Polyalkyleneimine-based polymers as dispersants

Abstract

TECHNICAL FIELD The present invention relates to polyalkyleneimine-based polymers useful as dispersants and methods for preparing the same. The present invention also relates to dispersants useful in solvent-based and water-based dispersion systems.

Description

[Technical Field]

[0001] TECHNICAL FIELD The present invention relates to polyalkyleneimine-based polymers useful as dispersants and methods for preparing the same. The present invention also relates to dispersants useful in solvent-based and water-based dispersion systems. [Background technology]

[0002] Dispersions containing solid dispersible particles such as organic or inorganic pigments are used for many different technical applications, such as coating materials, pigmenting plastic materials (including printing inks, textiles, glass, or ceramic products), formulating cosmetics, or preparing paint systems (especially automotive, industrial, and decorative paints).

[0003] The preparation of a dispersion involves incorporating a solid material, such as a pigment, into a liquid vehicle by replacing the pigment-air interface with a pigment-vehicle interface; this replacement is facilitated by the presence of a dispersant. While some organic vehicles have good particle wetting properties, dispersants are used to ensure a uniform and stable dispersion. Dispersants are also related to various process parameters involved in preparing the dispersion, such as dispersion time and energy requirements. An ideal dispersion consists of a homogeneous and stable suspension of solid material after any agglomerates and agglomerates have been reduced in size or broken down.

[0004] Dispersants improve various dispersion properties, such as the viscosity and rheological behavior of the millbase. Improved rheological behavior is characterized by favorable viscosity over a wide range of shear rates. Improved viscosity and rheological behavior improve application properties, such as increased coating flow and leveling, reduced spattering and sagging.

[0005] Dispersants are also a determining factor in the aesthetic and physical properties of coatings. Dispersants function as flow control agents, improving the spreading of the composition on the substrate surface and improving the flowability of the polymer film formed during curing, resulting in a smooth surface. As a result, dispersants reduce the formation of defects known as craters, which are caused by external impurities or impurities on the substrate surface.

[0006] Due to environmental concerns, the use of pigment dispersions based on aqueous vehicles and high solids dispersions based on organic solvents is particularly preferred. Depending on the type and polarity of the liquid phase (e.g., water, organic solvent, or a mixture thereof), an appropriate polymeric dispersant is selected.

[0007] In view of the wide range of applications of dispersions containing finely divided solid materials and the important role that dispersants play in their preparation, stability, and properties, there is an increasing need for improved dispersants that can aid in the preparation of dispersions with desired properties.

[0008] WO 1992 / 13911 A1 relates to acetoacetanilide-functionalized poly(alkylene glycols) prepared by reacting poly(alkylene glycol) monoamines, diamines, or triamines with isatoic anhydride, followed by acetoacetylation of the resulting aminobenzamides. WO 1992 / 13911 A1 suggests the use of said acetoacetanilide-functionalized poly(alkylene glycols) to prepare improved diarylide pigment compositions, which are further useful for preparing storage-stable printing inks, particularly gravure-type inks for publishing.

[0009] WO2008 / 107326A1 relates to acrylate, polyether, or polyester-based poly(alkyleneimine) graft polymers useful as pigment dispersants. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] WO1992 / 13911A1 [Patent Document 2] WO2008 / 107326A1 [Patent Document 3] US8,268,957B2 [Patent Document 4] WO2017 / 140538A1 [Non-patent literature]

[0011] [Non-Patent Document 1] W. Herbst, K. Hunger "Industrielle Organische Pigmente" 2nd Edition, 1995, VCH Verlagsgesellschaft, ISBN:3-527-28744-2 Summary of the Invention [Problem to be solved by the invention]

[0012] It is therefore an object of the present invention to provide a dispersant with improved pigment affinity and rheological behavior, as manifested by improved viscosity of the millbase at a given shear rate and gloss in surface coatings. Furthermore, it is desirable that the dispersant be usable in solvent-based and water-based systems. [Means for solving the problem]

[0013] It has been surprisingly found that polymers of the present invention, which have (a) a polyalkyleneimine backbone, (b) at least one aromatic moiety P.1 linked to a nitrogen atom of the polyalkyleneimine backbone via a carboxamide or carboximide group, (c) at least one polyester moiety P.2 linked to a nitrogen atom of the polyalkyleneimine backbone via a carboxamide, and (d) at least one aliphatic polyether moiety P.3 linked to a nitrogen atom of the polyalkyleneimine backbone via a direct bond or a linker, are useful as dispersants. The polymers of the present invention have high pigment affinity and can be used as dispersants in solvent-based as well as water-based systems.

[0014] Thus, the main aspects of the present invention are: a) a polyalkyleneimine backbone, b) at least one aromatic moiety P.1, which is linked to a nitrogen atom of the polyalkyleneimine backbone via a carboxamide or carboximide group; c) at least one polyester moiety P.2, which is bound to a nitrogen atom of the polyalkyleneimine backbone via a carboxamide, and d) at least one aliphatic polyether moiety P.3, which is attached to a nitrogen atom of the polyalkyleneimine backbone either directly or via a linker; The present invention relates to a polymer having the formula:

[0015] In another aspect, the present invention provides a method for preparing a polymer, comprising: i. reacting a polyalkyleneimine with an aromatic carboxylic acid, an aromatic carboxylic acid anhydride, or an amide- or imide-forming derivative of an aromatic carboxylic acid in an amount that will theoretically consume up to 90% of the total amount of primary and secondary nitrogen atoms in the polyalkyleneimine; ii. reacting the product of step (i) with a lactone monomer or a polyester moiety having a terminal carboxyl group obtainable from a lactone monomer; iii. reacting the product of step (ii) with an alkylene oxide or a polyether moiety having end groups selected from acrylate, isocyanato, and carboxylate; The present invention provides a method comprising:

[0016] In yet another aspect, the present invention provides a liquid composition in the form of a dispersion comprising a particulate solid material selected from the group consisting of pigments and fillers, and a liquid diluent, the particulate solid material being dispersed in the liquid diluent further comprising the polymer described above. DETAILED DESCRIPTION OF THE INVENTION

[0017] Before describing the compositions and formulations of the present invention, it is to be understood that the invention is not limited to the particular compositions and formulations described, as such compositions and formulations may, of course, vary. It is also to be understood that the terminology used herein is not intended to be limiting, as the scope of the present invention is to be limited only by the appended claims.

[0018] Hereinafter, when a group is defined to include at least some embodiments, it is intended to encompass a group consisting of only those embodiments. Furthermore, in the specification and claims, terms such as "first," "second," "third," "a," "b," "c," and similar terms are used to distinguish between similar elements and not necessarily to describe a sequential or chronological order. Terms so used are interchangeable under appropriate circumstances, and it is understood that the embodiments of the invention described herein may be performed in orders other than those described or illustrated herein. When terms such as "first," "second," "third," "(A)," "(B)," "(C)," or "(a)," "(b)," "(c)," "(d)," "i," "ii," and the like, relate to steps in a method, use, or analysis, there is no consistency in the time or time intervals between steps, unless specifically indicated to the contrary, above or below in this application. That is, steps may be performed simultaneously, or there may be time intervals of seconds, minutes, hours, days, weeks, months, or even years between steps.

[0019] Furthermore, throughout the specification, defined ranges are inclusive of the endpoints, i.e., "in the range of 1 to 10" means that both 1 and 10 are included in the range. For the avoidance of doubt, applicants reserve the right to equivalents pursuant to applicable law.

[0020] In the following sections, various aspects of the invention are defined in more detail. Each aspect so defined may be combined with any other aspect or aspects, unless expressly indicated to the contrary. In particular, any feature indicated as being preferred or advantageous may be combined with any other feature or features indicated as being preferred or advantageous.

[0021] References throughout this specification to "one embodiment" or "an embodiment" mean that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention. Thus, appearances of the phrase "in one embodiment" or "in an embodiment" in various places throughout this specification may, but do not necessarily all refer to the same embodiment. Furthermore, as used hereinafter, the terms "preferably," "more preferably," "even more preferably," "most preferably," and "particularly," or similar terms, are used in combination with optional features without limiting alternative possibilities. Thus, features introduced by these terms are optional features and are not intended to limit the scope of the claims in any way.

[0022] Furthermore, particular features, structures, or characteristics may be combined in any suitable manner, as would be apparent to one skilled in the art from this disclosure, in one or more embodiments. Furthermore, while some embodiments described herein may include only some features included in other embodiments, it will be understood by those skilled in the art that combinations of features from different embodiments are within the scope of the present invention and constitute different embodiments. For example, in the appended claims, any claimed embodiment may be used in any combination.

[0023] Furthermore, it should be noted that the terms "at least one," "one or more," or similar expressions indicating that a feature or element may be present one or more times are typically used only once when introducing each feature or element. In the following, when referring to each feature or element, in most cases the expressions "at least one" or "one or more" will not be repeated, despite the fact that each feature or element may be present one or more times.

[0024] Surprisingly, it has been found that the polymer of the present invention is useful as a dispersant not only in solvent-based systems but also in water-based systems. This dispersant has high pigment affinity. Therefore, dispersions containing finely divided solid materials, such as coating compositions, and containing the dispersant of the present invention have improved application properties, such as high stability and low viscosity. As a result, the dispersions produce surface coatings with low crater ranking.

[0025] Thus, the main aspects of the present invention are: a) a polyalkyleneimine backbone, b) at least one aromatic moiety P.1, which is linked to a nitrogen atom of the polyalkyleneimine backbone via a carboxamide or carboximide group; c) at least one polyester moiety P.2, which is bound to a nitrogen atom of the polyalkyleneimine backbone via a carboxamide, and d) at least one aliphatic polyether moiety P.3, which is attached to a nitrogen atom of the polyalkyleneimine backbone either directly or via a linker; The present invention relates to a polymer having the formula:

[0026] In a preferred embodiment of the invention, the polymer is a) a polyalkyleneimine backbone, b) at least one aromatic moiety P.1, which is linked to a nitrogen atom of the polyalkyleneimine backbone via a carboxamide or carboximide group; c) at least one polyester moiety P.2, which is bound to a nitrogen atom of the polyalkyleneimine backbone via a carboxamide, and d) at least one aliphatic polyether moiety P.3 attached by a direct bond to a nitrogen atom of the polyalkyleneimine backbone; Includes.

[0027] In another preferred embodiment of the present invention, the polymer a) a polyalkyleneimine backbone, b) at least one aromatic moiety P.1, which is linked to a nitrogen atom of the polyalkyleneimine backbone via a carboxamide or carboximide group; c) at least one polyester moiety P.2, which is bound to a nitrogen atom of the polyalkyleneimine backbone via a carboxamide, and d) at least one aliphatic polyether moiety P.3 attached via a linker to a nitrogen atom of the polyalkyleneimine backbone; Includes.

[0028] In the context of the present invention, the term "alkyl" as used herein refers to a group of the general formula C n H 2n+1 "Acyclic" refers to acyclic saturated aliphatic groups, including straight or branched chain alkyl saturated hydrocarbon groups, represented by the formula: (where n is the number of carbon atoms, 1, 2, 3, 4, etc.).

[0029] As used herein, the term "aryl" refers to a monocyclic or polycyclic, optionally substituted, aromatic group having 6 to 20 ring carbon atoms. The term "heteroaryl" refers to an "aryl" group as defined above that contains 1, 2, 3, 4, 5, or 6 heteroatoms such as N or O. The term "alkylaryl" refers to the alkyl-substituted analog of the "aryl" group as defined above.

[0030] In a preferred embodiment of the present invention, the polyalkyleneimine backbone has a weight average molecular weight in the range of 100 g / mol to 20,000 g / mol, determined according to DIN 55672-1.

[0031] In a more preferred embodiment of the present invention, the polyalkyleneimine backbone has a weight average molecular weight in the range of 400 g / mol to 10,000 g / mol, determined according to DIN 55672-1.

[0032] In a further preferred embodiment of the present invention, the polyalkyleneimine backbone has a weight average molecular weight in the range of 500 g / mol to 5,000 g / mol, determined according to DIN 55672-1.

[0033] In the most preferred embodiment of the present invention, the polyalkyleneimine backbone has a weight average molecular weight in the range of 500 g / mol to 2,500 g / mol, determined according to DIN 55672-1.

[0034] In a preferred embodiment of the present invention, the polyalkyleneimine backbone is a polyethyleneimine backbone.

[0035] In a particularly preferred embodiment of the invention, the polyethyleneimine backbone has a weight average molecular weight of 800 g / mol, determined in accordance with DIN 55672-1.

[0036] In another particularly preferred embodiment of the invention, the polyethyleneimine backbone has a weight average molecular weight of 2,000 g / mol, determined in accordance with DIN 55672-1.

[0037] In a preferred embodiment of the present invention, at least one aromatic moiety P.1 has the formula (P.1') and (P.1'')

[0038] [ka]

[0039] (wherein # indicates the position at which the aromatic moiety P.1 is attached to the nitrogen atom of the polyalkyleneimine backbone, Ar is selected from the group consisting of phenyl and naphthyl, wherein phenyl and naphthyl are each independently unsubstituted or substituted with 1, 2, 3, 4, or 5 groups selected from the group consisting of halogen, OH, C1-C4-alkyl, C1-C4-alkoxy, C(=O)-OH, C(=O)-NH2, NH2, NO2, NH-C(=O)-H, NH-C1-C4-alkyl, and NH-C(=O)-C1-C4-alkyl; Ar' is selected from the group consisting of 1,2-phenylene, 1,2-, 2,3-, or 1,8-naphthylene, wherein phenylene and naphthylene are each independently unsubstituted or substituted with 1, 2, 3, 4, or 5 groups selected from the group consisting of halogen, OH, C1-C4-alkyl, C1-C4-alkoxy, C(=O)-OH, C(=O)-NH2, NH2, NO2, NH-C(=O)-H, NH-C1-C4-alkyl, and NH-C(=O)-C1-C4-alkyl. is selected from the part.

[0040] In a preferred embodiment of the present invention, at least one aromatic moiety P.1 is selected from the group consisting of the formulae (P.1a), (P.1b), (P.1c), (P.1d), and (P.1e)

[0041] [ka]

[0042] (In the formula, # indicates the position where the aromatic moiety is bonded to the nitrogen atom of the polyalkyleneimine skeleton, R are the same or different and are selected from the group consisting of halogen, OH, C1-C4-alkyl, C1-C4-alkoxy, C(=O)-OH, C(=O)-NH2, NH2, NO2, NH-C(=O)-H, NH-C1-C4-alkyl, and NH-C(=O)-C1-C4-alkyl; k is 0, 1, 2, 3, or 4; R' is selected from the group consisting of hydrogen, C1-C4-alkyl, -C(=O)-H and -C(=O)-C1-C4-alkyl. The moiety is selected from the group consisting of:

[0043] In a more preferred embodiment of the present invention, at least one aromatic moiety P.1 of formula (p.1a) includes those in which R' is H and k=0.

[0044] In another more preferred embodiment of the invention, at least one aromatic moiety P.1 of formula (p.1c) contains k=0.

[0045] In yet another more preferred embodiment of the present invention, at least one aromatic moiety P.1 of formula (p.1e) comprises k=0.

[0046] In a preferred embodiment of the invention, the polyester moiety P.2 has the formula (P.2a)

[0047] [ka]

[0048] (In the formula, # indicates the position at which the compound is bonded to a nitrogen atom of the polyalkyleneimine skeleton, T 1 is hydrogen or R 1 -C(=O)- and R 1 is C1~C 24 is alkyl, A 1 and A 2 is C2~C 12 alkylene; m is an integer from 0 to 100, n is an integer from 0 to 100, m+n is an integer between 2 and 100. It is based on.

[0049] In a preferred embodiment of the present invention, the "m" repeat units and the "n" repeat units form a gradient, random, or block polymer structure.

[0050] In a more preferred embodiment of the present invention, T 1 is hydrogen, CH3(CH2)3-, CH3(CH2) 10 - and CH3(CH2) 16 - is selected from the group consisting of

[0051] In a particularly preferred embodiment of the present invention, T 1 is CH3(CH2) 10 -It is.

[0052] In another particularly preferred embodiment of the present invention, T 1 is H.

[0053] In a preferred embodiment of the present invention, A 1 and A 2 is -(CH2)5-, -(CH2)4-, -(CH2)3- and

[0054] [ka]

[0055] (In the formula, $ represents the position at which the polyester is bonded to an oxygen atom, and @ represents the position at which the polyester is bonded to a carbonyl group.) are each independently selected from

[0056] In a more preferred embodiment of the present invention, A 1 and A 2 are each independently selected from —(CH 2 ) 5 — and —(CH 2 ) 4 —.

[0057] In a more preferred embodiment of the present invention, m is an integer from 0 to 75, n is an integer from 0 to 75, m+n is an integer from 2 to 150.

[0058] In the most preferred embodiment of the present invention, m is an integer from 0 to 50; n is an integer from 0 to 50, m+n is an integer from 2 to 50.

[0059] In a more preferred embodiment of the present invention, A 1 and A 2 are identical.

[0060] In a particularly preferred embodiment of the present invention, A 1 and A 2 is -(CH2)5-.

[0061] In another particularly preferred embodiment of the present invention, A 1 and A 2 is -(CH2)4-.

[0062] In another particularly preferred embodiment of the present invention, A 1 and A 2 teeth,

[0063] [ka]

[0064] (wherein $ represents the position at which the polyester is bonded to an oxygen atom, and @ represents the position at which the polyester is bonded to a carbonyl group).

[0065] In a preferred embodiment of the present invention, A 1 and A 2 are different from each other, and the ratio of m to n is in the range of 10:1 to 1:10.

[0066] In a more preferred embodiment of the present invention, the ratio of m to n is in the range of 5:1 to 1:5.

[0067] In the most preferred embodiment of the present invention, the ratio of m to n is in the range of 2:1 to 1:2.

[0068] In a further preferred embodiment of the present invention, A 1 is -(CH2)5-, and A 2 is —(CH 2 ) 4 —, and the ratio of m to n is in the range of 10:1 to 1:10.

[0069] In the most preferred embodiment of the present invention, A 1 is -(CH2)5-, and A 2 is -(CH2)4-, and the ratio of m to n is in the range of 5:1 to 1:5.

[0070] In a particularly preferred embodiment of the present invention, A 1 is -(CH2)5-, and A 2 is -(CH2)4-, and the ratio of m to n is 2:1.

[0071] In a preferred embodiment of the present invention, at least one aliphatic polyether moiety P.3 is selected from the group consisting of (P.3a) and (P.3b)

[0072] [ka]

[0073] (In the formula, # indicates the position at which the compound is bonded to a nitrogen atom of the polyalkyleneimine skeleton, L is a linker, R 2 and R 3 are each independently selected from the group consisting of hydrogen and C1-C2-alkyl; p is an integer from 0 to 200; q is an integer from 0 to 200; p+q are integers from 2 to 200, T 2 is hydrogen, C1 to C 20 -Alkyl, C2-C 20 -Alkenyl, C(=O)-C2-C 20 -alkenyl or C(=O)-C1-C 20-Alkyl, C2-C 20 -Alkenyl has 1, 2, 3 or 4 olefinic C=C double bonds, C1-C 20 -1, 2, 3, or 4 non-adjacent CH groups of the alkyl may be replaced by O is selected from.

[0074] In a more preferred embodiment of the present invention, p is an integer from 0 to 100, q is an integer from 0 to 100, p+q is an integer from 2 to 100.

[0075] In a more preferred embodiment of the present invention, R 2 is H, and p is an integer from 2 to 100; q is 0, T 2 is H or CH3.

[0076] In a more preferred embodiment of the present invention, R 2 is CH3, and p is an integer from 2 to 100, q is 0, T 2 is H or CH3.

[0077] In a more preferred embodiment of the present invention, R 2 is H, and p is an integer from 1 to 100; R 3 is —CH3, and q is an integer from 1 to 100; p+q are integers from 2 to 150, T 2 is H or CH3.

[0078] In a preferred embodiment of the invention, the linker L is selected from the group consisting of (L.1), (L.2), (L.3) and (L.4).

[0079] [ka]

[0080] (In the formula, # indicates the position at which the compound is bonded to a nitrogen atom of the polyalkyleneimine skeleton, * indicates the position of attachment to the polyether moiety P.3, R 5 is H or CH3, Q is a direct bond or a divalent moiety selected from -O-, -N(H)-, and -S-; Y is O or NH; Z is C1 to C 24 Alkyl, C4-C 10 Cycloalkyl, C6-C 18 Aryl and C7-C 20 arylalkyl; A 1 and A 2 is C2~C 12 alkylene; m is an integer from 0 to 100, n is an integer from 0 to 100, m+n is an integer between 2 and 100. At least one selected from the group consisting of:

[0081] In a preferred embodiment of the present invention, R 5 is H.

[0082] In a more preferred embodiment of the present invention, R 5 is H and Q is O.

[0083] In the most preferred embodiment of the present invention, L.1

[0084] [ka]

[0085] is.

[0086] In a more preferred embodiment of the present invention, L.2

[0087] [ka]

[0088] is.

[0089] In a more preferred embodiment of the invention, Z is a C7 aralkyl.

[0090] In the most preferred embodiment of the present invention, Z is 2,4-toluoyl.

[0091] In a particularly preferred embodiment of the invention, L.3 is

[0092] [ka]

[0093] (In the formula, # indicates the position at which the compound is bonded to a nitrogen atom of the polyalkyleneimine skeleton, * indicates the position of attachment to the polyether moiety P.3, Y is O or NH is.

[0094] In a more preferred embodiment of the present invention, A 1 and A 2 is -(CH2)5-, -(CH2)4-, -(CH2)3- and

[0095] [ka]

[0096] (wherein $ represents the position at which the polyester is bonded to an oxygen atom, and @ represents the position at which the polyester is bonded to a carbonyl group, m is an integer from 0 to 100, n is an integer from 0 to 100, m+n is an integer between 2 and 100. are each independently selected from

[0097] In a more preferred embodiment of the present invention, A 1 and A 2 are identical.

[0098] In the most preferred embodiment of the present invention, A 1 and A 2 is -(CH2)5-.

[0099] In another most preferred embodiment of the present invention, A 1 and A 2 is -(CH2)4-.

[0100] In another particularly preferred embodiment of the present invention, A 1 and A 2 teeth,

[0101] [ka]

[0102] (wherein $ represents the position at which the polyester is bonded to an oxygen atom, and @ represents the position at which the polyester is bonded to a carbonyl group).

[0103] In a more preferred embodiment of the present invention, A 1 and A 2 are different from each other and are each independently selected from —(CH2)5—, —(CH2)4—, and —(CH2)3—.

[0104] In a more preferred embodiment of the present invention, m is an integer from 0 to 75, n is an integer from 0 to 75, m+n is an integer from 2 to 150.

[0105] In the most preferred embodiment of the present invention, m is an integer from 0 to 50; n is an integer from 0 to 50, m+n is an integer from 2 to 50.

[0106] In a preferred embodiment of the invention, the polymer is a) 0.5 to 25% by mass of a polyalkyleneimine skeleton relative to the total mass of the polymer; b) 0.5 to 25% by weight, relative to the total weight of the polymer, of at least one aromatic moiety P.1; c) 1 to 50% by weight, relative to the total weight of the polymer, of at least one polyester P.2, and d) 30 to 90% by weight, relative to the total weight of the polymer, of at least one aliphatic polyether moiety P.3 Includes.

[0107] In a more preferred embodiment of the present invention, the polymer is a) 1 to 20% by mass of a polyalkyleneimine skeleton relative to the total mass of the polymer; b) 1 to 20% by weight, relative to the total weight of the polymer, of at least one aromatic moiety P.1; c) 2 to 30% by weight, relative to the total weight of the polymer, of at least one polyester P.2, and d) 30 to 80% by weight, relative to the total weight of the polymer, of at least one aliphatic polyether moiety P.3 Includes.

[0108] In the most preferred embodiment of the present invention, the polymer is a) 2 to 15% by mass of a polyalkyleneimine skeleton relative to the total mass of the polymer; b) 2 to 15% by weight, relative to the total weight of the polymer, of at least one aromatic moiety P.1; c) 5 to 25% by weight, relative to the total weight of the polymer, of at least one polyester P.2, and d) 40 to 70% by weight, relative to the total weight of the polymer, of at least one aliphatic polyether moiety P.3 Includes.

[0109] In a preferred embodiment of the invention, the polymer has an amine number in the range of 10 to 1,000 mg KOH / g, determined according to DIN 53176:2002-11.

[0110] In a preferred embodiment of the present invention, the polymer has an acid number, determined according to DIN 53402:1990-09, in the range of 0 to 15 mg KOH / g, more preferably in the range of 0 to 12 mg KOH / g, even more preferably in the range of 0 to 10 mg KOH / g.

[0111] In another aspect, the present invention provides a method for preparing a polymer, comprising: i. reacting a polyalkyleneimine with an aromatic carboxylic acid, an aromatic carboxylic acid anhydride, or an amide- or imide-forming derivative of an aromatic carboxylic acid in an amount that will theoretically consume up to 90% of the total amount of primary and secondary nitrogen atoms in the polyalkyleneimine; ii. reacting the product of step (i) with a hydroxycarboxylic acid, a lactone monomer, or a polyester moiety having a terminal carboxyl group obtainable from a lactone monomer; iii. reacting the product of step (ii) with an alkylene oxide or a polyether moiety having end groups selected from acrylate, isocyanato, and carboxylate; The present invention provides a method comprising:

[0112] In yet another aspect, the present invention provides a method for preparing a polymer, comprising the steps of: i. reacting a polyalkyleneimine with an aromatic carboxylic acid, an aromatic carboxylic acid anhydride, or an amide- or imide-forming derivative of an aromatic carboxylic acid in an amount that will theoretically consume up to 90% of the total amount of primary and secondary nitrogen atoms in the polyalkyleneimine; ii. The product of step (i) - a polyester moiety having a terminal carboxyl group that can be obtained from a hydroxycarboxylic acid, a lactone monomer, or a lactone monomer, and - alkylene oxide or polyether moieties having end groups selected from acrylate, isocyanato, and carboxylate; and reacting the compound with The present invention provides a method comprising:

[0113] In yet another aspect, the present invention provides a method for preparing a polymer, comprising reacting a polyalkyleneimine with aromatic carboxylic acids, aromatic carboxylic acid anhydrides or amide- or imide-forming derivatives of aromatic carboxylic acids, - a polyester moiety having a terminal carboxyl group that can be obtained from a hydroxycarboxylic acid, a lactone monomer, or a lactone monomer, and - alkylene oxide or polyether moieties having end groups selected from acrylate, isocyanato, and carboxylate; The method includes reacting

[0114] In yet another aspect, the present invention provides a method for preparing a polymer, comprising the steps of: i. a polyalkyleneimine, aromatic carboxylic acids, aromatic carboxylic acid anhydrides or amide- or imide-forming derivatives of aromatic carboxylic acids, and - a polyester moiety having a terminal carboxyl group that can be obtained from a hydroxycarboxylic acid, a lactone monomer, or a lactone monomer; and reacting the ii. reacting the product of step (i) with an alkylene oxide or a polyether moiety having end groups selected from acrylate, isocyanato, and carboxylate; The present invention provides a method comprising:

[0115] In a preferred embodiment of the present invention, the aromatic carboxylic acid is

[0116] [ka]

[0117] wherein Ar is selected from the group consisting of phenyl and naphthyl, wherein phenyl and naphthyl are each independently unsubstituted or substituted with 1, 2, 3, 4, or 5 groups selected from the group consisting of halogen, OH, C1-C4-alkyl, C1-C4-alkoxy, C(=O)-OH, C(=O)-NH2, NH2, NO2, NH-C(=O)-H, NH-C1-C4-alkyl, and NH-C(=O)-C1-C4-alkyl.

[0118] In a preferred embodiment of the present invention, the aromatic carboxylic acid anhydride is

[0119] [ka]

[0120] wherein Ar' is selected from the group consisting of 1,2-phenylene, 1,2-, 2,3-, or 1,8-naphthylene, wherein phenylene and naphthylene are each independently unsubstituted or substituted with 1, 2, 3, 4, or 5 groups selected from the group consisting of halogen, OH, C1-C4-alkyl, C1-C4-alkoxy, C(=O)-OH, C(=O)-NH2, NH2, NO2, NH-C(=O)-H, NH-C1-C4-alkyl, and NH-C(=O)-C1-C4-alkyl.

[0121] In a preferred embodiment of the present invention, the aromatic carboxylic acid anhydrides have the formula (P.1d') and (P.1e')

[0122] [ka]

[0123] wherein R and k are defined above.

[0124] In a preferred embodiment of the present invention, the amide or imide forming derivative of an aromatic carboxylic acid is of formula (I)

[0125] [ka]

[0126] (In the formula, W is a chemical bond or a divalent moiety selected from the group consisting of -O-, -NH-, and -S-; A is a group of formula

[0127] [ka]

[0128] (In the formula, where #, k, and R are defined as above. wherein the aromatic group is an unsubstituted or substituted aromatic group selected from the group consisting of:

[0129] In a preferred embodiment of the invention, the compound of formula (I) has W=NH and A is

[0130] [ka]

[0131] where ## is defined as above and k=0. The compound of formula (I) is isatoic anhydride.

[0132] In a preferred embodiment of the present invention, the hydroxycarboxylic acid is 12-hydroxystearic acid.

[0133] In a preferred embodiment of the present invention, the lactone monomer is at least one selected from the group consisting of ε-caprolactone, γ-valerolactone, γ-butyrolactone, wherein the lactone monomer is unsubstituted or substituted with one, two or three substituents selected from the group consisting of methyl, hydroxy, and methoxy.

[0134] In a preferred embodiment of the present invention, the polyester moiety having a terminal carboxyl group is

[0135] [ka]

[0136] (In the formula, T 1 , A 1 , A 2 , m, and n are defined above).

[0137] In a preferred embodiment of the present invention, the alkylene oxide is at least one selected from the group consisting of ethylene oxide and propylene oxide.

[0138] In a preferred embodiment of the present invention, the polyether moiety having end groups selected from acrylate, isocyanato and carboxylate is

[0139] [ka]

[0140] (In the formula, R 5 , Q, R 2 , R 3 , T 2 , Y, and Z are defined as above) is selected from.

[0141] The dispersants of the present invention can be used in a wide range of applications, such as coatings, inks, and electronic materials. These dispersants can be used in industrial coatings for solvent-based systems, such as organic and inorganic pigment dispersions (e.g., alkyd, CAB (cellulose acetate butyrate), UV (ultraviolet), and TPA (thermoplastic acrylate) paint systems). These dispersants can also be used in water-based systems, such as printing inks and graphic arts.

[0142] In yet another aspect, the present invention provides a liquid composition in the form of a dispersion comprising a particulate solid material selected from the group consisting of pigments and fillers, and a liquid diluent, wherein the particulate solid material is dispersed in the liquid diluent, and the liquid diluent further comprises a polymer of the present invention.

[0143] In a preferred embodiment of the present invention, the mass ratio of particulate solid material to polymer is in the range of 100:1 to 1:2, more preferably 100:1 to 1:1, even more preferably 100:1 to 10:1, and most preferably 100:1 to 50:1.

[0144] In another preferred embodiment of the present invention, the weight ratio of particulate solid material to polymer is in the range of 50:1 to 1:2, more preferably 10:1 to 2:1, most preferably 5:1 to 2:1.

[0145] In a preferred embodiment of the present invention, the size of the solid particulate matter, expressed as mass-average particle size, is in the range of 1 nm to 20,000 nm, more preferably 10 nm to 10,000 nm, and most preferably 20 nm to 500 nm. Mass-average particle size can be determined by sieve analysis or light scattering.

[0146] The pigments can be inorganic or organic.

[0147] In a preferred embodiment of the present invention, the organic pigments are pigments and pearlescent flakes selected from the group consisting of azo, disazo, naphthol, benzimidazolone, condensed azo, metal complex, isoindolinone and isoindoline pigments, quinophthalone pigments, dioxazine pigments; polycyclic pigments selected from the group consisting of indigo, thioindigo, quinacridone, phthalocyanine, perylene, and perinone; anthraquinones such as aminoanthraquinones or hydroxyanthraquinones; anthrapyrimidines, indanthrones, flavanthrones, pyranthrones, anthanthrones, isoviolanthrones, diketopyrrolopyrroles, and carbazoles, such as carbazole violet. Further examples of organic pigments are described in W. Herbst, K. Hunger "Industrielle Organische Pigmente" 2 nd Edition, 1995, VCH Verlagsgesellschaft, ISBN: 3-527-28744-2.

[0148] In a preferred embodiment of the present invention, the inorganic pigment is selected from the group consisting of aluminum, aluminum oxide, calcium carbonate, silicon oxide and silicates, iron(III) oxide, chromium(III) oxide, titanium(IV) oxide, zirconium(IV) oxide, zinc oxide, zinc sulfide, zinc phosphate, mixed metal oxide phosphates, molybdenum sulfide, cadmium sulfide, carbon black or graphite, vanadates such as bismuth vanadate, chromates such as lead(IV) chromate, molybdates such as lead(IV) molybdate, and mixtures thereof, crystalline forms or modifications such as rutile, anatase, metal-like powders such as mica, talc, kaolin, and mixtures thereof.

[0149] In a preferred embodiment of the present invention, the pigment is carbon black, and the mass average particle size of the pigment is in the range of 100 nm to 300 nm.

[0150] In a preferred embodiment of the present invention, the filler is selected from the group consisting of calcium carbonate, silicates, glass fibers, glass beads, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour, other natural powders and fibers, synthetic fibers, and mixtures thereof.

[0151] The liquid diluent present in the dispersion will vary depending on the application.

[0152] For water-based formulations, the liquid diluent comprises water. The liquid diluent may further comprise a polar, water-miscible solvent such as a C1-C4 alkanol, e.g., methanol, ethanol, isopropanol, propanol, or n-butanol, a glycol ether such as butyl glycol or methoxypropylene glycol, a polyol, e.g., glycerol, ethylene glycol, diethylene glycol, triethylene, triethylene glycol, propylene glycol, or butyl diglycol, or mixtures thereof.

[0153] For solvent-based formulations, the liquid diluent is selected from low polarity solvents such as aliphatic hydrocarbons, esters such as butyl acetate, or glycol ethers such as methoxypropylene glycol, and glycol ether esters such as methoxypropylene glycol acetate, and mixtures thereof.

[0154] In a preferred embodiment of the present invention, the weight ratio of particulate solid material to liquid diluent is in the range of 100:1 to 1:50, more preferably in the range of 30:1 to 1:10.

[0155] Depending on the intended use, the dispersion may further comprise a binder and / or one or more additives, including but not limited to plasticizers, lubricants, emulsifiers, humectants, rheological additives, catalysts, flow aids, optical brighteners, flame retardants, preservatives, antistatic agents, and foaming agents.

[0156] In a preferred embodiment of the invention, the dispersion is in the form of a mill-base, which comprises a finely divided solid material, a dispersant of formula (I), a liquid diluent, and optionally additives, although mill-bases typically do not contain a binder.

[0157] In a preferred embodiment of the present invention, the dispersion is in the form of a coating composition. The coating composition comprises a particulate solid material, a dispersant of formula (I), a liquid diluent, and at least one binder, such as a film-forming polymer or prepolymer that forms a film upon curing. The coating composition may further comprise additives conventionally used in coating technology, such as plasticizers, lubricants, emulsifiers, rheological additives, catalysts, flow aids, optical brighteners, flame retardants, preservatives, antistatic agents, or foaming agents.

[0158] In a preferred embodiment of the present invention, the dispersion is in the form of an ink composition, such as a printing ink or gravure ink, which comprises a particulate solid material, a dispersant of formula (I), a liquid diluent, and also at least one binder conventionally used in ink technology, such as a film-forming polymer or prepolymer which forms a film upon curing.

[0159] The present invention provides one or more of the following advantages. 1) The dispersants of the present invention provide stable dispersions at high pigment loadings. 2) Dispersions containing the dispersants of the present invention have low viscosity. Even when a large amount of pigment is added, the viscosity of the dispersion is significantly reduced. 3) The dispersants of the present invention improve the rheological behavior of the dispersion, and furthermore, the rheological behavior of the dispersion does not change over time. 4) Surfaces coated with coating compositions containing the dispersants of the present invention exhibit high gloss and a reduced number of craters.

[0160] While not intending to limit the present disclosure to the specific embodiments described below, a list of embodiments is provided below to further illustrate the present disclosure.

[0161] 1. a) a polyalkyleneimine backbone, b) at least one aromatic moiety P.1, which is linked to a nitrogen atom of the polyalkyleneimine backbone via a carboxamide or carboximide group; c) at least one polyester moiety P.2, which is bound to a nitrogen atom of the polyalkyleneimine backbone via a carboxamide, and d) at least one aliphatic polyether moiety P.3, which is attached to a nitrogen atom of the polyalkyleneimine backbone either directly or via a linker; A polymer having the formula:

[0162] 2. The polymer of embodiment 1, wherein the polyalkyleneimine backbone has a weight average molecular weight in the range of 100 g / mol to 20,000 g / mol, determined according to DIN 55672-1.

[0163] 3. The polymer of embodiment 1 or 2, wherein the polyalkyleneimine backbone is a polyethyleneimine backbone.

[0164] 4. At least one aromatic moiety P.1 has the formula (P.1') and (P.1'')

[0165] [ka]

[0166] (In the formula, # indicates the position at which the aromatic moiety P.1 is attached to the nitrogen atom of the polyalkyleneimine backbone, Ar is selected from the group consisting of phenyl and naphthyl, wherein phenyl and naphthyl are each independently unsubstituted or substituted with 1, 2, 3, 4, or 5 groups selected from the group consisting of halogen, OH, C1-C4-alkyl, C1-C4-alkoxy, C(=O)-OH, C(=O)-NH2, NH2, NO2, NH-C(=O)-H, NH-C1-C4-alkyl, and NH-C(=O)-C1-C4-alkyl; Ar' is selected from the group consisting of 1,2-phenylene, 1,2-, 2,3-, or 1,8-naphthylene, wherein phenylene and naphthylene are each independently unsubstituted or substituted with 1, 2, 3, 4, or 5 groups selected from the group consisting of halogen, OH, C1-C4-alkyl, C1-C4-alkoxy, C(=O)-OH, C(=O)-NH2, NH2, NO2, NH-C(=O)-H, NH-C1-C4-alkyl, and NH-C(=O)-C1-C4-alkyl. 4. The polymer of any one of embodiments 1 to 3, wherein the polymer is selected from the group consisting of:

[0167] 5. At least one aromatic moiety P.1 is of the formula (P.1a), (P.1b), (P.1c), (P.1d), and (P.1e)

[0168] [ka]

[0169] (In the formula, # indicates the position where the aromatic moiety is bonded to the nitrogen atom of the polyalkyleneimine skeleton, R' is selected from the group consisting of hydrogen, C1-C4-alkyl, -C(=O)-H and -C(=O)-C1-C4-alkyl, k is 0, 1, 2, 3, or 4; R are the same or different and are a group selected from the group consisting of halogen, OH, C1-C4-alkyl, C1-C4-alkoxy, C(=O)-OH, C(=O)-NH2, NH2, NO2, NH-C(=O)-H, NH-C1-C4-alkyl, and NH-C(=O)-C1-C4-alkyl. 5. The polymer of any one of embodiments 1 to 4, wherein the polymer is selected from the group consisting of the moiety:

[0170] 6. The polyester moiety P.2 has the formula (P.2a)

[0171] [ka]

[0172] (In the formula, # indicates the position at which the compound is bonded to a nitrogen atom of the polyalkyleneimine skeleton, T 1 is hydrogen or R 1 -C(=O)- and R 1 is C1~C 24 is alkyl, A 1 and A 2 is C2~C 12 alkylene; m is an integer from 0 to 100, n is an integer from 0 to 100, m+n is an integer between 2 and 100. 6. The polymer of any one of embodiments 1 to 5, wherein

[0173] 7. T 1 is hydrogen, CH3(CH2)3-, CH3(CH2) 10 - and CH3(CH2) 16 7. The polymer of embodiment 6, selected from the group consisting of:

[0174] 8. A 1 and A 2 are each independently -(CH2)5-, -(CH2)4-, -(CH2)3-, and

[0175] [ka]

[0176] (In the formula, $ represents the position at which the polyester is bonded to an oxygen atom, and @ represents the position at which the polyester is bonded to a carbonyl group.) 7. The polymer of embodiment 6, selected from:

[0177] 9. m is an integer between 0 and 50; n is an integer from 0 to 50, m+n is an integer from 2 to 50; 7. The polymer of embodiment 6.

[0178] 10. The polymer of embodiment 6, wherein the "m" repeat units and the "n" repeat units form a gradient, random, or block polymer structure.

[0179] 11. At least one aliphatic polyether moiety P.3 comprises (P.3a) and (P.3b)

[0180] [ka]

[0181] (In the formula, # indicates the position at which the compound is bonded to a nitrogen atom of the polyalkyleneimine skeleton, L is a linker, R 2 and R 3 are each independently selected from the group consisting of hydrogen and C1-C2-alkyl; p is an integer from 0 to 200; q is an integer from 0 to 200; p+q are integers from 2 to 200, T 2 is hydrogen, C1 to C 20 -Alkyl, C2-C 20 -Alkenyl, C(=O)-C2-C 20 -alkenyl or C(=O)-C1-C 20 -Alkyl, C2-C 20 -Alkenyl has 1, 2, 3 or 4 olefinic C=C double bonds, C1-C 20 -1, 2, 3, or 4 non-adjacent CH groups of the alkyl may be replaced by O 11. The polymer of any one of embodiments 1 to 10, selected from:

[0182] 12. p is an integer between 0 and 100; q is an integer from 0 to 100, 12. The polymer of embodiment 11, wherein p+q is an integer from 2 to 100.

[0183] 13. R 2 is H, and p is an integer from 2 to 100; q is 0, T 2 is H.

[0184] 14. R 2 is H, and p is an integer from 1 to 100; R 3 is —CH3, and q is an integer from 1 to 100; p+q are integers from 2 to 150, T 2 is H, or CH.

[0185] 15. The linker L is selected from the group consisting of (L.1), (L.2), (L.3) and (L.4).

[0186] [ka]

[0187] (In the formula, # indicates the position at which the compound is bonded to a nitrogen atom of the polyalkyleneimine skeleton, * indicates the position of attachment to the polyether moiety P.3, R 5 is H or CH3, Q is a direct bond or a divalent moiety selected from -O-, -N(H)-, and -S-; Y is O or NH; Z is C1 to C 24 Alkyl, C4-C 10 Cycloalkyl, C6-C 18 Aryl and C7-C 20 arylalkyl; A 1 and A 2 is C2~C 12alkylene, and m is an integer from 0 to 100; n is an integer from 0 to 100, m+n is an integer between 2 and 100. 12. The polymer of embodiment 11, wherein the polymer is at least one selected from the group consisting of:

[0188] 16. R 5 is H.

[0189] 17. L.3 is

[0190] [ka]

[0191] (wherein # indicates the position of bonding to the nitrogen atom of the polyalkyleneimine skeleton, * indicates the position of bonding to the polyether moiety P.3, and Y is O or NH.) 16. The polymer of embodiment 15, wherein

[0192] 18. a) 0.5 to 25% by mass of a polyalkyleneimine skeleton relative to the total mass of the polymer; b) 0.5 to 25% by weight, relative to the total weight of the polymer, of at least one aromatic moiety P.1; c) 1 to 50% by weight, relative to the total weight of the polymer, of at least one polyester P.2, and d) The polymer according to any one of the preceding embodiments, comprising 30 to 90% by weight of at least one aliphatic polyether moiety P.3, relative to the total weight of the polymer.

[0193] 19. The polymer of any one of embodiments 1 to 18, wherein the polymer has an acid number, determined according to DIN 53402:1990-09, in the range of 0 to 15 mg KOH / g.

[0194] 20. A method for preparing a polymer according to any one of embodiments 1 to 19, comprising: i. reacting a polyalkyleneimine with an aromatic carboxylic acid, an aromatic carboxylic acid anhydride, or an amide- or imide-forming derivative of an aromatic carboxylic acid in an amount that will theoretically consume up to 90% of the total amount of primary and secondary nitrogen atoms in the polyalkyleneimine; ii. reacting the product of step (i) with a hydroxycarboxylic acid, a lactone monomer, or a polyester moiety having a terminal carboxyl group obtainable from a lactone monomer; iii. reacting the product of step (ii) with an alkylene oxide or a polyether moiety having end groups selected from acrylate, isocyanato, and carboxylate; A method comprising:

[0195] 21. A method for preparing a polymer according to any one of embodiments 1 to 19, comprising: i. reacting a polyalkyleneimine with an aromatic carboxylic acid, an aromatic carboxylic acid anhydride, or an amide- or imide-forming derivative of an aromatic carboxylic acid in an amount that will theoretically consume up to 90% of the total amount of primary and secondary nitrogen atoms in the polyalkyleneimine; ii. The product of step (i) - a polyester moiety having a terminal carboxyl group that can be obtained from a hydroxycarboxylic acid, a lactone monomer, or a lactone monomer, and - alkylene oxide or polyether moieties having end groups selected from acrylate, isocyanato, and carboxylate; and reacting the compound with A method comprising:

[0196] 22. A method for preparing a polymer according to any one of embodiments 1 to 19, comprising: aromatic carboxylic acids, aromatic carboxylic acid anhydrides or amide- or imide-forming derivatives of aromatic carboxylic acids, - a polyester moiety having a terminal carboxyl group that can be obtained from a hydroxycarboxylic acid, a lactone monomer, or a lactone monomer, and - alkylene oxide or polyether moieties having end groups selected from acrylate, isocyanato, and carboxylate; The method of claim 1, wherein the compound is a methyl group.

[0197] 23. A method for preparing a polymer according to any one of embodiments 1 to 19, comprising: i. a polyalkyleneimine, aromatic carboxylic acids, aromatic carboxylic acid anhydrides or amide- or imide-forming derivatives of aromatic carboxylic acids, and - a polyester moiety having a terminal carboxyl group that can be obtained from a hydroxycarboxylic acid, a lactone monomer, or a lactone monomer; and reacting the ii. reacting the product of step (i) with an alkylene oxide or a polyether moiety having end groups selected from acrylate, isocyanato, and carboxylate; A method comprising:

[0198] 24. An aromatic carboxylic acid is

[0199] [ka]

[0200] 24. The method of any one of embodiments 20 to 23, wherein Ar is as defined in any one of embodiments 1 to 19.

[0201] 25. An aromatic carboxylic acid anhydride is

[0202] [ka]

[0203] The method of any one of embodiments 20 to 24, wherein Ar′ is as defined in any one of embodiments 1 to 19.

[0204] 26. An amide or imide-forming derivative of an aromatic carboxylic acid is represented by the formula (I)

[0205] [ka]

[0206] (In the formula, W is a chemical bond or a divalent moiety selected from the group consisting of -O-, -NH-, and -S-; A is the formula

[0207] [ka]

[0208] wherein ##, k, and R are unsubstituted or substituted aromatic groups selected from the group consisting of: 26. The method of any one of embodiments 20 to 25, wherein the compound is selected from the group consisting of:

[0209] 27. The method of any one of embodiments 20 to 26, wherein the lactone monomer is at least one selected from the group consisting of ε-caprolactone, γ-valerolactone, and γ-butyrolactone, wherein the lactone monomer is unsubstituted or substituted with one, two, or three substituents selected from the group consisting of methyl, hydroxy, and methoxy.

[0210] 28. A polyester moiety having a terminal carboxyl group is

[0211] [ka]

[0212] (In the formula, T1 , A 1 , A 2 28. The method of any one of embodiments 20 to 27, wherein m and n are defined as in any one of embodiments 1 to 19.

[0213] 29. The method of any one of embodiments 20 to 28, wherein the hydroxycarboxylic acid is 12-hydroxystearic acid.

[0214] 30. The method of any one of embodiments 20 to 29, wherein the alkylene oxide is at least one selected from the group consisting of ethylene oxide and propylene oxide.

[0215] 31. A polyether moiety having end groups selected from acrylate, isocyanato, and carboxylate;

[0216] [ka]

[0217] (In the formula, R 5 , Q, R 2 , R 3 , T 2 , Y and Z are defined as in any one of embodiments 1 to 19. 31. The method of any one of embodiments 20 to 30, selected from:

[0218] 32. A liquid composition in the form of a dispersion comprising a particulate solid material selected from the group consisting of pigments and fillers, and a liquid diluent, wherein the particulate solid material is dispersed in the liquid diluent, further comprising the polymer of any one of embodiments 1 to 19.

[0219] 33. The liquid composition according to embodiment 32, wherein the mass ratio of particulate solid material to polymer ranges from 100:1 to 1:2.

[0220] 34. The liquid composition according to embodiment 32 or 33, in the form of a millbase, a coating composition or an ink.

[0221] 35. Use of a polymer according to any one of embodiments 1 to 19 as a component of a coating or ink composition.

[0222] While the invention has been described in terms of specific embodiments, certain 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]

[0223] The present invention is further illustrated by the following non-limiting examples. More particularly, the test methods specified below are part of the general disclosure of the application and are not limited to the specific examples.

[0224] material Lupasol® PR 8515 - Polyethyleneimine with an average molecular weight of 2,000 g / mol, determined in accordance with DIN 55672-1. Lupasol® FG - Polyethyleneimine with an average molecular weight of 800 g / mol, determined in accordance with DIN 55672-1. Desmodur® T 100SP - pure 2,4'-toluene diisocyanate (TDI), available from Covestro. Epomin® SP-200—Polyethyleneimine with an average molecular weight of 10,000 g / mol, available from Nippon Shokubai Co., Ltd., Japan. Carbon Black FW171 - A high color, high structure, post-treated amorphous carbon black available from Orion Engineered Carbons. Hypomer® FS-2050 - Hydroxylic acrylic resin solvent, available from Elementis. Jeffamine® M-600 - Polyetheramine with an average molecular weight of 600 g / mol, available from Huntsman, Belgium.

[0225] method Acid number: The acid number was determined according to DIN 53402:1990-09.

[0226] Amine number: The amine number was determined according to DIN 53176:2002-11.

[0227] Isocyanate (NCO) content: The isocyanate (NCO) content was determined according to DIN 14896:2009-07.

[0228] Viscosity: Viscosity was measured according to DIN 53019-1:2008-09 using a Thermo-Haake RheoStress 600 device in CR mode at 22°C and a shear rate of 1 sec -1 (Spindle CP50) was selected.

[0229] A) Preparation of dispersant i) Preparation of intermediates Intermediate A1: Copolymer of lauric acid, caprolactone, and valerolactone A mixture of lauric acid (10 g, 0.05 mol), ε-caprolactone (60 g, 0.5 mol), γ-valerolactone (20 g, 0.25 mol), and titanium(IV) butylate (0.5 g) as a catalyst was stirred at 170° C. until the solid content of the mixture exceeded 97%. The mixture was cooled to give Intermediate A1 as a yellowish liquid having an acid value of 32 mg KOH / g.

[0230] Intermediate B1: Copolymer of MPEG500 and acrylic anhydride A mixture of 50 g of poly(ethylene glycol) methyl ether (molecular weight 500 g / mol) and 12 g of acrylic anhydride was stirred at room temperature for 1 hour. The temperature of the reaction mixture was slowly raised to 80°C, and then the mixture was stirred at 80°C for 2 hours. The acrylic acid formed during the reaction was removed from the reaction mixture under vacuum to obtain Intermediate B1. The acrylic functional group content of Intermediate B1 was 1 H-NMR determination revealed it to be 0.95.

[0231] Intermediate B2: Copolymer of Jeffamine M2070 and itaconic acid A 500 mL four-neck flask equipped with a stirrer and thermometer and maintained under a nitrogen atmosphere was charged with 150 g of Jeffamine® PEMA 2070 (molecular weight 2,000 g / mol) and 9.76 g of itaconic acid, and the reaction mixture was stirred at room temperature for 1 hour. The temperature of the reaction mixture was increased to 80° C., the pressure was slowly reduced to 100 mbar, and the mixture was stirred under these conditions for 5 hours. The reaction temperature was increased to 120° C. while maintaining the pressure at 100 mbar, and the mixture was stirred for 5 hours. Intermediate B2 was obtained as a clear orange liquid with an acid value of 26 mg KOH / g.

[0232] Intermediate B3: Copolymer of Jeffamine M-600 and TDI100 To a reactor maintained at room temperature, 30 g of ethyl acetate and 14.4 g of Desmodur® T 100SP were added. 50 g of Jeffamine® M-600 (molecular weight 600 g / mol) was slowly added to the above mixture over 2 hours. The reaction mixture was slowly heated to 40° C. and then heated at 40° C. for 1 hour to obtain Intermediate B3 with an isocyanate content of 3.6%.

[0233] This intermediate must be freshly prepared before each use.

[0234] Intermediate C1: Copolymer of PEI 2000 and 1,8-naphthalic anhydride A mixture of 50 g of Lupasol® PR 8515 (polyethyleneimine, molecular weight 2,000 g / mol) and 50 g of 1,8-naphthalic anhydride was stirred at 150° C. under a nitrogen atmosphere until the acid value of the mixture was less than 5 mg KOH / g, yielding intermediate C1.

[0235] Intermediate C2: Copolymer of PEI 800 and isatoic anhydride A mixture of 50 g of Lupasol® FG (polyethyleneimine, molecular weight 800 g / mol) and 30 g of isatoic anhydride was stirred at room temperature for 1 hour. The temperature of the reaction mixture was slowly raised to 60° C. and then heated at 60° C. until no further carbon dioxide evolution occurred. Intermediate C2 was obtained, with an amine number of 860 mg KOH / g.

[0236] ii) Preparation of a dispersant from the intermediate prepared in step (i) Example 1 Preparation of Dispersant 1 (Two-Step Grafting) A mixture of 40 g of Intermediate A1, 40 g of Intermediate B1, and 10 g of Intermediate C1 was heated at 40° C. under a nitrogen atmosphere for 3 hours. The mixture was slowly heated to 170° C. under a nitrogen atmosphere, followed by the addition of 0.1 g of dibutyltin dilaurate (DBTL) catalyst, and the resulting mixture was heated at 170° C. until the acid value of the mixture was less than 10 mg KOH / g. Dispersant 1 was obtained as a brown viscous liquid with an acid value of 6 mg KOH / g.

[0237] (Examples 2 to 8) Preparation of Dispersants 2 to 8 (Two-Step Grafting) Dispersants 2 to 8 were prepared according to the same method as that for preparing Dispersant 1. The intermediates used in the preparation of Dispersants 2 to 8 and their amounts are shown in Table 1.

[0238] [Table 1]

[0239] Example 9: Preparation of Dispersant 9 (Grafting Based on One-Pot Process) A mixture of 5 g of Lupasol® PR8515 (polyethyleneimine, BASF, molecular weight 2,000 g / mol), 5 g of 1,8-naphthalic anhydride, 30 g of ε-caprolactone, and 50 g of Intermediate B1 was heated at 40° C. for 3 hours under a nitrogen atmosphere. The mixture was slowly heated to 100° C., followed by the addition of 0.1 g of DBTL catalyst, and the resulting mixture was heated to 170° C. until the solids content was greater than 95%. The resulting mixture was heated under vacuum until the acid number was less than 10 mg KOH / g. Dispersant 9 was obtained as a brown, viscous dispersant with an acid number of 5 mg KOH / g.

[0240] (Examples 10 to 15) Preparation of Dispersants 10 to 15 (Grafting Based on One-Pot Process) Dispersants 10-15 were prepared according to a method similar to that used to prepare Dispersant 9. The reactants used to prepare Dispersants 10-15 are shown in Table 2 below.

[0241] [Table 2]

[0242] Example 16: Preparation of Dispersant 16 (PEO Formation by Ethoxylation) A reactor was charged with 5 g of Lupasol® FG (polyethyleneimine, molecular weight 800 g / mol), 5 g of isatoic anhydride, 20 g of ε-caprolactone, and 0.1 g of DBTL catalyst, and the mixture was heated at 170°C until the solids content of the mixture exceeded 97%. The resulting mixture was cooled to 120°C, and 0.2 g of potassium tert-butoxide (KOtBu) was added to the mixture. 10 g of ethylene oxide was charged to the reactor over 15 minutes. The ethylene oxide pressure in the reactor was 2 bar. An additional 60 g of ethylene oxide was charged to the reactor over the next 12 hours. The reaction mixture was then cooled to 80°C, and all volatile by-products and residual monomers were removed under vacuum. Dispersant 16 was obtained as a brown, viscous dispersant with an acid value of 0 mg KOH / g.

[0243] Example 17: Preparation of Dispersant 17 (Propoxylation to Form PPO) A reactor was charged with 5 g of Lupasol® FG (polyethyleneimine, molecular weight 800 g / mol), 5 g of isatoic anhydride, 20 g of ε-caprolactone, and 0.1 g of DBTL catalyst, and the mixture was heated at 170°C until the solids content of the mixture exceeded 97%. The resulting material was cooled to 140°C, and 0.2 g of potassium tert-butoxide (KOtBu) was charged. 50 g of propylene oxide was charged to the reactor over 15 minutes. The propylene oxide pressure in the reactor was 2 bar. An additional 50 g of propylene oxide was charged to the reactor over the next 12 hours. The reaction mixture was then cooled to 80°C, and all volatile by-products and residual monomers were removed under vacuum. Dispersant 17 was obtained as a brown, viscous dispersant with an acid number of 0 mg KOH / g.

[0244] Example 18: Preparation of Dispersant 18 (PEO Formation by Ethoxylation) A reactor was charged with 5 g of Lupasol® PR8515 (polyethyleneimine, molecular weight 2,000 g / mol), 5 g of 1,8-naphthalic anhydride, 30 g of ε-caprolactone, and 0.1 g of DBTL catalyst, and the mixture was heated at 170°C until the solids content of the mixture exceeded 97%. The resulting mixture was cooled to 120°C, and 0.2 g of KOtBu was added. 5 g of ethylene oxide was charged to the reactor over 15 minutes. The ethylene oxide pressure in the reactor was 2 bar. An additional 35 g of ethylene oxide was charged to the reactor over the next 12 hours. The reaction mixture was then cooled to 80°C, and all volatile by-products and residual monomers were removed under vacuum. Dispersant 18 was obtained as a brown, viscous liquid with an acid value of 0 mg KOH / g.

[0245] Example 19: Preparation of Dispersant 19 (PEO Formation by Ethoxylation) A reactor was charged with 5 g of Lupasol® PR8515 (polyethyleneimine, molecular weight 2,000 g / mol), 5 g of 1,8-naphthalic anhydride, 30 g of ε-caprolactone, and 0.1 g of DBTL catalyst, and the mixture was heated at 170°C until the solids content of the mixture exceeded 97%. The resulting mixture was cooled to 100°C, and 0.2 g of KOtBu was added. 5 g of ethylene oxide was charged to the reactor over 15 minutes. The ethylene oxide pressure in the reactor was 2 bar. An additional 55 g of ethylene oxide was charged to the reactor over the next 12 hours. The reaction mixture was then cooled to 80°C, and all volatile by-products and residual monomers were removed under vacuum. Dispersant 19 was obtained as a brown, viscous liquid with an acid value of 0 mg KOH / g.

[0246] Example 20: Preparation of Dispersant 20 (PPO / PEO Formation by Alkoxylation) A reactor was charged with 5 g of Lupasol® FG (polyethyleneimine, molecular weight 800 g / mol), 5 g of 1,8-naphthalic anhydride, 20 g of ε-caprolactone, and 0.1 g of DBTL catalyst, and the mixture was heated at 170°C until the solids content of the mixture exceeded 97%. The resulting mixture was cooled to 140°C, and 0.2 g of KOtBu was added. 20 g of propylene oxide was charged to the reactor over 6 hours. The propylene oxide pressure in the reactor was 2 bar. An additional 50 g of ethylene oxide was charged to the reactor over the next 12 hours. The reaction mixture was then cooled to 80°C, and all volatile by-products and residual monomers were removed under vacuum. Dispersant 20 was obtained as a brown, viscous liquid with an acid value of 0 mg KOH / g.

[0247] Preparation of Dispersants for Comparative Studies (Comparative Dispersants 1 and 2) Comparative Dispersant 1: Copolymer of Epomin® SP-200 and Caprolactone The copolymer was prepared according to the procedure described in Example 20 of US Pat. No. 8,268,957 B2. A mixture of 6.66 g of Epomin® SP-200 (polyethyleneimine, molecular weight 10,000), 100.0 g of ε-caprolactone, and 0.5 g of dibutyltin dilaurate was stirred under nitrogen and heated to 180° C. until the solids content of the mixture reached 98% to obtain Comparative Dispersant 1.

[0248] Comparative Dispersant 2: Copolymer of polyethyleneimine, 1,8-naphthalic anhydride, caprolactone, valerolactone, and 12-hydroxystearic acid The copolymer was prepared according to Example 4 of WO2017 / 140538A1. A mixture of 8 g of polyethyleneimine, 1.8 g of 1,8-naphthalic anhydride, 60 g of ε-caprolactone, 20 g of γ-valerolactone, and 10 g of 12-hydroxystearic acid was stirred at 100°C until a homogeneous mixture was obtained. The mixture was heated and stirred at 180°C under a nitrogen atmosphere for 12 hours. Comparative Dispersant 2 was obtained as a viscous liquid with an amine number of 33 mg KOH / g and an acid number of 9 mg KOH / g.

[0249] B) Performance test i) Preparation of test coating compositions To test the dispersing effect of the obtained samples, resin-free pigment concentrates (mill bases) were prepared, followed by the preparation of coating compositions.

[0250] Step 1: Preparation of the millbase or pigment concentrate A resin-free millbase (aqueous pigment concentrate) having a composition according to Formulation 1 was prepared.

[0251] [Table 3]

[0252] The milling process was carried out using glass beads in a Scandex Shaker for 4 hours to obtain a dispersion or mill base, which was filtered and stored at room temperature overnight.

[0253] The rheological behavior of the mill-bases was evaluated in CR mode with a Thermo-Haake RheoStress 600 instrument. The viscosities of the mill-bases were determined and the results are summarized in Table 2.

[0254] [Table 4]

[0255] From Table 2 it is clear that the millbases prepared using the dispersants of the present invention have low millbase viscosities. Conversely, the millbases prepared using the comparative dispersants have high viscosities.

[0256] Thus, the dispersants of the present invention provide lower viscosity millbase and coating compositions at the same pigment loading.

[0257] Step 2: Preparation of the coating composition The coating composition was prepared by dispersing 1.0 g of the millbase obtained in step 1 (Formulation 1) in 9.0 g of Hypomer® FS-2050 resin using a Dispermat® at 2,000 rpm for 2 minutes.

[0258] ii) Application examples The coating composition obtained in step 2 was applied to a polyester film with a thickness of 75 μm and dried in an oven for 30 minutes at 130° C. The surface coating was evaluated and the results are summarized in Table 3.

[0259] [Table 5]

[0260] From Table 3, it can be seen that the performance of the coating composition prepared using the dispersant of the present invention was significantly superior, showing satisfactory results such as a low crater ranking, compared to the coating compositions prepared using the dispersants of Comparative Examples 1 and 2.

Claims

1. a) 0.5 to 25% by weight of a polyalkyleneimine backbone relative to the total weight of the polymer; b) at least one aromatic moiety P.1 linked to a nitrogen atom of the polyalkyleneimine backbone via a carboxamide or carboximide group, in an amount of 0.5 to 25% by weight relative to the total weight of the polymer; c) at least one polyester moiety P.2 linked to a nitrogen atom of the polyalkyleneimine backbone via a carboxamide, in an amount of 1 to 50% by weight relative to the total weight of the polymer; and d) at least one aliphatic polyether moiety P.3 attached to a nitrogen atom of the polyalkyleneimine backbone via a direct bond or a linker, in an amount of 30 to 90% by weight, relative to the total weight of the polymer; and The at least one aromatic moiety P.1 has the formula (P.1') and (P.1'') 【Chemical 1】 (In the formula, # indicates the position at which the aromatic moiety P.1 is attached to the nitrogen atom of the polyalkyleneimine backbone, Ar is selected from the group consisting of phenyl and naphthyl, wherein phenyl and naphthyl are each independently unsubstituted or substituted with 1, 2, 3, 4, or 5 groups selected from the group consisting of halogen, OH, C1-C4-alkyl, C1-C4-alkoxy, C(=O)-OH, C(=O)-NH2, NH2, NO2, NH-C(=O)-H, NH-C1-C4-alkyl, and NH-C(=O)-C1-C4-alkyl; Ar' is selected from the group consisting of 1,2-phenylene, 1,2-, 2,3-, or 1,8-naphthylene, wherein phenylene and naphthylene are each independently unsubstituted or substituted with one, two, three, or four groups selected from the group consisting of halogen, OH, C1-C4-alkyl, C1-C4-alkoxy, C(=O)-OH, C(=O)-NH2, NH2, NO2, NH-C(=O)-H, NH-C1-C4-alkyl, and NH-C(=O)-C1-C4-alkyl. The polymer is selected from the group consisting of

2. 2. The polymer of claim 1, wherein the polyalkyleneimine backbone has a weight average molecular weight in the range of 100 g / mol to 20,000 g / mol, determined according to DIN 55672-1.

3. 3. The polymer according to claim 1, wherein the polyalkyleneimine backbone is a polyethyleneimine backbone.

4. The at least one aromatic moiety P.1 is represented by the formula (P.1a), (P.1b), (P.1c), (P.1d), and (P.1e): 【Chemistry 2】 (In the formula, # indicates the position where the aromatic moiety is bonded to the nitrogen atom of the polyalkyleneimine skeleton, R' is hydrogen, C 1 ~C 4 -Alkyl, -C(=O)-H and -C(=O)-C 1 ~C 4 -alkyl, k is 0, 1, 2, 3, or 4; R may be the same or different and may be halogen, OH, C 1 ~C 4 -Alkyl, C 1 ~C 4 -Alkoxy, C(=O)-OH, C(=O)-NH 2 , N.H. 2 , NO 2 , NH-C(=O)-H, NH-C 1 ~C 4 -Alkyl, and NH-C(=O)-C 1 ~C 4 -alkyl) 4. The polymer of claim 1, wherein the polymer is selected from the group consisting of the moieties

5. The polyester moiety P.2 has the formula (P.2a) 【Chemistry 3】 (In the formula, # indicates the position at which the group is bonded to a nitrogen atom of the polyalkyleneimine skeleton, T 1 is hydrogen or R 1 -C(=O)- and R 1 is C 1 ~C 24 is alkyl, A 1 and A 2 is C 2 ~C 12 alkylene; m is an integer from 0 to 100, n is an integer from 0 to 100, m+n is an integer between 2 and 100.

5. The polymer according to claim 1, wherein the R is a group

6. The at least one aliphatic polyether moiety P.3 comprises (P.3a) and (P.3b) 【Chemistry 4】 (In the formula, # indicates the position at which the group is bonded to a nitrogen atom of the polyalkyleneimine skeleton, L is a linker, R 2 and R 3 is hydrogen and C 1 ~C 2 -alkyl; p is an integer from 0 to 200, q is an integer from 0 to 200; p+q are integers between 2 and 200, T 2 is hydrogen, C 1 ~C 20 -Alkyl, C 2 ~C 20 -Alkenyl, C(=O)-C 2 ~C 20 -alkenyl or C(=O)-C 1 ~C 20 -alkyl, C 2 ~C 20 -alkenyl has 1, 2, 3 or 4 olefinic C=C double bonds, C 1 ~C 20 - 1, 2, 3, or 4 non-adjacent CH of alkyl 2 The group may be replaced by O.

6. The polymer according to claim 1, wherein the polymer is selected from

7. The linker L is (L.1), (L.2), (L.3) and (L.4) 【Chemistry 5】 (In the formula, # indicates the position at which the group is bonded to a nitrogen atom of the polyalkyleneimine skeleton, * indicates the position of attachment to the polyether moiety P.3, R 5 is H or CH 3 and Q is a direct bond or a divalent moiety selected from -O-, -N(H)-, and -S-; Y is O or NH; Z is C 1 ~C 24 Alkylene, C 4 ~C 10 Cycloalkylene, C 6 ~C 18 Arylene, and C 7 ~C 20 aryl alkylene; A 1 and A 2 is C 2 ~C 12 alkylene; m is an integer from 0 to 100, n is an integer from 0 to 100, m+n is an integer between 2 and 100.

7. The polymer of claim 6, wherein the polymer is at least one selected from the group consisting of:

8. 8. The polymer according to claim 1, wherein the polymer has an acid number in the range of 0 to 15 mg KOH / g, determined according to DIN 53402:1990-09.

9. 9. A method for preparing a polymer according to any one of claims 1 to 8, comprising the steps of: i. reacting a polyalkyleneimine with an aromatic carboxylic acid, an aromatic carboxylic acid anhydride, or an amide- or imide-forming derivative of an aromatic carboxylic acid in an amount that will theoretically consume up to 90% of the total amount of primary and secondary nitrogen atoms in the polyalkyleneimine; ii. reacting the product of step (i) with a hydroxycarboxylic acid, a lactone monomer, or a polyester moiety having a terminal carboxyl group obtainable from a lactone monomer; iii. reacting the product of step (ii) with an alkylene oxide or a polyether moiety having end groups selected from acrylate, isocyanato, and carboxylate; A method comprising:

10. 9. A method for preparing a polymer according to any one of claims 1 to 8, comprising the steps of: i. reacting a polyalkyleneimine with an aromatic carboxylic acid, an aromatic carboxylic acid anhydride, or an amide- or imide-forming derivative of an aromatic carboxylic acid in an amount that will theoretically consume up to 90% of the total amount of primary and secondary nitrogen atoms in the polyalkyleneimine; ii. The product of step (i) - a polyester moiety having a terminal carboxyl group that can be obtained from a hydroxycarboxylic acid, a lactone monomer, or a lactone monomer, and - alkylene oxide or polyether moieties having end groups selected from acrylate, isocyanato, and carboxylate; and reacting the compound with A method comprising:

11. 9. A method for preparing the polymer of any one of claims 1 to 8, comprising reacting a polyalkyleneimine with aromatic carboxylic acids, aromatic carboxylic acid anhydrides or amide- or imide-forming derivatives of aromatic carboxylic acids, - a polyester moiety having a terminal carboxyl group that can be obtained from a hydroxycarboxylic acid, a lactone monomer, or a lactone monomer, and - alkylene oxide or polyether moieties having end groups selected from acrylate, isocyanato, and carboxylate; The method of claim 1, wherein the compound is a methyl group.

12. 9. A method for preparing a polymer according to any one of claims 1 to 8, comprising the steps of: i. a polyalkyleneimine, aromatic carboxylic acids, aromatic carboxylic acid anhydrides or amide- or imide-forming derivatives of aromatic carboxylic acids, and - a polyester moiety having a terminal carboxyl group that can be obtained from a hydroxycarboxylic acid, a lactone monomer, or a lactone monomer; and reacting the ii. reacting the product of step (i) with an alkylene oxide or a polyether moiety having end groups selected from acrylate, isocyanato, and carboxylate; A method comprising:

13. 9. A liquid composition in the form of a dispersion comprising a particulate solid material selected from the group consisting of pigments and fillers, and a liquid diluent, said particulate solid material being dispersed in said liquid diluent further comprising a polymer according to any one of claims 1 to 8.

14. 9. Use of a polymer according to any one of claims 1 to 8 as a component of a coating or ink composition.

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