular be obtained by forming compounds of formula (I) using a mixture of at least two different alcohols R'-OH, in particular corresponding to R4-OH and R5-OH.

[0068] In particular, the mixture of compounds of formula (I) - at least one compound of formula (I) in which the R' groups are different, one R' group corresponding to R4 and the other R' group corresponding to R5; - optionally compounds of formula (I) in which the R' groups are identical and correspond to R4; optionally, compounds of formula (I) in which the R' groups are identical and correspond to R5 wherein R4 and R5 are as described above for R'.

[0069] The mixture of compounds of formula (I) may in particular comprise compounds of formula (Ia), optionally in admixture with compounds of formula (Ib) and / or compounds of formula (Ic): [ka] (In the above formula, all R groups are identical and are as described above for R'; all R5 groups are identical and are as described above for R'; R4 group is different from R5)

[0070] The R4 group may be more hydrophobic than the R5 group; and / or the R5 group may have a higher molecular weight than the molecular weight of the R4 group.

[0071] The molecular weights of the R4 and R5 groups can be different. In particular, the R4 group can have a lower molecular weight than the R5 group. More particularly, the difference between the molecular weights of the R4 and R5 groups can be at least 50, at least 100, at least 150, at least 200, at least 300, or at least 350 g / mol.

[0072] The chemical nature of the R4 and R5 groups may differ. In particular, the R4 group may be more hydrophobic than the R5 group.

[0073] The R4 and R5 groups are groups of the formula -[(CR a R b ) n -O] m -Y groups, and Y, R a , R b , n and m are as described above. Alternatively, the R group can be a linear or branched C-C 30 alkyl, and the R5 group is of the formula -[(CR a R b )nO] m -Y (wherein Y, R a , R b , n and m are as defined above).

[0074] The total molar amount of R5 groups, in particular the least hydrophobic groups and / or those with the highest molecular weight, may in particular account for more than 20%, in particular 25% to 95%, 30% to 90%, 35% to 85%, or 40% to 80% of the total molar amount of R4 and R5 groups of all products having one or more functional groups selected from urea, urethane, and mixtures thereof in the composition according to the invention, excluding aprotic solvents.

[0075] The composition according to the invention may in particular comprise a mixture of compounds of formula (I), said mixture comprising at least two different compounds of formula (I) with different R' groups. The mixture may comprise at least two different compounds of formula (I) with R' groups having different molecular weights. The mixture may comprise at least two different compounds of formula (I) with R' groups having different chemical properties, in particular hydrophilicity.

[0076] Compositions comprising at least two compounds of formula (I) with different R' groups can in particular be obtained by forming diurea-diurethane compounds of formula (I) using a mixture of at least three different alcohols R'-OH, in particular corresponding to R4-OH, R5-OH and R6-OH.

[0077] The mixture of compounds of formula (I) - at least one compound of formula (I) in which the R' groups are different, one of the R' groups corresponding to R4 and the other R' group corresponding to R5; and - at least one compound of formula (I) in which the R' groups are different, one R' group corresponding to R4 and the other R' group corresponding to R6; - optionally compounds of formula (I) in which the R' groups are different, one of the R' groups corresponding to R5 and the other R' group corresponding to R6; - optionally compounds of formula (I) in which the R' groups are identical and correspond to R4; - optionally compounds of formula (I) in which the R' groups are identical and correspond to R5; optionally, compounds of formula (I) in which the R' groups are identical and correspond to R6 and R 4 , R 5 and R6 is as described above for R'.

[0078] The mixture of compounds of formula (I) may in particular comprise a compound of formula (Ia), a compound of formula (Id), and optionally one or more compounds of formula (Ib), (Ic), (Ie) or (If), as depicted below: [ka] (In the above formula, all R groups are identical and are as described above for R'; all R5 groups are identical and are as described above for R'; all R groups are identical and are as described above for R'; The R4 group is different from R5; The R4 group is different from R6; The R5 group is different from R6).

[0079] The R4 group may be more hydrophobic than the R5 and / or R6 groups; and / or the R4 group may have a lower molecular weight than the R5 and / or R6 groups.

[0080] The molecular weights of the R4, R5, and R6 groups can be different. In particular, the R4 group can have a lower molecular weight than the R5 group; and / or the R4 group can have a lower molecular weight than the R6 group; and / or the R5 group can have a lower molecular weight than the R6 group. More particularly, the R4 group has a lower molecular weight than the R5 and R6 groups. Even more particularly, the difference between the molecular weight of the R4 group and the R5 group; and / or the difference between the molecular weight of the R4 group and the R6 group; and / or the difference between the molecular weight of the R5 group and the R6 group can be at least 50, at least 100, at least 150, at least 200, at least 300, or at least 350 g / mol.

[0081] The R4, R5, and R6 groups may have different chemical properties. In particular, the R4 group may be more hydrophobic than the R5 group; and / or the R4 group may be more hydrophobic than the R6 group; and / or the R5 group may be more hydrophobic than the R6 group. More particularly, the R4 group may be more hydrophobic than the R5 and R6 groups.

[0082] The R4 group is a linear or branched C1-C 30 alkyl, and the R5 and R6 groups have different molecular weights and the formula -[(CR a R b ) n -O] m -Y groups, and Y, R a , R b , n and m are as described above.

[0083] The total molar amount of R5 and R6 groups, in particular the total molar amount of the least hydrophobic groups and / or the groups with the highest molecular weight, may in particular account for more than 20%, in particular 25% to 95%, 30% to 90%, 35% to 85%, or 40% to 80% of the total molar amount of R4, R5 and R6 groups of all products having one or more functional groups selected from urea, urethane and mixtures thereof in the composition according to the present invention, excluding aprotic solvents.

[0084] According to a preferred embodiment, more than 20 mol %, in particular 25 mol % to 95 mol %, 30 mol % to 90 mol %, 35 mol % to 85 mol %, or 40 mol % to 80 mol % of all R′ groups contained in the compound of formula (I) are hydrophilic groups, in particular −[(CR a R b ) n -O] m -Y group.

[0085] The R' group may in particular be the residue of one or more alcohols of formula R'-OH, excluding the OH group. The alcohols R'-OH are in particular C1 to C6 substituted with an OH group. 30 Alkanes, C2 to C substituted with OH groups 30 Alkenes, C5 to C substituted with OH groups 12 Cycloalkanes, C6 to C substituted with OH groups12 Arenes, C7 to C substituted with OH groups 12 Arylalkanes, HO-[(CR a R b ) n -O] m -Y and HO-[(CR c R d ) p -C(=O)O] q You can choose from -Z, Y and Z are C1 to C 30 Alkyl, C2 to C 30 Alkenyl, C5 to C 12 Cycloalkyl, C6 to C 12 Aryl and C7 to C 12 independently selected from arylalkyl; R a , R b , R c and R d is independently selected from H and methyl, in particular H; each n is independently equal to 2, 3, or 4, particularly n is 2; m is in the range of 1 to 30, particularly m is in the range of 2 to 25; p ranges from 3 to 5, and in particular p is 5; q ranges from 1 to 20, and in particular q ranges from 2 to 10.

[0086] C1 to C substituted with OH groups 30 Alkanes include, in particular, octan-1-ol, octan-2-ol, X 1-6 -Methylheptan-1-ol, 2-ethylhexan-1-ol, nonan-1-ol, X 1-7 -methyloctan-1-ol, decan-1-ol, X 1-8 -methylnonan-1-ol, undecan-1-ol, X 1-9 -Methyldecan-1-ol, Dodecan-1-ol, X 1-10 -Methylundecane-1-ol, Tridecan-1-ol, X 1-11 -methyldodecan-1-ol, 2,5,9-trimethyldecan-1-ol, tetradecan-1-ol, X1-12 -Methyltridecan-1-ol, Pentadecane-1-ol, X 1-13 -methyltetradecan-1-ol, hexadecan-1-ol, X 1-14 -Methylpentadecan-1-ol, Heptadecan-1-ol, X 1-15 -methylhexadecan-1-ol, octadecan-1-ol, X 1-16 -Methylheptadecan-1-ol, nonadecan-1-ol, X 1-17 -methyloctadecan-1-ol, icosan-1-ol, X 1-18 -methylnonadecan-1-ol, henicosan-1-ol, X 1-19 -Methylicosan-1-ol, Docosan-1-ol, X 1-20 2-octylhexyl methyl ether, 2-octyl methyl ether, 2-hexyl methyl ether, 2-hexyl methyl ether, 2-hexyl methyl ether, 2-hexyl methyl ether, 2-hexyl methyl ether, 2-hexyl methyl ether, 2-hexyl methyl ether, 2-hexyl methyl ether, 2-hexyl methyl ether, 2-hexyl methyl ether, 2-hexyl methyl ether, 2-hexyl methyl ether, 2-hexyl methyl ether, 2-octyl methyl ether, 2-hexyl methyl ether, 2-octyl methyl ether, 2-decyl methyl ether, 6-methyl methyl ether, and isomers thereof, wherein X a-b represents an integer that can take any value between a and b, and X a-b indicates the position of the alkyl substituent on the alkane. X 1-11 2,5,9-Trimethyldodecan-1-ol is dodecane substituted with an OH group at the 1-position and a methyl group at the 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, or 11-position, such as 2-methyldodecan-1-ol or 11-methyldodecan-1-ol. The term "isomer" is understood to mean an alkyl group containing the same number of carbon atoms but with a different substitution scheme, for example, an ethyl group instead of a methyl or more methyl substituents. Thus, 2,5,9-trimethyldecan-1-ol is an isomer of 2-methyldodecan-1-ol and 11-methyldodecan-1-ol. Preferably, the C1 to C2 substituted with an OH group are 30The alkane is selected from 11-methyldodecan-1-ol and 2,5,9-trimethyldecan-1-ol.

[0087] C2 to C substituted with OH groups 30 Alkenes are particularly well known as Y 2-5 -Hexen-1-ol, Y 2-6 -hepten-1-ol, Y 2-7 -octen-1-ol, Y 2-8 -nonen-1-ol, Y 2-9 -Decen-1-ol, Y 2-10 -Undecen-1-ol, Y 2-11 -dodecen-1-ol, Y 2-12 -Tridecen-1-ol, Y 2-13 -tetradecen-1-ol, Y 2-15 -Hexadecen-1-ol, Y 2-17 -octadecen-1-ol, Y 2-19 -Icosen-1-ol, Y 2-21 -docosene-1-ol, heptadeca-8,11-dien-1-ol, octadeca-9,12-dien-1-ol, nonadeca-10,13-dien-1-ol, icosa-11,14-dien-1-ol, docosa-13,16-dien-1-ol, octadeca-5,9,12-trien-1-ol, octadeca-6,9,12-trien-1-ol, octadeca-9,12,15-trien-1-ol, octadeca-9,11,13-trien-1-ol, icosa-8,11,14-trien-1-ol, icosa-11,14,17-trien-1-ol, wherein X a-b represents an integer that can take any value between a and b, and X a-b indicates the position of the double bond of the alkene. 2-5 -Hexen-1-ol is hexene substituted in the 1-position with OH, and the double bond can be in the 2-, 3-, 4- or 5-position.

[0088] C5 to C substituted with OH groups 12The cycloalkane may in particular be chosen from cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol, cyclononanol, cyclodecanol, cycloundecanol and cyclododecanol, preferably cyclopentanol and cyclohexanol.

[0089] C6 to C substituted with OH groups 12 The arenes may in particular be chosen from phenol, 1- or 2-naphthol, 2-, 3- or 4-phenylphenol, 2-, 3- or 4-methylphenol, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dimethylphenol and 2,4,6-, 2,3,5- or 2,3,6-trimethylphenol.

[0090] C7 to C substituted with OH groups 12 The arylalkane may in particular be chosen from benzyl alcohol, 2-phenylethan-1-ol, 3-phenylpropan-1-ol, 4-phenylbutan-1-ol and 2-phenylbutan-1-ol, preferably benzyl alcohol and 2-phenylethan-1-ol.

[0091] Alcohol HO-[(CR a R b ) n -O] m -Y is in particular a C1 to C2 alkyl group substituted with an OH group as described above. 30 Alkoxylated derivatives of alkanes, C2 to C substituted with OH groups as described above 30 Alkoxylated derivatives of alkenes, C5 to C substituted with OH groups as described above 12 Alkoxylated derivatives of cycloalkanes, C6 to C substituted with OH groups as described above 12 Alkoxylated derivatives of arenes, C7 to C substituted with OH groups as described above 12 The alkoxylated derivatives may be selected from alkoxylated derivatives of arylalkanes. The alkoxylated derivatives may in particular be ethoxylated, propoxylated and / or butoxylated derivatives, preferably ethoxylated derivatives. Preferably, the alcohol HO-[(CRa R b ) n -O] m -Y is selected from polyethylene glycol monomethyl ether (MPEG), polyethylene glycol monoethyl ether and polyethylene glycol monobutyl ether; more preferentially MPEG having a number average molecular weight of 200 to 1000 g / mol (in particular MPEG-250, MPEG-350, MPEG-400, MPEG-450, MPEG-500, MPEG-550, MPEG-650 or MPEG-750), or triethylene glycol monobutyl ether (also known as butyl triglycol (BTG)).

[0092] Alcohol HO-[(CR c R d ) p -C(=O)O] q -Z is in particular a C1 to C2 alkyl group substituted with an OH group as described above. 30 Polyester derivatives of alkanes, C2 to C substituted with OH groups as described above 30 Polyester derivatives of alkenes, C5 to C substituted with OH groups as described above 12 Polyester derivatives of cycloalkanes, C6 to C substituted with OH groups as described above 12 Polyester derivatives of arenes, C7 to C substituted with OH groups as described above 12 It may be a polyester derivative of an arylalkane. The polyester derivative may in particular comprise a polyester moiety obtained by ring-opening polymerization of a lactone, preferably chosen from γ-butyrolactone, δ-valerolactone, ε-caprolactone and mixtures thereof.

[0093] [R2 groups] A compound of formula (I) contains two R2 groups. The R2 groups of one and the same compound of formula (I) may be the same or different. A composition of the present invention may contain a mixture of compounds of formula (I) having the same R2 group. A composition of the present invention may contain a mixture of compounds of formula (I) having different R2 groups. For example, some compounds of the mixture may have the same R2 group and some compounds of the mixture may have different R2 groups.

[0094] Each R group may result from the use of a diisocyanate of formula OCN-R-NCO to form the diurea-diurethane compound of formula (I). The R group may correspond to the residue of a diisocyanate of formula OCN-R-NCO, excluding the NCO group. The R groups and corresponding diisocyanates of formula OCN-R-NCO described below also apply to the method of the present invention.

[0095] Each R2 is independently a divalent group selected from an aliphatic group, an alicyclic group, an aromatic group, and an araliphatic group.

[0096] According to one embodiment, each R2 is independently an aromatic group.

[0097] In particular, each R2 independently has the formula: [ka] (wherein the symbol · represents the point of attachment to the urea or urethane group of formula (I)). is an aromatic group having the formula:

[0098] More particularly, each R2 independently represents the formula: [ka] (wherein the symbol · represents the point of attachment to the urea or urethane group of formula (I)). is an aromatic group having one of the following formulas:

[0099] In particular, the thixotropic compositions according to the invention are characterized in that more than 85 mol%, more than 90 mol%, more than 95 mol%, more than 97 mol%, more than 98 mol%, more than 99 mol%, or 100 mol% of all R groups in the compounds of formula (I) are of the formula: [ka] (wherein the symbol · represents the point of attachment to the urea or urethane group of formula (I)). The aromatic group may be:

[0100] In particular, in the thixotropic compositions of the present invention, 86 mol% to 100 mol%, 90 mol% to 100 mol%, 95 mol% to 100 mol%, 97 mol% to 100 mol%, 98 mol% to 100 mol%, 99 mol% to 100 mol%, or 100 mol% of all R groups in the compound of formula (I) are represented by the formula: [ka] (wherein the symbol · represents the point of attachment to the urea or urethane group of formula (I)). The aromatic group may be:

[0101] The R2 group is bonded on one side to a urethane group (resulting from the reaction of the isocyanate group of the diisocyanate OCN-R2-NCO with the OH group of the alcohol R'OH) and on the other side to a urea group (resulting from the reaction of the other isocyanate group of the diisocyanate OCN-R2-NCO with the NH2 group of the diamine H2N-R3-NH2).

[0102] Even more particularly, each R2 independently represents the formula: [ka] is an aromatic group of the formula:

[0103] When R2 is asymmetric, there may be one side of the R2 group that is preferably attached to the urethane group and the other side that is preferably attached to the urea group. Without wishing to be bound by any theory, the Applicant Company hypothesizes that the least hindered side of the R2 group is preferably attached to the urethane group.

[0104] In particular, the thixotropic compositions according to the invention are characterized in that more than 60 mol%, more than 65 mol%, more than 70 mol%, more than 75 mol%, more than 80 mol%, more than 85 mol%, or more than 90 mol% of all R groups in the compounds of formula (I) are of the formula: [ka] The aromatic group may be:

[0105] In particular, in the thixotropic composition according to the present invention, 61 mol% to 100 mol%, 65 mol% to 100 mol%, 70 mol% to 100 mol%, 75 mol% to 100 mol%, 80 mol% to 100 mol%, 85 mol% to 100 mol%, or 90 mol% to 100 mol% of all R groups in the compound of formula (I) are represented by the following formula: [ka] The aromatic group may be:

[0106] The R2 group may in particular be the residue of one or more diisocyanates of formula OCN-R2-NCO, which lack the NCO group. The diisocyanate of formula OCN-R2-NCO may be toluene diisocyanate (TDI). The TDI may be in the form of one or more isomers selected from toluene-2,4-diisocyanate and toluene-2,6-diisocyanate.

[0107] In the present invention, it is advantageous to use TDI containing a high proportion of toluene-2,4-diisocyanate, in fact TDI containing only toluene-2,4-diisocyanate. The applicant company believes that the asymmetry of this compound makes it possible to reduce the amount of by-products in the composition, especially the compound of formula (II). This allows a high proportion, in fact even exclusively, of the compound of the following formula: [ka] It is then possible to obtain compounds of formula (I) having an R2 group according to

[0108] In particular, the diisocyanate of formula OCN-R2-NCO is a TDI containing more than 85 mol%, more than 90 mol%, more than 95 mol%, more than 97 mol%, more than 98 mol%, more than 99 mol%, or 100 mol% toluene-2,4-diisocyanate, based on the total amount of toluene diisocyanate isomers. More particularly, the diisocyanate of formula OCN-R2-NCO is a TDI containing 86 mol% to 100 mol%, 90 mol% to 100 mol%, 95 mol% to 100 mol%, 97 mol% to 100 mol%, 98 mol% to 100 mol%, 99 mol% to 100 mol%, or 100 mol% toluene-2,4-diisocyanate, based on the total amount of toluene diisocyanate isomers. Preferably, the diisocyanate of formula OCN-R2-NCO is a TDI containing 100 mole % toluene-2,4-diisocyanate based on the total amount of toluene diisocyanate isomers.

[0109] [R3 groups] Compounds of formula (I) contain an R group. Compositions of the present invention may contain mixtures of compounds of formula (I) having the same R group. Compositions of the present invention may contain mixtures of compounds of formula (I) having different R groups.

[0110] Each R group may result from the use of a diamine of formula HN-R-NH to form the diurea-diurethane compound of formula (I). The R group may correspond to the residue of a diamine of formula HN-R-NH, excluding the NH group. The R groups and corresponding diamines of formula HN-R-NH described below also apply to the methods of the present invention.

[0111] Each R3 is independently a divalent group selected from an aliphatic group, an alicyclic group, an aromatic group, an araliphatic group, and a heterocyclic group.

[0112] According to certain embodiments, each R3 is independently C2-C 24 Alkylene, -(CR h R i ) s -[A-(CR j R k ) t ] u -,-(CR1R m ) v -CY-(CR n R o ) w -and-(CR p R q ) x -CY-(CH2) y -CY-(CR r R s ) z - is a group selected from; In the above formula, A is O or NX; R h , R i , R j , R k , R l , R m , R n , R o , R p , R q , R r and R s is independently selected from H and methyl, in particular H; X is C1 to C6 alkyl, in particular methyl or ethyl; CY is a ring selected from phenyl, cyclohexyl, naphthyl, decahydronaphthyl, piperazinyl, triazinyl, and pyridinyl, which ring is unsubstituted or substituted with 1 to 3 C1-C4 alkyl groups; s ranges from 2 to 4, and in particular s is 2; t ranges from 2 to 4, and in particular t is 2; u ranges from 1 to 30; v, w, x, y, and z independently range from 0 to 4.

[0113] Each R3, in particular, 24 Alkylene and -(CR m ) v -CY-(CR n R o ) w a group selected from In particular, C2-C 18 Alkylene and -(CH2) v -CY-(CH2) w -, wherein CY is a cyclohexyl or phenyl ring, which ring is unsubstituted or substituted with 1 to 3 C1-C4 alkyl groups, and v and w range from 0 to 1. It is possible.

[0114] More particularly, each R3 is selected from the group consisting of C2-C6 alkylene and the following formula: [ka] (wherein the symbol · represents the point of attachment to the urea group of the compound of formula (I)). It can be a group selected from groups having the formula:

[0115] In particular, the thixotropic compositions according to the invention are characterized in that more than 85 mol%, more than 90 mol%, more than 95 mol%, more than 97 mol%, more than 98 mol%, more than 99 mol%, or 100 mol% of all R groups in the compounds of formula (I) are of the formula: [ka] It can be a group of

[0116] In particular, in the thixotropic compositions of the present invention, 86 mol% to 100 mol%, 90 mol% to 100 mol%, 95 mol% to 100 mol%, 97 mol% to 100 mol%, 98 mol% to 100 mol%, 99 mol% to 100 mol%, or 100 mol% of all R groups in the compound of formula (I) are represented by the formula: [ka] It can be a group of

[0117] The R group may in particular be the residue of a diamine(s) of formula H2N-R3-NH2 without an NH2 group. Diamines of formula H2N-R3-NH2 are those having C2 to C 24 Aliphatic diamines, C6 to C 18 Alicyclic diamines, C6 to C 24 Aromatic diamines, C7 to C 26 Aromatic and aliphatic diamines and C3 to C 18 It may be selected from heterocyclic diamines.

[0118] C2 to C 24Aliphatic diamines are diamines of the formula H2N-R3-NH2, where R3 is an aliphatic group containing 2 to 24 carbon atoms. Aliphatic diamines can be linear or branched, preferably linear. Aliphatic diamines can be polyetheramines, i.e., diamines of the formula H2N-R3-NH2, where R3 contains ether (-O-) linkages, more particularly ethylene oxide (-O-CH2-CH2) and / or propylene oxide (-O-CH2-CHCH3-) units. Aliphatic diamines can be polyalkyleneimines, i.e., diamines of the formula H2N-R3-NH2, where R3 is interrupted by one or more tertiary amine groups (-NX-, where X is a C1 to C6 alkyl). Aliphatic diamines may be interrupted by one or more tertiary amine groups. Examples of suitable linear aliphatic diamines are 1,2-ethylenediamine, 1,3-propylenediamine, 1,4-tetramethylenediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,8-octamethylenediamine, 1,12-dodecamethylenediamine, and mixtures thereof; preferably 1,2-ethylenediamine, 1,5-pentamethylenediamine, and 1,6-hexamethylenediamine. Examples of suitable branched aliphatic diamines are 1,2-propylenediamine, 2,2-dimethyl-1,3-propanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, and mixtures thereof. Examples of polyetheramines are compounds sold by Huntsman under the Jeffamine® reference name, in particular the Jeffamine® D, ED, and EDR series (diamines). These series include in particular the following references: Jeffamine® D-230, Jeffamine® D-400, Jeffamine® D-2000, Jeffamine® D-4000, Jeffamine® ED-600, Jeffamine® ED-900, Jeffamine® ED-2003, Jeffamine® EDR-148 and Jeffamine® EDR-176. An example of a polyalkyleneimine is 3,3′-diamino-N-methyldipropylamine.

[0119] C6 to C 18 Cycloaliphatic diamines are diamines of the formula H2N-R3-NH2, where R3 is an alicyclic group containing 6 to 18 carbon atoms. Examples of suitable cycloaliphatic diamines are 1,2-, 1,3- or 1,4-diaminocyclohexane, 2-methylcyclohexane-1,3-diamine, 4-methylcyclohexane-1,3-diamine, isophoronediamine, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, diaminodecahydronaphthalene, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexylmethane, bis(aminomethyl)norbornane and mixtures thereof; Preferred are 1,3- or 1,4-bis(aminomethyl)cyclohexane, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, isophoronediamine and 4,4'-diaminodicyclohexylmethane.

[0120] C6 to C 24 Aromatic diamines are diamines of the formula H2N-R3-NH2, where R3 is an aromatic group containing 6 to 24 carbon atoms. Examples of suitable aromatic diamines are ortho-, meta- and para-phenylenediamine, ortho-, meta- and para-tolylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether and mixtures thereof; preferably ortho-, meta- and para-phenylenediamine.

[0121] C7 to C 26 Araliphatic diamines are diamines of the formula HN-R-NH, where R is an araliphatic group containing from 7 to 26 carbon atoms. Examples of suitable araliphatic diamines are ortho-, meta-, and para-xylylenediamine, 4,4'-diaminodiphenylmethane, and mixtures thereof; preferably ortho-, meta-, and para-xylylenediamine.

[0122] C3 to C 18Heterocyclic diamines are diamines of the formula HN-R-NH, where R is a heterocyclic group containing 3 to 18 carbon atoms. Examples of suitable heterocyclic diamines are 1,2-diaminopiperazine, 1,4-diaminopiperazine, 1,4-bis(3-aminopropyl)piperazine, 2,3-, 2,6- and 3,4-diaminopyridine, 2,4-diamino-1,3,5-triazine and mixtures thereof.

[0123] [Aprotic solvents] The thixotropic composition according to the present invention comprises an aprotic solvent. The thixotropic composition may comprise a mixture of aprotic solvents.

[0124] According to one embodiment, the aprotic solvent is selected from dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, N-propylpyrrolidone, N-butylpyrrolidone, N,N,N',N'-tetramethylurea and mixtures thereof, in particular, the aprotic solvent is selected from dimethyl sulfoxide, N-butylpyrrolidone and mixtures thereof.

[0125] The thixotropic composition may in particular comprise from 20% to 95% by weight, in particular from 40% to 80% by weight, more particularly from 50% to 70% by weight of aprotic solvent relative to the weight of the thixotropic composition.

[0126] [Diurethane compounds] The thixotropic composition according to the present invention may further comprise a diurethane compound. The thixotropic composition may comprise a mixture of diurethane compounds.

[0127] Diurethane compounds may be by-products resulting from the process for preparing the thixotropic compositions of the present invention described below, since the reaction of a diisocyanate of formula OCN-R2-NCO with an alcohol of formula R'-OH to form a monoisocyanate adduct of formula R'-OC(=O)-NH-R2-NCO may also produce diurethanes when the alcohol is in stoichiometric excess relative to the diisocyanate.

[0128] Without wishing to be bound by any theory, the Applicant Company believes that the diurethane can stabilize the thixotropic composition and reduce the number of by-products obtained during its preparation. The presence of the diurethane in the thixotropic composition makes it possible to eliminate or significantly reduce the amount of salts, especially lithium salts, or surfactants, compared to prior art compositions.

[0129] The diurethane compound is in particular a compound of formula (II): [ka] wherein R′ and R2 are as described above for compounds of formula (I). The compound may correspond to the compound

[0130] According to a particular embodiment, the thixotropic composition comprises from 20% to 95%, in particular from 25% to 85%, more particularly from 35% to 75% by mole of compounds of formula (II) relative to the total molar amount of compounds having one or more functional groups selected from urea, urethane and mixtures thereof, excluding the aprotic solvent.

[0131] [Polyurea-diurethane compound] The thixotropic composition according to the present invention may further comprise a polyurea-diurethane compound. The thixotropic composition may comprise a mixture of polyurea-diurethane compounds.

[0132] The polyurea-diurethane compound may be a by-product resulting from the process for preparing the thixotropic composition according to the present invention, as described below. This is because, when the reaction medium contains a diisocyanate of the formula OCN-R2-NCO, polyurea-diurethane may also be produced by the reaction between a monoisocyanate adduct of the formula R'-OC(=O)-NH-R2-NCO and a diamine of the formula H2N-R3-NH2. The diisocyanate may in particular be a residual diisocyanate resulting from the reaction of a diisocyanate of the formula OCN-R2-NCO with an alcohol of the formula R'-OH to form a monoisocyanate adduct of R'-OC(=O)-NH-R2-NCO.

[0133] The polyurea-diurethane compounds are in particular those of formula (III): [ka] wherein R', R2 and R3 are as described above for compounds of formula (I); z is 1 to 10.

[0134] Since polyurea-diurethane compounds are generally solids, it is advantageous to limit their amount in the thixotropic composition. It is possible to reduce the content of residual diisocyanates by carrying out a distillation step before the reaction of the monoisocyanate adduct with the diamine, but this is not inconsiderable and requires special plant. The composition according to the present invention has a low content of polyurea-diurethane compounds, even though the preparation method does not require a distillation step for residual diisocyanates. This is possible, in particular, by adjusting the molar ratios of the reactants used in the preparation method of the thixotropic composition described below.

[0135] According to certain embodiments, the thixotropic composition comprises less than 4% by mole, in particular 3.0% to 1.5%, 2.0% to 1.0%, or 1.0% to 0% of a compound of formula (III) relative to the total molar amount of compounds having one or more functional groups selected from urea, urethane and mixtures thereof, excluding the aprotic solvent.

[0136] [Method for preparing thixotropic composition] The thixotropic composition according to the present invention can be prepared according to the method described below.

[0137] The preparation method according to the present invention comprises step a), step b), and optionally one or more additional steps which can be carried out before step a), between steps a) and b), and / or after step b).

[0138] Step a) is a step in which at least one diisocyanate of formula OCN-R2-NCO reacts with at least one alcohol of formula R'-OH to form at least one monoisocyanate adduct of formula R'-OC(=O)-NH-R2-NCO.

[0139] Step b) is a compound of formula (I): [ka] (In the above formula, Each R' is an alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, -[(CR a R b ) n -O] m -Y and ·-[(CR c R d ) p -C(=O)O] q - independently selected from Z; The symbol · represents the point of attachment to the urethane group of formula (I); each R2 is independently a divalent group selected from an aliphatic group, an alicyclic group, an aromatic group, and an araliphatic group; each R3 is independently a divalent group selected from an aliphatic group, an alicyclic group, an aromatic group, an araliphatic group, and a heterocyclic group; Y and Z are independently selected from alkyl, alkenyl, cycloalkyl, aryl, and arylalkyl; R a , R b , R c and R d is independently selected from H and methyl, in particular H; each n is independently equal to 2, 3, or 4, particularly n is 2; m is in the range of 1 to 30, particularly m is in the range of 2 to 25; p ranges from 3 to 5, and in particular p is 5; q ranges from 1 to 20, and specifically q ranges from 2 to 10) reacting the at least one monoisocyanate adduct obtained in step a) with at least one diamine of formula H2N-R3-NH2 to form at least one compound of formula

[0140] The R', R2 and R3 groups, the diisocyanate of formula OCN-R2-NCO, the alcohol of formula R'-OH, and the diamine of formula H2N-R3-NH2 may be as described above for compounds of formula (I). The particular embodiments described for compounds of formula (I) also apply to the methods of the present invention.

[0141] Step a) can be carried out, in particular, by gradually adding at least one alcohol to a reactor containing at least one diisocyanate. The at least one diisocyanate can be in particular in a molten state. The rate of addition of the at least one alcohol can be controlled to limit exothermic heat generation. In particular, the rate of addition of the at least one alcohol can be controlled to maintain the temperature of the reaction medium below 60°C, in particular between 20 and 60°C, between 25 and 55°C, or between 30 and 40°C.

[0142] Step a) is carried out at a molar ratio of the total amount of alcohols to the total amount of diisocyanates of 1.10 to 1.80. In particular, the molar ratio of the total amount of alcohols to the total amount of diisocyanates in step a) ranges from 1.20 to 1.60, more particularly from 1.25 to 1.45, and even more particularly from 1.30 to 1.40.

[0143] The ratio of alcohol to diisocyanate in step a) makes it possible to limit the amount of residual diisocyanate at the end of step a). The amount of residual diisocyanate at the end of step a) corresponds to the amount of diisocyanate introduced in step a) that has not reacted with the at least one alcohol. Controlling the amount of residual diisocyanate at the end of step a) advantageously makes it possible to limit the formation of insoluble substances in step b), in particular compounds of formula (III) above. According to a particular embodiment, the amount of residual diisocyanate in the reaction mixture at the end of step a) is less than 6 mol %, in particular 0 to 5 mol %, 0.01 to 4.5 mol %, or 0.05 to 4 mol %, relative to the molar amount of all compounds having one or more functional groups selected from urethane, isocyanate, and mixtures thereof.

[0144] The ratio of alcohol to diisocyanate in step a) advantageously makes it possible to avoid carrying out a step of removing the residual diisocyanate, since the amount of residual diisocyanate at the end of step a) is sufficiently small so as not to result in the excessive formation of insoluble substances in step b), in particular the compound of formula (III) above. According to a particular embodiment, the process according to the invention does not comprise a step of distillation of the residual diisocyanate, in particular a step of distillation of the residual diisocyanate between steps a) and b).

[0145] Depending on the ratio of alcohol to diisocyanate in step a), one or more diurethane compounds as described above may be formed. Diurethane compounds may result in particular from the reaction of an alcohol of formula R'-OH with a monoisocyanate adduct of formula R'-OC(=O)-NH-R2-NCO. Thus, the reaction mixture obtained in step a) may contain a monoisocyanate adduct of formula R'-OC(=O)-NH-R2-NCO and a diisocyanate adduct of formula (II): [ka] wherein R' and R2 are as described above.

[0146] Without wishing to be bound by any theory, the Applicant Company believes that the presence of the diurethane compound in the thixotropic composition makes it possible to stabilize the urea bonds formed in step b), and therefore, compared to prior art methods, the amount of stabilizer (especially salts, such as lithium salts, or surfactants) added in step b) can be significantly reduced, and in fact can even be eliminated.

[0147] When the addition of at least one alcohol is complete, step a) can be continued until the NCO number of the reaction mixture reaches the theoretical NCO number. The NCO number at the end of step a) can be less than 200 mg KOH / g. In particular, the NCO number at the end of step a) can be 5 to 150 mg KOH / g, 25 to 125 mg KOH / g, 50 to 100 mg KOH / g, or 60 to 80 mg KOH / g. The NCO number at the end of step a) can be measured in particular according to the method described below. The theoretical NCO number at the end of step a) can be calculated in particular according to the method described below.

[0148] Step b) can in particular be carried out by gradually adding the mixture obtained in step a) to a reactor containing at least one diamine and optionally an aprotic solvent and / or a salt. The rate of addition of the mixture obtained in step a) can be controlled to limit the heat generation. In particular, the rate of addition of the mixture obtained in step a) can be controlled to maintain the temperature of the reaction medium below 80°C, in particular between 20 and 80°C, between 30 and 70°C or between 40 and 60°C.

[0149] Once the addition of the at least one monoisocyanate adduct is complete, step b) can be continued until the NCO value of the reaction mixture reaches the desired value. The NCO value of the composition obtained by the method of the present invention can be in particular less than 0.5 mg KOH / g, in particular less than 0.2 mg KOH / g, more particularly less than 0.1 mg KOH / g, and even more particularly 0 mg KOH / g. The NCO value of the composition can in particular be determined according to the method described below.

[0150] Step b) is carried out in the presence of less than 0.2 moles of salt per mole of diamine used. In particular, step b) is carried out in the presence of 0 to 0.19, 0 to 0.15, 0 to 0.1, 0 to 0.05, 0 to 0.02, 0 to 0.01, or 0 moles of salt per mole of diamine used. The salt may, in particular, be as described above for the thixotropic composition.

[0151] Step b) may be carried out in the presence of less than 0.2 moles of surfactant per mole of diamine used. In particular, step b) is carried out in the presence of 0 to 0.19, 0 to 0.15, 0 to 0.1, 0 to 0.05, 0 to 0.02, 0 to 0.01, or 0 moles of surfactant per mole of diamine used. The surfactant may, in particular, be as described above for the thixotropic composition.

[0152] The molar ratio of the total amount of monoisocyanate adducts to the total amount of diamines in step b) can be in the range of 1.8 to 2.2. In particular, the molar ratio of the total amount of monoisocyanate adducts to the total amount of diamines in step b) is in the range of 1.9 to 2.1, more particularly 1.95 to 2.05, and even more particularly 1.98 to 2.02.

[0153] To reduce the viscosity of the composition and dissolve the resulting compounds, a solvent can be added in step a) and / or step b) and / or between steps a) and b). In particular, step a) and / or step b) can be carried out in the presence of an aprotic solvent. The viscosity of the reaction medium obtained at the end of step a) can be reduced by adding an aprotic solvent. The aprotic solvent can in particular be as described above for the thixotropic composition.

[0154] The process according to the invention can be carried out in step a) using an alcohol or a mixture of alcohols.

[0155] According to a first embodiment, in step a), at least one diisocyanate is reacted with a single alcohol of formula R1-OH to form at least one monoisocyanate adduct of formula R1-OC(=O)-NH-R2-NCO, In step b), a compound of formula (I'): [ka] (In the above formula, The R groups are identical and are as described above for R'; The product obtained in step a) is reacted with at least one diamine of formula H2N-R3-NH2 to form at least one compound of formula H2N-R3-NH2, wherein R2 and R3 are as described above.

[0156] The alcohol R1-OH of the first embodiment is in particular a linear or branched C1-C2 alkyl group substituted with OH. 30 It can be alkyl.

[0157] According to a second embodiment, in step a) at least one diisocyanate is reacted with at least two different alcohols of formulae R4-OH and R5-OH to form a mixture of at least two monoisocyanate adducts of formulae R4-OC(=O)-NH-R2-NCO and R5-OC(=O)-NH-R2-NCO, In step b), the mixture obtained in step a) is reacted with at least one diamine of formula H2N-R3-NH2 to form at least one compound of formula (Ia), optionally in admixture with a compound of formula (Ib) and / or a compound of formula (Ic): [ka] (In the above formula, all R groups are identical and are as described above for R'; all R5 groups are identical and are as described above for R'; The R4 group is different from R5).

[0158] The R4 and R5 groups and the alcohols of formula R4-OH and R5-OH may in particular be as described above for compounds of formula (I).

[0159] In a second embodiment, the alcohol R4-OH may be more hydrophobic than the alcohol R5-OH; and / or the alcohol R5-OH may have a higher molecular weight than the molecular weight of the alcohol R4-OH.

[0160] In a second embodiment, the molecular weights of the alcohols R4-OH and R5-OH can be different. In particular, R4-OH can have a lower molecular weight than R5-OH. More particularly, the difference between the molecular weight of R4-OH and the molecular weight of R5-OH can be at least 50, at least 100, at least 150, at least 200, at least 300, or at least 350 g / mol.

[0161] In a second embodiment, the chemical nature of the alcohols R4-OH and R5-OH may be different. In particular, the alcohol R4-OH may be more hydrophobic than the alcohol R5-OH.

[0162] In a second embodiment, the alcohols R4-OH and R5-OH have the formula HO-[(CR a R b ) n -O] m -Y may be an alcohol of Y, R a , R b , n and m are as described above. Alternatively, the alcohol R4-OH can be a linear or branched C1-C 30 The alcohol R5-OH can be Y, R a , R b , n and m are as described above, a R b ) n -O] m -Y alcohol.

[0163] In a second embodiment, the total molar amount of alcohols R5-OH, in particular the least hydrophobic alcohols and / or the alcohols with the highest molecular weight, may in particular represent more than 20%, in particular between 25% and 95%, between 30% and 90%, between 35% and 85%, or between 40% and 80% of the total molar amount of alcohols R4-OH and R5-OH introduced in step a).

[0164] In a second embodiment, the alcohols R5-OH, in particular the least hydrophobic alcohols and / or the alcohols with the highest molecular weight, can be reacted with a diisocyanate before the alcohols R4-OH, in particular the most hydrophobic alcohols and / or the alcohols with the lowest molecular weight, are introduced into the reaction mixture of step a).

[0165] According to a third embodiment, in step a), a diisocyanate is reacted with a mixture of at least three different alcohols of formulae R4-OH, R5-OH and R6-OH to form a mixture of at least three monoisocyanate adducts of formulae R4-OC(=O)-NH-R2-NCO, R5-OC(=O)-NH-R2-NCO and R6-OC(=O)-NH-R2-NCO, In step b), the mixture obtained in step a) is reacted with at least one diamine of formula H2N-R3-NH2 to form a compound of formula (Ia), a compound of formula (Id), and optionally one or more compounds of formula (Ib), (Ic), (Ie) or (If), as represented below: [ka] (In the above formula, all R groups are identical and are as described above for R'; all R5 groups are identical and are as described above for R'; all R groups are identical and are as described above for R'; The R4 group is different from R5; The R4 group is different from R6; The R5 group is different from R6).

[0166] The R4, R5 and R6 groups and the alcohols of formula R4-OH, R5-OH and R6-OH may in particular be as described above for compounds of formula (I).

[0167] In a third embodiment, the alcohol R4-OH may be more hydrophobic than the alcohol R5-OH and / or the alcohol R6-OH, and / or the alcohol R4-OH may have a lower molecular weight than the molecular weight of the alcohol R5-OH and / or the molecular weight of the alcohol R6-OH.

[0168] In a third embodiment, the molecular weights of the alcohols R4-OH, R5-OH, and R6-OH may be different. In particular, R4-OH may have a lower molecular weight than R5-OH; and / or R4-OH may have a lower molecular weight than R6-OH; and / or R5-OH may have a lower molecular weight than R6-OH. More particularly, the alcohol R4-OH has a lower molecular weight than the alcohols R5-OH and R6-OH. Even more particularly, the difference between the molecular weight of R4-OH and the molecular weight of R5-OH; and / or the difference between the molecular weight of R4-OH and the molecular weight of R6-OH; and / or the difference between the molecular weight of R5-OH and the molecular weight of R6-OH may be at least 50, at least 100, at least 150, at least 200, at least 300, or at least 350 g / mol.

[0169] The alcohols R4-OH, R5-OH, and R6-OH may have different chemical properties. In particular, R4-OH may be more hydrophobic than R5-OH; and / or R4-OH may be more hydrophobic than R6-OH; and / or R5-OH may be more hydrophobic than R6-OH. More particularly, the alcohol R4-OH may be more hydrophobic than the alcohols R5-OH and R6-OH.

[0170] In a third embodiment, the alcohol R4-OH is a linear or branched C1-C1 alkyl group substituted with OH. 30 The alcohols R5-OH and R6-OH may be Y, R a , R b , n and m are as described above, b ) n -O] m -Y alcohol.

[0171] The total molar amount of alcohols R5-OH and R6-OH, in particular the total molar amount of the least hydrophobic alcohols and / or the alcohols with the highest molecular weight, may in particular represent more than 20%, in particular from 25% to 95%, from 30% to 90%, from 35% to 85%, or from 40% to 80% of the total molar amount of alcohols R4-OH, R5-OH and R6-OH introduced in step a).

[0172] The alcohols R5-OH and R6-OH, in particular the least hydrophobic alcohols and / or the alcohols with the highest molecular weight, can in particular be reacted with a diisocyanate before the alcohol R4-OH, in particular the most hydrophobic alcohols and / or the alcohols with the lowest molecular weight, is introduced into the reaction mixture of step a).

[0173] [Binder composition] The thixotropic composition according to the invention is advantageously incorporated into a binder composition in order to modify its rheology, in particular to give it a thixotropic or pseudoplastic effect.

[0174] The binder composition according to the present invention comprises a binder and the above-described thixotropic composition.

[0175] According to a particular embodiment, the binder composition is a coating composition, in particular a varnish, a primer, a surface gel, a paint or ink composition, an adhesive, glue or mastic composition, a molding composition, a composite composition, a chemical sealing composition, a leak sealant composition, a photocrosslinkable composition for stereolithography or for 3D printing of objects, in particular by inkjet printing.

[0176] The binder composition may in particular comprise from 0.5% to 15% by weight, in particular from 1% to 10% by weight, more particularly from 2% to 7% by weight of the thixotropic composition, relative to the weight of the binder composition.

[0177] The binder composition may in particular be an aqueous or solvent-based composition. Preferably, the binder composition is an aqueous composition.

[0178] According to certain embodiments, the binder compositions according to the invention are crosslinkable, including those that are self-crosslinkable at ambient temperature, by thermal and / or chemical (in particular by addition of crosslinking agents such as peroxides, epoxy resins, melamine / formaldehyde resins, blocked or unblocked polyisocyanates, anhydrides, amines, hydrazides, aziridines or alkoxysilanes), or by irradiation under radiation such as UV (in the presence of at least one photoinitiator) and / or EB (electron beam without initiator), or non-crosslinkable. The binder compositions can be one-component crosslinkable (a single reactive component) or two-component crosslinkable (binders based on two components that react together by mixing during use).

[0179] The binder may be a binder (binding agent) commonly used in the field of coatings, varnishes, and paints, such as those described in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A18, pp. 368-426, VCH, Weinheim, 1991. According to certain embodiments, the binder is selected from the group consisting of nitrocellulose, cellulose esters (e.g., cellulose acetate or cellulose butyrate), vinyl resins (e.g., polyolefins such as polyethylene or polyisobutylene, olefin-based copolymers such as ethylene-vinyl acetate copolymers, or modified polyolefins such as chlorinated or chlorosulfonylated polyethylene or polypropylene), fluorinated polymers (e.g., polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene (FEP) copolymers, ethylene-tetrafluoroethylene (ETFE) copolymers, polyvinylidene fluoride (PVDF)), polyvinyl esters (e.g., polyvinyl acetate or vinyl acetate-based copolymers), polyvinyl acetates, and the like. alcohols, polyvinyl acetals, polyvinyl ethers, acrylic resins, alkyd resins, polyester- or polyamide-grafted or diurea-diurethane-modified alkyd resins, saturated or unsaturated polyester resins, polyurethanes, crosslinkable two-component polyurethanes, epoxy resins, silicone resins, polysiloxanes, phenolic resins, epoxy-amine (crosslinkable two-component) reaction systems, polysulfide polymers, (meth)acrylate polyfunctional oligomers or acrylated acrylic oligomers or allyl polyfunctional oligomers, elastomers (for example SBR, polychloroprene or butyl rubber), silanized prepolymers (for example silanized polyethers, silanized polyurethanes or silanized polyether-urethanes), and mixtures thereof.

[0180] The binder may be an aqueous dispersion of polymer or copolymer particles, also known as a latex. The polymer or copolymer may be chosen in particular from acrylic, styrene / acrylic, vinyl acetate / acrylic or ethylene / vinyl acetate polymers or copolymers.

[0181] In more particular cases, the binder may be chosen from the following crosslinkable two-component reactive systems: epoxy-amine or epoxy-polyamide systems comprising at least one epoxy resin containing at least two epoxy groups and at least one amino or polyamide compound containing at least two amine groups, polyurethane systems comprising at least one polyisocyanate and at least one polyol, polyol-melamine systems, and polyester systems based on at least one epoxy or a polyol reactive with at least one acid or one corresponding anhydride.

[0182] In other particular cases, the binder may be a crosslinkable two-component polyurethane system or a crosslinkable two-component polyester system starting from an epoxy-carboxylic acid or anhydride reaction system, or from a polyol-carboxylic acid or anhydride system, or from a polyol-melamine reaction system, the polyol being a hydroxylated acrylic resin, or a polyester or polyether polyol.

[0183] In particular, the binder composition according to the present invention is a two-component polyurethane composition based on a hydroxylated acrylic dispersion.

[0184] The binder composition according to the present invention may contain other ingredients such as, for example, fillers, plasticizers, wetting agents, or pigments.

[0185] [use] The thixotropic composition according to the present invention is used as a rheological agent, particularly as a thixotropic agent.

[0186] Thus, by incorporating a thixotropic composition into a binder composition, it is possible to modify its rheology and in particular to give it a thixotropic effect.

[0187] For the purposes of illustrating the invention, the following examples demonstrate, without limiting in any way, the performance qualities of the additives according to the invention. [Example]

[0188] [Measurement method] The measurement methods used in this patent application are described below: [NCO value] The NCO number is quantitatively determined using a Metrohm (848Titrino Plus) titrator equipped with a Metrohm reference 6.0229.100 measuring probe. The sample to be analyzed is weighed and placed in a 250 ml screw-cap Erlenmeyer flask. In step a), 50 ml of dexylene is added, and in step b), 50 ml of DMSO is added, and the Erlenmeyer flask is sealed. The sample is completely dissolved by magnetic stirring with heating if necessary. If heating is required to dissolve the sample, the mixture is allowed to return to ambient temperature before the next step. Using a 15 ml precision pipette, 15 ml of 0.15 N dibutylamine in xylene is added. The Erlenmeyer flask is sealed and left to react for 15 minutes with gentle stirring. In step a), 100 ml of isopropanol is added, and in step b), 100 ml of DMSO is added, carefully rinsing the walls of the Erlenmeyer flask. The titration is carried out with 0.1 N aqueous hydrochloric acid solution with magnetic stirring, according to the instructions for use of the selected titrator. A blank determination (without sample) is carried out under the same conditions. The NCO number is calculated according to the following formula:

number

[0189] [Theoretical NCO value at the end of step a)] The theoretical NCO number at the end of step a) is calculated according to the following equation:

number

[0190] [Brookfield® Viscosity] Viscosity was measured at 23°C using a Brookfield® viscometer (spindle: S5) according to standard NF EN ISO 2555 June 2018. A cylindrical spindle rotates around its axis at a constant rotational speed within the product being tested. The resistance that the fluid exerts on the spindle depends on the viscosity of the product. This resistance causes a twist in the spiral spring, which is reflected in the viscosity value.

[0191] [Thixotropy index] The thixotropy index was measured by dividing the viscosity obtained using a Brookfield® viscometer at a speed of 5 revolutions per minute at 23°C by the viscosity obtained using the same viscometer at a speed of 50 revolutions per minute.

[0192] [Starting materials] In the examples, the following starting materials were used: [Table 1]

[0193] [Preparation of alcohol mixture] [Mixture A] 411.76 g of MPEG 350 (1.177 mol) and 588.2 g of MPEG 500 (1.177 mol) were mixed in a 1 liter round bottom flask equipped with a thermometer and a stirrer for 10 minutes at ambient temperature and under an inert atmosphere to obtain a clear liquid.

[0194] [Mixture B] 189.2 g of MPEG 350 (0.54 mol) and 810.8 g of MPEG 500 (1.62 mol) were mixed in a 1 liter round bottom flask equipped with a thermometer and a stirrer for 10 minutes at ambient temperature and under an inert atmosphere to obtain a clear liquid.

[0195] [Mixture C] 120.8 g of BTG (0.59 mol) and 879.2 g of MPEG500 (1.76 mol) were mixed in a 1 liter round bottom flask equipped with a thermometer and a stirrer for 10 minutes at ambient temperature and under an inert atmosphere to obtain a clear liquid.

[0196] [Preparation of Hemi-adduct] [Semi-adduct A] 145.3 g of Desmodur® T100 (0.835 mol) was charged into a 500 ml reactor equipped with a thermometer, a condenser, and a stirrer. 354.7 g of Mixture A (0.835 mol) was added via a dropping funnel over 1 hour, while maintaining the temperature of the mixture below 40° C. At the end of the addition, the mixture was left stirring for 3 hours, and the NCO number was measured every hour until a theoretical NCO number of 93.6 mg KOH / g was reached.

[0197] [Semi-additive B] 113.18 g of Desmodur® T100 (0.65 mol) were charged into a 500 ml reactor equipped with a thermometer, a condenser, and a stirrer. 386.82 g of Mixture A (0.91 mol) were added via a dropping funnel over 1 hour, while maintaining the temperature of the mixture below 40° C. At the end of the addition, the mixture was left stirring for 3 hours, and the NCO number was measured every hour until a theoretical NCO number of 43.8 mg KOH / g was reached.

[0198] [Semi-adduct C] 105.95 g of Desmodur® T100 (0.61 mol) was charged into a 500 ml reactor equipped with a thermometer, a condenser, and a stirrer. 394.1 g of Mixture B (0.85 mol) was added via a dropping funnel over 1 hour, while maintaining the temperature of the mixture below 40° C. At the end of the addition, the mixture was left stirring for 3 hours, and the NCO number was measured every hour until a theoretical NCO number of 41 mg KOH / g was reached.

[0199] [Semi-adduct D] 112.87 g of Desmodur® T100 (0.65 mol) were charged into a 500 ml reactor equipped with a thermometer, a condenser, and a stirrer. 387.13 g of mixture C (0.91 mol) were added via a dropping funnel over 1 hour, while maintaining the temperature of the mixture below 40° C. At the end of the addition, the mixture was left stirring for 3 hours, and the NCO number was measured every hour until a theoretical NCO number of 43.7 mg KOH / g was reached.

[0200] [Semi-adduct E] 98.76 g of Desmodur® T100 (0.57 mol) and 14.1 g of Desmodur® T80 (0.081 mol) were charged into a 500 ml reactor equipped with a thermometer, a condenser, and a stirrer. 387.13 g of mixture C (0.91 mol) were added via a dropping funnel over 1 hour, while maintaining the temperature of the mixture below 40° C. At the end of the addition, the mixture was left stirring for 3 hours, and the NCO number was measured every hour until a theoretical NCO number of 43.7 mg KOH / g was reached.

[0201] [Semi-adduct F] 118.4 g of Desmodur® T100 (0.68 mol) and 16.9 g of Desmodur® T80 (0.1 mol) were charged into a 500 ml reactor equipped with a thermometer, a condenser, and a stirrer. 364.7 g of mixture C (0.86 mol) were added via a dropping funnel over 1 hour, while maintaining the temperature of the mixture below 40° C. At the end of the addition, the mixture was left stirring for 3 hours, and the NCO number was measured every hour until a theoretical NCO number of 78.5 mg KOH / g was reached.

[0202] [Preparation of urea-urethane] Example C1 - Comparative Example 4.5 g of LiCl (0.106 mol) was dissolved in 300 g of DMSO (3.8 mol) and 19.25 g of MXDA (0.14 mol) at 80 °C in a 500 ml reactor equipped with a thermometer, a condenser, and a stirrer. Subsequently, 176.25 g of hemi-adduct A (0.28 mol) was added via a dropping funnel over 1 hour while maintaining the temperature of the mixture below 60 °C. At the end of the addition, the mixture was left stirring for 30 minutes to obtain a clear liquid product at ambient temperature. The solids content of the mixture was 40%.

[0203] Example 1 - Inventive Example 53.96 mg of LiCl (1.27 mmol) was dissolved in 300 g of DMSO (3.8 mol) and 19.57 g of MXDA (0.144 mol) at 80°C in a 500 ml reactor equipped with a thermometer, a condenser, and a stirrer. Subsequently, 180.38 g of hemi-adduct A (0.288 mol) was added via a dropping funnel over 1 hour, while maintaining the temperature of the mixture below 60°C. At the end of the addition, the mixture was left stirring for 30 minutes to obtain a clear liquid product at ambient temperature. The solids content of the mixture was 40%.

[0204] Example 2 - Inventive Example 29.48 mg of LiCl (0.695 mmol) was dissolved in 300 g of DMSO (3.8 mol) and 10.69 g of MXDA (0.079 mol) at 80°C in a 500 ml reactor equipped with a thermometer, a condenser, and a stirrer. Subsequently, 189.28 g of hemi-adduct B (0.157 mol) was added via a dropping funnel over 1 hour, while maintaining the temperature of the mixture below 60°C. At the end of the addition, the mixture was left stirring for 30 minutes to obtain a clear liquid product at ambient temperature. The solids content of the mixture was 40%.

[0205] Example 3 - Inventive Example 11.39 mg of LiCl (0.269 mmol) was dissolved in 300 g of DMSO (3.8 mol) and 10.32 g of MXDA (0.076 mol) at 80°C in a 500 ml reactor equipped with a thermometer, a condenser, and a stirrer. Subsequently, 189.67 g of hemi-adduct B (0.152 mol) was added via a dropping funnel over 1 hour, while maintaining the temperature of the mixture below 60°C. At the end of the addition, the mixture was left stirring for 30 minutes to obtain a clear liquid product at ambient temperature. The solids content of the mixture was 40%.

[0206] Example 4 - Inventive Example 1.04 mg of LiCl (0.0245 mmol) was dissolved in 300 g of DMSO (3.8 mol) and 9.42 g of MXDA (0.07 mol) at 80 °C in a 500 ml reactor equipped with a thermometer, a condenser, and a stirrer. Subsequently, 190.57 g of hemi-adduct C (0.14 mol) was added via a dropping funnel over 1 hour, while maintaining the temperature of the mixture below 60 °C. At the end of the addition, the mixture was left stirring for 30 minutes to obtain a clear liquid product at ambient temperature. The solids content of the mixture was 40%.

[0207] Example 5 - Inventive Example 1.09 mg of LiCl (0.0257 mmol) was dissolved in 300 g of DMSO (3.8 mol) and 9.93 g of MXDA (0.075 mol) at 80 °C in a 500 ml reactor equipped with a thermometer, a condenser, and a stirrer. Subsequently, 190.07 g of hemi-adduct D (0.15 mol) was added via a dropping funnel over 1 hour, while maintaining the temperature of the mixture below 60 °C. At the end of the addition, the mixture was left stirring for 30 minutes to obtain a clear liquid product at ambient temperature. The solids content of the mixture was 40%.

[0208] Example 6 - Inventive Example 1.14 mg of LiCl (0.0269 mmol) was dissolved in 300 g of DMSO (3.8 mol) and 10.3 g of MXDA (0.076 mol) at 80 °C in a 500 ml reactor equipped with a thermometer, a condenser, and a stirrer. Subsequently, 189.68 g of hemi-adduct E (0.152 mol) was added via a dropping funnel over 1 hour, while maintaining the temperature of the mixture below 60 °C. At the end of the addition, the mixture was left stirring for 30 minutes to obtain a clear liquid product at ambient temperature. The solids content of the mixture was 40%.

[0209] Example 7 - Inventive Example 1.9 mg of LiCl (0.045 mmol) was dissolved in 300 g of DMSO (3.8 mol) and 17.28 g of MXDA (0.127 mol) at 80 °C in a 500 ml reactor equipped with a thermometer, a condenser, and a stirrer. Subsequently, 182.72 g of hemi-adduct F (0.254 mol) was added via a dropping funnel over 1 hour, while maintaining the temperature of the mixture below 60 °C. At the end of the addition, the mixture was left stirring for 30 minutes to obtain a clear liquid product at ambient temperature. The solids content of the mixture was 40%.

[0210] Example 8 - Inventive Example 112.5 g of DMSO (1.44 mol) and 3.91 g of MXDA (0.029 mol) were mixed in a 250 ml reactor equipped with a thermometer, a condenser, and a stirrer. Subsequently, 71.09 g of hemi-adduct D (0.058 mol) was added via a dropping funnel over 1 hour while maintaining the temperature of the mixture below 60° C. At the end of the addition, the mixture was left stirring for 30 minutes to obtain a clear liquid product at ambient temperature. The solids content of the mixture was 40%.

[0211] [Table 2]

[0212] [Table 3]

[0213] Despite the presence of less salt than that shown in the prior art, or indeed no salt at all, the compositions according to the invention have excellent stability over time.

[0214] [Application Test] [Formulation F1] A paint formulation F1 was prepared with the following ingredients: [Table 4]

[0215] Aqueous coating formulation F1 was prepared using a high-speed disperser (HSD). In the first step, component A was prepared by adding various components and dispersing at 2000 rpm for 15 minutes. Subsequently, component B was prepared separately by adding a coalescing agent to the resin at a dispersion speed of 800 rpm and continuing dispersion at the same speed for 10 minutes. Subsequently, component B was added to component A, and dispersion was continued at 800 rpm for 10 minutes. Finally, additives Byk® 024 and Byk® 333 were added, and formulation F1 was dispersed at 800 rpm for 10 minutes.

[0216] [Compound Characterization] The additives of Comparative Example C1 and Examples 1 to 7 according to the present invention were evaluated in Formulation F1 by slowly adding 2.01 parts of the rheological additive to 200 grams of the paint F1 at a dispersion speed of 800 rpm. The mixture was then dispersed for 3 minutes at 1300 rpm using a 3.5 cm diameter dispersion blade. The resulting mixture was stored at 23°C + / - 1°C for 24 hours before measuring the rheological properties, without homogenizing the mixture before measurement.

[0217] [Table 5]

[0218] Paint formulations containing the rheological additives of the present invention exhibit rheological performance qualities comparable to, and in fact superior to, prior art additives.

Claims

1. Formula (I): [C26] (In the above formula, Each R' is an alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, -[(CR ａ R ｂ ) ｎ -O] ｍ -Y and -[(CR ｃ R ｄ ) ｐ -C(=O)O] ｑ - independently selected from Z; The symbol represents the point of attachment to the urethane group of formula (I); Each R ２ are independently a divalent group selected from an aliphatic group, an alicyclic group, an aromatic group, and an araliphatic group; Each R ３ are independently a divalent group selected from an aliphatic group, an alicyclic group, an aromatic group, an araliphatic group, and a heterocyclic group; Y and Z are independently selected from alkyl, alkenyl, cycloalkyl, aryl, and arylalkyl; R ａ , R ｂ , R ｃ and R ｄ is independently selected from H and methyl, in particular H; each n is independently equal to 2, 3, or 4, particularly n is 2; m ranges from 1 to 30, particularly m ranges from 2 to 25; p ranges from 3 to 5, in particular p is 5; q is in the range of 1 to 20, particularly q is in the range of 2 to 10.

1. A thixotropic composition comprising a compound of formula (I) or a mixture of compounds of formula (I) and an aprotic solvent, characterized in that the composition contains less than 0.1 moles of salt per urea group in the composition, excluding the aprotic solvent.

2. 2. The thixotropic composition of claim 1, characterized in that the composition comprises from 0 to less than 0.1 moles, or from 0 to 0.09 moles, or from 0 to 0.07 moles, or from 0 to 0.05 moles, or from 0 to 0.03 moles, or from 0 to 0.01 moles, or from 0 to 0.01 moles of salt per urea group in the composition, excluding aprotic solvents.

3. The salt is selected from metal salts, ionic liquids, and ammonium salts; in particular, the salt is a metal salt selected from halides, acetates, formates, or nitrates; more particularly, the salt is a lithium salt; even more particularly, the salt is LiCl, LiNO ３ 3. The thixotropic composition according to claim 1, characterized in that the lithium salt is selected from the group consisting of Li, LiBr and mixtures thereof.

4. A thixotropic composition according to any one of claims 1 to 3, characterized in that the composition contains less than 0.1 moles of surfactant per urea group in the composition.

5. 5. The thixotropic composition according to claim 1 , characterized in that the NCO number of the thixotropic composition is less than 0.5 mg KOH / g, in particular less than 0.2 mg KOH / g, more particularly less than 0.1 mg KOH / g, even more particularly 0 mg KOH / g.

6. 6. A thixotropic composition according to claim 1 , characterized in that the composition contains from 5% to 80%, in particular from 15% to 75%, more particularly from 25% to 65% of compounds of formula (I) in molar proportions relative to the total molar amount of compounds carrying one or more functional groups selected from urea, urethane and mixtures thereof, excluding the aprotic solvent.

7. The composition comprises a compound of formula (II): [C27] (In the above formula, R' and R ２ is as defined in claim 1) 7. A thixotropic composition according to claim 1, further comprising at least one compound of the formula:

8. 8. A thixotropic composition according to claim 7, characterized in that the composition comprises, by mole, from 20% to 95%, in particular from 25% to 85%, more particularly from 35% to 75% of compounds of formula (II) relative to the total molar amount of compounds carrying one or more functional groups selected from urea, urethane and mixtures thereof, excluding the aprotic solvent.

9. The composition comprises a mixture of compounds of formula (I), said mixture comprising at least one compound of formula (I) having different R′ groups; In particular, the mixture of compounds of formula (I) - the R' groups are different and one of the R' groups is R ４ and the other R′ group corresponds to R ５ at least one compound of formula (I) corresponding to Optionally, the R′ groups are identical and R ４ Compounds of formula (I) corresponding to Optionally, the R′ groups are identical and R ５ Compounds of formula (I) corresponding to Including R ４ and R ５ A thixotropic composition according to any one of claims 1 to 8, characterized in that R' is as described for R' in claim 1 or 8.

10. the mixture of compounds of formula (I) comprises at least two different compounds of formula (I) in which the R' groups are different; In particular, the mixture of compounds of formula (I) - the R' groups are different and one of the R' groups is R ４ and the other R′ group corresponds to R ５ At least one compound of formula (I) corresponding to - the R' groups are different and one of the R' groups is R ４ and the other R′ group corresponds to R ６ at least one compound of formula (I) corresponding to Optionally, the R′ groups are different and one of the R′ groups is R ５ and the other R′ group corresponds to R ６ Compounds of formula (I) corresponding to Optionally, the R′ groups are identical and R ４ Compounds of formula (I) corresponding to Optionally, the R′ groups are identical and R ５ Compounds of formula (I) corresponding to Optionally, the R′ groups are identical and R ６ Compounds of formula (I) corresponding to Including R ４ , R ５ and R ６ 10. A thixotropic composition according to claim 1, characterized in that R' is as described above for R'.

11. More than 20 mol %, in particular 25 mol % to 95 mol %, 30 mol % to 90 mol %, 35 mol % to 85 mol %, or 40 mol % to 80 mol % of all R′ groups in the compounds of formula (I) are hydrophilic groups, in particular .-[(CR ａ R ｂ ) ｎ -O] ｍ A thixotropic composition according to any one of claims 1 to 10, characterized in that it is a -Y group.

12. Each R ２ are independently an aromatic group; in particular a group of the formula: [C28] An aromatic group having the formula: More specifically, the compound of the formula: [C29] an aromatic group according to one of the above formulae, wherein the symbol · represents the point of attachment to the urea or urethane group of formula (I); Even more specifically, the compound of the formula: [C30] 12. The thixotropic composition according to claim 1, wherein the aromatic group is one of the following:

13. All R in the compound of formula (I) ２ Greater than 85 mol%, greater than 90 mol%, greater than 95 mol%, greater than 97 mol%, greater than 98 mol%, greater than 99 mol%, or 100 mol% of the groups are of the formula: [C31] where the symbol * represents the point of attachment to the urea or urethane group of formula (I); In particular, all R ２ Greater than 60 mol%, greater than 65 mol%, greater than 70 mol%, greater than 75 mol%, greater than 80 mol%, greater than 85 mol%, or greater than 90 mol% of the groups are of the formula: [C32] 13. The thixotropic composition according to claim 1, wherein the aromatic group is:

14. Each R ３ But independently, C ２ -C ２４ Alkylene, -(CR ｈ R ｉ ) ｓ - [A-(CR ｊ R ｋ ) ｔ ] ｕ -, -(CR １ R ｍ ) ｖ -CY-(CR ｎ R ｏ ) ｗ - and - (CR ｐ R ｑ ) ｘ -CY-(CH ２ ) ｙ -CY-(CR ｒ R ｓ ) ｚ - is a group selected from In the above formula, A is O or NX; R ｈ , R ｉ , R ｊ , R ｋ , R ｌ , R ｍ , R ｎ , R ｏ , R ｐ , R ｑ , R ｒ and R ｓ is independently selected from H and methyl, in particular H; X is C １ From C ６ alkyl, in particular methyl or ethyl; CY is a ring selected from phenyl, cyclohexyl, naphthyl, decahydronaphthyl, piperazinyl, triazinyl and pyridinyl, which ring is unsubstituted or has 1 to 3 C １ -C ４ is substituted with an alkyl group; s ranges from 2 to 4, in particular s is 2; t ranges from 2 to 4, in particular t is 2; u ranges from 1 to 30; 14. A thixotropic composition according to claim 1, wherein v, w, x, y and z are independently in the range of 0 to 4.

15. Each R ３ But independently, C ２ -C ２４ Alkylene and -(CR １ R ｍ ) ｖ -CY-(CR ｎ R ｏ ) ｗ A group selected from -; In particular, C ２ -C １８ Alkylene and -(CH ２ ) ｖ -CY-(CH ２ ) ｗ -, wherein CY is a cyclohexyl or phenyl ring, which is unsubstituted or has 1 to 3 C １ -C ４ substituted with an alkyl group, v and w being groups ranging from 0 to 1; More specifically, C ２ -C ６ Alkylene and the formula: [C33] (wherein the symbol . represents the point of attachment of the compound of formula (I) to the urea group).

15. The thixotropic composition according to claim 1 , wherein the aryl group is a group selected from the groups having the formula:

16. a) Formula R'-O-C(=O)-NH-R ２ To form at least one monoisocyanate adduct of —NCO, ２ reacting at least one diisocyanate of -NCO with at least one alcohol of formula R'-OH, in which the molar ratio of the total amount of alcohol to the total amount of diisocyanate is in the range of from 1.10 to 1.80, in particular from 1.20 to 1.60, more particularly from 1.25 to 1.45, and even more particularly from 1.30 to 1.40; b) Formula (I) [C34] (In the above formula, R', R ２ and R ３ is as defined in claim 1), at least one monoisocyanate adduct obtained in step a) is reacted with at least one compound of formula H in the presence of less than 0.2 mole of a metal salt per mole of diamine used ２ N-R ３ -NH ２ with at least one diamine of A method for preparing a thixotropic composition comprising:

17. 17. The process according to claim 16, characterized in that step b) is carried out in the presence of 0 to 0.19, 0 to 0.15, 0 to 0.1, 0 to 0.05, 0 to 0.02, 0 to 0.01 or 0 moles of salt per mole of diamine used.

18. 18. The process according to claim 16 or 17, characterized in that step b) is carried out in the presence of less than 0.2 mol, in particular from 0 to 0.19, from 0 to 0.15, from 0 to 0.1, from 0 to 0.05, from 0 to 0.02, from 0 to 0.01 or from 0 mol, of surfactant per mole of diamine used.

19. 19. The process according to any one of claims 16 to 18, characterized in that it does not comprise a distillation step of residual diisocyanate, in particular a distillation step of residual diisocyanate between steps a) and b).

20. 20. The process according to any one of claims 16 to 19, characterized in that the amount of residual diisocyanate in the reaction mixture at the end of step a) is less than 6 mol %, in particular from 0 mol % to 5 mol %, from 0.01 mol % to 4.5 mol %, or from 0.05 mol % to 4 mol %, based on the molar amount of all compounds carrying one or more functional groups selected from urethane and isocyanate.

21. In step a), a compound of formula R １ -OC(=O)-NH-R ２ To form at least one monoisocyanate adduct of —NCO, at least one diisocyanate is represented by the formula R １ Reacts with a single alcohol of -OH, In step b), a compound of formula (I'): [C35] (In the above formula, R １ The groups are the same and are as described for R′ in claim 1; R ２ and R ３ is as defined in claim 1) to form at least one compound of formula H ２ N-R ３ -NH ２ Reacts with at least one diamine of 21. The method according to any one of claims 16 to 20, characterized in that

22. In step a), a compound of formula R ４ -OC(=O)-NH-R ２ -NCO and R ５ -OC(=O)-NH-R ２ To form a mixture of at least two monoisocyanate adducts of —NCO, at least one diisocyanate is represented by the formula R ４ -OH and R ５ with at least two different alcohols of —OH, In step b), optionally in admixture with a compound of formula (Ib) and / or a compound of formula (Ic), a compound of formula (Ia): [C36] (In the above formula, All R ４ The groups are identical and are as described for R' in claim 1; All R ５ The groups are identical and are as described for R' in claim 1; R ４ The group is R ５ and the mixture obtained in step a) is reacted with a compound of formula H ２ N-R ３ -NH ２ Reacts with at least one diamine of 21. The method according to any one of claims 16 to 20, characterized in that

23. In step a), a compound of formula R ４ -OC(=O)-NH-R ２ -NCO, R ５ -OC(=O)-NH-R ２ -NCO and R ６ -OC(=O)-NH-R ２ To form a mixture of at least three monoisocyanate adducts of —NCO, a diisocyanate is selected from the group consisting of the formula R ４ -OH, R ５ -OH and R ６ with a mixture of at least three different alcohols having —OH; In step b), [C37] (In the above formula, All R ４ The groups are identical and are as described for R' in claim 1; All R ５ The groups are identical and are as described for R' in claim 1; All R ６ The groups are identical and are as described for R' in claim 1; R ４ The group is R ５ Unlike; R ４ The group is R ６ Unlike; R ５ The group is R ６ and optionally one or more compounds of formula (Ib), (Ic), (Ie) or (If) are formed by reacting the mixture obtained in step a) with a compound of formula H ２ N-R ３ -NH ２ Reacts with at least one diamine of 21. The method according to any one of claims 16 to 20, characterized in that

24. 24. A binder composition comprising a binder and a thixotropic composition prepared according to any one of claims 1 to 15 or according to the method of any one of claims 16 to 23.

25. 24. Use of a thixotropic composition according to any one of claims 1 to 15 or prepared according to the method according to any one of claims 16 to 23 as a rheological agent, in particular a thixotropic agent.

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