Rheology control additives containing furan compounds

Abstract

The present invention relates to a composition comprising as component (A) at least one cyclic ether (CE), and as component (B) a urea compound (CU), wherein the composition is obtained or obtainable by a process comprising at least the following steps: providing a composition (M1) comprising toluene diisocyanate; adding a composition (M2) comprising at least one monohydroxyl compound (CM) having formula (I) to obtain a composition (M3) comprising at least one monoisocyanate adduct, wherein in step (ii) the molar ratio of the at least one monohydroxyl compound having general formula (I) to the toluene diisocyanate is in the range of > 1.0 : 1.0 to < 1.5 : 1.0; and adding a composition (M4) comprising at least one diamine, at least one cyclic ether to obtain the urea compound (CU). The present invention further relates to a process for the preparation of a composition according to the present invention and the use of said composition as thixotropic agent in liquid compositions for paint and coating formulations, adhesives, paint lacquers, PVC plastisols, inks and cement formulations.

Description

[0001] This invention relates to a composition comprising at least one cyclic ether (CE) as component (A) and a urea compound (CU) as component (B), wherein the composition is obtained or can be obtained by a method comprising at least the following steps: providing a composition (M1) comprising toluene diisocyanate; adding a composition (M2) comprising at least one monohydroxy compound (CM) having formula (I) to obtain a composition (M3) comprising at least one monoisocyanate adduct, wherein in step (ii), the molar ratio of the at least one monohydroxy compound having general formula (I) to the toluene diisocyanate is in the range of > 1.0 : 1.0 to ≤ 1.5 : 1.0; and adding a composition (M4) comprising at least one diamine and at least one cyclic ether to obtain the urea compound (CU). The invention further relates to a method for preparing a composition according to the invention and the use of said composition as a thixotropic agent in liquid compositions for use in paint and coating formulations, adhesives, paint lacquer, PVC plastisol, inks, and cement formulations.

[0002] The existing technology uses urea carbamate polymers as rheology modifiers in paint and coating formulations.

[0003] Urea carbamate polymers are typically prepared via a two-step process, in which a monohydroxy compound is reacted in the presence of a diisocyanate to synthesize a monoisocyanate adduct; and in a second step, the monoisocyanate adduct is reacted with a diamine in the presence of a lithium salt and a support solvent.

[0004] The mechanism by which urea-carbamates alter the rheological properties of coating systems involves the formation of reversible hydrogen bonds. Once urea-carbamate additives are incorporated into the coating, hydrogen bonds form between the additives, and the coating gels. Upon application of shear (mixing, shaking, etc.), the hydrogen bonds break and the coating becomes flowable. After the shear force is removed, the hydrogen bonds are re-established, and the coating gels again.

[0005] Urea carbamate rheology modifiers are based on well-defined stoichiometric ratios. Isocyanate groups can react with any compound containing reactive hydrogen. The reaction of isocyanates with alcohols produces carbamates. The reaction of isocyanates with amines produces ureas, and the reaction of isocyanates with water produces intermediates that decompose to produce carbon dioxide and amines; the amines further react to form ureas again. Other potential isocyanate co-reactants include carboxylic acids, carbamates, and ureas. For the preparation of polymeric materials, each molecule of the reactive pair must have at least two functional groups. The properties of urea carbamate polymers depend on factors such as the degree of branching and the position of the functional groups in the reactive pair, the content (ratio) of active groups, and the physical state of the starting materials.

[0006] Different methods have been proposed in the prior art to obtain urea carbamate polymers.

[0007] US 4,383,068 and US 3,8939,56 describe methods in which a polyisocyanate adduct of a monohydric alcohol with a diisocyanate, and, where appropriate, the diisocyanate reacts with primary and / or secondary polyamines in the forced presence of a binder to form a urea adduct. These urea carbamate polymers are prepared in a binder or carrier medium. These binders then possess rheological control properties. Rheology control agents cannot be prepared independently without these carrier media and therefore have only limited usefulness.

[0008] US 4,522,986 describes urethane-urea compounds prepared by reacting NCO-terminated urethane prepolymers with ethanolamine to form hydroxyurea-terminated rheology control agents. These NCO-terminated urethane prepolymers are obtained by reacting a polyether polyol with a stoichiometric excess of an aliphatic cyclic polyisocyanate. The urethane-urea compounds are separated by concentration as a waxy substance or by dilution with acetone. Insoluble diurea compounds are separated as crystals, removed by filtration, and discarded. A disadvantage associated with this method is the reaction of a stoichiometric excess of diisocyanate with an alkanolamine, which must then be removed and discarded because these ureas are insoluble in the polymer solution and will cause degradation.

[0009] EP 0 006 252 provides a method for preparing thixotropic agents and describes the preparation of urea carbamates in an aprotic solvent in the presence of lithium chloride by reacting isocyanate adducts with polyamines. A disadvantage of the product prepared in this manner is the undefined structure of the urea carbamate due to the preparation method. The method does not provide a route to obtain pure monoadducts, but rather forms a mixture of monoadducts and diisocyanates, which react with diamines and result in uncontrolled elongation of the urea-carbamate chain. In the described method, 1 mol of diisocyanate is first reacted with 1 mol of a monohydric alcohol. This method partially produces the desired NCO-functionalized monoadduct and also produces diadducts without any NCO functional groups. Furthermore, a certain proportion of the monomeric diisocyanate remains unreacted. The proportions of these different compounds can vary depending on the availability of NCO groups and the applied reaction conditions (such as temperature and time). All these adducts prepared in this manner contain a considerable amount of unreacted diisocyanate, which leads to uncontrolled chain extension of urea carbamate and polymerization of urea during further reaction with polyamines in the presence of lithium chloride. These products then tend to precipitate and can only be held in solution with great difficulty.

[0010] US 6,420,466 describes a method for preparing thixotropic agents containing urea-carbamates, wherein a monohydroxy compound is reacted with an excess of toluene diisocyanate, wherein unreacted portions of toluene are removed from the reaction mixture, and the resulting monoisocyanate adduct is further reacted with a diamine in the presence of a lithium salt. A disadvantage of this method is that the subsequent removal of the stoichiometric excess diisocyanate by vacuum distillation is a complex and expensive process. Furthermore, due to the intentionally prepared diurea-carbamates, only a few active urea groups can be incorporated into the molecule, and therefore, the efficiency of these urea-carbamates is limited.

[0011] WO2020 / 182944 discloses a composition comprising one or more urea-based compounds with a number-average molecular weight (Mn) between 350 g / mol and 30,000 g / mol and one or more N-substituted caprolactam derivatives.

[0012] Despite the fact that urea carbamate polymers have been commercially prepared and used for many years, there remains a persistent need for a method to prepare urea carbamate polymers that does not require a diisocyanate distillation step. The challenge for researchers is to reduce free diisocyanate in the first step, resulting in the formation of a monoisocyanate adduct—that is, a monoisocyanate adduct without free diisocyanate—which, when reacted with a diamine in the second step, leads to a more defined structure in the urea carbamate polymer.

[0013] WO2022 / 043175 and WO2019 / 096611 also disclose polyurea rheology modifiers prepared using a method without a distillation step.

[0014] The object of this invention is to provide a method for preparing storage-stable urea carbamate polymers, which can be prepared in a simple and economical manner, avoiding the disadvantages associated with the presence of free diisocyanates, and to provide a urea carbamate polymer that imparts thickening and thixotropic properties to paint and coating formulations when used in such formulations.

[0015] According to the present invention, this objective has been achieved by a composition comprising...

[0016] (a) at least one cyclic ether (CE) having a molecular weight in the range of 80 to 500 g / mol as component (A), wherein the amount is in the range of 10 to 80 wt% based on the weight of the composition, and

[0017] (b) A urea compound (CU) as component (B), the amount of which is in the range of 10 to 80 wt% based on the weight of the composition, wherein the total amount of the components of the composition is 100 wt%.

[0018] The composition is obtained or can be obtained by a method comprising at least the following steps:

[0019] (i) Provide a composition (M1) comprising toluene diisocyanate;

[0020] (ii) Adding a composition (M2) comprising at least one monohydroxy compound (CM) having formula (I) to obtain a composition (M3) comprising at least one monoisocyanate adduct, wherein in step (ii), the molar ratio of the at least one monohydroxy compound having general formula (I) to the toluene diisocyanate is in the range of > 1.0 : 1.0 to ≤ 1.5 : 1.0;

[0021] (iii) Adding a composition (M4) comprising at least one diamine and at least one cyclic ether to obtain a urea compound (CU);

[0022] The monohydroxy compound (CM) has the general formula (I).

[0023] R 1 -OH(I),

[0024] in

[0025] R 1 Selected from straight or branched, substituted or unsubstituted C4-C 22Alkyl, straight or branched, substituted or unsubstituted C4-C 22 Alkenyl, substituted or unsubstituted C6-C 12 Cycloalkyl, straight or branched, substituted or unsubstituted C7-C 24 Aryl groups, and substituted or unsubstituted C6-C 24 Aryl ,

[0026] Having the formula R 11 (OC n H 2n ) x - group,

[0027] Having the formula R 11 [OC(=O)-C v H 2v ] x - groups, and

[0028] Having the formula R 11 (OC n H 2n ) x-1 [OC(=O)-C v H 2v ] x - group,

[0029] in

[0030] R 11 Selected from straight or branched, substituted or unsubstituted C4-C 22 Alkyl, straight or branched, substituted or unsubstituted C4-C 22 Alkenyl, substituted or unsubstituted C6-C 12 Cycloalkyl, straight or branched, substituted or unsubstituted C7-C 24 Aryl groups, and substituted or unsubstituted C6-C 24 Aryl ,

[0031] n is an integer from 2 to 4.

[0032] x is an integer from 1 to 15, and

[0033] v is an integer between 4 and 6.

[0034] According to the present invention, the composition is obtained by a method comprising steps (i), (ii), and (iii). The method may also include additional steps.

[0035] According to step (i), a composition (M1) comprising toluene diisocyanate is provided. The composition (M1) comprises toluene diisocyanate and may contain other components, such as a solvent.

[0036] In the context of this invention, other solvents may be used. According to the invention, the solvent used in this method does not contain additional cyclic ethers. In particular, polar aprotic solvents may be used.

[0037] According to step (ii), a composition (M2) comprising at least one monohydroxy compound (CM) of formula (I) is added to obtain a composition (M3) comprising at least one monoisocyanate adduct, wherein in step (ii), the molar ratio of at least one monohydroxy compound of general formula (I) to toluene diisocyanate is in the range of > 1.0 : 1.0 to ≤ 1.5 : 1.0. The composition (M2) comprises the monohydroxy compound (CM) and may also comprise additional components.

[0038] According to step (iii), a composition (M4) comprising at least one diamine and at least one cyclic ether (CE) is added to obtain a urea compound (CU). The composition (M4) comprises at least one diamine and at least one cyclic ether, but may also contain other components.

[0039] The composition comprises a cyclic ether (CE) as component (A) in an amount ranging from 10 to 80 wt% based on the weight of the composition, wherein the total amount of the components in the composition is 100 wt%. Furthermore, the composition comprises a urea compound (CU) as component (B) in an amount ranging from 10 to 80 wt% based on the weight of the composition, wherein the total amount of the components in the composition is 100 wt%. The composition preferably comprises a salt compound as component (C) in an amount ranging from 0 to 25 wt% based on the weight of the composition, wherein the total amount of the components in the composition is 100 wt%. The composition preferably comprises an organic solvent as component (D) in an amount ranging from 0 to 50 wt% based on the weight of the composition, more preferably from 10 to 50 wt%, wherein the total amount of the components in the composition is 100 wt%.

[0040] Therefore, according to another embodiment, the present invention also relates to a composition as disclosed above, wherein the composition comprises:

[0041] (a) The cyclic ether (CE) as component (A) is present in an amount ranging from 10 to 80 wt% based on the weight of the composition.

[0042] (b) A urea compound (CU) as component (B), wherein the amount is in the range of 10 to 80 wt% based on the weight of the composition.

[0043] (c) A salt compound as component (C), the amount of which is in the range of 0 to 25 wt% based on the weight of the composition.

[0044] (d) The organic solvent as component (D), the amount of which is in the range of 10 to 50 wt% based on the weight of the composition.

[0045] The total amount of the components in the composition is 100 wt%.

[0046] The composition according to the invention comprises at least one cyclic ether (CE) as component (A) and a urea compound (CU) as component (B).

[0047] Surprisingly, the presence of cyclic ethers (CE) and the use of an excess of a monohydroxy compound represented by the general formula R-OH relative to diisocyanate, i.e., a molar ratio of the monohydroxy compound to toluene diisocyanate in the range of ≥ 1.0 : 1 to ≤ 1.5 : 1, have been found to result in the formation of urea carbamate polymers with advantageous properties. According to the invention, the presence of cyclic ethers (CE) leads to good thickening properties and a favorable eco-friendly composition.

[0048] It has been unexpectedly discovered that, in methods for preparing urea carbamate polymers, a monoisocyanate adduct obtained by reacting a monohydroxy compound represented by R-OH with toluene diisocyanate in a molar ratio > 1.0 : 1.0 to ≤ 1.5 : 1.0, when reacted with a diamine in the presence of a polar aprotic solvent and a lithium salt, provides a urea carbamate polymer without the need for a diisocyanate distillation step. This method provides a urea carbamate polymer that is stable and imparts thixotropic properties to formulations when used as an additive in paint and coating formulations. The urea carbamate polymer according to the invention is used as a thixotropic agent in paint and coating formulations, varnishes, clear coats, paper coatings, wood coatings, adhesives, inks, cosmetic formulations, detergent formulations, textiles and drilling mud, plaster formulations, PVC plastisols, and cement formulations.

[0049] This invention relates to a method for preparing urea carbamate polymers for use as additives in solvent-containing, solvent-free, and water-based paint and coating formulations to impart thixotropic properties to said formulations, thereby enabling the use of urea carbamate polymers obtained by the method of this invention to modify the rheological characteristics of paint and coating formulations, varnishes, clear coats, paper coatings, wood coatings, adhesives, inks, cosmetic formulations, detergent formulations, textiles and drilling muds, plaster formulations, PVC plastisols, and cement formulations.

[0050] As used in this article, the term "thixotropic effect" refers to the property of a viscous or gel-like product that becomes more liquid when it undergoes more prolonged and more vigorous deformation (e.g., by stirring).

[0051] As used herein, the term "alkyl" refers to an acyclic saturated aliphatic group consisting only of carbon and hydrogen atoms, including straight-chain or branched alkyl residues. Furthermore, the alkyl residues are preferably unsubstituted.

[0052] As used herein, the term "alkenyl" refers to an acyclic, unsaturated hydrocarbon residue, including straight-chain or branched alkenyl residues, and containing at least one double bond, preferably one, two, or three double bonds. Furthermore, the alkenyl residue is preferably unsubstituted. Representative examples of alkenyl groups include, but are not limited to, 1-hexenyl, 2-hexenyl, 1-heptenyl, 2-heptenyl, 1-octenyl, 2-octenyl, 1-nonenyl, 2-nonenyl, 1-decenyl, 2-decenyl, 1-undecenyl, 2-undecenyl, 1-dodecenyl, 2-dodecenyl, 1-tetraceneenyl, 2-tetraceneenyl, 1-tetradecenyl, 2-tetradecenyl, 1-pentadecanenyl, 2-pentadecanenyl, 1-hexadecenyl, 2-hexadecenyl, 1-heptadecenyl, 2-heptadecenyl, 1-octadecenyl, 2-octadecenyl, 1-nonadecanenyl, 2-nonadecanenyl, 1-eicosenecanenyl, and 2-eicosenecanenyl.

[0053] In the context of this invention and as used herein, the term "cycloalkyl" refers to a saturated cyclic hydrocarbon residue comprising 6, 7, 8, 9, 10, 11, or 12 atoms as ring members. The cycloalkyl is preferably unsubstituted.

[0054] As used herein, "branched" refers to an atomic chain with one or more side chains attached. Branching occurs by replacing substituents (e.g., hydrogen atoms) with covalently bonded aliphatic portions.

[0055] The term "aralkyl" refers to a group derived from an alkyl group by substituting one or more hydrogen atoms with an aryl group. Furthermore, the aralkyl residues are preferably unsubstituted. Representative examples of aralkyl groups include, but are not limited to, benzyl, o-tolyl, m-tolyl, p-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl, and mesitylene.

[0056] The term "aryl" refers to an aromatic carbon ring with 6 to 30 ring members, including both monocyclic, bicyclic, and tricyclic systems. Non-limiting examples of aryl groups include indenyl, phenyl, and naphthyl.

[0057] In the context of this invention, the term "monoisocyanate adduct" refers to the addition product of a monohydroxy compound having the general formula (I) and toluene diisocyanate. Monoisocyanate adducts have a free reactive isocyanate group that reacts with a diamine.

[0058] The term "polar aprotic solvent" refers to a solvent made of polar molecules with relatively high relative permittivity (or dielectric constant) (greater than 15) and permanent dipole moment, which cannot supply suitable unstable hydrogen atoms to form strong hydrogen bonds.

[0059] The term "theoretical NCO content" refers to the NCO content theoretically calculated based on only half the amount of NCO groups from the TDI feedstock that reacts with R-OH.

[0060] Suitable cyclic ethers that can be used according to the present invention can be monocyclic ethers, bicyclic ethers, or polycyclic ethers. Monocyclic compounds having two or more ether groups can also be used. Suitable ethers have a molecular weight in the range of 80 to 500 g / mol, more preferably in the range of 80 to 250 g / mol. Preferably, bicyclic ethers having a molecular weight in the range of 80 to 250 g / mol are used.

[0061] Therefore, according to another embodiment, the present invention also relates to compositions as disclosed above, wherein the cyclic ether is a bicyclic ether having a molecular weight in the range of 80 to 250 g / mol.

[0062] Dimethyl isosorbide (DMI) and dihydro-L-glucanone (DHGS) have been found to be particularly suitable. Therefore, according to other embodiments, the present invention also relates to compositions as disclosed above, wherein the cyclic ether is selected from the group consisting of dimethyl isosorbide (DMI) and dihydro-L-glucanone (DHGS).

[0063] Preferably, the toluene diisocyanate is selected from 2,4-toluene diisocyanate or a mixture of isomers of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, more preferably a mixture of isomers of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate.

[0064] Therefore, according to another embodiment, the present invention also relates to compositions as disclosed above, wherein the toluene diisocyanate is selected from 2,4-toluene diisocyanate and mixtures of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate.

[0065] In embodiments of the invention, 2,4-toluene diisocyanate is present in the isomer mixture in an amount ranging from ≥ 85.0 wt.-% to ≤ 99.9 wt.-% of the total weight of the isomer mixture, preferably from ≥ 90.0 wt.-% to ≤ 99.9 wt.-% of the 2,4-isomer, and most preferably from ≥ 95.0 wt.-% to ≤ 99.9 wt.-% of the 2,4-isomer.

[0066] In embodiments of the invention, the molar ratio of at least one monohydroxy compound having general formula (I) to toluene diisocyanate is in the range of > 1.0 : 1.0 to ≤ 1.5 : 1.0, preferably in the range of ≥ 1.005 : 1.0 to ≤ 1.45 : 1.0, more preferably in the range of ≥ 1.01 : 1.0 to ≤ 1.4 : 1.0, even more preferably in the range of ≥ 1.025 : 1.0 to ≤ 1.35 : 1.0, further more preferably in the range of ≥ 1.050 : 1.0 to ≤ 1.3 : 1.0 or in the range of ≥ 1.075 : 1.0 to ≤ 1.25 : 1.0, and most preferably in the range of ≥ 1.1 : 1.0 to ≤ 1.2 : 1.0 or ≥ 1.005 : 1.0 to ≤ Within the range of 1.2 to 1.0.

[0067] Preferably, in a monohydroxy compound having general formula (I), R is a straight-chain or branched alkyl group selected from the group consisting of: n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecanyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecanyl, n-eicosyl, n-eicosyl, n-eicosyl, 2-ethylhexyl, 2-propyl-heptyl, 2-butyl-1-octyl, 2-pentyl-1-nonyl, isobutyl, isopentyl, isohexyl, isoheptyl, isooctyl, isodecanyl, isoundecyl, isododecyl, isotridecyl, isotetradecyl, isopentadecanyl, isohexadecyl, isoheptadecyl, isooctadecyl, isononadecanyl, isoeicosyl, isoeicosyl, and isoeicosyl.

[0068] In embodiments of the invention, in a monohydroxy compound having general formula (I), R is a straight-chain or branched alkenyl group selected from the group consisting of: 1-hexenyl, 2-hexenyl, 1-heptenyl, 2-heptenyl, 1-octenyl, 2-octenyl, 1-nonenyl, 2-nonenyl, 1-decenyl, 2-decenyl, 1-undecenyl, 2-undecenyl, 1-dodecenyl, 2-dodecenyl, 1-tetracenyl, 2-tetracenyl, 1-tetradecenyl, 2-tetradecenyl, 1-pentadecanenyl, 2-pentadecanenyl, 1- Hexadecenyl, 2-hexadecenyl, 1-heptadecenyl, 2-heptadecenyl, 1-octadecenyl, 2-octadecenyl, 1-nonadecanenyl, 2-nonadecanenyl, 1-eicosenoenyl, 2-eicosenoenyl, cis-7-decenyl, cis-9-octadecenyl (oleenyl), cis-8,11-heptadecadienyl, cis-9,12-octadecadienyl (linoleenyl), cis-10,13-nonadecanadienyl and cis-6,9,12-octadectrienyl.

[0069] In embodiments of the invention, in a monohydroxy compound having general formula (I), R is a cycloalkyl group selected from the group consisting of cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, and cyclododecyl.

[0070] In embodiments of the invention, in a monohydroxy compound having general formula (I), R is an aralkyl group selected from the group consisting of: benzyl, o-tolyl, m-tolyl, p-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl and mesitylene.

[0071] In embodiments according to the invention, in monohydroxy compounds having general formula (I), R is a compound having formula C m H 2m+1 (OC n H 2n ) x - groups, where m is an integer from 1 to 22, n is an integer from 2 to 4, and x is an integer from 1 to 15.

[0072] In embodiments according to the invention, in monohydroxy compounds having general formula (I), R is a compound having formula H(OC) n H 2n ) x - groups, where m is an integer from 1 to 22, n is an integer from 2 to 4, and x is an integer from 1 to 15.

[0073] In embodiments according to the invention, in monohydroxy compounds having general formula (I), R is a compound having formula Cm H 2m+1 [OC(=O)-C v H 2v ] x - groups, where m is an integer from 1 to 22, n is an integer from 2 to 4, x is an integer from 1 to 15 and v is an integer from 4 to 6.

[0074] In embodiments according to the invention, in monohydroxy compounds having general formula (I), R is a compound having formula C m H 2m+1 (OC n H 2n ) x-1 [OC(=O)-C v H 2v ] x - groups, where m is an integer from 1 to 22, n is an integer from 2 to 4, x is an integer from 1 to 15 and v is an integer from 4 to 6.

[0075] In an embodiment of the invention, in general formula (I), m is an integer from 1 to 4.

[0076] In an embodiment of the invention, n is 2 in general formula (I).

[0077] In an embodiment of the invention, x is an integer from 3 to 10 in general formula (I).

[0078] According to another embodiment, the present invention also relates to compositions as disclosed above, wherein at least one monohydroxy compound having formula (I) is selected from triethylene glycol monobutyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, butanol, isotriadecyl alcohol, oleyl alcohol, Guerbert alcohol containing 8 to 20 carbon atoms, linoleyl alcohol, lauryl alcohol, stearyl alcohol, cyclohexanol, benzyl alcohol, 4-dodecylphenol, ethoxylated triphenylmethanol and ethoxylated 4-dodecylphenol.

[0079] According to the present invention, at least one monohydroxy compound having general formula (I) is preferably selected from the group consisting of: triethylene glycol monobutyl ether, methoxy polyethylene glycol, butanol, isotriadecyl alcohol, oleyl alcohol, guerbert alcohol containing 8 to 20 carbon atoms, linoleyl alcohol, lauryl alcohol, stearyl alcohol, cyclohexanol and benzyl alcohol, and preferably selected from the group consisting of: triethylene glycol monobutyl ether, 2-ethylhexanol and methoxy polyethylene glycol.

[0080] Guerbert alcohol is represented by the general formula (X).

[0081] (X),

[0082] Where p is 1, 2, 3 or 4.

[0083] The abbreviation for gerbert alcohol is used for 2-alkyl-substituted 1-alkanols, whose industrial synthesis is described in particular in H. Machemer, Angewandte Chemie, Vol. 64, pp. 213-220 (1952) and G. Dieckelmann and HJ Heinz in The Basics of Industrial Oleochemistry, pp. 145-145 (1988).

[0084] In the examples, Gerbert alcohol is selected from 2-ethylhexanol, 2-propyl-heptanol, 2-butyl-1-octanol and 2-pentyl-1-nonanol.

[0085] In an embodiment of the invention, at least one monohydroxy compound having general formula (I) in step (ii) is added during a time period ranging from ≥ 3 hours to ≤ 50 hours, preferably from ≥ 3 hours to ≤ 30 hours, and more preferably from ≥ 3 hours to ≤ 20 hours.

[0086] In an embodiment of the invention, in step ii), the temperature is in the range of ≥ 20°C to ≤ 60°C, preferably in the range of ≥ 25°C to ≤ 55°C, and more preferably in the range of ≥ 30°C to ≤ 50°C.

[0087] In embodiments of the invention, in step (ii), a solvent (D) is optionally added, wherein the solvent used in the method does not contain additional cyclic ethers. The solvent used should be substantially inert to the reaction. While the use of a solvent may not be necessary during the formation of the urethane prepolymer, its use may be desirable to maintain the reactants in a liquid state and to allow for better temperature control during the reaction by acting as a heat sink and, if desired, a reflux medium. In any case, the prepolymer is in solution during its reaction with the diamine to form the urea-urethane. Examples of other solvents that do not contain reactive hydrogen are esters, ethers, ketone esters, ketones, ethylene glycol-ether-esters, chlorinated hydrocarbons, aliphatic and alicyclic hydrocarbons, pyrrolidones, hydrogenated furans, and mixtures thereof. According to the invention, the solvent (D) is different from the cyclic ether (CE).

[0088] In a preferred embodiment of the invention, the optional solvent is selected from the group consisting of acetone, benzene, ethyl acetate, butyl acetate, diethyl ether, carbon tetrachloride, and chlorobenzene.

[0089] Suitable diamines that can be used according to the present invention are known in principle. Therefore, according to other embodiments, the present invention also relates to compositions as disclosed above, wherein at least one diamine is selected from diamines having formulas (IIa), (IIb), (IIc), (IId), and (IIe);

[0090] -H2N-R 3 -NH2(IIa),

[0091] Where R 3 It is -C y H 2y -And y is an integer from 2 to 12.

[0092] -Diamines having formula (IIb)

[0093] ,

[0094] -Diamines having formula (IIc)

[0095] ,

[0096] -Diamines having the formula (IId)

[0097] ,and

[0098] -Diamines having the formula (IIe),

[0099]

[0100] In equations (IIc), (IId), and (IIe), R 4 They are the same or different and are selected from H, CH3-, C2H5- and C3H7-, and R 5 Selected from -CH2-, -C2H4-, -C3H6- and -C6H 12 -

[0101] Preferably, at least one diamine is selected from the group consisting of: 4,4-diamino-diphenylmethane, 3,3-dimethyl-4,4-diamino-diphenylmethane, 2,2-bis(4-aminocyclohexyl)-propane, N,N-dimethyl-4,4-diamino-diphenylmethane, (3-methyl-4-aminocyclohexyl)-(3-methyl-4-aminophenyl)-methane, 4,4-diaminodicyclohexylmethane, isomer phenylenediamine, ethylenediamine, hexamethylenediamine, 4,4-methylenebis(cyclohexylamine), 1,12-diaminododecane, neopentyldiamine, 1,2-propanediamine and 1,3-propanediamine, 1,8-octanediamine and 1,12-dodecanediamine.

[0102] Typically, urea compounds (CU) have a weight-average molecular weight in the range of ≥ 300 g / mol to ≤ 5000 g / mol as determined according to DIN 55672-2.

[0103] Preferably, the obtained urea carbamate has a weight-average molecular weight in the range of ≥ 500 g / mol to ≤ 3000 g / mol, preferably in the range of ≥ 700 g / mol to ≤ 3000 g / mol, more preferably in the range of ≥ 1000 g / mol to ≤ 2500 g / mol, and even more preferably in the range of ≥ 1500 g / mol to ≤ 2500 g / mol, as determined according to DIN 55672-1.

[0104] Therefore, according to another embodiment, the present invention also relates to compositions as disclosed above, wherein the urea compound (CU) has a weight-average molecular weight in the range of ≥ 300 g / mol to ≤ 5000 g / mol as determined according to DIN 55672-2.

[0105] Preferably, at least one solvent (D) is a polar aprotic solvent, particularly a polar aprotic solvent selected from the group consisting of: dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, N-propylpyrrolidone, N-butylpyrrolidone, or comparable alkylpyrrolidones or mixtures thereof, N,N,N',N'-tetramethylurea, acetonitrile, acetone, and hexamethyl-phosphotriamide.

[0106] Therefore, according to another embodiment, the present invention also relates to compositions as disclosed above, wherein at least one polar aprotic solvent is selected from the group consisting of: dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, N-propylpyrrolidone, N-butylpyrrolidone, N,N,N',N'-tetramethylurea, hexamethyl-phosphotriamide, and methyl 5-(dimethylamino)-2-methyl-5-oxovalerate.

[0107] In embodiments of the invention, the weight ratio of toluene diisocyanate to an optional solvent is in the range of ≥ 0.5:1.0 to ≤ 5.0:1.0, preferably in the range of ≥ 1.0:1.0 to ≤ 4.5:1.0, more preferably in the range of ≥ 1.5:1.0 to ≤ 4.0:1.0, more preferably in the range of ≥ 2.0:1.0 to ≤ 3.5:1.0, and most preferably in the range of ≥ 2.5:1.0 to ≤ 3.0:1.0.

[0108] According to another embodiment, the present invention also relates to compositions as disclosed above, wherein the salt is a metal salt selected from the group consisting of lithium chloride, lithium nitrate, lithium bromide and sodium dioctyl sulfosuccinate.

[0109] More preferably, the lithium salt is selected from the group consisting of lithium chloride, lithium nitrate and lithium bromide.

[0110] In embodiments of the invention, the lithium salt is present in an equivalent weight range of ≥ 0.3 to ≤ 1.5 mol relative to at least one diamine, preferably ≥ 0.5 to ≤ 1.0 mol.

[0111] The conditions applied in steps (i) to (iii) of the method according to the invention can vary over a wide range. Preferably, in step (iii), the temperature is ≥ 30°C. o C to ≤ 100 o Within the range of C, preferably ≥ 40 o C to ≤ 80 o Within the range of C, and more preferably within ≥ 40 o C to ≤ 60 o Within the range of C.

[0112] Preferably, any solvent added in step (i) or (ii) is removed at the end of step (iii).

[0113] In an embodiment of the invention, in step (ii), the NCO content obtained by titration is less than 110%, preferably less than 105%, of the "theoretical NCO content." Here, the "theoretical NCO content" is theoretically calculated based on only half the amount of NCO groups from the TDI feedstock reacting with R-OH. In an embodiment of the invention, in step (iii), the NCO content is preferably 0%.

[0114] According to another aspect, the present invention also relates to a method for preparing the composition disclosed above, the method comprising the following steps:

[0115] (i) Provide a composition (M1) comprising toluene diisocyanate;

[0116] (ii) Adding a composition (M2) comprising at least one monohydroxy compound (CM) having formula (I) to obtain a composition (M3) comprising at least one monoisocyanate adduct, wherein in step (ii), the molar ratio of the at least one monohydroxy compound having general formula (I) to the toluene diisocyanate is in the range of > 1.0 : 1.0 to ≤ 1.5 : 1.0;

[0117] (iii) Adding a composition (M4) comprising at least one diamine and at least one cyclic ether (CE) to obtain a urea compound (CU);

[0118] The monohydroxy compound (CM) has the general formula (I).

[0119] R 1 -OH(I),

[0120] in

[0121] R 1 Selected from straight or branched, substituted or unsubstituted C4-C 22 Alkyl, straight or branched, substituted or unsubstituted C4-C 22 Alkenyl, substituted or unsubstituted C6-C 12 Cycloalkyl, straight or branched, substituted or unsubstituted C7-C 24 Aryl groups, and substituted or unsubstituted C6-C 24 Aryl ,

[0122] Having the formula R 11 (OC n H 2n ) x - group,

[0123] Having the formula R 11 [OC(=O)-C v H 2v ] x - groups, and

[0124] Having the formula R 11 (OC n H 2n ) x-1 [OC(=O)-C v H 2v ] x - group,

[0125] in

[0126] R 11 Selected from straight or branched, substituted or unsubstituted C4-C 22 Alkyl, straight or branched, substituted or unsubstituted C4-C 22 Alkenyl, substituted or unsubstituted C6-C 12 Cycloalkyl, straight or branched, substituted or unsubstituted C7-C 24 Aryl groups, and substituted or unsubstituted C6-C 24 Aryl ,

[0127] n is an integer from 2 to 4.

[0128] x is an integer from 1 to 15, and

[0129] v is an integer between 4 and 6.

[0130] For preferred embodiments, please refer to the above disclosure.

[0131] Furthermore, the present invention provides a liquid composition comprising, based on the total weight of the liquid composition, ≥ 0.01 wt.-% to ≤ 10.0 wt.-%, preferably in the range of ≥ 0.1 wt.-% to ≤ 7.0 wt.-%, more preferably in the range of ≥ 0.1 wt.-% to ≤ 5.0 wt.-%, and even more preferably in the range of ≥ 0.1 wt.-% to ≤ 3.0 wt.-%, of a urea carbamate obtained according to the method of the present invention; and based on the total weight of the liquid composition, ≥ 15.0 wt.-% to ≤ 99.9 wt.-%, preferably ≥ 25.0 wt.-% to ≤ 90.0 wt.-%, more preferably ≥ 35.0 wt.-% to ≤ 85.0 wt.-%, even more preferably ≥ 50.0 wt.-% to ≤ 80.0 wt.-%, and most preferably ≥ 55.0 wt.-% to ≤ 75.0 wt.-%. wt.-% of at least one component selected from the group consisting of: pigment paste, binder, filler, solvent, defoamer, neutralizer, wetting agent, pigment dispersant, preservative and water.

[0132] Therefore, according to another aspect, the present invention also relates to a liquid composition comprising, based on the total weight of the liquid composition, ≥ 0.01 wt.-% to ≤ 10.0 wt.-% of the composition according to any one of claims 1 to 10; and based on the total weight of the liquid composition, ≥ 15.0 wt.-% to ≤ 99.9 wt.-% of at least one component selected from the group consisting of: pigment paste, binder, filler, solvent, defoamer, neutralizer, wetting agent, pigment dispersant, preservative and water.

[0133] Preferably, the composition is a water-based or solvent-based paint and coating formulation, varnish, clear varnish, paper coating, wood coating, adhesive, ink, cosmetic formulation, detergent formulation, textile and drilling mud, gypsum formulation, cement composition, formulation for gypsum board, formulation for hydraulic adhesives such as mortar, formulation for ceramics and for leather, and preferably water-based and solvent-based paint and coating formulation, adhesive, ink and cement formulation.

[0134] In the embodiments, the present invention provides the use of urea carbamates obtained according to the method of the present invention as thixotropic agents in liquid compositions for use in paint and coating formulations, adhesives, paint varnishes, PVC plastisols, inks and cement formulations, preferably for use in water-based and solvent-based paint and coating formulations, adhesives, inks and cement formulations.

[0135] In a preferred embodiment, the liquid composition is a water-based or solvent-based paint and coating formulation. Paint and coating compositions used for the purposes of this invention are those applied from a liquid phase to a substrate and, with the formation of a film, form a protective or functional and / or decorative surface. Substrates refer to, for example, wood, metal, polymer films, polymer parts, paper, leather, fingernails and toenails, and building materials such as masonry, concrete, and plaster. The coating materials discussed can be uncolored, colored, or dye-containing coating materials, which may further contain, alone or in mixtures, different types of binders, along with other additives such as fillers, binders, neutralizers, pigments, defoamers, wetting agents, pigment dispersants, etc. Several examples of additives used in coating formulations are:

[0136] According to another embodiment, the present invention also relates to a liquid composition as disclosed above, wherein the composition is a paint, water-based coating formulation, solvent-based coating formulation, varnish, clear varnish, paper coating, wood coating, adhesive, ink, cosmetic formulation, detergent formulation, textile and drilling mud, gypsum formulation, cement composition, formulation for gypsum board, formulation for hydraulic adhesives such as mortar, formulation for ceramics, and formulation for leather.

[0137] Suitable fillers are, for example, organic or inorganic particulate materials, such as calcium carbonate and silicates, as well as inorganic fibrous materials, such as glass fibers. Applications can also be found in organic fillers such as carbon fibers, and mixtures of organic and inorganic fillers, such as mixtures of glass fibers and carbon fibers or mixtures of carbon fibers and inorganic fillers.

[0138] Suitable binders are those commonly used, such as those described in 30 Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, Volume A18, pp. 368-426, VCH, Weinheim 1991, Germany. Generally, film-forming binders are based on thermoplastic or thermosetting resins. Examples include alkyd, acrylic, unsaturated or saturated polyester resins, acrylate and methacrylate resins, nitrocellulose, cellulose acetobutyrate, alkyd-amino resins, alkyd resins, melamine resins, urea resins, silicone resins, phenolic resins, melamine, epoxy resins, and polyurethane resins and mixtures thereof. Resins that can be cured by radiation or air drying can also be used. Binders can also be derived from polyvinyl alcohol and polyvinyl butyral. Binders include latex polymers prepared by emulsion polymerization. For architectural coatings, particularly preferred latex polymers are those based on acrylic emulsion polymers, styrene-acrylic emulsion polymers, vinyl acetate-acrylic emulsion polymers, or emulsion polymers based on ethylene and vinyl acetate.

[0139] Organic or inorganic pigments are suitable as additives. Examples of organic pigments include colored and pearlescent pigments such as azo pigments, diazo pigments, naphthol pigments, benzimidazolone pigments, azo condensation pigments, metal complex pigments, isoindolineone pigments, quinolineone pigments, and dioxazine pigments; polycyclic pigments such as indigo, thioindigo, quinacridone, phthalocyanine, perylene, perylene ketone, anthraquinones such as aminoanthraquinone or hydroxyanthraquinone, anthraquinone, indanthrene, flavonoid anthraquinone, pinanthraquinone, anthraquinone, isoviolet anthraquinone, diketopyrrolopyrrole, and carbazoles such as carbazole violet. Other examples of organic pigments can be found in the following monograph: W. Herbst, K. Hunger, “Industrielle Organische Pigmente [Industrial Organic Pigments]”, 2nd ed., 1995, VCH Verlagsgesellschaft, ISBN: 3 527 28744 2. Examples of inorganic pigments are titanium dioxide, metal flakes such as aluminum, as well as aluminum oxide, iron oxide (III), chromium oxide (III), titanium oxide (IV), zirconium oxide (IV), zinc oxide, zinc sulfide, zinc phosphate, mixed metal oxide phosphates, molybdenum sulfide, cadmium sulfide, graphite, vanadates such as bismuth vanadate, chromates such as lead chromate (IV), molybdates such as lead molybdate (IV), and mixtures thereof.

[0140] Suitable neutralizing agents are inorganic bases, organic bases, and combinations thereof. Examples of inorganic bases include, but are not limited to, alkali metal hydroxides (especially lithium, sodium, potassium, magnesium, and ammonium), and alkali metal salts of inorganic acids, such as sodium borate (borax), sodium phosphate, sodium pyrophosphate, etc.; and mixtures thereof. Examples of organic bases include, but are not limited to, triethanolamine (TEA), diisopropanolamine, triisopropanolamine, aminomethylpropanol (2-amino-2-methyl-1-propanol), dodecylamine, cocoamine, oleylamine, morpholine, tripentylamine, triethylamine, tetra(hydroxypropyl)ethylenediamine, L-arginine, methylglucosamine, isopropylamine, aminomethylpropanol, tromethamine (2-amino-2-hydroxymethyl-1,3-propanediol), and PEG-15 cocoamine. Alternatively, other basic materials may be used alone or in combination with the aforementioned inorganic and organic bases.

[0141] Suitable defoamers are selected from a wide range of defoamers used, such as silicone-based defoamers, emulsion defoamers, star polymer-based defoamers, powder defoamers, and oil-based defoamers.

[0142] The method of the present invention is simple and economical because it does not require a diisocyanate distillation step.

[0143] This method provides a stable urea carbamate polymer that imparts a thixotropic effect to paint and coating formulations when used as an additive.

[0144] The present invention also relates to the use of the compositions disclosed above or compositions obtained or obtainable according to the methods disclosed above as thixotropic agents in liquid compositions for use in paint and coating formulations, adhesives, paint varnishes, PVC plastisols, inks and cement formulations.

[0145] Further embodiments of the invention can be found in the claims and examples. It should be understood that the features mentioned above and set forth below according to the subject matter / method / use of the invention can be used not only in the combinations specified in their respective circumstances, but also in other combinations without departing from the scope of the invention. For example, combinations of preferred features with particularly preferred features, or combinations of features not further characterized with particularly preferred features, are therefore implicitly covered, even if such combinations are not explicitly mentioned.

[0146] The invention is further illustrated by the following set of embodiments and combinations of embodiments derived from the indicated dependencies and reverse references. In particular, it should be noted that in each instance of reference to the series of embodiments, such as in the context of the term "composition as described in any one of Examples 1 to 4," each embodiment in this series is intended to clearly disclose to those skilled in the art that the wording of this term should be understood by those skilled in the art to be synonymous with "composition as described in any one of Examples 1, 2, 3, and 4." Furthermore, it should be clearly noted that the following set of embodiments represents a suitable structural portion of the general description of preferred aspects of the invention and therefore appropriately supports, but does not represent, the claims of the invention.

[0147] 1. A composition comprising

[0148] (a) at least one cyclic ether (CE) having a molecular weight in the range of 80 to 500 g / mol as component (A), wherein the amount is in the range of 10 to 80 wt% based on the weight of the composition, and

[0149] (b) A urea compound (CU) as component (B), the amount of which is in the range of 10 to 80 wt% based on the weight of the composition, wherein the total amount of the components of the composition is 100 wt%.

[0150] The composition is obtained or can be obtained by a method comprising at least the following steps:

[0151] (i) Provide a composition (M1) comprising toluene diisocyanate;

[0152] (ii) Adding a composition (M2) comprising at least one monohydroxy compound (CM) having formula (I) to obtain a composition (M3) comprising at least one monoisocyanate adduct, wherein in step (ii), the molar ratio of the at least one monohydroxy compound having general formula (I) to the toluene diisocyanate is in the range of > 1.0 : 1.0 to ≤ 1.5 : 1.0;

[0153] (iii) Adding a composition (M4) comprising at least one diamine and at least one cyclic ether (CE) to obtain the urea compound (CU);

[0154] The monohydroxy compound (CM) has the general formula (I).

[0155] R 1 -OH(I),

[0156] in

[0157] R 1 Selected from straight or branched, substituted or unsubstituted C4-C22 Alkyl, straight or branched, substituted or unsubstituted C4-C 22 Alkenyl, substituted or unsubstituted C6-C 12 Cycloalkyl, straight or branched, substituted or unsubstituted C7-C 24 Aryl groups, and substituted or unsubstituted C6-C 24 Aryl,

[0158] Having the formula R 11 (OC n H 2n ) x - group,

[0159] Having the formula R 11 [OC(=O)-C v H 2v ] x - groups, and

[0160] Having the formula R 11 (OC n H 2n ) x-1 [OC(=O)-C v H 2v ] x - group,

[0161] in

[0162] R 11 Selected from straight or branched, substituted or unsubstituted C4-C 22 Alkyl, straight or branched, substituted or unsubstituted C4-C 22 Alkenyl, substituted or unsubstituted C6-C 12 Cycloalkyl, straight or branched, substituted or unsubstituted C7-C 24 Aryl groups, and substituted or unsubstituted C6-C 24 Aryl,

[0163] n is an integer from 2 to 4.

[0164] x is an integer from 1 to 15, and

[0165] v is an integer between 4 and 6.

[0166] 2. The composition according to Example 1, wherein the composition comprises

[0167] (a) The cyclic ether (CE) as component (A), in an amount ranging from 10 to 80 wt% based on the weight of the composition.

[0168] (b) The urea compound (CU) as component (B), wherein the amount is in the range of 10 to 80 wt% based on the weight of the composition.

[0169] (c) A salt compound as component (C), the amount of which is in the range of 0 to 25 wt% based on the weight of the composition.

[0170] (d) An organic solvent as component (D), the amount of which is in the range of 10 to 50 wt% based on the weight of the composition, wherein the solvent used in this method does not contain additional cyclic ethers.

[0171] The total amount of the components in the composition is 100 wt%.

[0172] 3. The composition according to Example 1 or Example 2, wherein the cyclic ether is a monocyclic or bicyclic ether having a molecular weight in the range of 80 to 250 g / mol.

[0173] 4. The composition according to any one of Examples 1 to 3, wherein the cyclic ether is selected from the group consisting of dimethyl isosorbide (DMI) and dihydro-L-glucanone (DHGS).

[0174] 5. The composition according to any one of Examples 1 to 4, wherein the toluene diisocyanate is selected from 2,4-toluene diisocyanate and mixtures of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate.

[0175] 6. The composition according to any one of Examples 1 to 5, wherein the at least one monohydroxy compound having formula (I) is selected from triethylene glycol monobutyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, butanol, isotriadecyl alcohol, oleyl alcohol, Guerbert alcohol containing 8 to 20 carbon atoms, linoleyl alcohol, lauryl alcohol, stearyl alcohol, cyclohexanol, benzyl alcohol, 4-dodecylphenol, ethoxylated triphenylmethanol, ethoxylated 4-dodecylphenol and methoxy polyethylene glycol and mixtures thereof.

[0176] 7. The composition according to any one of Examples 1 to 6, wherein the at least one diamine is selected from diamines having formula (IIa), (IIb), (IIc), (IId), and (IIe);

[0177] -H2N-R 3 -NH2(IIa),

[0178] Where R 3 It is -C y H 2y -And y is an integer from 2 to 12.

[0179] -Diamines having formula (IIb)

[0180] ,

[0181] -Diamines having formula (IIc)

[0182] ,

[0183] -Diamines having the formula (IId)

[0184] ,and

[0185] -Diamines having the formula (IIe),

[0186]

[0187] In equations (IIc), (IId), and (IIe), R 4 They are the same or different and are selected from H, CH3-, C2H5- and C3H7-, and R 5 Selected from -CH2-, -C2H4-, -C3H6- and -C6H 12 -

[0188] 8. The composition according to any one of Examples 1 to 7, wherein the urea compound (CU) has a weight-average molecular weight in the range of ≥ 300 g / mol to ≤ 5000 g / mol as determined according to DIN55672-2.

[0189] 9. The composition according to any one of Examples 2 to 8, wherein the at least one polar aprotic solvent is selected from the group consisting of: dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, N-propylpyrrolidone, N-butylpyrrolidone, N,N,N',N'-tetramethylurea, hexamethyl-phosphotriamide and methyl 5-(dimethylamino)-2-methyl-5-oxovalerate.

[0190] 10. The composition according to any one of Examples 2 to 9, wherein the salt is a metal salt selected from the group consisting of lithium chloride, lithium nitrate, lithium bromide, and sodium dioctyl sulfosuccinate.

[0191] 11. A method for preparing a composition according to any one of Examples 1 to 10, comprising the following steps:

[0192] (i) Provide a composition (M1) comprising toluene diisocyanate;

[0193] (ii) Adding a composition (M2) comprising at least one monohydroxy compound (CM) having formula (I) to obtain a composition (M3) comprising at least one monoisocyanate adduct, wherein in step (ii), the molar ratio of the at least one monohydroxy compound having general formula (I) to the toluene diisocyanate is in the range of > 1.0 : 1.0 to ≤ 1.5 : 1.0;

[0194] (iii) Adding a composition (M4) comprising at least one diamine and at least one cyclic ether (CE) to obtain the urea compound (CU);

[0195] The monohydroxy compound (CM) has the general formula (I).

[0196] R 1 -OH(I),

[0197] in

[0198] R 1 Selected from straight or branched, substituted or unsubstituted C4-C 22 Alkyl, straight or branched, substituted or unsubstituted C4-C 22 Alkenyl, substituted or unsubstituted C6-C 12 Cycloalkyl, straight or branched, substituted or unsubstituted C7-C 24 Aryl groups, and substituted or unsubstituted C6-C 24 Aryl,

[0199] Having the formula R 11 (OC n H 2n ) x - group,

[0200] Having the formula R 11 [OC(=O)-C v H 2v ] x - groups, and

[0201] Having the formula R 11 (OC n H 2n ) x-1 [OC(=O)-C v H 2v ] x - group,

[0202] in

[0203] R 11 Selected from straight or branched, substituted or unsubstituted C4-C 22Alkyl, straight or branched, substituted or unsubstituted C4-C 22 Alkenyl, substituted or unsubstituted C6-C 12 Cycloalkyl, straight or branched, substituted or unsubstituted C7-C 24 Aryl groups, and substituted or unsubstituted C6-C 24 Aryl,

[0204] n is an integer from 2 to 4.

[0205] x is an integer from 1 to 15, and

[0206] v is an integer between 4 and 6.

[0207] 12. A liquid composition comprising, based on the total weight of the liquid composition, ≥ 0.01 wt.-% to ≤ 10.0 wt.-% of the composition according to any one of Examples 1 to 10; and based on the total weight of the liquid composition, ≥ 15.0 wt.-% to ≤ 99.9 wt.-% of at least one component selected from the group consisting of: pigment paste, binder, filler, solvent, defoamer, neutralizer, wetting agent, pigment dispersant, preservative, and water.

[0208] 13. The liquid composition according to Example 12, wherein the composition is a paint, water-based coating formulation, solvent-based coating formulation, varnish, clear varnish, paper coating, wood coating, adhesive, ink, cosmetic formulation, detergent formulation, textile, drilling mud, gypsum formulation, cement composition, formulation for gypsum board, formulation for hydraulic adhesives such as mortar, formulation for ceramics, and formulation for leather.

[0209] 14. The use of the composition according to any one of Examples 1 to 10 or the composition obtained or obtainable according to the method according to Example 11 as a thixotropic agent in a liquid composition for use in paint and coating formulations, adhesives, paint varnishes, PVC plastisols, inks and cement formulations.

[0210] 15. A composition comprising

[0211] (a) as component (A) at least one cyclic ether (CE) selected from the group consisting of monocyclic or bicyclic ethers having a molecular weight in the range of 80 to 250 g / mol, wherein the amount is in the range of 10 to 80 wt% based on the weight of the composition, and

[0212] (b) A urea compound (CU) as component (B), the amount of which is in the range of 10 to 80 wt% based on the weight of the composition, wherein the total amount of the components of the composition is 100 wt%.

[0213] The composition is obtained or can be obtained by a method comprising at least the following steps:

[0214] (i) Provide a composition (M1) comprising toluene diisocyanate;

[0215] (ii) Adding a composition (M2) comprising at least one monohydroxy compound (CM) having formula (I) to obtain a composition (M3) comprising at least one monoisocyanate adduct, wherein in step (ii), the molar ratio of the at least one monohydroxy compound having general formula (I) to the toluene diisocyanate is in the range of > 1.0 : 1.0 to ≤ 1.5 : 1.0;

[0216] (iii) Adding a composition (M4) comprising at least one diamine and at least one cyclic ether (CE) to obtain the urea compound (CU);

[0217] The monohydroxy compound (CM) has the general formula (I).

[0218] R 1 -OH(I),

[0219] in

[0220] R 1 Selected from straight or branched, substituted or unsubstituted C4-C 22 Alkyl, straight or branched, substituted or unsubstituted C4-C 22 Alkenyl, substituted or unsubstituted C6-C 12 Cycloalkyl, straight or branched, substituted or unsubstituted C7-C 24 Aryl groups, and substituted or unsubstituted C6-C 24 Aryl,

[0221] Having the formula R 11 (OC n H 2n ) x - group,

[0222] Having the formula R 11 [OC(=O)-C v H 2v ] x - groups, and

[0223] Having the formula R 11 (OC n H 2n ) x-1 [OC(=O)-C v H 2v ] x - group,

[0224] in

[0225] R 11 Selected from straight or branched, substituted or unsubstituted C4-C 22 Alkyl, straight or branched, substituted or unsubstituted C4-C 22 Alkenyl, substituted or unsubstituted C6-C 12 Cycloalkyl, straight or branched, substituted or unsubstituted C7-C 24 Aryl groups, and substituted or unsubstituted C6-C 24 Aryl,

[0226] n is an integer from 2 to 4.

[0227] x is an integer from 1 to 15, and

[0228] v is an integer between 4 and 6.

[0229] 16. The composition according to Example 15, wherein the composition comprises

[0230] (a) The cyclic ether (CE) as component (A), in an amount ranging from 10 to 80 wt% based on the weight of the composition.

[0231] (b) The urea compound (CU) as component (B), wherein the amount is in the range of 10 to 80 wt% based on the weight of the composition.

[0232] (c) A salt compound as component (C), the amount of which is in the range of 0 to 25 wt% based on the weight of the composition.

[0233] (d) An organic solvent as component (D), the amount of which is in the range of 10 to 50 wt% based on the weight of the composition, wherein the solvent used in this method does not contain additional cyclic ethers.

[0234] The total amount of the components in the composition is 100 wt%.

[0235] 17. The composition according to any one of Examples 15 to 16, wherein the cyclic ether is selected from the group consisting of dimethyl isosorbide (DMI) and dihydro-L-glucanone (DHGS).

[0236] 18. The composition according to any one of Examples 15 to 17, wherein the toluene diisocyanate is selected from 2,4-toluene diisocyanate and mixtures of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate.

[0237] 19. The composition according to any one of Examples 15 to 18, wherein the at least one monohydroxy compound having formula (I) is selected from triethylene glycol monobutyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, butanol, isotriadecyl alcohol, oleyl alcohol, Guerbert alcohol containing 8 to 20 carbon atoms, linoleyl alcohol, lauryl alcohol, stearyl alcohol, cyclohexanol, benzyl alcohol, 4-dodecylphenol, ethoxylated triphenylmethanol, ethoxylated 4-dodecylphenol and methoxylated polyethylene glycol and mixtures thereof.

[0238] 20. The composition according to any one of Examples 15 to 19, wherein the at least one diamine is selected from diamines having formula (IIa), (IIb), (IIc), (IId), and (IIe);

[0239] -H2N-R 3 -NH2(IIa),

[0240] Where R 3 It is -C y H 2y -And y is an integer from 2 to 12.

[0241] -Diamines having formula (IIb)

[0242] ,

[0243] -Diamines having formula (IIc)

[0244] ,

[0245] -Diamines having the formula (IId)

[0246] ,and

[0247] -Diamines having the formula (IIe),

[0248]

[0249] In equations (IIc), (IId), and (IIe), R 4 They are the same or different and are selected from H, CH3-, C2H5- and C3H7-, and R 5 Selected from -CH2-, -C2H4-, -C3H6- and -C6H 12 -

[0250] 21. The composition according to any one of Examples 15 to 20, wherein the urea compound (CU) has a weight-average molecular weight in the range of ≥ 300 g / mol to ≤ 5000 g / mol as determined according to DIN 55672-2.

[0251] 22. The composition according to any one of Examples 16 to 21, wherein the at least one polar aprotic solvent is selected from the group consisting of: dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, N-propylpyrrolidone, N-butylpyrrolidone, N,N,N',N'-tetramethylurea, hexamethyl-phosphotriamide, and methyl 5-(dimethylamino)-2-methyl-5-oxovalerate.

[0252] 23. The composition according to any one of Examples 16 to 22, wherein the metal salt catalyst is selected from the group consisting of lithium chloride, lithium nitrate, lithium bromide and sodium dioctyl sulfosuccinate.

[0253] 24. A method for preparing a composition according to any one of Examples 15 to 23, comprising the following steps:

[0254] (i) Provide a composition (M1) comprising toluene diisocyanate;

[0255] (ii) Adding a composition (M2) comprising at least one monohydroxy compound (CM) having formula (I) to obtain a composition (M3) comprising at least one monoisocyanate adduct, wherein in step (ii), the molar ratio of the at least one monohydroxy compound having general formula (I) to the toluene diisocyanate is in the range of > 1.0 : 1.0 to ≤ 1.5 : 1.0;

[0256] (iii) Adding a composition (M4) comprising at least one diamine and at least one cyclic ether (CE) to obtain the urea compound (CU), wherein the cyclic ether is selected from the group consisting of monocyclic ethers or bicyclic ethers having a molecular weight in the range of 80 to 250 g / mol;

[0257] The monohydroxy compound (CM) has the general formula (I).

[0258] R 1 -OH(I),

[0259] in

[0260] R 1 Selected from straight or branched, substituted or unsubstituted C4-C 22 Alkyl, straight or branched, substituted or unsubstituted C4-C22 Alkenyl, substituted or unsubstituted C6-C 12 Cycloalkyl, straight or branched, substituted or unsubstituted C7-C 24 Aryl groups, and substituted or unsubstituted C6-C 24 Aryl,

[0261] Having the formula R 11 (OC n H 2n ) x - group,

[0262] Having the formula R 11 [OC(=O)-C v H 2v ] x - groups, and

[0263] Having the formula R 11 (OC n H 2n ) x-1 [OC(=O)-C v H 2v ] x - group,

[0264] in

[0265] R 11 Selected from straight or branched, substituted or unsubstituted C4-C 22 Alkyl, straight or branched, substituted or unsubstituted C4-C 22 Alkenyl, substituted or unsubstituted C6-C 12 Cycloalkyl, straight or branched, substituted or unsubstituted C7-C 24 Aryl groups, and substituted or unsubstituted C6-C 24 Aryl,

[0266] n is an integer from 2 to 4.

[0267] x is an integer from 1 to 15, and

[0268] v is an integer between 4 and 6.

[0269] 25. A liquid composition comprising, based on the total weight of the liquid composition, ≥ 0.01 wt.-% to ≤ 10.0 wt.-% of the composition according to any one of Examples 15 to 23; and based on the total weight of the liquid composition, ≥ 15.0 wt.-% to ≤ 99.9 wt.-% of at least one component selected from the group consisting of: pigment paste, binder, filler, solvent, defoamer, neutralizer, wetting agent, pigment dispersant, preservative, and water.

[0270] 26. The liquid composition according to Example 25, wherein the composition is a paint, water-based coating formulation, solvent-based coating formulation, varnish, clear varnish, paper coating, wood coating, adhesive, ink, cosmetic formulation, detergent formulation, textile, drilling mud, gypsum formulation, cement composition, formulation for gypsum board, formulation for hydraulic adhesives such as mortar, formulation for ceramics, and formulation for leather.

[0271] 27. The use of the composition according to any one of Examples 15 to 23 or the composition obtained or obtainable according to the method according to Example 24 as a thixotropic agent in a liquid composition for use in paint and coating formulations, adhesives, paint varnishes, PVC plastisols, inks and cement formulations.

[0272] 28. A composition comprising

[0273] (a) at least one cyclic ether (CE) selected from the group consisting of dimethyl isosorbide (DMI) and dihydro-L-glucanone (DHGS) as component (A), wherein the amount is in the range of 10 to 80 wt% based on the weight of the composition, and

[0274] (b) A urea compound (CU) as component (B), the amount of which is in the range of 10 to 80 wt% based on the weight of the composition, wherein the total amount of the components of the composition is 100 wt%.

[0275] The composition is obtained or can be obtained by a method comprising at least the following steps:

[0276] (i) Provide a composition (M1) comprising toluene diisocyanate;

[0277] (ii) Adding a composition (M2) comprising at least one monohydroxy compound (CM) having formula (I) to obtain a composition (M3) comprising at least one monoisocyanate adduct, wherein in step (ii), the molar ratio of the at least one monohydroxy compound having general formula (I) to the toluene diisocyanate is in the range of > 1.0 : 1.0 to ≤ 1.5 : 1.0;

[0278] (iii) Adding a composition (M4) comprising at least one diamine and at least one cyclic ether (CE) to obtain the urea compound (CU);

[0279] The monohydroxy compound (CM) has the general formula (I).

[0280] R 1 -OH(I),

[0281] in

[0282] R 1 Selected from straight or branched, substituted or unsubstituted C4-C 22 Alkyl, straight or branched, substituted or unsubstituted C4-C 22 Alkenyl, substituted or unsubstituted C6-C 12 Cycloalkyl, straight or branched, substituted or unsubstituted C7-C 24 Aryl groups, and substituted or unsubstituted C6-C 24 Aryl,

[0283] Having the formula R 11 (OC n H 2n ) x - group,

[0284] Having the formula R 11 [OC(=O)-C v H 2v ] x - groups, and

[0285] Having the formula R 11 (OC n H 2n ) x-1 [OC(=O)-C v H 2v ] x - group,

[0286] in

[0287] R 11 Selected from straight or branched, substituted or unsubstituted C4-C 22 Alkyl, straight or branched, substituted or unsubstituted C4-C 22 Alkenyl, substituted or unsubstituted C6-C 12 Cycloalkyl, straight or branched, substituted or unsubstituted C7-C 24 Aryl groups, and substituted or unsubstituted C6-C 24 Aryl,

[0288] n is an integer from 2 to 4.

[0289] x is an integer from 1 to 15, and

[0290] v is an integer between 4 and 6.

[0291] 29. The composition according to Example 28, wherein the composition comprises

[0292] (a) The cyclic ether (CE) as component (A), in an amount ranging from 10 to 80 wt% based on the weight of the composition.

[0293] (b) The urea compound (CU) as component (B), wherein the amount is in the range of 10 to 80 wt% based on the weight of the composition.

[0294] (c) A salt compound as component (C), the amount of which is in the range of 0 to 25 wt% based on the weight of the composition.

[0295] (d) An organic solvent as component (D), the amount of which is in the range of 10 to 50 wt% based on the weight of the composition, wherein the solvent used in this method does not contain additional cyclic ethers.

[0296] The total amount of the components in the composition is 100 wt%.

[0297] 30. The composition according to any one of Examples 28 to 29, wherein the toluene diisocyanate is selected from 2,4-toluene diisocyanate and mixtures of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate.

[0298] 31. The composition according to any one of Examples 28 to 30, wherein the at least one monohydroxy compound having formula (I) is selected from triethylene glycol monobutyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, butanol, isotridecyl alcohol, oleyl alcohol, Guerbert alcohol containing 8 to 20 carbon atoms, linoleyl alcohol, lauryl alcohol, stearyl alcohol, cyclohexanol, benzyl alcohol, 4-dodecylphenol, ethoxylated triphenylmethanol, ethoxylated 4-dodecylphenol and methoxylated polyethylene glycol and mixtures thereof.

[0299] 32. The composition according to any one of Examples 28 to 31, wherein the at least one diamine is selected from diamines having formulas (IIa), (IIb), (IIc), (IId), and (IIe);

[0300] -H2N-R 3 -NH2(IIa),

[0301] Where R 3 It is -C y H 2y -And y is an integer from 2 to 12.

[0302] -Diamines having formula (IIb)

[0303] ,

[0304] -Diamines having formula (IIc)

[0305] ,

[0306] -Diamines having the formula (IId)

[0307] ,and

[0308] -Diamines having the formula (IIe),

[0309]

[0310] In equations (IIc), (IId), and (IIe), R 4 They are the same or different and are selected from H, CH3-, C2H5- and C3H7-, and R 5 Selected from -CH2-, -C2H4-, -C3H6- and -C6H 12 -

[0311] 33. The composition according to any one of Examples 28 to 32, wherein the urea compound (CU) has a weight-average molecular weight in the range of ≥ 300 g / mol to ≤ 5000 g / mol as determined according to DIN 55672-2.

[0312] 34. The composition according to any one of Examples 29 to 33, wherein the at least one polar aprotic solvent is selected from the group consisting of: dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, N-propylpyrrolidone, N-butylpyrrolidone, N,N,N',N'-tetramethylurea, hexamethyl-phosphotriamide and methyl 5-(dimethylamino)-2-methyl-5-oxovalerate.

[0313] 35. The composition according to any one of Examples 29 to 34, wherein the salt is a metal salt selected from the group consisting of lithium chloride, lithium nitrate, lithium bromide, and sodium dioctyl sulfosuccinate.

[0314] 36. A method for preparing the composition according to any one of Examples 28 to 35, comprising the following steps:

[0315] (i) Provide a composition (M1) comprising toluene diisocyanate;

[0316] (ii) Adding a composition (M2) comprising at least one monohydroxy compound (CM) having formula (I) to obtain a composition (M3) comprising at least one monoisocyanate adduct, wherein in step (ii), the molar ratio of the at least one monohydroxy compound having general formula (I) to the toluene diisocyanate is in the range of > 1.0 : 1.0 to ≤ 1.5 : 1.0;

[0317] (iii) Adding a composition (M4) comprising at least one diamine and at least one cyclic ether (CE) to obtain the urea compound (CU), wherein the cyclic ether is selected from the group consisting of dimethyl isosorbide (DMI) and dihydrol-L-glucanone (DHGS);

[0318] The monohydroxy compound (CM) has the general formula (I).

[0319] R 1 -OH(I),

[0320] in

[0321] R 1 Selected from straight or branched, substituted or unsubstituted C4-C 22 Alkyl, straight or branched, substituted or unsubstituted C4-C 22 Alkenyl, substituted or unsubstituted C6-C 12 Cycloalkyl, straight or branched, substituted or unsubstituted C7-C 24 Aryl groups, and substituted or unsubstituted C6-C 24 Aryl,

[0322] Having the formula R 11 (OC n H 2n ) x - group,

[0323] Having the formula R 11 [OC(=O)-C v H 2v ] x - groups, and

[0324] Having the formula R 11 (OC n H 2n ) x-1 [OC(=O)-C v H 2v ] x - group,

[0325] in

[0326] R 11 Selected from straight or branched, substituted or unsubstituted C4-C 22 Alkyl, straight or branched, substituted or unsubstituted C4-C 22 Alkenyl, substituted or unsubstituted C6-C 12 Cycloalkyl, straight or branched, substituted or unsubstituted C7-C 24 Aryl groups, and substituted or unsubstituted C6-C 24 Aryl,

[0327] n is an integer from 2 to 4.

[0328] x is an integer from 1 to 15, and

[0329] v is an integer between 4 and 6.

[0330] 37. A liquid composition comprising, based on the total weight of the liquid composition, ≥ 0.01 wt.-% to ≤10.0 wt.-% of the composition according to any one of Examples 28 to 35; and based on the total weight of the liquid composition, ≥ 15.0 wt.-% to ≤99.9 wt.-% of at least one component selected from the group consisting of: pigment paste, binder, filler, solvent, defoamer, neutralizer, wetting agent, pigment dispersant, preservative, and water.

[0331] 38. The liquid composition according to Example 37, wherein the composition is a paint, water-based coating formulation, solvent-based coating formulation, varnish, clear varnish, paper coating, wood coating, adhesive, ink, cosmetic formulation, detergent formulation, textile, drilling mud, gypsum formulation, cement composition, formulation for gypsum board, formulation for hydraulic adhesives such as mortar, formulation for ceramics, and formulation for leather.

[0332] 39. The use of the composition according to any one of Examples 28 to 35 or the composition obtained or obtainable according to the method according to Example 36 as a thixotropic agent in a liquid composition for use in paint and coating formulations, adhesives, paint varnishes, PVC plastisols, inks and cement formulations.

[0333] The following are illustrative embodiments of the invention, but these embodiments do not limit the invention. In particular, the invention also covers those embodiments derived from dependent references specified below and combinations thereof. Example

[0334] TDI T100: 2,4-Toluene diisocyanate (TDI) from Covestro.

[0335] TDI T80: A mixture of isomers of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate (TDI) from BASF.

[0336] TDI T98, T97, T96, T95, etc. are blends of TDI T100 and TDI T80. For example, T98 is a blend of TDI T100 and TDI T80 in a ratio of 90:10, and T90 is a blend of TDI T100 and TDI T80 in a ratio of 50:50.

[0337] Example 1

[0338] In a 5-necked 200 ml Sulfier flask equipped with a top stirrer, thermometer, reflux condenser, and diaphragm, ' Isocyanates 17.4 g of TDI T 100 (100 mmol) and 10 g of ethyl acetate were purged with nitrogen. The solution was then heated at 45°C. alcohol '21.6 g of butyltriethylene glycol (BTG) (105 mmol) was fed into the reactor over a 10-hour period. The molar ratio of the monohydroxy compound R-OH to TDI was 1.05:1. The reaction was exothermic, and the internal temperature was maintained below 50°C. After the feed was complete, the reaction continued until the NCO value (NCO%) reached the theoretically calculated value (theoretically, half of the NCO groups from TDI were consumed in this step).' Salt '2.6 g of lithium nitrate,' diamine 6.2 g of m-xylenediamine (m-XDA) (46 mmol) and cyclic ethers (and, optionally for Examples 2 to 19) solvent 70 g of dimethyl isosorbide (DMI) was mixed at room temperature. The resulting mixture was fed into a monoisocyanate adduct obtained at 60°C. The reaction was exothermic, and the internal temperature remained below 80°C. The resulting mixture was heated to 80°C and held until the NCO value was 0%. Ethyl acetate was then distilled off under vacuum. The resulting urea carbamate polymer (product) was a pale yellow, transparent liquid that flowed freely at room temperature. The product remained stable (without precipitation or gel formation) after storage under ambient conditions (>1 month).

[0339] Example 1 has a molecular weight of 2070 g / mol, as determined by GPC (according to DIN 55672-2, N,N-dimethylacetamide, 1 mL / min, PMMA standard); and its PDI is 1.1.

[0340] Examples 2 to 19

[0341] Examples 2 to 19 were prepared in a manner similar to that of Example 1, wherein Isocyanates , alcohol '、 Salt '、' diamine '、' Cyclic ethers 'and' solvent The quantity and type of variation. Table 1 provides details of representative examples 2 to 19 of the method according to the invention.

[0342] Table 1

[0343]

[0344] Comparison Example 1:

[0345] In a 5-necked 200 ml Sulfier flask equipped with a top stirrer, thermometer, reflux condenser, and diaphragm, 17.4 g of TDI (TDI isomers (wt.-%) 2,4-isomer: 94, 2,6-isomer: 6) and 10 g of ethyl acetate were purged with nitrogen. 21.6 g of butyltriethylene glycol (BTG) (105 mmol) was fed into the reactor over a 3-hour period at 45°C. The molar ratio of the monohydroxy compound R-OH to TDI was 1.05:1. The reaction was exothermic, and the internal temperature was maintained below 50°C. After the feed was complete, the reaction continued until an NCO value (NCO%) of 8.6% was reached. 2.6 g of lithium nitrate, 6.2 g of m-xylenediamine (m-XDA) (46 mmol), and 48 g of dimethyl sulfoxide (DMSO) were mixed at room temperature. The resulting mixture was fed into a monoisocyanate adduct obtained at 60°C. The reaction was exothermic, and the internal temperature remained below 80°C. The resulting mixture was heated to 80°C and held until the NCO value was 0%. Ethyl acetate was then distilled off under vacuum. The resulting urea-carbamate polymer (product) was a pale yellow, transparent liquid that flowed freely at room temperature. The product remained stable (without precipitation or gel formation) after storage under ambient conditions (>2 months).

[0346] Comparison Example 2:

[0347] Preparation of urea carbamate compound C2

[0348] In a 5-necked 200 ml Sulfier flask equipped with a top stirrer, thermometer, reflux condenser, and diaphragm, a mixture containing 17.4 g of TDI T100 (100 mmol) and 10 g of ethyl acetate was purged with nitrogen. 5.4 g of triethylene glycol monobutyl ether (26.2 mmol), 13.8 g of poly(ethylene glycol) methyl ether (MW 350 g / mol 39.4 mmol), 19.7 g of poly(ethylene glycol) methyl ether (MW 500 g / mol 38.4 mmol), and 0.03 g of p-toluenesulfonic acid were mixed and fed into the reactor at 45°C over a 10-hour period. The resulting mixture was stirred at 45°C until the NCO value (NCO%) stabilized to obtain a reaction mixture containing the monoisocyanate adduct.

[0349] 2.6 g of lithium nitrate, 6.2 g of m-xylenediamine (46 mmol), and 65 g of dimethyl sulfoxide were mixed at room temperature, and the mixture was fed into a reaction mixture containing a monoisocyanate adduct at 60°C for 5 hours. The resulting mixture was heated to 80°C and stirred at the same temperature until the NCO content was 0.

[0350] Ethyl acetate was distilled off under reduced pressure to obtain C2, a pale yellow, transparent liquid that flows freely at room temperature.

[0351] The molecular weight of U6 is 2900 g / mol, as determined by GPC (according to DIN 55672-2, N,N-dimethylacetamide, 1 mL / min, PMMA standard); and its PDI is 1.3.

[0352] Urea carbamate compound C2 remains stable (without precipitation or gel formation) when stored under ambient conditions (> 2 months).

[0353] Performance testing:

[0354] For solvent-based applications, the coating solution (Formulation 1, prepared according to Table 2) was stirred at 2000 rpm for 5 min using a Dispermat and then allowed to stand overnight at room temperature before measuring the viscosity. Examples of the prepared formulation were added to investigate the thixotropic effect of the additive on the coating. Formulation 2, identical to Formulation 1, was prepared, but without adding examples. Formulation 2 without examples was considered as a reference.

[0355] The shear jump measurement was started at a shear rate of 0.05 s⁻¹ for 200 seconds, and then immediately followed by a high shear rate of 250 s⁻¹ for 60 seconds, after which the shear rate was immediately reduced to 0.05 s⁻¹ for 200 seconds.

[0356] To investigate the thixotropic effect of the examples, viscosity was measured at the following intervals:

[0357] i) The viscosity at t = 199 seconds, just before the application of high shear.

[0358] ii) The viscosity at t = 201 seconds, exactly after the application of high shear.

[0359] iii) The viscosity at t = 259 seconds is exactly after removing the high shear.

[0360] iv) Viscosity at t = 450 seconds, after removing high shear for a long time.

[0361] Table 2

[0362]

[0363] Table 3 provides viscosity measurements at different time intervals.

[0364]

[0365] For water-based applications, a formulation for viscosity measurement was prepared by adding 0.6 wt% of the sample to water. The mixture was shaken by hand for 30 seconds and then allowed to stand overnight at room temperature before measuring the viscosity (shear jump test as described above). Viscosity measurements at different time intervals are provided in Table 3.

[0366]

[0367] As is evident from the results provided in the table above, the viscosity of the formulations with examples decreased immediately and significantly after applying high shear (i.e., 250 s⁻¹ for 60 seconds). An increase in viscosity was observed immediately after the high shear was removed. This means that the formulations with examples exhibit a significant recovery of viscosity. Therefore, the examples prepared according to the method of the invention impart a thixotropic effect to the formulations when added, as demonstrated by the immediate decrease in viscosity after applying shear stress and the gradual recovery of viscosity over time after removing the shear stress. All examples according to the invention remain stable (without precipitation or gel formation) when stored under ambient conditions (>1 month).

[0368] References:

[0369] US 4,383,068

[0370] US 3,893,956

[0371] US 4,522,986

[0372] EP 0 006 252

[0373] US 6,420,466

[0374] WO2020 / 182944

[0375] WO2022 / 043175

[0376] WO2019 / 096611

[0377] H. Machemer, Angewandte Chemie, Vol. 64, pp. 213-220 (1952)

[0378] G. Dieckelmann and HJ Heinz, "The Basics of Industrial Oleochemistry", pp. 145-145 (1988)

[0379] Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, Volume A18, pp. 368-426, VCH, Weinheim 1991, Germany.

Claims

1. A composition comprising (a) at least one cyclic ether (CE) having a molecular weight in the range of 80 to 500 g / mol as component (A), wherein the amount is in the range of 10 to 80 wt% based on the weight of the composition, and (b) A urea compound (CU) as component (B), the amount of which is in the range of 10 to 80 wt% based on the weight of the composition, wherein the total amount of the components of the composition is 100 wt%. The composition is obtained or can be obtained by at least the following methods: (i) Provide a composition (M1) comprising toluene diisocyanate; (ii) Adding a composition (M2) comprising at least one monohydroxy compound (CM) having formula (I) to obtain a composition (M3) comprising at least one monoisocyanate adduct, wherein in step (ii), the molar ratio of the at least one monohydroxy compound having general formula (I) to the toluene diisocyanate is in the range of > 1.0 : 1.0 to ≤ 1.5 : 1.0; (iii) Adding a composition (M4) comprising at least one diamine and at least one cyclic ether (CE) to obtain the urea compound (CU); The monohydroxy compound (CM) has the general formula (I). R 1 -OH(I), in R 1 Selected from straight or branched, substituted or unsubstituted C4-C 22 Alkyl, straight or branched, substituted or unsubstituted C4-C 22 Alkenyl, substituted or unsubstituted C6-C 12 Cycloalkyl, straight or branched, substituted or unsubstituted C7-C 24 Aryl groups, and substituted or unsubstituted C6-C 24 Aryl, Having the formula R 11 (OC n H 2n ) x - group, Having the formula R 11 [OC(=O)-C v H 2v ] x - groups, and Having the formula R 11 (OC n H 2n ) x-1 [OC(=O)-C v H 2v ] x - group, in R 11 Selected from straight or branched, substituted or unsubstituted C4-C 22 Alkyl, straight or branched, substituted or unsubstituted C4-C 22 Alkenyl, substituted or unsubstituted C6-C 12 Cycloalkyl, straight or branched, substituted or unsubstituted C7-C 24 Aryl groups, and substituted or unsubstituted C6-C 24 Aryl, n is an integer from 2 to 4. x is an integer from 1 to 15, and v is an integer between 4 and 6.

2. The composition according to claim 1, wherein, The composition contains (a) The cyclic ether (CE) as component (A), in an amount ranging from 10 to 80 wt% based on the weight of the composition. (b) The urea compound (CU) as component (B), wherein the amount is in the range of 10 to 80 wt% based on the weight of the composition. (c) A salt compound as component (C), the amount of which is in the range of 0 to 25 wt% based on the weight of the composition. (d) An organic solvent as component (D), the amount of which is in the range of 10 to 50 wt% based on the weight of the composition, wherein the solvent used in this method does not contain additional cyclic ethers. The total amount of the components in the composition is 100 wt%.

3. The composition according to claim 1 or claim 2, wherein, The cyclic ether (CE) is a monocyclic or bicyclic ether with a molecular weight in the range of 80 to 250 g / mol.

4. The composition according to any one of claims 1 to 3, wherein, The cyclic ether (CE) is selected from the group consisting of dimethyl isosorbide (DMI) and dihydro-L-glucosidone (DHGS).

5. The composition according to any one of claims 1 to 4, wherein, The toluene diisocyanate is selected from 2,4-toluene diisocyanate and mixtures of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate.

6. The composition according to any one of claims 1 to 5, wherein, The at least one monohydroxy compound having formula (I) is selected from the group consisting of: triethylene glycol monobutyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, butanol, isotridecyl alcohol, oleyl alcohol, Guerbert alcohol containing 8 to 20 carbon atoms, linoleyl alcohol, lauryl alcohol, stearyl alcohol, cyclohexanol, benzyl alcohol, 4-dodecylphenol, ethoxylated triphenylmethanol, ethoxylated 4-dodecylphenol and methoxylated polyethylene glycol and mixtures thereof.

7. The composition according to any one of claims 1 to 6, wherein, The at least one diamine is selected from diamines having the formulas (IIa), (IIb), (IIc), (IId), and (IIe); -H2N-R 3 -NH2(IIa), Where R 3 It is -C y H 2y -And y is an integer from 2 to 12. -Diamines having formula (IIb) ， -Diamines having formula (IIc) ， -Diamines having the formula (IId) ,and -Diamines having the formula (IIe), In equations (IIc), (IId), and (IIe), R 4 They are the same or different and are selected from H, CH3-, C2H5- and C3H7-, and R 5 Selected from -CH2-, -C2H4-, -C3H6- and -C6H 12 - 8. The composition according to any one of claims 1 to 7, wherein, The urea compound (CU) has a weight-average molecular weight in the range of ≥ 300 g / mol to ≤ 5000 g / mol as determined according to DIN55672-2.

9. The composition according to any one of claims 2 to 8, wherein, The at least one solvent (D) is a polar aprotic solvent, preferably a polar aprotic solvent selected from the group consisting of: dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, N-propylpyrrolidone, N-butylpyrrolidone, N,N,N',N'-tetramethylurea, hexamethyl-phosphotriamide and methyl 5-(dimethylamino)-2-methyl-5-oxovalerate.

10. The composition according to any one of claims 2 to 9, wherein, This salt is a metal salt selected from the group consisting of lithium chloride, lithium nitrate, lithium bromide, and sodium dioctyl sulfosuccinate.

11. A method for preparing a composition according to any one of claims 1 to 10, comprising: (i) Provide a composition (M1) comprising toluene diisocyanate; (ii) Adding a composition (M2) comprising at least one monohydroxy compound (CM) having formula (I) to obtain a composition (M3) comprising at least one monoisocyanate adduct, wherein in step (ii), the molar ratio of the at least one monohydroxy compound having general formula (I) to the toluene diisocyanate is in the range of > 1.0 : 1.0 to ≤ 1.5 : 1.0; (iii) Adding a composition (M4) comprising at least one diamine and at least one cyclic ether (CE) to obtain the urea compound (CU); The monohydroxy compound (CM) has the general formula (I). R 1 -OH(I), in R 1 Selected from straight or branched, substituted or unsubstituted C4-C 22 Alkyl, straight or branched, substituted or unsubstituted C4-C 22 Alkenyl, substituted or unsubstituted C6-C 12 Cycloalkyl, straight or branched, substituted or unsubstituted C7-C 24 Aryl groups, and substituted or unsubstituted C6-C 24 Aryl, Having the formula R 11 (OC n H 2n ) x - group, Having the formula R 11 [OC(=O)-C v H 2v ] x - groups, and Having the formula R 11 (OC n H 2n ) x-1 [OC(=O)-C v H 2v ] x - group, in R 11 Selected from straight or branched, substituted or unsubstituted C4-C 22 Alkyl, straight or branched, substituted or unsubstituted C4-C 22 Alkenyl, substituted or unsubstituted C6-C 12 Cycloalkyl, straight or branched, substituted or unsubstituted C7-C 24 Aryl groups, and substituted or unsubstituted C6-C 24 Aryl, n is an integer from 2 to 4. x is an integer from 1 to 15, and v is an integer between 4 and 6.

12. A liquid composition comprising, based on the total weight of the liquid composition, an amount of the composition according to any one of claims 1 to 10 in the amount of ≥ 0.01 wt.-% to ≤ 10.0 wt.-%; and based on the total weight of the liquid composition, at least one component selected from the group consisting of ≥ 15.0 wt.-% to ≤ 99.9 wt.-%: pigment paste, binder, filler, solvent, defoamer, neutralizer, wetting agent, pigment dispersant, preservative, and water.

13. The liquid composition according to claim 12, wherein, The composition is a paint, water-based coating formulation, solvent-based coating formulation, varnish, clear varnish, paper coating, wood coating, adhesive, ink, cosmetic formulation, detergent formulation, textile, drilling mud, gypsum formulation, cement composition, formulation for gypsum board, formulation for hydraulic adhesives such as mortar, formulation for ceramics, and formulation for leather.

14. The use of the composition according to any one of claims 1 to 10 or the composition obtained or obtainable according to the method according to claim 11 as a thixotropic agent in a liquid composition for use in paint and coating formulations, adhesives, paint varnishes, PVC plastisols, inks and cement formulations.

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