urea carbamate compounds

Abstract

The present invention relates to urea urethane compounds obtainable by reacting a mixture of toluene diisocyanate with a monohydric alcohol, followed by reaction with a diamine. The invention provides a process for the preparation of urea urethane compounds, liquid compositions comprising the urea urethane compounds, and the use of the urea urethane compounds as thickening agents and thixotropic agents for water-based and solvent-based paint and coating formulations, lacquers, varnishes, paper coatings, wood coatings, adhesives, inks, cosmetic formulations, detergent formulations, textile and drilling mud formulations, PVC plastisol and cement formulations.

Description

Invention Field

[0001] This invention relates to urea carbamate compounds obtained by reacting a mixture of toluene diisocyanate and a monohydric alcohol, and methods for preparing the same. Furthermore, this invention relates to the use of liquid compositions containing urea carbamate compounds as thixotropic agents in paint and coating formulations, adhesives, paint lacquer, PVC plastisol, inks, and cement formulations. Background of the Invention

[0003] Urea carbamate compounds are useful as thixotropic agents or rheology modifiers in liquid compositions such as paints and coatings formulations. Urea carbamate compounds are capable of forming reversible hydrogen bonds. They form hydrogen bonds with components of the liquid composition and form a gel. When shear forces are applied, such as through mixing or shaking, the hydrogen bonds break and the liquid composition becomes flowable. After the shear force is removed, the hydrogen bonds are restored and the liquid composition gels again.

[0004] Urea carbamate compounds are prepared from diisocyanates. Isocyanates react with alcohols to form carbamates, and isocyanates react with amines to form ureas. The properties of urea carbamate compounds depend on the reactants and their ratio. There has always been a need to obtain urea carbamate compounds with desired properties, such as thixotropic behavior. Furthermore, it is desirable for urea carbamate compounds to act as thixotropic agents in aqueous coating compositions.

[0005] Different methods have been proposed in the prior art to obtain urea carbamate compounds.

[0006] US 4383068 and US 3893956 describe methods for forming urea adducts by reacting a monohydric alcohol with a diisocyanate and, if suitable, a diisocyanate with a primary and / or secondary polyamine in the presence of a binder. These urea carbamate compounds are prepared in a binder or carrier medium. These binders then possess rheology-modifying properties. Rheology modifiers cannot be prepared alone without these carrier media and therefore have limited applicability.

[0007] US 4522986 describes urethane-urea compounds prepared by reacting NCO-terminated urethane prepolymers with ethanolamine to form hydroxyurea-terminated rheology modifiers. 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 to a waxy substance or by dilution with acetone. Insoluble diurea compounds are separated as crystalline substances, removed by filtration, and discarded.

[0008] EP 0006252 provides a method for preparing thixotropic agents and describes urea carbamates prepared by reacting isocyanate adducts with polyamines in an aprotic solvent in the presence of lithium chloride. A disadvantage of the product obtained in this manner is that the structure of the urea carbamate is not well-defined due to the preparation method. This method does not yield pure monoadducts, but rather a mixture of monoadducts and diisocyanates, which react with the diamine, leading to uncontrolled growth of the urea-carbamate chain. In this method, 1 mol of diisocyanate is first reacted with 1 mol of a monohydric alcohol. This method partially yields the desired NCO-functionalized monoadduct, but also prepares 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 accessibility of the NCO groups and the reaction conditions used, such as temperature and time. All of these adducts prepared in this manner contain a considerable amount of unreacted diisocyanate, which, upon further reaction with polyamines in the presence of lithium chloride, leads to uncontrolled chain extension of urea carbamate and results in polymerized urea. These products then tend to precipitate and can only be retained in solution with great difficulty.

[0009] US 6420466 describes a method for preparing a thixotropic agent containing a urea-carbamate, wherein a monohydroxy compound is reacted with an excess of toluene diisocyanate, thereby removing the unreacted toluene moiety from the reaction mixture. The resulting monoisocyanate adduct is further reacted with a diamine in the presence of a lithium salt. A drawback of this method is that the subsequent removal of the stoichiometric excess diisocyanate by vacuum distillation is a complex and expensive process. Furthermore, the efficiency of these urea-carbamates is limited because only a few active urea groups can bind to the molecule due to the intentionally prepared diurea-carbamates.

[0010] Although urea carbamate polymers have been commercially prepared and used for many years, there remains a need for a method to prepare urea carbamate compounds without requiring a diisocyanate distillation step. The challenge is to reduce free diisocyanate in the first step to form a monoisocyanate adduct, i.e., without free diisocyanate, which reacts with the diamine in the second step to form a more defined urea carbamate polymer structure.

[0011] Therefore, one object of the present invention is to provide urea carbamate compounds that are storage stable and impart the desired thickening and thixotropic properties to compositions such as paints and coatings formulations. Furthermore, another object of the present invention is to provide a method for preparing urea carbamate compounds that eliminates the need for a diisocyanate distillation step, thereby providing a simpler and more economical method that avoids the disadvantages associated with the presence of free diisocyanates.

[0012] Invention Summary

[0013] Surprisingly, the urea carbamate compounds of the present invention, prepared by reacting toluene diisocyanate with a mixture of at least two monohydric alcohols in a specific ratio, followed by reaction with at least one diamine, exhibit excellent storage stability. Furthermore, these compounds impart the desired thickening and thixotropic properties to liquid compositions such as paint and coating formulations, adhesives, varnishes, PVC plastisols, inks, and cement formulations. Moreover, the method for preparing the urea carbamate compounds does not require a diisocyanate distillation step.

[0014] Therefore, one aspect of the present invention is a urea carbamate compound that can be obtained by the following means:

[0015] (i) Cause the following substances to react:

[0016] a. Toluene diisocyanate, and

[0017] b. A mixture of monohydric alcohols, comprising:

[0018] (b1) At least one monohydric alcohol of formula (I):

[0019] R 1 -OH(I),

[0020] in

[0021] R 1 Selected from linear or branched, substituted or unsubstituted C4-C 22 Alkyl, linear or branched, substituted or unsubstituted C4-C 22 Alkenyl, substituted or unsubstituted C6-C 12 Cycloalkyl (linear or branched), linear or branched, substituted or unsubstituted C7-C 24 Aryl groups, and substituted or unsubstituted C6-C 24 Aryl,

[0022] Formula R 11 (OC n H 2n ) x - group,

[0023] Formula R 11 [OC(=O)-C v H 2v ] x - groups, and

[0024] Formula R 11 (OC n H 2n ) x-1 [OC(=O)-C v H 2v ]x - group,

[0025] in

[0026] R 11 Selected from linear or branched, substituted or unsubstituted C4-C 22 Alkyl, linear or branched, substituted or unsubstituted C4-C 22 Alkenyl, substituted or unsubstituted C6-C 12 Cycloalkyl, linear or branched, substituted or unsubstituted C7-C 24 Aryl groups, and substituted or unsubstituted C6-C 24 Aryl,

[0027] n is an integer between 2 and 4.

[0028] x is an integer from 1 to 15, and

[0029] v is an integer between 4 and 6; and

[0030] (b2) At least one monohydric alcohol of formula (II):

[0031] R 2 -OH(II),

[0032] Where R 2 It is formula C p H 2p+1 (OC q H 2q ) r - group,

[0033] p is an integer between 1 and 3.

[0034] q is an integer between 2 and 4, and

[0035] r is an integer from 1 to 50.

[0036] The molar ratio of at least one monohydric alcohol of formula (I) to at least one monohydric alcohol of formula (II) is in the range of 10:1 to 1:10, and

[0037] The molar ratio of the total amount of the monohydric alcohol mixture to toluene diisocyanate is in the range of >1.0:1.0 to ≤1.5:1.0;

[0038] To obtain a mixture containing at least two monoisocyanate adducts;

[0039] ii) React the mixture containing at least two monoisocyanate adducts obtained in step (i) with at least one diamine to obtain a urea carbamate compound.

[0040] Another aspect of the present invention is a method for preparing urea carbamate compounds. The method includes:

[0041] i. Introduce toluene diisocyanate into the reactor;

[0042] ii. Mix at least one monohydric alcohol of formula (I) and at least one monohydric alcohol of formula (II) to obtain a mixture comprising a monohydric alcohol;

[0043] iii. The mixture obtained in step (ii) is added to a reactor and the monohydric alcohol is reacted with toluene diisocyanate to obtain a mixture containing at least two monoisocyanate adducts;

[0044] iv. To prepare a mixture by mixing at least one diamine, at least one polar aprotic solvent, and at least one metal salt catalyst; and

[0045] v. The mixture obtained in step (iv) is added to a reactor to react with the mixture obtained in step (iii) containing at least two monoisocyanate adducts to obtain a urea carbamate compound.

[0046] Another aspect of the invention relates to a liquid composition comprising an amount of a urea carbamate compound in the range of ≥0.01% by weight to ≤10.0% by weight based on the total weight of the liquid composition.

[0047] Another aspect of the present invention relates to the use of urea carbamate compounds in liquid compositions as thixotropic agents for paint and coating formulations, adhesives, varnishes, PVC plastisols, inks, and cement formulations. Invention Details

[0049] Before describing the compositions and formulations of the present invention, it should be understood that the invention is not limited to the specific compositions and formulations described, as such compositions and formulations can certainly be modified. It should also be understood that the terminology used herein is not intended to be limiting, as the scope of the invention is limited only by the appended claims.

[0050] If a group is defined below as comprising at least a certain number of embodiments, this is also intended to include a group preferably consisting only of these embodiments. Furthermore, the terms 'first,' 'second,' 'third,' or 'a', 'b', 'c', etc., used in the specification and claims are used to distinguish similar elements and are not necessarily used to describe a sequential or chronological order. It should be understood that such terms are interchangeable where appropriate and that embodiments of the invention described herein can be operated in orders other than those described or shown herein. Where the terms 'first,' 'second,' 'third,' or '(A)', '(B)' and '(C)' or '(a)', '(b)', '(c)', '(d)', 'i', 'ii', etc., relate to steps of a method or use or analysis, there is no temporal or time interval coherence between the steps; that is, these steps can be performed simultaneously or there can be time intervals of seconds, minutes, hours, days, weeks, months, or even years between these steps, unless otherwise specified in this application as described in the context.

[0051] Furthermore, the ranges defined throughout this specification include end values; that is, the range 1-10 implies that both 1 and 10 are included within this range. For the avoidance of doubt, the applicant should be granted authorization for any equivalent scheme in accordance with applicable law.

[0052] The various aspects of the invention are defined in more detail in the following paragraphs. The aspects thus defined may be combined with any one or more other aspects unless explicitly stated otherwise. Specifically, any feature shown as preferred or advantageous may be combined with any one or more other features shown as preferred or advantageous.

[0053] Throughout this specification, references to "one embodiment" or "an embodiment" mean that the specific feature, structure, or characteristic described in relation to that embodiment is included in at least one embodiment of the invention. Therefore, the phrase "in one embodiment" or "in an embodiment" appearing in various places throughout the specification does not necessarily all refer to the same embodiment.

[0054] Furthermore, these specific features, structures, or characteristics can be combined in any suitable manner in one or more embodiments, as will be apparent to those skilled in the art from this disclosure. Moreover, although some embodiments described herein include some, but not others, features included in other embodiments, combinations of features from different embodiments are intended to be within the scope of the invention and form different embodiments, as will be understood by those skilled in the art. For example, in the appended claims, any claimed embodiment can be used in any combination.

[0055] Surprisingly, the urea carbamate compounds of the present invention have been found to possess excellent storage stability, and these compounds impart the desired thickening effect and thixotropic properties to liquid compositions such as paint and coating formulations, adhesives, varnishes, PVC plastisols, inks, and cement formulations. The urea carbamate compounds of the present invention are useful in aqueous formulations as well as organic solvent-based formulations.

[0056] Surprisingly, it has been found that urea carbamate compounds with the desired thickening effect and thixotropic properties can be prepared by using a mixture of appropriately selected monohydric alcohols. The thickening effect and thixotropic properties of urea carbamate compounds depend on the monohydric alcohols of formula (I) and (II) constituting the mixture, and their amounts. Therefore, by selecting appropriate monohydric alcohols of formula (I) and (II) and their suitable amounts, urea carbamate compounds with the desired thickening effect and thixotropic properties can be obtained.

[0057] This invention relates to urea carbamate compounds used as additives in solvent-based, solvent-free, and water-based paint and coating formulations to impart thixotropic properties to the compositions. Urea carbamate compounds can be used to modify the rheological properties of paint and coating formulations, lacquer, varnish, paper coatings, wood coatings, adhesives, inks, cosmetic formulations, detergent formulations, textile and drilling mud formulations, PVC plastisols, and cement formulations.

[0058] Therefore, one aspect of the present invention is a urea carbamate compound that can be obtained by the following means:

[0059] (i) Cause the following substances to react:

[0060] a. Toluene diisocyanate, and

[0061] b. A mixture of monohydric alcohols, comprising:

[0062] (b1) At least one monohydric alcohol of formula (I):

[0063] R 1 -OH(I),

[0064] in

[0065] R 1 Selected from linear or branched, substituted or unsubstituted C4-C 22 Alkyl, linear or branched, substituted or unsubstituted C4-C 22 Alkenyl, substituted or unsubstituted C6-C 12 Cycloalkyl, linear or branched, substituted or unsubstituted C7-C 24 Aryl groups, and substituted or unsubstituted C6-C 24 Aryl,

[0066] Formula R 11 (OC n H 2n ) x - group,

[0067] Formula R 11 [OC(=O)-C v H 2v ] x - groups, and

[0068] Formula R 11 (OC n H 2n ) x-1 [OC(=O)-C v H 2v ] x - group,

[0069] in

[0070] R 11 Selected from linear or branched, substituted or unsubstituted C4-C 22 Alkyl, linear or branched, substituted or unsubstituted C4-C 22 Alkenyl, substituted or unsubstituted C6-C 12 Cycloalkyl, linear or branched, substituted or unsubstituted C7-C 24 Aryl groups, and substituted or unsubstituted C6-C 24 Aryl,

[0071] n is an integer between 2 and 4.

[0072] x is an integer from 1 to 15, and

[0073] v is an integer between 4 and 6; and

[0074] (b2) At least one monohydric alcohol of formula (II):

[0075] R 2 -OH(II),

[0076] Where R 2 It is formula C p H 2p+1 (OC q H 2q ) r - group,

[0077] p is an integer between 1 and 3.

[0078] q is an integer between 2 and 4, and

[0079] r is an integer from 1 to 50.

[0080] The molar ratio of at least one monohydric alcohol of formula (I) to at least one monohydric alcohol of formula (II) is in the range of 10:1 to 1:10, and

[0081] The molar ratio of the total amount of the monohydric alcohol mixture to toluene diisocyanate is in the range of >1.0:1.0 to ≤1.5:1.0;

[0082] To obtain a mixture comprising at least two monoisocyanate adducts; and

[0083] ii) React the mixture containing at least two monoisocyanate adducts obtained in step (i) with at least one diamine to obtain a urea carbamate compound.

[0084] In the context of this invention, the term "thixotropic effect" as used herein refers to the time-dependent shear-thinning property exhibited by a viscous fluid or gel-like product. The product is thick or viscous under static conditions and undergoes agitation, shear stress, or other stresses over time. Upon removal of the agitation or shear stress, the product reverts to a more viscous state in a time-dependent manner.

[0085] In the context of this invention, the term alkyl refers to an acyclic saturated aliphatic group, including those of the general formula C1. n H 2n+1 The linear and branched alkyl saturated hydrocarbon groups are represented, where n is the number of carbon atoms 1, 2, 3, 4, etc.

[0086] Preferred to have C4-C 22 Examples of linear unsubstituted alkyl groups on carbon atoms are butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptyl, octadecyl, nonadecanyl, eicosyl, dodecyl, and dodecyl.

[0087] Preferred to have C4-C 22 Examples of branched unsubstituted alkyl groups of carbon atoms are 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 1-methylpentyl, 2-methylpentyl, 2-methylhexyl, 3-methylhexyl, 1-methylheptyl, 2-methylheptyl, 3-methylheptyl, 1-methyloctyl, 2-methyloctyl, 1-methylnonyl, 1-ethylpropyl, 1-ethylbutyl, 2-ethylbutyl, 1-ethylpentyl, 2-ethylpentyl, 1-ethylhexyl, 2-ethylhexyl, 1-ethylheptyl, 2-ethylheptyl, 1-ethyloctyl, 2-ethyloctyl, 1-propylbutyl, 1-propylpentyl, 2-propylpentyl, 1-propylhexyl, 2-propylhexyl, 1-propylheptyl, 2-propylheptyl, 3-propylheptyl, and 4-propylheptyl. 1-Butylpentyl, 1-Butylhexyl and 2-Butylhexyl.

[0088] The term substituted alkyl refers to an alkyl group in which some or all of the hydrogen atoms are replaced by substituents, preferably selected from hydroxyl, halogen, cyano, C1-C4 alkyl and C1-C4 alkoxy groups.

[0089] In the context of this invention, the term alkenyl, as used herein, refers to an acyclic unsaturated aliphatic group having at least one double bond, including those of the general formula Calkenyl. n H 2n-1 The linear and branched alkenyl unsaturated hydrocarbon groups are represented, where n is the number of carbon atoms, such as 1, 2, 3, 4, etc.

[0090] Preferred to have C4-C 22Examples of linear unsubstituted alkenyl groups on carbon atoms include but-1-enyl, but-2-enyl, but-3-enyl, pent-1-enyl, pent-2-enyl, pent-3-enyl, pent-4-enyl, hex-1-enyl, hex-2-enyl, hex-3-enyl, hex-4-enyl, hex-5-enyl, hep-1-enyl, hep-2-enyl, hep-3-enyl, hep-4-enyl, hep-5-enyl, hep-6-enyl, oct-1-enyl, oct-2-enyl, oct-3-enyl, oct-4-enyl, oct-5-enyl, oct-6-enyl, oct-7-enyl, non-1-enyl, non-2-enyl, non-3-enyl, non-4-enyl, non-5-enyl, non-6-enyl, non-7-enyl, non-8-enyl, dec- 1-Alkenyl, dec-2-Alkenyl, dec-3-Alkenyl, dec-4-Alkenyl, dec-5-Alkenyl, dec-6-Alkenyl, dec-7-Alkenyl, dec-8-Alkenyl, dec-9-Alkenyl, undec-1-Alkenyl, undec-2-Alkenyl, undec-3-Alkenyl, undec-4-Alkenyl, undec-5-Alkenyl, undec-6-Alkenyl, undec-7-Alkenyl, undec-8-Alkenyl, undec-9-Alkenyl, undec-10-Alkenyl, dodec-1-Alkenyl, dodec-2-Alkenyl, dodec-3-Alkenyl, dodec-4-Alkenyl, dodec-5-Alkenyl, dodec-6-Alkenyl, dodec-7-Alkenyl, dodec-8-Alkenyl, dodec-9-Alkenyl, dodec-10-Alkenyl, dodec-11 -alkenyl, tridecyl-1-alkenyl, tridecyl-2-alkenyl, tridecyl-3-alkenyl, tridecyl-4-alkenyl, tridecyl-5-alkenyl, tridecyl-6-alkenyl, tridecyl-7-alkenyl, tridecyl-8-alkenyl, tridecyl-9-alkenyl, tridecyl-10-alkenyl, tridecyl-11-alkenyl, tridecyl-12-alkenyl, tetradecyl-1-alkenyl, tetradecyl-2-alkenyl, tetradecyl-3-alkenyl, tetradecyl-4-alkenyl, tetradecyl-5-alkenyl, tetradecyl-6-alkenyl, tetradecyl-7-alkenyl, tetradecyl-8-alkenyl, tetradecyl-9-alkenyl, tetradecyl-10-alkenyl, tetradecyl-11-alkenyl, tetradecyl-12-alkenyl, tetradecyl-13-alkenyl, pentadecyl-1-alkenyl, pentadecyl- 2-Alkenyl, pentadecyl-3-alkenyl, pentadecyl-4-alkenyl, pentadecyl-5-alkenyl, pentadecyl-6-alkenyl, pentadecyl-7-alkenyl, pentadecyl-8-alkenyl, pentadecyl-9-alkenyl, pentadecyl-10-alkenyl, pentadecyl-11-alkenyl, pentadecyl-12-alkenyl, pentadecyl-13-alkenyl, pentadecyl-14-alkenyl, hexadecyl-1-alkenyl, hexadecyl-2-alkenyl, hexadecyl-3-alkenyl, hexadecyl-4-alkenyl, hexadecyl-5-alkenyl, hexadecyl-6-alkenyl, hexadecyl-7-alkenyl, hexadecyl-8-alkenyl, hexadecyl-9-alkenyl, hexadecyl-10-alkenyl, hexadecyl-11-alkenyl, hexadecyl-12-alkenyl, hexadecyl-13-alkenyl, hexadecyl-14-alkenylHexadec-15-enyl, heptadecan-1-enyl, heptadecan-2-enyl, heptadecan-3-enyl, heptadecan-4-enyl, heptadecan-5-enyl, heptadecan-6-enyl, heptadecan-7-enyl, heptadecan-8-enyl, heptadecan-9-enyl, heptadecan-10-enyl, heptadecan-11-enyl, heptadecan-12-enyl, heptadecan-13-enyl, heptadecan-14-enyl, heptadecan-15-enyl, heptadecan-16-enyl, octadec-1-enyl, octadec-2-enyl, octadec-3-enyl, octadec-4-enyl, octadec-5-enyl, octadec-6-enyl, octadec-7-enyl, octadec-8-enyl, octadec-9-enyl, octadec-10- Alkenyl, octadec-11-alkenyl, octadec-12-alkenyl, octadec-13-alkenyl, octadec-14-alkenyl, octadec-15-alkenyl, octadec-16-alkenyl, octadec-17-alkenyl, nonadecano-1-alkenyl, nonadecano-2-alkenyl, nonadecano-3-alkenyl, nonadecano-4-alkenyl, nonadecano-5-alkenyl, nonadecano-6-alkenyl, nonadecano-7-alkenyl, nonadecano-8-alkenyl, nonadecano-9-alkenyl, nonadecano-10-alkenyl, nonadecano-11-alkenyl, nonadecano-12-alkenyl, nonadecano-13-alkenyl, nonadecano-14-alkenyl, nonadecano-15-alkenyl, nonadecano-16-alkenyl, nonadecano-17-alkenyl, nonadecano-18-alkenyl, eicosane-1 -alkenyl, eicosene-2-alkenyl, eicosene-3-alkenyl, eicosene-4-alkenyl, eicosene-5-alkenyl, eicosene-6-alkenyl, eicosene-7-alkenyl, eicosene-8-alkenyl, eicosene-9-alkenyl, eicosene-10-alkenyl, eicosene-11-alkenyl, eicosene-12-alkenyl, eicosene-13-alkenyl, eicosene-14-alkenyl, eicosene-15-alkenyl, eicosene-16-alkenyl, eicosene-17-alkenyl, eicosene-18-alkenyl, eicosene-19-alkenyl, docosahexa-1-alkenyl, docosahexa-2-alkenyl, docosahexa-3-alkenyl, docosahexa-4-alkenyl, docosahexa-5-alkenyl, docosahexa-6-alkenyl, docosahexa-7-alkenyl, docosahexa-1-alkenyl C8-alkenyl, C9-alkenyl, C10-alkenyl, C11-alkenyl, C12-alkenyl, C13-alkenyl, C14-alkenyl, C15-alkenyl, C16-alkenyl, C17-alkenyl, C18-alkenyl, C19-alkenyl, C20-alkenyl, C1-alkenyl, C2-2-alkenyl, C3-alkenyl, C4-alkenyl, C5-alkenyl, C6-alkenyl, C7-alkenyl, C8-alkenyl, C9-alkenyl, C10-alkenyl, C11-alkenylC12-12-enyl, C13-enyl, C14-enyl, C15-enyl, C16-enyl, C17-enyl, C18-enyl, C19-enyl, C20-enyl, and C21-enyl.

[0091] In the context of this invention, the term cycloalkyl as used herein refers to a 6-12 member saturated alicyclic group, including branched cycloalkyl saturated hydrocarbons, both monocyclic and bicyclic.

[0092] Preferred C6-C 12 Examples of cycloalkyl groups are cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclododecyl, cycloundecyl, and cyclooctadecyl.

[0093] In the context of this invention, the term aryl is used to refer to an alkyl group substituted with an aryl group. The aryl group is phenyl or naphthyl, preferably phenyl.

[0094] Preferred C7-C 24 Examples of aralkyl groups are benzyl, phenethyl, phenyl-1-propyl, phenyl-2-propyl, phenyl-1-butyl, phenyl-2-butyl, phenyl-1-pentyl, phenyl-1-hexyl, o-tolyl, m-tolyl, p-tolyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5-xylyl, and base.

[0095] In the context of this invention, the term "aryl" as used herein refers to an aromatic carbon ring with 6-24 ring members, including monocyclic, bicyclic, and tricyclic systems. Preferred examples of aryl groups are indenyl, phenyl, and naphthyl.

[0096] In the context of this invention, the term “polar aprotic solvent” as used herein refers to a solvent composed of polar molecules having a relatively high relative permittivity (or dielectric constant) greater than 15 and a permanent dipole moment that cannot provide suitable unstable hydrogen atoms to form strong hydrogen bonds.

[0097] In the context of this invention, the term "monoisocyanate adduct" as used herein refers to the addition product of toluene diisocyanate (TDI) with a monohydroxy compound of general formula (I) or general formula (II). The monoisocyanate adduct has a free reactive isocyanate group that reacts with a diamine.

[0098] In the context of this invention, the term "theoretical NCO content" as used herein refers to the content of isocyanate (NCO) calculated theoretically based on only half the amount of NCO groups in TDI.

[0099] In a preferred embodiment, the urea carbamate compound can be obtained by the following means:

[0100] (i) Cause the following substances to react:

[0101] a. Toluene diisocyanate, and

[0102] b. A mixture of monohydric alcohols, comprising:

[0103] (b1) At least one monohydric alcohol of formula (I):

[0104] R 1 -OH(I),

[0105] in

[0106] R 1 Selected from linear or branched, substituted or unsubstituted C4-C 22 Alkyl, linear or branched, substituted or unsubstituted C4-C 22 Alkenyl, substituted or unsubstituted C6-C 12 Cycloalkyl, linear or branched, substituted or unsubstituted C7-C 24 Aryl groups, and substituted or unsubstituted C6-C 24 Aryl, and

[0107] (b2) At least one monohydric alcohol of formula (II):

[0108] R 2 -OH(II),

[0109] Where R 2 It is formula C p H 2p+1 (OC q H 2q ) r - group,

[0110] p is an integer between 1 and 3.

[0111] q is an integer between 2 and 4, and

[0112] r is an integer from 1 to 50.

[0113] The molar ratio of at least one monohydric alcohol of formula (I) to at least one monohydric alcohol of formula (II) is in the range of 10:1 to 1:10, and

[0114] The molar ratio of the total amount of the monohydric alcohol mixture to toluene diisocyanate is in the range of >1.0:1.0 to ≤1.5:1.0;

[0115] To obtain a mixture containing at least two monoisocyanate adducts;

[0116] ii) React the mixture containing at least two monoisocyanate adducts obtained in step (i) with at least one diamine to obtain a urea carbamate compound.

[0117] In a preferred embodiment, the urea carbamate compound can be obtained by the following means:

[0118] (i) Cause the following substances to react:

[0119] a. Toluene diisocyanate, and

[0120] b. A mixture of monohydric alcohols, comprising:

[0121] (b1) At least one monohydric alcohol of formula (I):

[0122] R 1 -OH(I),

[0123] in

[0124] R 1 Selected from:

[0125] Formula R 11 (OC n H 2n ) x - group,

[0126] Formula R 11 [OC(=O)-C v H 2v ] x - groups, and

[0127] Formula R 11 (OC n H 2n ) x-1 [OC(=O)-C v H 2v ] x - group,

[0128] in

[0129] R 11 Selected from linear or branched, substituted or unsubstituted C4-C 22 Alkyl, linear or branched, substituted or unsubstituted C4-C 22 Alkenyl, substituted or unsubstituted C6-C 12 Cycloalkyl, linear or branched, substituted or unsubstituted C7-C 24 Aryl groups, and substituted or unsubstituted C6-C 24 Aryl,

[0130] n is an integer between 2 and 4.

[0131] x is an integer from 1 to 15, and

[0132] v is an integer between 4 and 6; and

[0133] (b2) At least one monohydric alcohol of formula (II):

[0134] R 2 -OH(II),

[0135] Where R 2 It is formula C p H 2p+1 (OC q H 2q ) r - group,

[0136] p is an integer between 1 and 3.

[0137] q is an integer between 2 and 4, and

[0138] r is an integer from 1 to 50.

[0139] The molar ratio of at least one monohydric alcohol of formula (I) to at least one monohydric alcohol of formula (II) is in the range of 10:1 to 1:10, and

[0140] The molar ratio of the total amount of the monohydric alcohol mixture to toluene diisocyanate is in the range of >1.0:1.0 to ≤1.5:1.0;

[0141] To obtain a mixture containing at least two monoisocyanate adducts;

[0142] ii) React the mixture containing at least two monoisocyanate adducts obtained in step (i) with at least one diamine to obtain a urea carbamate compound.

[0143] In a more preferred embodiment, the urea carbamate compound can be obtained by:

[0144] (i) Cause the following substances to react:

[0145] a. Toluene diisocyanate, and

[0146] b. A mixture of monohydric alcohols, comprising:

[0147] (b1) At least one monohydric alcohol of formula (I):

[0148] R 1 -OH(I),

[0149] in

[0150] R 1 It is formula R 11 (OC n H2n ) x - group,

[0151] in

[0152] R 11 Selected from linear or branched, substituted or unsubstituted C4-C 22 Alkyl, linear or branched, substituted or unsubstituted C4-C 22 Alkenyl, substituted or unsubstituted C6-C 12 Cycloalkyl, linear or branched, substituted or unsubstituted C7-C 24 Aryl groups, and substituted or unsubstituted C6-C 24 Aryl,

[0153] n is an integer between 2 and 4, and

[0154] x is an integer from 1 to 15, and

[0155] (b2) At least one monohydric alcohol of formula (II):

[0156] R 2 -OH(II),

[0157] Where R 2 It is formula C p H 2p+1 (OC q H 2q ) r - group,

[0158] p is an integer between 1 and 3.

[0159] q is an integer between 2 and 4, and

[0160] r is an integer from 1 to 50.

[0161] The molar ratio of at least one monohydric alcohol of formula (I) to at least one monohydric alcohol of formula (II) is in the range of 10:1 to 1:10, and

[0162] The molar ratio of the total amount of the monohydric alcohol mixture to toluene diisocyanate is in the range of >1.0:1.0 to ≤1.5:1.0;

[0163] To obtain a mixture containing at least two monoisocyanate adducts;

[0164] ii) React the mixture containing at least two monoisocyanate adducts obtained in step (i) with at least one diamine to obtain a urea carbamate compound.

[0165] In a preferred embodiment, the toluene diisocyanate is selected from 2,4-toluene diisocyanate and mixtures of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate.

[0166] In a more preferred embodiment, the toluene diisocyanate is 2,4-toluene diisocyanate.

[0167] In the most preferred embodiment, toluene diisocyanate is a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate.

[0168] 2,4-Toluene diisocyanate is available as a commercially available product. Mixtures of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate having known compositions are also commercially available. A mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate having intermediate compositions can be prepared by mixing these two commercially available products.

[0169] Surprisingly, it was also observed that the thickening effect and thixotropic properties of the urea carbamate compounds of the present invention were enhanced, thus differing from those mixtures obtained by physically mixing urea carbamate compounds using a single monohydric alcohol. Therefore, it is clear that the properties of the urea carbamate compounds obtained according to the present invention are not merely the additive properties of individual urea carbamate compounds obtained using a single monohydric alcohol.

[0170] It has been observed that the properties of the urea carbamate compounds of the present invention depend on the monohydric alcohols of formula (I) and (II) used.

[0171] In a more preferred embodiment, R 1 It is selected from butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 1-methylpentyl, 2-methylpentyl, 2-methylhexyl, 3-methylhexyl, 1-ethylpropyl, 1-ethylbutyl, 2-ethylbutyl, cyclohexyl, phenyl, tolyl, xylyl, 4-dodecylphenyl, benzyl, and phenethyl.

[0172] In a more preferred embodiment, R 11 It is selected from butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 1-methylpentyl, 2-methylpentyl, 2-methylhexyl, 3-methylhexyl, 1-ethylpropyl, 1-ethylbutyl, 2-ethylbutyl, cyclohexyl, phenyl, tolyl, xylyl, 4-dodecylphenyl, benzyl, and phenethyl.

[0173] In the preferred embodiment, in formula (I)

[0174] R 11 Is it linear or branched, substituted or unsubstituted C4-C? 22 alkyl,

[0175] n is an integer between 2 and 4, and

[0176] x is an integer between 2 and 10.

[0177] In a more preferred embodiment, in formula (I)

[0178] R 11 Is it linear or branched, substituted or unsubstituted C4-C? 12 alkyl,

[0179] n is an integer between 2 and 3, and

[0180] x is an integer between 2 and 6.

[0181] In an even more preferred embodiment, in formula (I)

[0182] R 11 It is linear, unsubstituted C4-C 12 alkyl,

[0183] n is an integer between 2 and 3, and

[0184] x is an integer between 2 and 6.

[0185] In the most preferred embodiment, in equation (I), R 11 It is a n-butyl group, n is 2, and x is 3.

[0186] In a more preferred embodiment, at least one monohydric alcohol of formula (I) is selected from butyltriethylene glycol, butyl diethylene glycol, butyl tetraethylene glycol, butanol, isotriadecyl alcohol, oleyl alcohol, guerbert alcohol containing 8-20 carbon atoms, linoleyl alcohol, lauryl alcohol, stearyl alcohol, cyclohexanol, benzyl alcohol, 4-dodecylphenol, ethoxylated triphenylmethanol and ethoxylated 4-dodecylphenol.

[0187] In the most preferred embodiment, at least one monohydric alcohol of formula (I) is butyl triethylene glycol ether.

[0188] In a preferred embodiment, in formula (II)

[0189] p is an integer between 1 and 2.

[0190] q is an integer between 2 and 4, and

[0191] r is an integer between 5 and 50.

[0192] In a more preferred embodiment, in formula (II)

[0193] p is an integer between 1 and 2.

[0194] q is an integer between 2 and 3, and

[0195] r is an integer between 5 and 25.

[0196] In an even more preferred embodiment, in formula (II)

[0197] p is an integer between 1 and 2.

[0198] q is an integer between 2 and 3, and

[0199] r is an integer between 5 and 15.

[0200] In the most preferred embodiment, in equation (II), p is 1, q is 2, and r is an integer from 5 to 15.

[0201] In the most preferred embodiment, at least one monohydric alcohol of formula (II) is methoxy polyethylene glycol (MPEG).

[0202] MPEG is based on the fact that the degree of polymerization of polyethylene glycol, i.e., the r value, has different properties and molecular weights.

[0203] In a particularly preferred embodiment, at least one monohydric alcohol of formula (II) is methoxy polyethylene glycol (MPEG) having a molecular weight of 350 g / mol as determined according to DIN 55672-1.

[0204] In a particularly preferred embodiment, at least one monohydric alcohol of formula (II) is methoxy polyethylene glycol (MPEG) having a molecular weight of 500 g / mol as determined according to DIN 55672-1.

[0205] In a particularly preferred embodiment, at least one monohydric alcohol of formula (II) is a mixture of methoxy polyethylene glycol (MPEG) having a molecular weight of 350 g / mol and methoxy polyethylene glycol (MPEG) having a molecular weight of 500 g / mol, the molecular weights of which are determined according to DIN 55672-1, and the molar ratio of MPEG having a molecular weight of 350 g / mol to MPEG having a molecular weight of 500 g / mol is in the range of 1:10 to 10:1.

[0206] The molar ratio of at least one monohydric alcohol of formula (I) to at least one monohydric alcohol of formula (II) is important for determining the properties of the urea carbamate compounds of the present invention. It was found that the thickening effect and thixotropic properties of the urea carbamate compounds changed with variations in the molar ratio.

[0207] In a preferred embodiment, the molar ratio of at least one monohydric alcohol of formula (I) to at least one monohydric alcohol of formula (II) is in the range of 10:1 to 1:10, more preferably in the range of 5:1 to 1:10, even more preferably in the range of 2:1 to 1:6; and most preferably in the range of 1.5:1.0 to 1:5.

[0208] In a particularly preferred embodiment, the molar ratio of at least one monohydric alcohol of formula (I) to at least one monohydric alcohol of formula (II) is 1:3.

[0209] In a particularly preferred embodiment, the molar ratio of at least one monohydric alcohol of formula (I) to at least one monohydric alcohol of formula (II) is 1:4.

[0210] The total amount of the monohydric alcohol mixture and the molar ratio of toluene diisocyanate are greater than 1.0:1.0. This ratio ensures that toluene diisocyanate reacts completely to form urea during the reaction. Since toluene diisocyanate is completely consumed, separation steps such as distillation of toluene diisocyanate are not required.

[0211] In a preferred embodiment, the molar ratio of the total amount of the monohydric alcohol mixture to toluene diisocyanate is in the range of >1.0:1.0 to ≤1.5:1.0, more preferably in the range of ≥1.005:1.0 to ≤1.45:1.0, even more preferably in the range of ≥1.005:1.0 to ≤1.4:1.0, even more preferably in the range of ≥1.01:1.0 to ≤1.35:1.0, and most preferably in the range of ≥1.005:1.0 to ≤1.2:1.0.

[0212] In a particularly preferred embodiment, the molar ratio of the total amount of the monohydric alcohol mixture to the toluene diisocyanate is 1.05:1.0.

[0213] In a preferred embodiment, at least one diamine is selected from diamines of formulas (IIIa), (IIIb), (IIIc), (IIId), and (IIIe);

[0214] -H2N-R 3 -NH2(IIIa),

[0215] Where R 3 It is -C y H 2y -And y is an integer between 2 and 12.

[0216] - Diamine of formula (IIIb):

[0217]

[0218] - Diamine of formula (IIIc):

[0219]

[0220] - Diamines of formula (IIId):

[0221] and

[0222] - Diamine of formula (IIIe):

[0223]

[0224] In equations (IIIc), (IIId), and (IIIe), R 4 Same or different and selected from H, CH3-, C2H5- and C3H7-, R 5 Selected from -CH2-, -C2H4-, -C3H6- and -C6H 12 -

[0225] In a preferred embodiment, at least one diamine is selected from 4,4-diaminodiphenylmethane, 3,3-dimethyl-4,4-diaminodiphenylmethane, 2,2-bis(4-aminocyclohexyl)propane, N,N-dimethyl-4,4-diaminodiphenylmethane, (3-methyl-4-aminocyclohexyl)-(3-methyl-4-aminophenyl)methane, m-phenylenediamine, p-phenylenediamine, ethylenediamine, hexamethylenediamine, 4,4-methylenebis(cyclohexylamine), and 1,12-diaminododecane.

[0226] In the most preferred embodiment, at least one diamine is m-phenylenediamine.

[0227] In a preferred embodiment, the urea carbamate compound of the present invention has a weight-average molecular weight in the range of ≥300 g / mol to ≤5000 g / mol as determined according to DIN55672-2.

[0228] In a more preferred embodiment, the urea carbamate compound of the present invention is determined according to DIN55672-2 to have a weight-average molecular weight in the range of ≥1000 g / mol to ≤4000 g / mol; most preferably in the range of ≥2000 g / mol to ≤3500 g / mol.

[0229] In a preferred embodiment, the urea carbamate compound of the present invention has a polydispersity index in the range of 1.0 to 3.0; more preferably in the range of 1.0 to 2.0; and most preferably in the range of 1.1 to 1.8.

[0230] Another aspect of the present invention relates to a method for preparing urea carbamate compounds. The method includes the following steps:

[0231] i. Introduce toluene diisocyanate into the reactor;

[0232] ii. Mix at least one monohydric alcohol of formula (I) and at least one monohydric alcohol of formula (II) to obtain a mixture comprising a monohydric alcohol;

[0233] iii. The mixture obtained in step (ii) is added to a reactor and the monohydric alcohol is reacted with toluene diisocyanate to obtain a mixture containing at least two monoisocyanate adducts;

[0234] iv. To prepare a mixture by mixing at least one diamine, at least one polar aprotic solvent, and at least one metal salt catalyst; and

[0235] v. The mixture obtained in step (iv) is added to a reactor to react with the mixture obtained in step (iii) containing at least two monoisocyanate adducts to obtain a urea carbamate compound.

[0236] In a preferred embodiment, step (i) further includes introducing at least one solvent selected from ethyl acetate, acetone and methyl ethyl ketone (more preferably ethyl acetate) into the reactor.

[0237] In a preferred embodiment, step (i) further comprises premixing toluene diisocyanate with at least one solvent and introducing the mixture of toluene diisocyanate with at least one solvent into a reactor; wherein the at least one solvent is selected from ethyl acetate, acetone and methyl ethyl ketone; more preferably ethyl acetate.

[0238] In a preferred embodiment, the mixture containing a monohydric alcohol obtained in step (ii) further comprises at least one catalyst selected from p-toluenesulfonic acid, H2SO4, HCl and acetic acid; more preferably p-toluenesulfonic acid.

[0239] In a preferred embodiment, the mixture containing monohydric alcohol obtained in step (ii) is added to the reactor within a time period ranging from ≥1 hour to ≤50 hours; more preferably from ≥2 hours to ≤30 hours; even more preferably from ≥3 hours to ≤20 hours; and most preferably from ≥3 hours to ≤15 hours.

[0240] In a preferred embodiment, the reaction of the monohydric alcohol with toluene diisocyanate in step (iii) is carried out at a temperature in the range of ≥20°C to ≤60°C; more preferably ≥25°C to ≤60°C; even more preferably ≥30°C to ≤50°C; and most preferably ≥40°C to ≤50°C.

[0241] In a preferred embodiment, at least one polar 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, hexamethylphosphotriamide, and methyl 5-(dimethylamino)-2-methyl-5-oxovalerate (N-butylbutyrolactam); more preferably, dimethyl sulfoxide, N,N-dimethylformamide, N-methylpyrrolidone, N-butylpyrrolidone, and methyl 5-(dimethylamino)-2-methyl-5-oxovalerate (N-butylbutyrolactam); most preferably, dimethyl sulfoxide, N-butylpyrrolidone, and methyl 5-(dimethylamino)-2-methyl-5-oxovalerate.

[0242] In a preferred embodiment, the metal salt catalyst is selected from lithium chloride, lithium nitrate, lithium bromide, and sodium dioctyl succinate sulfonate; more preferably, lithium nitrate and sodium dioctyl succinate sulfonate.

[0243] In a preferred embodiment, the mixture obtained in step (iv) is added to the reactor over a period of time ranging from ≥1 hour to ≤20 hours, more preferably from ≥1 hour to ≤15 hours, even more preferably from ≥2 hours to ≤10 hours, and most preferably from ≥3 hours to ≤10 hours.

[0244] In a preferred embodiment, the reaction of at least one diamine with at least two monoisocyanate adducts in step (v) is carried out at a temperature in the range of ≥20°C to ≤100°C, more preferably ≥40°C to ≤100°C, and even most preferably ≥50°C to ≤90°C.

[0245] In a preferred embodiment, the molar ratio of the metal salt catalyst to at least one diamine is in the range of 0.3:1.0 to 1.0:1.5, more preferably in the range of 0.5:1.0 to 1.0:1.0.

[0246] In a preferred embodiment, the NCO content determined by titration in step (iii) is less than 110% of the "theoretical NCO content," preferably less than 105%. The "theoretical NCO content" is based on R... 1 -OH and R 2 The theoretical calculations show that only half the amount of NCO groups in the TDI feedstock reacted with the mixture of -OH groups is used.

[0247] In a preferred embodiment, the NCO content is 0% in step (v).

[0248] Therefore, toluene diisocyanate reacts completely to form urea during the reaction. Since toluene diisocyanate is completely consumed, no separation steps such as distillation of toluene diisocyanate are required.

[0249] Another aspect of the invention relates to a liquid composition comprising a urea carbamate compound obtained according to the invention or by the method thereof, in an amount ranging from ≥0.01% by weight to ≤10.0% by weight, based on the total weight of the liquid composition.

[0250] In a preferred embodiment, the liquid composition contains an amount of urea carbamate compound in the range of ≥0.1 wt% to 7.0 ≤ wt%, even more preferably in the range of ≥0.1 wt% to ≤5.0 wt%, and most preferably in the range of ≥0.1 wt% to ≤3.0 wt%, based on the total weight of the liquid composition.

[0251] In a preferred embodiment, the liquid composition further comprises at least one component selected from pigment paste, binder, filler, solvent, defoamer, neutralizer, wetting agent, pigment dispersant, preservative and water.

[0252] In a preferred embodiment, the liquid composition is a paint, water-based coating formulation, solvent-based coating formulation, lacquer, varnish, paper coating, wood coating, adhesive, ink, cosmetic formulation, detergent formulation, textile, drilling mud formulation, cement composition, gypsum board formulation, hydraulic adhesive formulation such as mortar formulation, ceramic and leather formulation.

[0253] Another aspect of the present invention relates to the use of urea carbamate compounds obtained according to the present invention or by the method according to the present invention as thixotropic agents in liquid compositions for use in paint and coating formulations, adhesives, varnishes, PVC plastisols, inks and cement formulations.

[0254] In a preferred embodiment, the liquid composition is a water-based or solvent-based paint and coating formulation. The paint and coating compositions used for the purposes of this invention are those applied from a liquid phase to a substrate and form a protective, functional, and / or decorative surface by forming a film. 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. Coatings can be uncolored, colored, or dye-containing, and may contain various types of binders, alone or in mixtures, and other additives such as fillers, adhesives, neutralizers, pigments, defoamers, wetting agents, pigment dispersants, etc.

[0255] Some examples of additives used in coating formulations are as follows:

[0256] filler

[0257] Suitable fillers include organic or inorganic particulate materials, such as calcium carbonate and silicates, and inorganic fibrous materials, such as glass fibers. 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, may also be used.

[0258] adhesives

[0259] Suitable adhesives 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, Germany 1991. Typically, film-forming adhesives 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 resins, epoxy resins, and polyurethane resins, and mixtures thereof. Resins that can be cured by radiation or air drying may also be used. Adhesives may also be derived from polyvinyl alcohol and polyvinyl butyral. Adhesives 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.

[0260] pigment

[0261] Organic or inorganic pigments are suitable as additives. Examples of organic pigments are colored pigments and mother-of-pearl pigments, such as azo, diazo, naphthol, benzimidazolone, azo condensates, metal complexes, isoindolineone, quinoline, and dioxazine pigments; polycyclic pigments, such as indigo, thioindigo, quinacridones, phthalocyanines, perylenes, perinones, anthraquinones, such as aminoanthraquinones or hydroxyanthraquinones, anthraquinones, indanones, flavanones, pinantrones, anthraquinones, isoviolanthrones, diketopyrrolopyrroles, and carbazoles, such as carbazole violet. Other examples of organic pigments can be found in the following monograph: W. Herbst, K. Huange, “Industrielle Organische Pigmente”, 2nd ed., 1995, VCH Verlagsgesellschaft, ISBN: 3527287442. Examples of inorganic pigments are titanium dioxide, metal flakes such as aluminum and alumina, 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.

[0262] Neutralizing agent

[0263] 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 substances may be used alone or in combination with the above-mentioned inorganic and organic bases.

[0264] Defoamer

[0265] Suitable defoamers are selected from a wide range of defoamers used, such as siloxane-based defoamers, emulsion defoamers, star polymer-based defoamers, powder defoamers, and oil-based defoamers.

[0266] This invention provides one or more of the following advantages:

[0267] 1. A stable urea carbamate compound, used as an additive in paint and coating formulations to impart a thixotropic effect to the formulations.

[0268] 2. A stable urea carbamate compound, used as an additive in water-based and organic solvent-based paint and coating formulations to impart a thixotropic effect to the formulations.

[0269] 3. A simple and economical method for preparing urea carbamate compounds, since a diisocyanate distillation step is not required.

[0270] Further examples of embodiments of this disclosure are provided below, but it is not intended to limit this disclosure to the specific embodiments listed below.

[0271] 1. Urea carbamate compounds that can be obtained through the following methods:

[0272] (i) Cause the following substances to react:

[0273] a. Toluene diisocyanate, and

[0274] b. A mixture of monohydric alcohols, comprising:

[0275] (b1) At least one monohydric alcohol of formula (I):

[0276] R 1 -OH(I),

[0277] in

[0278] R 1 Selected from linear or branched, substituted or unsubstituted C4-C 22 Alkyl, linear or branched, substituted or unsubstituted C4-C 22 Alkenyl, substituted or unsubstituted C6-C 12 Cycloalkyl, linear or branched, substituted or unsubstituted C7-C 24 Aryl groups, and substituted or unsubstituted C6-C 24 Aryl,

[0279] Formula R 11 (OC n H 2n ) x - group,

[0280] Formula R 11 OC(=O)-C v H 2v ] x - groups, and

[0281] Formula R 11 (OC n H 2n ) x-1 [OC(=O)-C v H 2v] x - group,

[0282] in

[0283] R 11 Selected from linear or branched, substituted or unsubstituted C4-C 22 Alkyl, linear or branched, substituted or unsubstituted C4-C 22 Alkenyl, substituted or unsubstituted C6-C 12 Cycloalkyl, linear or branched, substituted or unsubstituted C7-C 24 Aryl groups, and substituted or unsubstituted C6-C 24 Aryl,

[0284] n is an integer between 2 and 4.

[0285] x is an integer from 1 to 15, and

[0286] v is an integer between 4 and 6; and

[0287] (b2) At least one monohydric alcohol of formula (II):

[0288] R 2 -OH(II),

[0289] Where R 2 It is formula C p H 2p+1 (OC q H 2q ) r - group,

[0290] p is an integer between 1 and 3.

[0291] q is an integer between 2 and 4, and

[0292] r is an integer from 1 to 50.

[0293] The molar ratio of at least one monohydric alcohol of formula (I) to at least one monohydric alcohol of formula (II) is in the range of 10:1 to 1:10, and

[0294] The molar ratio of the total amount of the monohydric alcohol mixture to toluene diisocyanate is in the range of >1.0:1.0 to ≤1.5:1.0;

[0295] To obtain a mixture containing at least two monoisocyanate adducts;

[0296] ii) React the mixture containing at least two monoisocyanate adducts obtained in step (i) with at least one diamine to obtain a urea carbamate compound.

[0297] 2. The urea carbamate compound according to embodiment 1, wherein the toluene diisocyanate is selected from 2,4-toluene diisocyanate and a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate.

[0298] 3. A urea carbamate compound according to embodiment 1 or 2, wherein in formula (I)

[0299] R 11 Is it linear or branched, substituted or unsubstituted C4-C? 22 alkyl,

[0300] n is an integer between 2 and 4, and

[0301] x is an integer between 2 and 10.

[0302] 4. A urea carbamate compound according to any one of embodiments 1-3, wherein in formula (II)

[0303] p is an integer between 1 and 2.

[0304] q is an integer between 2 and 4, and

[0305] r is an integer between 5 and 50.

[0306] 5. A urea carbamate compound according to any one of embodiments 1-4, wherein at least one monohydric alcohol of formula (I) is selected from butyltriethylene glycol, butyl diethylene glycol, butyl tetraethylene glycol, butanol, isotriadecyl alcohol, oleyl alcohol, guerbert alcohol containing 8-20 carbon atoms, linoleyl alcohol, lauryl alcohol, stearyl alcohol, cyclohexanol, benzyl alcohol, 4-dodecylphenol, ethoxylated triphenylmethanol and ethoxylated 4-dodecylphenol.

[0307] 6. A urea carbamate compound according to any one of embodiments 1-5, wherein at least one monohydric alcohol of formula (II) is methoxy polyethylene glycol.

[0308] 7. A urea carbamate compound according to any one of embodiments 1-6, wherein the molar ratio of the total amount of the monohydric alcohol mixture to toluene diisocyanate is in the range of >1.0:1.0 to <1.5:1.0.

[0309] 8. A urea carbamate compound according to any one of embodiments 1-7, wherein at least one diamine is selected from diamines of formula (IIIa), (IIIb), (IIIc), (IIId) and (IIIe);

[0310] -H2N-R 3 -NH2(IIIa),

[0311] Where R 3 It is -C y H2y -And y is an integer between 2 and 12.

[0312] - Diamine of formula (IIIb):

[0313]

[0314] - Diamine of formula (IIIc):

[0315]

[0316] - Diamines of formula (IIId):

[0317] and

[0318] - Diamine of formula (IIIe):

[0319]

[0320] In equations (IIIc), (IIId), and (IIIe), R 4 Same or different and selected from H, CH3-, C2H5- and C3H7-, R 5 Selected from -CH2-, -C2H4-, -C3H6- and -C6H 12 -

[0321] 9. A urea carbamate compound according to any one of embodiments 1-8, wherein at least one diamine is selected from 4,4-diaminodiphenylmethane, 3,3-dimethyl-4,4-diaminodiphenylmethane, 2,2-bis(4-aminocyclohexyl)propane, N,N-dimethyl-4,4-diaminodiphenylmethane, (3-methyl-4-aminocyclohexyl)-(3-methyl-4-aminophenyl)methane, m-phenylenediamine, p-phenylenediamine, ethylenediamine, hexamethylenediamine, 4,4-methylenebis(cyclohexylamine), and 1,12-diaminododecane.

[0322] 10. A urea carbamate compound according to any one of embodiments 1-9, having a weight-average molecular weight in the range of ≥300 g / mol to ≤5000 g / mol as determined according to DIN 55672-2.

[0323] 11. A urea carbamate compound according to any one of embodiments 1-10, having a polydispersity index in the range of 1.0 to 3.0.

[0324] 12. A method for preparing a urea carbamate compound according to any one of embodiments 1-11, comprising:

[0325] i. Introduce toluene diisocyanate into the reactor;

[0326] ii. Mix at least one monohydric alcohol of formula (I) and at least one monohydric alcohol of formula (II) to obtain a mixture comprising a monohydric alcohol;

[0327] iii. The mixture obtained in step (ii) is added to a reactor and the monohydric alcohol is reacted with toluene diisocyanate to obtain a mixture containing at least two monoisocyanate adducts;

[0328] iv. To prepare a mixture by mixing at least one diamine, at least one polar aprotic solvent, and at least one metal salt catalyst; and

[0329] v. The mixture obtained in step (iv) is added to a reactor to react with the mixture obtained in step (iii) containing at least two monoisocyanate adducts to obtain a urea carbamate compound.

[0330] 13. The method according to embodiment 12, wherein the mixture containing a monohydric alcohol obtained in step (ii) further comprises at least one catalyst selected from p-toluenesulfonic acid, H2SO4, HCl and acetic acid.

[0331] 14. The method according to embodiment 12 or 13, wherein the mixture containing monohydric alcohol obtained in step (ii) is added to the reactor over a time period ranging from ≥1 hour to ≤50 hours.

[0332] 15. The method according to any one of embodiments 12-14, wherein the reaction of the monohydric alcohol with toluene diisocyanate in step (iii) is carried out at a temperature in the range of ≥20°C to ≤60°C.

[0333] 16. The method according to any one of embodiments 12-15, wherein at least one polar 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, hexamethylphosphotriamide and methyl 5-(dimethylamino)-2-methyl-5-oxovalerate.

[0334] 17. The method according to any one of embodiments 12-16, wherein the metal salt catalyst is selected from lithium chloride, lithium nitrate, lithium bromide and sodium dioctyl succinate sulfonate.

[0335] 18. The method according to any one of embodiments 12-17, wherein the mixture obtained in step (iv) is added to the reactor over a time period ranging from ≥1 hour to ≤20 hours.

[0336] 19. The method according to any one of embodiments 12-18, wherein the reaction of at least one diamine with at least two monoisocyanate adducts in step (v) is carried out at a temperature in the range of ≥20°C to ≤100°C.

[0337] 20. The method according to any one of embodiments 12-19, wherein the molar ratio of the metal salt catalyst to at least one diamine is in the range of 0.3:1.0 to 1.0:1.5.

[0338] 21. A liquid composition comprising a urea carbamate compound obtained according to any one of embodiments 1-11 or according to any one of embodiments 12-20, in an amount ranging from ≥0.01% by weight to ≤10.0% by weight, based on the total weight of the liquid composition.

[0339] 22. The liquid composition according to embodiment 21 further comprises at least one component selected from pigment paste, binder, filler, solvent, defoamer, neutralizer, wetting agent, pigment dispersant, preservative and water.

[0340] 23. A liquid composition according to embodiment 21 or 22, wherein the liquid composition is a paint, water-based coating formulation, solvent-based coating formulation, lacquer, varnish, paper coating, wood coating, adhesive, ink, cosmetic formulation, detergent formulation, textile, drilling mud formulation, cement composition, gypsum board formulation, hydraulic adhesive formulation such as mortar formulation, ceramic and leather formulation.

[0341] 24. The urea carbamate compound obtained according to any one of embodiments 1-11 or any one of embodiments 12-20 is used as a thixotropic agent in a liquid composition for use in paint and coating formulations, adhesives, varnishes, PVC plastisols, inks and cement formulations.

[0342] Although the invention has been described with respect to specific embodiments thereof, some modifications and equivalents will be apparent to those skilled in the art and are intended to be included within the scope of the invention. Example

[0343] The present invention is described in detail by the following non-limiting working embodiments. More specifically, the test methods described below are part of the general disclosure of this application and are not limited to the specific working embodiments.

[0344] Material

[0345] T80A, also known as "TDI T80", is a mixture of 80%-20% of the 2,4 and 2,6 isomers of toluene diisocyanate, available from BASF SE.

[0346] T100SP, also known as "TDI T100", is pure 2,4-toluene diisocyanate (TDI) and is available from Covestro AG.

[0347] TDI T98, T97, T96, T95, etc. are T100SP and T80A is a blend obtained by mixing according to calculation. For example, T98 is obtained by... T100SP and T80A is obtained by mixing at a weight ratio of 90:10, and T90 is obtained by mixing... T100SP and T80A is obtained by mixing in a 50:50 weight ratio.

[0348] method

[0349] Viscosity

[0350] The viscosity of the sample was determined by a rheometer according to DIN 53019 or calculated by the value from a Brabender plasticity tester.

[0351] NCO content

[0352] The theoretical NCO content is calculated as follows:

[0353] Theoretical NCO content = 0.2411 * M TDI / (M TDI +M R-OH +M 溶剂 )*100%

[0354] M TDI The weight of TDI added to the reactor

[0355] M R-OH R added to the reactor 1 -OH and R 2 The weight of the mixture of -OH

[0356] M 溶剂 (Optional) Weight of solvent added to the reactor

[0357] Molecular weight and polydispersity index (PDI)

[0358] Molecular weight and polydispersity index were determined according to DIN 55672-1 and DIN 55672-2.

[0359] I. Preparation of urea carbamate compounds

[0360] Example 1: Preparation of urea carbamate compound U1

[0361] In a 5-necked 200 ml Sulfier flask equipped with a top stirrer, thermometer, reflux condenser, and diaphragm, a mixture containing 17.4 g TDI T90 (100 mmol) and 10 g ethyl acetate was purged with nitrogen. 10.8 g butyl triethylene glycol ether (52.3 mmol) and 19.0 g poly(ethylene glycol) methyl ether (MW 350 g / mol 54.3 mmol) were mixed, and the alcohol mixture was 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 a mixture of monoisocyanate adducts.

[0362] 2.6 g of lithium nitrate, 6.2 g of m-toluenediamine (46 mmol), and 57 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.

[0363] Ethyl acetate was distilled off under reduced pressure to obtain U1, a pale yellow, transparent liquid that flows freely at room temperature.

[0364] U1 has a molecular weight of 2400 g / mol, as determined by GPC (according to DIN 55672-2, N,N-dimethylacetamide, 1 mL / min, PMMA standard); its PDI is 1.2. The urea carbamate compound U1 remains stable (no precipitation or gel formation) after storage under ambient conditions (>2 months).

[0365] Example 2: Preparation of urea carbamate compound U2

[0366] In a 5-necked 200 ml Sulfier flask equipped with a top stirrer, thermometer, reflux condenser, and diaphragm, a mixture containing 17.4 g TDI T85 (100 mmol) and 10 g ethyl acetate was purged with nitrogen. 5.4 g butyl triethylene glycol ether (26.2 mmol), 39.0 g poly(ethylene glycol) methyl ether (MW 500 g / mol 78.0 mmol), and 0.03 g p-toluenesulfonic acid were mixed, and the alcohol mixture was 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 a mixture of monoisocyanate adducts.

[0367] 2.6 g of lithium nitrate, 6.2 g of m-toluenediamine (46 mmol), and 70 g of dimethyl sulfoxide were mixed at room temperature, and this 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.

[0368] Ethyl acetate was distilled off under reduced pressure to obtain U2, a pale yellow, transparent liquid that flows freely at room temperature.

[0369] U2 has a molecular weight of 2600 g / mol, as determined by GPC (according to DIN 55672-2, N,N-dimethylacetamide, 1 mL / min, PMMA standard); its PDI is 1.3. The urea carbamate compound U2 remains stable (no precipitation or gel formation) after storage under ambient conditions (>2 months).

[0370] Example 3: Preparation of urea carbamate compound U3

[0371] In a 5-necked 200 ml Sulfier flask equipped with a top stirrer, thermometer, reflux condenser, and diaphragm, a mixture containing 17.4 g TDI T95 (100 mmol) and 10 g ethyl acetate was purged with nitrogen. 4.3 g butyl triethylene glycol ether (20.8 mmol) and 29.0 g poly(ethylene glycol) methyl ether (MW 350 g / mol 82.8 mmol) were mixed, and the alcohol mixture was 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 a mixture of monoisocyanate adducts.

[0372] 2.6 g of lithium nitrate, 6.2 g of m-toluenediamine (46 mmol), and 60 g of dimethyl sulfoxide were mixed at room temperature, and this 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.

[0373] Ethyl acetate was distilled off under reduced pressure to obtain U3, a pale yellow, transparent liquid that flows freely at room temperature.

[0374] U3 has a molecular weight of 2800 g / mol, as determined by GPC (according to DIN 55672-2, N,N-dimethylacetamide, 1 mL / min, PMMA standard); its PDI is 1.2. The urea carbamate compound U3 remains stable (no precipitation or gel formation) after storage under ambient conditions (>2 months).

[0375] Example 4: Preparation of urea carbamate compound U4

[0376] In a 5-necked 200 ml Sulfier flask equipped with a top stirrer, thermometer, reflux condenser, and diaphragm, a mixture containing 17.4 g TDI T100 (100 mmol) and 10 g ethyl acetate was purged with nitrogen. 4.3 g butyl triethylene glycol ether (20.8 mmol), 15.0 g poly(ethylene glycol) methyl ether (MW 350 g / mol 42.8 mmol), 21.0 g poly(ethylene glycol) methyl ether (MW 500 g / mol 42.0 mmol), and 0.03 g p-toluenesulfonic acid were mixed, and the alcohol mixture was 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 a mixture of monoisocyanate adducts.

[0377] 2.6 g of lithium nitrate, 6.2 g of m-toluenediamine (46 mmol), and 65 g of dimethyl sulfoxide were mixed at room temperature, and this 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.

[0378] Ethyl acetate was distilled off under reduced pressure to obtain U4, a pale yellow, transparent liquid that flows freely at room temperature.

[0379] U4 has a molecular weight of 2900 g / mol, as determined by GPC (according to DIN 55672-2, N,N-dimethylacetamide, 1 mL / min, PMMA standard); its PDI is 1.3. The urea carbamate compound U4 remains stable (no precipitation or gel formation) after storage under ambient conditions (>2 months).

[0380] Example 5: Preparation of urea carbamate compound U5

[0381] In a 5-necked 200 ml Sulfier flask equipped with a top stirrer, thermometer, reflux condenser, and diaphragm, a mixture containing 17.4 g TDI T88 (100 mmol) and 10 g ethyl acetate was purged with nitrogen. 4.3 g butyl triethylene glycol ether (20.8 mmol), 18 g poly(ethylene glycol) methyl ether (MW 350 g / mol 51.4 mmol), and 16 g poly(ethylene glycol) methyl ether (MW 500 g / mol 32.0 mmol) were mixed, and the alcohol mixture was 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 a mixture of monoisocyanate adducts.

[0382] 2.6 g of lithium nitrate, 6.2 g of m-toluenediamine (46 mmol), and 60 g of dimethyl sulfoxide were mixed at room temperature, and this 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.

[0383] Ethyl acetate was distilled off under reduced pressure to obtain U5, a pale yellow, transparent liquid that flows freely at room temperature.

[0384] U5 has a molecular weight of 2700 g / mol, as determined by GPC (according to DIN 55672-2, N,N-dimethylacetamide, 1 mL / min, PMMA standard); its PDI is 1.3. The urea carbamate compound U5 remains stable (no precipitation or gel formation) after storage under ambient conditions (>2 months).

[0385] Example 6: Preparation of urea carbamate compound U6

[0386] In a 5-necked 200 ml Sulfier flask equipped with a top stirrer, thermometer, reflux condenser, and diaphragm, a mixture containing 17.4 g TDI T100 (100 mmol) and 10 g ethyl acetate was purged with nitrogen. 5.4 g butyl triethylene glycol ether (26.2 mmol), 13.8 g poly(ethylene glycol) methyl ether (MW 350 g / mol 39.4 mmol), 19.7 g poly(ethylene glycol) methyl ether (MW 500 g / mol 38.4 mmol), and 0.03 g p-toluenesulfonic acid were mixed, and the alcohol mixture was 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 a mixture of monoisocyanate adducts.

[0387] 2.6 g of lithium nitrate, 6.2 g of m-toluenediamine (46 mmol), and 65 g of dimethyl sulfoxide were mixed at room temperature, and this 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.

[0388] Ethyl acetate was distilled off under reduced pressure to obtain U6, a pale yellow, transparent liquid that flows freely at room temperature.

[0389] U6 has a molecular weight of 2900 g / mol, as determined by GPC (according to DIN 55672-2, N,N-dimethylacetamide, 1 mL / min, PMMA standard); its PDI is 1.3. The urea carbamate compound U6 remains stable (no precipitation or gel formation) after storage under ambient conditions (>2 months).

[0390] Example 7: Preparation of urea carbamate compound U7

[0391] In a 5-necked 200 ml Sulfier flask equipped with a top stirrer, thermometer, reflux condenser, and diaphragm, a mixture containing 17.4 g TDI T95 (100 mmol) and 10 g ethyl acetate was purged with nitrogen. 4.3 g butyl triethylene glycol ether (20.8 mmol), 15 g poly(ethylene glycol) methyl ether (MW 350 g / mol 42.8 mmol), 21 g poly(ethylene glycol) methyl ether (MW 500 g / mol 42.0 mmol), and 0.03 g p-toluenesulfonic acid were mixed, and the alcohol mixture was 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 a mixture of monoisocyanate adducts.

[0392] 2.6 g of lithium nitrate, 6.2 g of m-toluenediamine (46 mmol), and 65 g of N-methylpyrrolidine 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.

[0393] Ethyl acetate was distilled off under reduced pressure to obtain U7, a pale yellow, transparent liquid that flows freely at room temperature.

[0394] U7 has a molecular weight of 2500 g / mol, as determined by GPC (according to DIN 55672-2, N,N-dimethylacetamide, 1 mL / min, PMMA standard); its PDI is 1.3. The urea carbamate compound U7 remains stable (no precipitation or gel formation) after storage under ambient conditions (>2 months).

[0395] Example 8: Preparation of urea carbamate compound U8

[0396] In a 5-necked 200 ml Sulfier flask equipped with a top stirrer, thermometer, reflux condenser, and diaphragm, a mixture containing 17.4 g TDI T100 (100 mmol) and 10 g ethyl acetate was purged with nitrogen. 5.4 g butyl triethylene glycol ether (26.2 mmol), 13.8 g poly(ethylene glycol) methyl ether (MW 350 g / mol 39.4 mmol), 19.7 g poly(ethylene glycol) methyl ether (MW 500 g / mol 39.4 mmol), and 0.03 g p-toluenesulfonic acid were mixed, and the alcohol mixture was 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 a mixture of monoisocyanate adducts.

[0397] 2.6 g of lithium nitrate, 6.2 g of m-toluenediamine (46 mmol), and 65 g of methyl 5-(dimethylamino)-2-methyl-5-oxovalerate 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.

[0398] Ethyl acetate was distilled off under reduced pressure to obtain U8, a pale yellow, transparent liquid that flows freely at room temperature.

[0399] U8 has a molecular weight of 2700 g / mol, as determined by GPC (according to DIN 55672-2, N,N-dimethylacetamide, 1 mL / min, PMMA standard); its PDI is 1.3. The urea carbamate compound U8 remains stable (no precipitation or gel formation) after storage under ambient conditions (>2 months).

[0400] Example 9: Preparation of urea carbamate compound U9

[0401] In a 5-necked 200 ml Sulfier flask equipped with a top stirrer, thermometer, reflux condenser, and diaphragm, a mixture containing 17.4 g TDI T85 (100 mmol) and 10 g ethyl acetate was purged with nitrogen. 5.4 g butyl triethylene glycol ether (26.2 mmol), 39 g poly(ethylene glycol) methyl ether (MW 500 g / mol 78.0 mmol), and 0.03 g p-toluenesulfonic acid were mixed, and the alcohol mixture was 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 a mixture of monoisocyanate adducts.

[0402] 3.0 g of sodium dioctyl succinate sulfonate, 6.2 g of m-toluenediamine (46 mmol), and 70 g of dimethyl sulfoxide were mixed at room temperature, and this 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.

[0403] Ethyl acetate was distilled off under reduced pressure to obtain U9, a pale yellow, transparent liquid that flows freely at room temperature.

[0404] U9 has a molecular weight of 2950 g / mol, as determined by GPC (according to DIN 55672-2, N,N-dimethylacetamide, 1 mL / min, PMMA standard); its PDI is 1.2. The urea carbamate compound U9 remains stable (no precipitation or gel formation) after storage under ambient conditions (>1 month).

[0405] II. Comparative Example

[0406] Two urea carbamate compounds (C1 and C2) were prepared using only one alcohol; butyl triethylene glycol ether (BGE) was used in the first case and polyethylene glycol methyl ether was used in the second case.

[0407] Furthermore, a third urea carbamate compound is obtained by physically mixing the first and second urea carbamate compounds obtained above.

[0408] Comparative Example 1: Preparation of urea carbamate compounds (C1) using butyl triethylene glycol ether as the sole alcohol.

[0409] Urea carbamate compounds were prepared using butyl triethylene glycol ether (BGE) as the sole alcohol, following the procedure disclosed in Example 7 of WO2019096611A1.

[0410] Comparative Example 2: Preparation of urea carbamate compound (C2) using polyethylene glycol methyl ether as the sole alcohol.

[0411] In a 5-necked 200 ml Sulfier flask equipped with a top stirrer, thermometer, reflux condenser, and diaphragm, a mixture containing 17.4 g TDI T90 (100 mmol) and 10 g ethyl acetate was purged with nitrogen. 38.5 g of poly(ethylene glycol) methyl ether (MW 350 g / mol 110 mmol) was 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.

[0412] 2.6 g of lithium nitrate, 6.2 g of m-toluenediamine (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.

[0413] Ethyl acetate was distilled off under reduced pressure to give a urea carbamate compound (C2). C2 is a pale yellow, transparent liquid that flows freely at room temperature.

[0414] The molecular weight of C2 is 2400 g / mol, as determined by GPC (according to DIN 55672-2, N,N-dimethylacetamide, 1 mL / min, PMMA standard); its PDI is 1.1.

[0415] The product remains stable (without precipitation or gel formation) after being stored under environmental conditions (>2 months).

[0416] Comparative Example 3: Urea carbamate compound (C3) prepared by mixing C1 and C2.

[0417] The contrast urea carbamate compound C3 was prepared by mixing C1 (20 wt%) and C2 (80 wt%).

[0418] III. Storage stability of urea carbamate compounds

[0419] The storage stability of the urea carbamate compounds of the present invention (Examples U1-U9) was investigated over a period of two months. Similarly, the storage stability of comparative examples C1-C3 was investigated. Based on the details provided in Table 1, the urea carbamate compounds were graded from 1 to 4, with 1 being the best and 4 being the worst.

[0420] Urea carbamate compounds of grades 1-3 are considered acceptable for use as additives in coating formulations.

[0421] Table 1

[0422]

[0423] The results of the storage stability study are provided in Table 2 below.

[0424] Table 2

[0425] Example grade U1, U2, U3, U4, U5, U6, U7 and U8 1 U9 2 Comparative examples C1, C2, and C3 1

[0426] III. Performance Testing

[0427] Thixometry measurement

[0428] The thixotropy of urea carbamate compounds U1-U9 was determined by shear jump measurement. A formulation for viscosity measurement was prepared by adding 0.5 wt% of the compound to water. The mixture was shaken by hand for 30 seconds and then allowed to stand.

[0429] Viscosity was measured at 0.05 s⁻¹. -1 The shear rate is applied for 200 seconds initially, then immediately for 250 seconds. -1 A high shear rate was applied for 60 seconds, followed immediately by a reduction in shear rate to 0.05 s. -1 It lasts for 200 seconds.

[0430] Prepare a control sample that does not contain urea carbamate compounds.

[0431] The comparative samples were prepared in the same manner as the samples for U1-U9, except that the urea carbamate compounds of this application were replaced by urea carbamate compounds C1-C3.

[0432] The viscosity measurements in Table 3 are as follows:

[0433] The viscosity at t=199, immediately before the application of high shear,

[0434] The viscosity at t=201, immediately after the application of high shear

[0435] The viscosity at t=259, immediately after the removal of the high shear.

[0436] The viscosity at t=450°C remains for a long time after the removal of high shear.

[0437] Viscosity measurements at different time intervals are provided in Table 3.

[0438] Table 3: Viscosity Measurement

[0439]

[0440]

[0441] The results provided in Table 3 clearly show that the viscosity of formulations containing urea carbamate compounds U1-U9 is significantly lower immediately after the application of high shear (i.e., 250 s). -1 The viscosity decreased significantly after 60 seconds. Furthermore, the viscosity increased immediately after the removal of the high shear. Therefore, formulations containing urea carbamate compounds U1-U9 exhibited significant viscosity recovery.

[0442] Therefore, adding the urea carbamate compound of the present invention to a formulation imparts a thixotropic effect to the formulation, as demonstrated by the decrease in viscosity of the formulation immediately after the application of shear stress and the gradual recovery of viscosity as a function of time after the removal of shear stress.

[0443] In contrast, the urea carbamate compounds exhibited poor water solubility or thixotropic effects.

Claims

1. Urea carbamate compounds that can be obtained through the following methods: (i) Cause the following substances to react: a. Toluene diisocyanate, and b. A mixture of monohydric alcohols, comprising: (b1) At least one monohydric alcohol of formula (I): R 1 -OH (I), in R 1 For formula R 11 (OC n H 2n ) x - group, in R 11 Selected from linear or branched, substituted or unsubstituted C4-C 22 Alkyl groups, and substituted or unsubstituted C6-C 12 cycloalkyl, n is an integer between 2 and 4, and x is an integer from 1 to 15; and (b2) At least one monohydric alcohol of formula (II): R 2 -OH(II), Where R 2 It is formula C p H 2p+1 (OC q H 2q ) r - group, p is an integer between 1 and 3. q is an integer between 2 and 4, and r is an integer from 1 to 50. The molar ratio of at least one monohydric alcohol of formula (I) to at least one monohydric alcohol of formula (II) is in the range of 2:1 to 1:10, and The molar ratio of the total amount of the monohydric alcohol mixture to toluene diisocyanate is in the range of >1.0:1.0 to ≤1.5:1.0; To obtain a mixture containing at least two monoisocyanate adducts; ii) React the mixture containing at least two monoisocyanate adducts obtained in step (i) with at least one diamine to obtain a urea carbamate compound.

2. The urea carbamate compound of claim 1, wherein the toluene diisocyanate is selected from 2,4-toluene diisocyanate and mixtures of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate.

3. The urea carbamate compound according to claim 1, wherein at least one monohydric alcohol of formula (I) is selected from butyl triethylene glycol, butyl diethylene glycol and butyl tetraethylene glycol.

4. The urea carbamate compound according to claim 2, wherein at least one monohydric alcohol of formula (I) is selected from butyl triethylene glycol, butyl diethylene glycol and butyl tetraethylene glycol.

5. The urea carbamate compound according to claim 1, wherein at least one monohydric alcohol of formula (II) is methoxy polyethylene glycol.

6. The urea carbamate compound according to claim 2, wherein at least one monohydric alcohol of formula (II) is methoxy polyethylene glycol.

7. The urea carbamate compound according to claim 3, wherein at least one monohydric alcohol of formula (II) is methoxy polyethylene glycol.

8. The urea carbamate compound according to claim 4, wherein at least one monohydric alcohol of formula (II) is methoxy polyethylene glycol.

9. The urea carbamate compound according to any one of claims 1-8, wherein the molar ratio of the total amount of the monohydric alcohol mixture to toluene diisocyanate is in the range of >1.0:1.0 to <1.5:1.

0.

10. The urea carbamate compound according to any one of claims 1-8, wherein at least one diamine is selected from diamines of formula (IIIa), (IIIb), (IIIc), (IIId) and (IIIe); - H2N-R 3 -NH2 (IIIa), Where R 3 It is -C y H 2y -And y is an integer between 2 and 12. - Diamine of formula (IIIb): ， - Diamines of formula (IIIc): ， - Diamines of formula (IIId): ,and - Diamines of formula (IIIe): in, In equations (IIIc), (IIId), and (IIIe), R 4 Same or different and selected from H, CH3-, C2H5- and C3H7-, R 5 Selected from -CH2-, -C2H4-, -C3H6- and -C6H 12 - 11. The urea carbamate compound according to claim 9, wherein at least one diamine is selected from diamines of formula (IIIa), (IIIb), (IIIc), (IIId), and (IIIe); - H2N-R 3 -NH2 (IIIa), Where R 3 It is -C y H 2y -And y is an integer between 2 and 12. - Diamine of formula (IIIb): ， - Diamines of formula (IIIc): ， - Diamines of formula (IIId): ,and - Diamines of formula (IIIe): in, In equations (IIIc), (IIId), and (IIIe), R 4 Same or different and selected from H, CH3-, C2H5- and C3H7-, R 5 Selected from -CH2-, -C2H4-, -C3H6- and -C6H 12 - 12. The urea carbamate compound according to any one of claims 1-8 and 11, having a weight-average molecular weight in the range of ≥300 g / mol to ≤5000 g / mol as determined according to DIN 55672-2.

13. The urea carbamate compound according to claim 9, having a weight-average molecular weight in the range of ≥300 g / mol to ≤5000 g / mol as determined according to DIN 55672-2.

14. The urea carbamate compound according to claim 10, having a weight-average molecular weight in the range of ≥300 g / mol to ≤5000 g / mol as determined according to DIN 55672-2.

15. A method for preparing a urea carbamate compound according to any one of claims 1-14, comprising: i. Introduce toluene diisocyanate into the reactor; ii. Mix at least one monohydric alcohol of formula (I) and at least one monohydric alcohol of formula (II) to obtain a mixture comprising a monohydric alcohol; iii. The mixture obtained in step (ii) is added to a reactor and the monohydric alcohol is reacted with toluene diisocyanate to obtain a mixture containing at least two monoisocyanate adducts; iv. To prepare a mixture by mixing at least one diamine, at least one polar aprotic solvent, and at least one metal salt catalyst; and v. The mixture obtained in step (iv) is added to a reactor to react with the mixture obtained in step (iii) containing at least two monoisocyanate adducts to obtain a urea carbamate compound.

16. The method of claim 15, wherein the mixture containing a monohydric alcohol obtained in step (ii) further comprises at least one catalyst selected from p-toluenesulfonic acid, H2SO4, HCl and acetic acid.

17. The method of claim 15, wherein at least one polar 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, hexamethylphosphotriamide, and methyl 5-(dimethylamino)-2-methyl-5-oxovalerate.

18. The method of claim 16, wherein at least one polar 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, hexamethylphosphotriamide, and methyl 5-(dimethylamino)-2-methyl-5-oxovalerate.

19. The method according to any one of claims 15-18, wherein the metal salt catalyst is selected from lithium chloride, lithium nitrate, lithium bromide and sodium dioctyl succinate sulfonate.

20. The method according to any one of claims 15-18, wherein the molar ratio of the metal salt catalyst to at least one diamine is in the range of 0.3:1.0 to 1.0:1.

5.

21. The method of claim 19, wherein the molar ratio of the metal salt catalyst to at least one diamine is in the range of 0.3:1.0 to 1.0:1.

5.

22. A liquid composition comprising a urea carbamate compound according to any one of claims 1-14 or a urea carbamate compound obtained by the method according to any one of claims 15-21, in an amount ranging from ≥0.01% by weight to ≤10.0% by weight, based on the total weight of the liquid composition.

23. The liquid composition of claim 22, wherein the liquid composition is a paint, a water-based coating formulation, a solvent-based coating formulation, a paper coating, a wood coating, an adhesive, an ink, a cosmetic formulation, a detergent formulation, a textile, a drilling mud formulation, a cement composition, a gypsum board formulation, a hydraulic adhesive formulation, a ceramic and leather formulation.

24. The liquid composition of claim 22, wherein the liquid composition is a lacquer, varnish, or mortar formulation.

25. The urea carbamate compound according to any one of claims 1-14 or the urea carbamate compound obtained by the method according to any one of claims 15-21, used as a thixotropic agent in a liquid composition for use in paint and coating formulations, adhesives, PVC plastisols, inks and cement formulations.

26. The use of a urea carbamate compound according to any one of claims 1-14 or a urea carbamate compound obtained by the method according to any one of claims 15-21 as a thixotropic agent in a liquid composition for use in paint varnishes.

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