Alkoxylated polymeric n-(hydroxyalkyl)amines as wetting agents and as components of defoamer compositions

Abstract

The present invention relates to a polymer obtainable by condensing at least one N-(hydroxyalkyl)amine and reacting the condensation product with a glycidyl ether and to a process for preparing said polymer. The present invention further relates to the use of the polymer as wetting agent and as component of a defoamer composition. The present invention further relates to a coating composition comprising the polymer as wetting agent and to a defoamer composition comprising the polymer.

Description

Invention Field

[0001] This invention relates to a polymer obtained by condensing at least one N-(hydroxyalkyl)amine and reacting the condensation product with glycidyl ether, and a method for preparing said polymer. The invention further relates to the use of the polymer as a wetting agent and as a component of an antifoaming composition. The invention further relates to a coating composition comprising the polymer as a wetting agent and an antifoaming composition comprising the polymer. Background of the Invention

[0003] Polymers obtained by condensing N-(hydroxyalkyl)amines can be used in a wide variety of applications, such as additives for coating compositions, detergents for laundry, demulsifiers for oilfield emulsions, viscosity modifiers, wetting agents, thickeners, defoamers, and lubricants. These polymers can be used as tackifiers (primers), flow improvers, or thixotropic agents in the production of paints, coatings, adhesives, and sealants, and can also be used as components in defoamer compositions.

[0004] Polyalkanolamines obtained by condensation of N-(hydroxyalkyl)amines in the presence of acidic or basic catalysts or metal salts have been described in US 2407895A, EP 0441198B1 or US 5393463A.

[0005] The use of polyalkanolamines as demulsifiers for oilfield emulsions has been described in US 4731481A, US 4505839A, US4840748A, or US 4404362A. The use of polyalkanolamines as demulsifiers and defoamers has also been described in EP0441198B1 and US 5393463A.

[0006] Quaternized polydialkylolamines and their use as textile auxiliaries are described in EP 0057398A2 and EP 0160872A2.

[0007] Polycationic dye transfer inhibitors based on quaternized polytriethanolamine or polytriisopropanolamine have been described in EP0934382B1.

[0008] Compounds that can be used as demulsifiers, lubricants or papermaking additives, prepared by reacting polyalkanolamines with dichloroxylene or diglycidyl ether, have been described in DE 3206459A1 and DE 3136281A1.

[0009] Compounds prepared by reacting polyalkanolamines with urea or urethane derivatives and their use as demulsifiers are described in EP 0444515B1.

[0010] However, it is difficult to obtain N-(hydroxyalkyl)amine condensates with the desired properties suitable for a wide range of applications. In particular, it is difficult to obtain N-(hydroxyalkyl)amine condensates with high molecular weights. Furthermore, obtaining amphiphilic polymers is a challenge.

[0011] N-(hydroxyalkyl)amine condensation involving a loss of 0.5–1.5 mol water / mol N-(hydroxyalkyl)amine yields water-soluble, viscous condensates. However, these condensates have low molecular weights and degrees of condensation. When further N-(hydroxyalkyl)amine condensation is permitted, the reaction mixture passes through a highly viscous gel phase that is technically no longer controllable, and the resulting condensates are completely insoluble in water.

[0012] When the condensation products of N-(hydroxyalkyl)amines are used as wetting agents, the compositions tend to foam due to their surface activity. Foaming is accompanied by many disadvantages, especially on a larger scale. Therefore, it is desirable for the condensation products of N-(hydroxyalkyl)amines to have a low foaming tendency. Furthermore, it is desirable for the condensation products of N-(hydroxyalkyl)amines to be used as components in antifoaming compositions.

[0013] Therefore, the object of the present invention is to provide a polymer obtainable by the condensation of N-(hydroxyalkyl)amines, which possesses desired properties such as high molecular weight, particularly high molecular weight and amphiphilicity, thus making it suitable as a wetting agent in water-based coating systems. Furthermore, it is desirable that the polymer exhibit low foaming properties. Additionally, it is desirable that the polymer can be used as a component of defoamer compositions. Invention Overview

[0015] The polymers of the present invention have been found to possess desirable properties such as high molecular weight, high degree of condensation, and amphiphilicity, and are suitable for a wide variety of applications. Furthermore, these polymers exhibit low foaming properties.

[0016] Therefore, one aspect of the present invention relates to a polymer P that can be obtained as follows:

[0017] (a) Self-condensation of at least one N-(hydroxyalkyl)amine of formula (I):

[0018]

[0019] in

[0020] A1, A2, and A3 may be the same or different and are selected from unsubstituted linear or branched C1-C4 alkylene groups, R1, R 1* R2 and R 2* The same or different and selected from H, substituted or unsubstituted linear or branched C1-C4 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C6-C 18 Aryl and substituted or unsubstituted linear or branched C7-C18 Aryl groups,

[0021] R3 is selected from H, substituted or unsubstituted linear or branched C1-C4 alkyl groups, substituted or unsubstituted C3-C6 cycloalkyl groups, and substituted or unsubstituted C6-C4 alkyl groups. 18 Aryl, substituted or unsubstituted linear or branched C7-C 18 Arane and Among them, R4 and R 4* The same or different and selected from H, substituted or unsubstituted linear or branched C1-C4 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C6-C 18 Aryl and substituted or unsubstituted linear or branched C7-C 18 Aryl alkyl group and # indicate the connection point with A3, yielding intermediate (Q); or

[0022] At least one N-(hydroxyalkyl)amine of formula (I) is co-condensed with Z, wherein Z is at least one compound selected from Z1, Z2 and Z3.

[0023] in

[0024] Z1 is at least one diol of the formula HO-R8-OH, wherein R8 is selected from substituted or unsubstituted linear or branched C2-C diols. 18 Alkylene and substituted or unsubstituted C3-C6 cycloalkylene, wherein R8 is optionally substituted with at least one linear or branched C1-C3 alkyl group and R8 is optionally spaced by oxygen atoms, and

[0025] Z2 is selected from polyoxyethylene, polyoxypropylene, polytetramethylene ether glycol and their copolymers, and has a weight-average molecular weight (M). w The content of polyoxyethylene is 100-1500 g / mol.

[0026] Z3 is formula R 11 (OH) m polyols, where m is an integer selected from 3 to 6 and R 11 Is it a linear or branched C3-C with m-valence substitution or no substitution? 10 Alkyl, substituted or unsubstituted C4-C 10 Cycloalkyl and substituted or unsubstituted linear or branched C7-C 10 Aryl alkyl groups;

[0027] Obtain the intermediate (Q); and

[0028] (b) React the intermediate (Q) obtained in step (a) with at least one glycidyl ether of formula (II):

[0029]

[0030] in

[0031] R9 is a linear or branched C6-C that has been substituted or not substituted. 20 alkyl;

[0032] Wherein the ratio of the number of moles of hydroxyl groups in intermediate (Q) calculated based on its hydroxyl value in step (b) to the number of moles of glycidyl ethers of at least one formula (II) is in the range of 0.03:1 to 1:3; and

[0033] The amount of N-(hydroxyalkyl)amine of at least one formula (I) is in the range of 10-90% by weight and the amount of glycidyl ether of at least one formula (II) is in the range of 10-90% by weight, each based on the total weight of polymer P.

[0034] Another aspect of the present invention relates to a method for preparing polymer P.

[0035] Another aspect of the invention relates to the use of polymer P as a wetting agent.

[0036] Another aspect of the present invention relates to the use of polymer P as an antifoaming agent.

[0037] Another aspect of the present invention relates to the use of polymer P in coating compositions.

[0038] Another aspect of the invention relates to the use of polymer P in defoamer compositions.

[0039] Another aspect of the present invention is an antifoaming composition comprising polymer P as described above.

[0040] Another aspect of the present invention is a coating composition comprising polymer P as described above.

[0041] Another aspect of the invention relates to an article coated with a coating composition comprising polymer P.

[0042] The polymers of this invention possess high molecular weight, amphiphilicity, low critical aggregation concentration (CAC), enhanced wetting properties, and low foaming properties. Therefore, they can be used as wetting agents in water-based coating compositions. They can also be used as components in defoamer compositions.

[0043] Detailed description

[0044] 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.

[0045] 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 succession or temporal order. It should be understood that such terms are interchangeable where appropriate and embodiments of the invention described herein can operate in orders other than those described or shown herein. Where the terms 'first,' '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 stated above or below.

[0046] Furthermore, the ranges defined throughout this specification also include end values; that is, the range 1-10 indicates that both 1 and 10 are included within this range. For the avoidance of ambiguity, the applicant should be authorized for any equivalent under applicable law.

[0047] 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 expressly stated otherwise. Any feature shown as preferred or advantageous may in particular be combined with any one or more other features shown as preferred or advantageous.

[0048] Throughout this specification, references to "an embodiment" or "an embodiment" refer to specific features, structures, or characteristics described in connection with that embodiment, which are included in at least one embodiment of the invention. Therefore, the appearance of the phrase "in one embodiment" or "in an embodiment" in various places throughout this specification does not necessarily all refer to the same embodiment.

[0049] Furthermore, this particular feature, structure, or characteristic 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 other features, but not all, in other embodiments, combinations of features from different embodiments are intended to be within the scope of the invention and to 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.

[0050] It has been surprisingly discovered that the polymers of the present invention possess desirable properties such as high molecular weight, high degree of condensation, and amphiphilicity, which makes these polymers suitable for a wide variety of applications.

[0051] These polymers are amphiphilic and possess enhanced wetting properties; therefore, they can be used as wetting agents in water-based coating compositions. Coating compositions containing the polymers of this invention exhibit excellent adhesive or adhesion properties. Furthermore, these polymers have been found to be suitable as components of defoamer compositions.

[0052] The polymer of this invention is an alkoxylated polymer of N-(hydroxyalkyl)amine prepared by reacting an N-(hydroxyalkyl)amine condensation product with glycidyl ether. The N-(hydroxyalkyl)amine condensation product includes polymers obtained by the individual condensation of N-(hydroxyalkyl)amine and copolymers obtained by the condensation of N-(hydroxyalkyl)amine with other monomers. The glycidyl ether reacts at the hydroxyl groups present in the N-(hydroxyalkyl)amine condensation product.

[0053] The nucleophilic ring-opening of the epoxide proceeds by attacking the oxygen nucleophile present in the N-(hydroxyalkyl)amine condensation product, and the reaction provides a hydroxyl-containing product due to the opening of the epoxide. The hydroxyl-containing product thus obtained can then react further with another epoxide molecule. Therefore, this sequential reaction with the epoxide continues until the glycidyl ether is completely consumed.

[0054] The molecular weight of the polymers of this invention can be controlled by using an appropriate amount of glycidyl ether. Therefore, polymers with high molecular weights can be obtained by using a large amount of glycidyl ether. The properties of the polymers of this invention can be controlled by selecting a suitable glycidyl ether with appropriate hydrophilic or hydrophobic groups and by using an appropriate amount thereof.

[0055] Therefore, one aspect of the present invention relates to a polymer P that can be obtained as follows:

[0056] (a) Self-condensation of at least one N-(hydroxyalkyl)amine of formula (I):

[0057]

[0058] in

[0059] A1, A2, and A3 may be the same or different and are selected from unsubstituted linear or branched C1-C4 alkylene groups.

[0060] R1, R 1* R2 and R 2′* The same or different and selected from H, substituted or unsubstituted linear or branched C1-C4 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C6-C 18Aryl and substituted or unsubstituted linear or branched C7-C 18 Aryl groups,

[0061] R3 is selected from H, substituted or unsubstituted linear or branched C1-C4 alkyl groups, substituted or unsubstituted C3-C6 cycloalkyl groups, and substituted or unsubstituted C6-C4 alkyl groups. 18 Aryl, substituted or unsubstituted linear or branched C7-C 18 Araneyl and Among them, R4 and R 4* The same or different and selected from H, substituted or unsubstituted linear or branched C1-C4 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C6-C 18 Aryl and substituted or unsubstituted linear or branched C7-C 18 Aryl alkyl group and # indicate the connection point with A3, yielding intermediate (Q); or

[0062] At least one N-(hydroxyalkyl)amine of formula (I) is co-condensed with Z, wherein Z is at least one compound selected from Z1, Z2 and Z3.

[0063] in

[0064] Z1 is at least one diol of the formula HO-R8-OH, wherein R8 is selected from substituted or unsubstituted linear or branched C2-C diols. 18 Alkylenes and substituted or unsubstituted C3-C6 cycloalkylenes, and

[0065] R8 may be optionally substituted with at least one linear or branched C1-C3 alkyl group and R8 may be spaced by oxygen atoms.

[0066] Z2 is selected from polyoxyethylene, polyoxypropylene, polytetramethylene ether glycol and their copolymers, and has a weight-average molecular weight (M). w ) is 100-1500 g / mol of polyoxyethylene, and

[0067] Z3 is formula R 11 (OH) m polyols, where m is an integer selected from 3 to 6 and R 11 Is it a linear or branched C3-C with m-valence substitution or no substitution? 10 Alkyl, substituted or unsubstituted C4-C 10 Cycloalkyl and substituted or unsubstituted linear or branched C7-C 10 Aryl alkyl groups;

[0068] Obtain the intermediate (Q); and

[0069] (b) React the intermediate (Q) obtained in step (a) with at least one glycidyl ether of formula (II):

[0070]

[0071] in

[0072] R9 is a linear or branched C6-C that has been substituted or not substituted. 20 alkyl;

[0073] The ratio of the number of moles of hydroxyl groups in intermediate (Q) calculated based on its hydroxyl value in step (b) to the number of moles of glycidyl ether of at least one formula (II) is in the range of 0.03:1 to 1:3; and the amount of N-(hydroxyalkyl)amine of at least one formula (I) is in the range of 10-90% by weight and the amount of glycidyl ether of at least one formula (II) is in the range of 10-90% by weight, each based on the total weight of polymer P.

[0074] In the context of this invention, the term alkyl as used herein refers to acyclic saturated aliphatic hydrocarbon groups, including those derived from the general formula C1. n H 2n+1 The term represents a linear alkyl saturated hydrocarbon group, where n is the number of carbon atoms 1, 2, 3, 4, etc. Examples of preferred alkyl groups in this class are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, and eicosyl. The term substituted alkyl refers to an alkyl group in which some or all of the hydrogen atoms are replaced by a substituent, preferably selected from hydroxyl, halogen, cyano, C1-C4 alkyl, and C1-C4 alkoxy groups.

[0075] In the context of this invention, the term cycloalkyl as used herein refers to a saturated or partially unsaturated monocyclic or bicyclic hydrocarbon group. The preferred term cycloalkyl refers to a monocyclic hydrocarbon group (C3-C8 cycloalkyl, C3-C6 cycloalkyl) having 3-8, preferably 3-6, carbon atoms. Examples of such preferred cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. The term substituted cycloalkyl refers to a cycloalkyl group in which some or all of the hydrogen atoms are replaced by a substituent, preferably selected from hydroxyl, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy groups. Preferably, the cycloalkyl group is unsubstituted or contains 1, 2, or 3 C1-C4 alkyl groups.

[0076] In the context of this invention, the term aryl as used herein refers to phenyl or naphthyl, preferably phenyl. The term substituted aryl refers to an aryl group in which some or all of its hydrogen atoms are replaced by substituents, preferably selected from hydroxyl, halogen, cyano, C1-C4 alkyl, and C1-C4 alkoxy groups. Preferably, the aryl group is unsubstituted or has one, two, or three substituents.

[0077] In the context of this invention, the term alkylene as used herein refers to a saturated divalent linear or branched hydrocarbon group. Examples of this class of preferred alkylene groups include methylene, 1,2-ethylene, 1,3-propylene, 1,2-propylene, 2-methyl-1,2-propylene, 2,2-dimethyl-1,3-propylene, 1,4-butylene, 1,3-butylene (=1-methyl-1,3-propylene), 1,2-butylene, 2,3-butylene, 2-methyl-1,3-butylene, 3-methyl-1,3-butylene (=1,1-dimethyl-1,3-propylene), 1,4-pentylene, 1,5-pentylene, 2,5-pentylene, 2-methyl-2,5-pentylene (=1,1-dimethyl-1,3-butylene), and 1,6-hexylene.

[0078] In the context of this invention, the term glycidyl epoxide as used herein refers to ether compounds having a glycidyl group (3-propane-2,3-epoxy) and an alkyl or alkylaryl group. Examples of alkyl glycidyl ethers are hexyl glycidyl ether (=1-hexyloxy-2,3-epoxypropane), octyl glycidyl ether (=1-octyloxy-2,3-epoxypropane), and n-decyl glycidyl ether (=1-decyloxy-2,3-epoxypropane). Examples of alkylaryl glycidyl epoxides are benzyl glycidyl ether.

[0079] As used herein, the term "condensation" refers to a chemical reaction in which a small molecule, such as water, is formally lost while a covalent bond is formed between two corresponding functional groups. The preferred term condensation refers to etherification that occurs concurrently with a dehydration reaction.

[0080] The term 'self-condensation' as used herein refers to a condensation reaction carried out by a single monomer, namely an N-(hydroxyalkyl)amine of formula (I).

[0081] As used herein, the term 'co-condensation' refers to a condensation reaction involving two or more monomers, one of which is an N-(hydroxyalkyl)amine of formula (I) and the other is a compound such as a glycol, polyol, or polyethylene oxide.

[0082] In a preferred embodiment, polymer P can be obtained as follows:

[0083] (a) Self-condensation of at least one N-(hydroxyalkyl)amine of formula (I):

[0084]

[0085] in

[0086] A1, A2, and A3 may be the same or different and are selected from unsubstituted linear or branched C1-C4 alkylene groups, R1, R 1* R2 and R 2′*The same or different and selected from H, substituted or unsubstituted linear or branched C1-C4 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C6-C 18 Aryl and substituted or unsubstituted linear or branched C7-C 18 Aryl groups,

[0087] R3 is selected from H, substituted or unsubstituted linear or branched C1-C4 alkyl groups, substituted or unsubstituted C3-C6 cycloalkyl groups, and substituted or unsubstituted C6-C4 alkyl groups. 18 Aryl, substituted or unsubstituted linear or branched C7-C 18 Araneyl and Among them, R4 and R 4* The same or different and selected from H, substituted or unsubstituted linear or branched C1-C4 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C6-C 18 Aryl and substituted or unsubstituted linear or branched C7-C 18 Aryl alkyl group and # indicate the connection point with A3, yielding intermediate (Q); and

[0088] (b) React the intermediate (Q) obtained in step (a) with at least one glycidyl ether of formula (II):

[0089]

[0090] in

[0091] R9 is a linear or branched C6-C that has been substituted or not substituted. 20 alkyl;

[0092] The number of molar hydroxyl groups of the intermediate (Q) calculated based on its hydroxyl value in step (b) is related to the minimum

[0093] The molar ratio of glycidyl ether of formula (II) is in the range of 0.03:1 to 1:3; and the amount of N-(hydroxyalkyl)amine of at least one formula (I) is in the range of 10-90% by weight and the amount of glycidyl ether of at least one formula (II) is in the range of 10-90% by weight, each based on the total weight of polymer P.

[0094] In a preferred embodiment, polymer P can be obtained as follows:

[0095] (a) Co-condensing at least one N-(hydroxyalkyl)amine of formula (I) with Z1:

[0096]

[0097] in

[0098] A1, A2, and A3 may be the same or different and are selected from unsubstituted linear or branched C1-C4 alkylene groups, R1, R 1* R2 and R 2′* The same or different and selected from H, substituted or unsubstituted linear or branched C1-C4 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C6-C 18 Aryl and substituted or unsubstituted linear or branched C7-C 18 Aryl groups,

[0099] R3 is selected from H, substituted or unsubstituted linear or branched C1-C4 alkyl groups, substituted or unsubstituted C3-C6 cycloalkyl groups, and substituted or unsubstituted C6-C4 alkyl groups. 18 Aryl, substituted or unsubstituted linear or branched C7-C 18 Araneyl and Among them, R4 and R 4* The same or different and selected from H, substituted or unsubstituted linear or branched C1-C4 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C6-C 18 Aryl and substituted or unsubstituted linear or branched C7-C 18 Aryl group and # indicates the connection point with A3;

[0100] and

[0101] Z1 is at least one diol of the formula HO-R8-OH, wherein R8 is selected from substituted or unsubstituted linear or branched C2-C diols. 18 An alkylene group and a substituted or unsubstituted C3-C6 cycloalkylene group, wherein R8 is optionally substituted with at least one linear or branched C1-C3 alkyl group and R8 is optionally spaced by oxygen atoms, yields intermediate (Q); and

[0102] (b) React the intermediate (Q) obtained in step (a) with at least one glycidyl ether of formula (II):

[0103]

[0104] in

[0105] R9 is a linear or branched C6-C that has been substituted or not substituted. 20 alkyl;

[0106] The ratio of the number of moles of hydroxyl groups in intermediate (Q) calculated based on its hydroxyl value in step (b) to the number of moles of glycidyl ether of at least one formula (II) is in the range of 0.03:1 to 1:3; and the amount of N-(hydroxyalkyl)amine of at least one formula (I) is in the range of 10-90% by weight and the amount of glycidyl ether of at least one formula (II) is in the range of 10-90% by weight, each based on the total weight of polymer P.

[0107] In a preferred embodiment, the weight ratio of at least one N-(hydroxyalkyl)amine of formula (I) to the amount of Z1 is in the range of 4:1 to 10:1, more preferably 1:1 to 10:1.

[0108] In a preferred embodiment, polymer P can be obtained as follows:

[0109] (a) Co-condensing at least one N-(hydroxyalkyl)amine of formula (I) with Z2:

[0110]

[0111] in

[0112] A1, A2, and A3 may be the same or different and are selected from unsubstituted linear or branched C1-C4 alkylene groups, R1, R 1* R2 and R 2′* The same or different and selected from H, substituted or unsubstituted linear or branched C1-C4 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C6-C 18 Aryl and substituted or unsubstituted linear or branched C7-C 18 Aryl groups,

[0113] R3 is selected from H, substituted or unsubstituted linear or branched C1-C4 alkyl groups, substituted or unsubstituted C3-C6 cycloalkyl groups, and substituted or unsubstituted C6-C4 alkyl groups. 18 Aryl, substituted or unsubstituted linear or branched C7-C 18 Araneyl and Among them, R4 and R 4* The same or different and selected from H, substituted or unsubstituted linear or branched C1-C4 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C6-C 18 Aryl and substituted or unsubstituted linear or branched C7-C 18 Aryl group and # indicates the connection point with A3;

[0114] and

[0115] Z2 is selected from polyoxyethylene, polyoxypropylene, polytetramethylene ether glycol and their copolymers, and has a weight-average molecular weight (M). wThe content of polyoxyethylene is 100-1500 g / mol.

[0116] Obtain the intermediate (Q); and

[0117] (b) React the intermediate (Q) obtained in step (a) with at least one glycidyl ether of formula (II):

[0118]

[0119] in

[0120] R9 is a linear or branched C6-C that has been substituted or not substituted. 20 alkyl;

[0121] The number of molar hydroxyl groups of the intermediate (Q) calculated based on its hydroxyl value in step (b) is related to the minimum

[0122] The molar ratio of glycidyl ether of formula (II) is in the range of 0.03:1 to 1:3; and the amount of N-(hydroxyalkyl)amine of at least one formula (I) is in the range of 10-90% by weight and the amount of glycidyl ether of at least one formula (II) is in the range of 10-90% by weight, each based on the total weight of polymer P.

[0123] In a preferred embodiment, the weight ratio of at least one N-(hydroxyalkyl)amine of formula (I) to the amount of Z2 is in the range of 4:1 to 10:1, more preferably 1:1 to 10:1.

[0124] In a preferred embodiment, polymer P can be obtained as follows:

[0125] (a) Co-condensing at least one N-(hydroxyalkyl)amine of formula (I) with Z3:

[0126]

[0127] in

[0128] A1, A2, and A3 may be the same or different and are selected from unsubstituted linear or branched C1-C4 alkylene groups, R1, R 1* R2 and R 2′* The same or different and selected from H, substituted or unsubstituted linear or branched C1-C4 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C6-C 18 Aryl and substituted or unsubstituted linear or branched C7-C 18 Aryl groups,

[0129] R3 is selected from H, substituted or unsubstituted linear or branched C1-C4 alkyl groups, substituted or unsubstituted C3-C6 cycloalkyl groups, and substituted or unsubstituted C6-C4 alkyl groups.18 Aryl, substituted or unsubstituted linear or branched C7-C 18 Araneyl and Among them, R4 and R 4* The same or different and selected from H, substituted or unsubstituted linear or branched C1-C4 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C6-C 18 Aryl and substituted or unsubstituted linear or branched C7-C 18 Aryl group and # indicates the connection point with A3;

[0130] and

[0131] Z3 is formula R 11 (OH) m polyols, where m is an integer selected from 3 to 6 and R 11 Is it a linear or branched C3-C with m-valence substitution or no substitution? 10 Alkyl, substituted or unsubstituted C4-C 10 Cycloalkyl and substituted or unsubstituted linear or branched C7-C 10 Aryl alkyl groups;

[0132] Obtain the intermediate (Q); and

[0133] (b) React the intermediate (Q) obtained in step (a) with at least one glycidyl ether of formula (II):

[0134]

[0135] in

[0136] R9 is a linear or branched C6-C that has been substituted or not substituted. 20 alkyl;

[0137] Wherein the ratio of the number of moles of hydroxyl groups in intermediate (Q) calculated based on its hydroxyl value in step (b) to the number of moles of glycidyl ethers of at least one formula (II) is in the range of 0.03:1 to 1:3; and

[0138] The amount of N-(hydroxyalkyl)amine of at least one formula (I) is in the range of 10-90% by weight and the amount of glycidyl ether of at least one formula (II) is in the range of 10-90% by weight, each based on the total weight of polymer P.

[0139] In a preferred embodiment, the weight ratio of at least one N-(hydroxyalkyl)amine of formula (I) to the amount of Z3 is in the range of 4:1 to 10:1, more preferably 1:1 to 10:1.

[0140] In a preferred embodiment, intermediate (Q) can be obtained by co-condensing at least one N-(hydroxyalkyl)amine of formula (I) with Z, wherein Z is a mixture of two or more compounds selected from Z1, Z2 and Z3, and wherein the at least one N-(hydroxyalkyl)amine of formula (I), Z, Z1, Z2 and Z3 are as defined above.

[0141] In a preferred embodiment, the weight ratio of at least one N-(hydroxyalkyl)amine of formula (I) to the amount of Z is in the range of 4:1 to 10:1, more preferably 1:1 to 10:1.

[0142] In a more preferred embodiment, intermediate (Q) can be obtained by co-condensing at least one N-(hydroxyalkyl)amine of formula (I) with Z, wherein Z is a mixture of Z1 and Z2. Z comprises 5-95% by weight of Z1 and 5-95% by weight of Z2, each based on the total weight of Z.

[0143] 1) Condensation product—intermediate Q

[0144] The condensation product—intermediate Q—is obtained by condensing at least one N-(hydroxyalkyl)amine of formula (I).

[0145] In a preferred embodiment, the at least one N-(hydroxyalkyl)amine of formula (I) includes the N-(hydroxyalkyl)amine of formula (Ia):

[0146]

[0147] In a preferred embodiment, the at least one N-(hydroxyalkyl)amine of formula (I) is a mixture comprising N-(hydroxyalkyl)amines of formula (Ia) and / or (Ib).

[0148]

[0149] in

[0150] A5, A6, and A7 may be the same or different and are selected from unsubstituted C1-C4 alkylene groups.

[0151] R5, R 5* R6 and R 6* The same or different and selected from H, substituted or unsubstituted linear or branched C1-C4 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C6-C 18 Aryl and substituted or unsubstituted linear or branched C7-C 18 Aryl groups,

[0152] R7 is selected from hydrogen, substituted or unsubstituted C1-C4 alkyl groups, substituted or unsubstituted C3-C6 cycloalkyl groups, and substituted or unsubstituted C6-C4 cycloalkyl groups.18 Aryl and substituted or unsubstituted linear or branched C7-C 18 Aryl alkyl groups, wherein the amount of N-(hydroxyalkyl)amine of formula (Ia) is in the range of 70-100% by weight and the amount of N-(hydroxyalkyl)amine of formula (Ib) is in the range of 0-30% by weight, each based on the total weight of N-(hydroxyalkyl)amine of formula (I).

[0153] In a preferred embodiment, the N-(hydroxyalkyl)amine of formula (I) is a mixture comprising N-(hydroxyalkyl)amines of formula (Ia) and (Ib), wherein the amount of N-(hydroxyalkyl)amine of formula (Ia) is in the range of 30-99% by weight and the amount of N-(hydroxyalkyl)amine of formula (Ib) is in the range of 1-70% by weight, each based on the total weight of N-(hydroxyalkyl)amine of formula (I).

[0154] In a more preferred embodiment, the N-(hydroxyalkyl)amine of formula (I) is a mixture comprising N-(hydroxyalkyl)amines of formula (Ia) and (Ib), wherein the amount of N-(hydroxyalkyl)amine of formula (Ia) is in the range of 70-95% by weight and the amount of N-(hydroxyalkyl)amine of formula (Ib) is in the range of 5-30% by weight, each based on the total weight of N-(hydroxyalkyl)amine of formula (I).

[0155] In a preferred embodiment, A1, A2, and A3 may be the same or different and are selected from methylene, ethylene, n-propylene, n-butylene, isopropylene, 1-methylpropylene, and 2-methylpropylene.

[0156] In a preferred embodiment, A1, A2, and A3 are substituted alkyl groups, wherein one, two, or three hydrogens are replaced by substituents selected from hydroxyl, halogen, cyano-C1-C4 alkyl, and C1-C4 alkoxy groups.

[0157] In a more preferred embodiment, A1, A2, and A3 are identical and selected from methylene, ethylene, n-propylene, and isopropylene.

[0158] In the most preferred embodiment, A1, A2, and A3 are methylene groups.

[0159] In the preferred embodiment, R1, R 1* R2 and R 2* The same or different and selected from hydrogen, methyl, ethyl, propyl, butyl, isopropyl, 1-methylpropyl, 2-methylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, benzyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, 1-methyl-2-phenylethyl, 1-methyl-3-phenylpropyl, 2-methyl-3-phenylpropyl and methylnaphthyl.

[0160] In a more preferred embodiment, R1, R 1* R2 and R2* Same or different and selected from H and methyl.

[0161] In the optimal implementation scheme, R1, R 1* R2 and R 2* It's H.

[0162] In the most preferred embodiment, R1 and R2 are methyl groups and R 1* and R 2* It is hydrogen.

[0163] In a preferred embodiment, R3 is selected from hydrogen, methyl, ethyl, propyl, butyl, isopropyl, 1-methylpropyl, 2-methylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, benzyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, 1-methyl-2-phenylethyl, 1-methyl-3-phenylpropyl, 2-methyl-3-phenylpropyl, and methylnaphthyl.

[0164] In a more preferred embodiment, R3 is Among them, R4 and R 4* Same or different and selected from H and methyl.

[0165] In the most preferred embodiment, R4 and R 4* It is H, and therefore R3 is -CH2OH.

[0166] In the most preferred embodiment, R4 is H and R 4* It is a methyl group, and therefore R3 is -CH(CH3)OH.

[0167] In the preferred embodiment, R5, R 5* R6 and R 6* The same or different and selected from hydrogen, methyl, ethyl, propyl, butyl, isopropyl, 1-methylpropyl, 2-methylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, benzyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, 1-methyl-2-phenylethyl, 1-methyl-3-phenylpropyl, 2-methyl-3-phenylpropyl and methylnaphthyl.

[0168] In a more preferred embodiment, R5, R 5* R6 and R 6* Same or different and selected from hydrogen and methyl.

[0169] The condensation product—intermediate Q—can also be obtained by co-condensing at least one N-(hydroxyalkyl)amine of formula (I) with Z, wherein Z is at least one compound selected from Z1, Z2 and Z3.

[0170] Z1 is at least one diol of the formula HO-R8-OH, wherein R8 is as defined above.

[0171] In a preferred embodiment, R8 is selected from at least one of the following: ethylidene, propyleneide, butylidene, pentylene, hexylidene, heptylidene, octylidene, nonylidene, decylidene, undecylidene, dodecylidene, tridecylidene, tetradecylidene, pentadecylidene, hexadecylidene, heptadecanylidene, octadecylidene, 1-ethylpropyleneidene, 2-methylbutylidene, 1-methylpentylidene, 2-methylpentylidene, 3-methylpentylidene, 1-ethylbutylidene, 2-ethylbutylidene, 1-ethylpentylidene, 2-ethylpentylidene, 3-ethylpentylidene 1-Ethylhexene, 2-Ethylhexene, 3-Ethylhexene, 4-Ethylhexene, 1-Ethylheptene, 2-Ethylheptene, 3-Ethylheptene, 4-Ethylheptene, 5-Ethylheptene, 1-Ethyloctylene, 2-Ethyloctylene, 3-Ethyloctylene, 4-Ethyloctylene, 5-Ethyloctylene, 6-Ethyloctylene, 2,2-Dimethylpropylidene, 1-Propylbutylene, 1-Propylpentane, 2-Propylpentane, 1,4-Dihydroxycyclohexane, and -CH2CH2-(OCH2CH2-) n -CH2CH2-, wherein n is in the range of 3-10; more preferably selected from ethylidene, propyleneide, butylidene, pentylidene, hexylidene, heptylidene, octylidene, nonylidene, decylidene, undecylidene, dodecylidene, 2,2-dimethylpropyleneide, 2-ethylhexylidene, 1,4-dihydroxycyclohexane and -CH2CH2-(OCH2CH2-). n -CH2CH2-, wherein n is in the range of 3-10; even more preferably selected from ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, 2,2-dimethylpropylene, 2-ethylhexylene, 1,4-dihydroxycyclohexane and -CH2CH2-(OCH2CH2-). n -CH2CH2-, where n is in the range of 3-10.

[0172] In the most preferred embodiment, R8 is hexanediol.

[0173] In a preferred embodiment, the at least one N-(hydroxyalkyl)amine of formula (I) is co-condensed with Z2.

[0174] In the preferred embodiment, Z2 is the weight-average molecular weight (M). w The content of ethylene oxide is 100-500 g / mol.

[0175] In a preferred embodiment, Z2 is polyoxyethylene with a weight-average molecular weight of 200 g / mol.

[0176] In the preferred embodiment, Z2 is the weight-average molecular weight (M). w The content of polyoxypropylene is 100-500 g / mol.

[0177] In the preferred embodiment, Z2 is the weight-average molecular weight (M). w The polytetramethylene ether diol has a concentration of 200-1500, more preferably 200-1200 g / mol.

[0178] Polytetramethylene ether glycol is OHCH2CH2CH2CH2-(OCH2CH2CH2CH2-). n -CH2CH2CH2CH2OH, where n is in the range of 3-16.

[0179] In a preferred embodiment, Z2 is a polyoxyethylene copolymer comprising two or more polymers selected from polyethylene oxide, polypropylene oxide, and polytetramethylene ether glycol. The copolymer may be a random copolymer, a gradient copolymer, or a block copolymer.

[0180] In a preferred embodiment, the at least one N-(hydroxyalkyl)amine of formula (I) is co-condensed with Z3.

[0181] In the preferred embodiment, Z3 is of formula R 11 (OH) m polyols, where m is an integer selected from 3 to 6 and R 11 Is it a linear or branched C3-C with m-valence substitution or no substitution? 10 alkyl.

[0182] In a preferred embodiment, Z3 is at least one polyol selected from glycerol, tris(hydroxymethyl)ethane, tris(hydroxymethyl)propane, 1,2,3-butanetriol, 1,3,5-hexanetriol, pentaerythritol, 2,3,4,5-hexanetriol, 1,2,3,4-butanetriol, 6-methyl-1,2,3,4,5-heptanepentol, 1,1,2,3,4,5-pentanehexatonol, sorbitol (1,2,3,4,5,6-hexanehexatonol), tris(2-hydroxyethyl) isocyanurate, tris(2-hydroxypropyl) isocyanurate, tris(2-hydroxybutyl) isocyanurate, and tris(hydroxymethyl) isocyanurate.

[0183] In a preferred embodiment, intermediate (Q) can be obtained by co-condensing at least one N-(hydroxyalkyl)amine of formula (I) with Z, wherein Z is a mixture of two or more compounds selected from Z1, Z2 and Z3, and wherein the at least one N-(hydroxyalkyl)amine of formula (I), Z, Z1, Z2 and Z3 are as defined above.

[0184] In a preferred embodiment, the weight ratio of at least one N-(hydroxyalkyl)amine of formula (I) to the amount of Z is in the range of 4:1 to 10:1, more preferably 1:1 to 10:1.

[0185] In a more preferred embodiment, intermediate (Q) can be obtained by co-condensing at least one N-(hydroxyalkyl)amine of formula (I) with Z, wherein Z is a mixture of Z1 and Z2. Z comprises 5-95% by weight of Z1 and 5-95% by weight of Z2, each based on the total weight of Z.

[0186] 2) Glycidyl ether

[0187] The choice of glycidyl ether is important for the polymers disclosed herein. This is achieved by combining it with linear or branched C6-C polymers having R9 as either substituted or unsubstituted. 20 The polymer obtained by reacting alkyl glycidyl ethers of formula (II) provides the desired properties to this polymer:

[0188]

[0189] Polymers obtained by reacting with glycidyl ethers containing R9 as a lower alkyl group provide polymers with higher water solubility, making them unsuitable as wetting agents and defoamers. Similarly, polymers obtained by reacting with glycidyl ethers containing R9 as a lower alkyl group provide polymers with higher water solubility, making them unsuitable as wetting agents and defoamers. 20 Polymers obtained by reacting glycidyl ethers with alkyl chains exhibit high hydrophobicity but lack the desired amphiphilicity, making them unsuitable for the intended purpose. Therefore, selecting glycidyl ethers with optimal alkyl chains is crucial for obtaining polymers with suitable activity as wetting and defoaming agents.

[0190] In the preferred embodiment, R9 is selected from aliyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, eicosyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-methylheptyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 1-methyloctyl, 2-methyloctyl, 3-methyloctyl, 4-methyloctyl, 5-methyloctyl, 6-methyloctyl, 7-methyloctyl, 1-methylnonyl, 2-methylnonyl, 3-methylnonyl, 4-methylnonyl, 5-methylnonyl, 6-methylnonyl, 7-methylnonyl, 8-methylnonyl 1-Ethylbutyl, 2-Ethylbutyl, 1-Ethylpentyl, 2-Ethylpentyl, 3-Ethylpentyl, 1-Ethylhexyl, 2-Ethylhexyl, 3-Ethylhexyl, 4-Ethylhexyl, 1-Ethylheptyl, 2-Ethylheptyl, 3-Ethylheptyl, 4-Ethylheptyl, 5-Ethylheptyl, 1-Ethyloctyl, 2-Ethyloctyl, 3-Ethyloctyl, 4-Ethyloctyl, 5-Ethyloctyl, 6-Ethyloctyl, 1-Propyl 1-Propyl-butyl, 1-Propyl-pentyl, 2-Propyl-pentyl, 1-Propyl-hexyl, 2-Propyl-hexyl, 3-Propyl-hexyl, 1-Propyl-heptyl, 2-Propyl-heptyl, 3-Propyl-heptyl, 4-Propyl-heptyl, 1-Propyl-octyl, 2-Propyl-octyl, 3-Propyl-octyl, 4-Propyl-octyl, 5-Propyl-octyl, 1-Propyl-nonyl, 2-Propyl-nonyl, 3-Propyl-nonyl, 4-Propyl-nonyl, 5-Propyl-nonyl and 6-Propyl-nonyl.

[0191] In a preferred embodiment, R9 is at least one selected from the group consisting of oxyalkyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, and octadecyl.

[0192] In a more preferred embodiment, R9 is at least one selected from octyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, and hexadecyl.

[0193] In a more preferred embodiment, polymer P can be obtained by reacting the intermediate (Q) obtained in step (a) with a mixture containing two or more glycidyl ethers of formula (II).

[0194] In a more preferred embodiment, polymer P can be obtained by reacting the intermediate (Q) obtained in step (a) with a mixture comprising dodecyl glycidyl ether and tetradecyl glycidyl ether.

[0195] In a more preferred embodiment, polymer P can be obtained by reacting the intermediate (Q) obtained in step (a) with a mixture comprising dodecyl glycidyl ether, tetradecyl glycidyl ether and 2-ethylhexyl glycidyl ether.

[0196] Commercially available mixtures of glycidyl ethers can also be used in the reaction with Q. The commercially available mixture contains 2-5 glycidyl ethers in an amount of at least 5% by weight. The dominant glycidyl ether may be present in an amount of at least 50% by weight. The sum of the amounts of the two dominant glycidyl ethers may be at least 75% by weight of the mixture.

[0197] In a preferred embodiment, polymer P can be produced by reacting the intermediate (Q) obtained in step (a) with at least one glycidyl ether of formula (II):

[0198]

[0199] It is obtained by reacting with at least one diglycidyl ether of formula (IIa):

[0200]

[0201] Where R 10 Is it a substituted or unsubstituted linear or branched C3-C? 20 Alkylene, substituted or unsubstituted C3-C6 cycloalkylene and substituted or unsubstituted C6-C 18 Aryl; and

[0202] The amount of diglycidyl ether of at least one formula (IIa) is in the range of 1-20% by weight relative to the amount of glycidyl ether of formula (II).

[0203] In the preferred embodiment, R 10 It is selected from at least one of propylene, butylene, pentylene, hexylene, octylene, decylene, 2,2-dimethylpropylene, 1,4-dicyclohexylene, 1,4-cyclohexanedimethyl, polyethylene glycol, polypropylene glycol and p,p-isopropylidene diphenyl.

[0204] In a preferred embodiment, the amount of the at least one diglycidyl ether of formula (IIa) is in the range of 1-20% by weight relative to the amount of glycidyl ether of formula (II).

[0205] In a preferred embodiment, the ratio of the number of moles of hydroxyl groups of the intermediate (Q) calculated based on its hydroxyl value in step (b) to the number of moles of glycidyl ether of at least one formula (II) is in the range of 0.03:1 to 1:3, more preferably 0.1 to 1:2.5, most preferably 0.2 to 2.0, and even more preferably 0.5 to 1.5.

[0206] In a preferred embodiment, polymer P can be obtained as follows:

[0207] (a) Self-condensing at least one N-(hydroxyalkyl)amine of formula (I):

[0208]

[0209] in

[0210] R1, R 1* R2 and R 2′* Selected from H and methyl,

[0211] R3 is selected from H, methyl, and Among them, R4 and R 4* The same or different and selected from H and methyl; and

[0212] A1, A2, and A3 are identical and selected from methylene, ethylene, n-propylene, and isopropylene, yielding intermediate Q; and

[0213] (b) React the intermediate Q obtained in step (a) with at least one glycidyl ether of formula (II):

[0214]

[0215] in

[0216] R9 can be selected from alkyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, and octadecyl.

[0217] In a preferred embodiment, the at least one N-(hydroxyalkyl)amine of formula (I) is triethanolamine.

[0218] In a preferred embodiment, the at least one N-(hydroxyalkyl)amine of formula (I) is triisopropanolamine.

[0219] In a preferred embodiment, polymer P can be obtained as follows:

[0220] (a) Triethanolamine is subjected to self-condensation to obtain an intermediate Q with a degree of polymerization in the range of 3-300, calculated based on its hydroxyl value or the amount of water collected during the condensation process.

[0221] (b) Intermediate Q is reacted with a mixture of glycidyl ethers containing formulas (IIp) and (IIq) to give polymer P:

[0222]

[0223] In a preferred embodiment, polymer P can be obtained as follows:

[0224] (a) Co-condensing triethanolamine and 1,6-hexanediol to obtain intermediate Q with a degree of polymerization in the range of 3-300, calculated based on its hydroxyl value or the amount of water collected during the condensation, wherein the molar ratio of triethanolamine to 1,6-hexanediol is 2:1; and

[0225] (b) Intermediate Q is reacted with a mixture of glycidyl ethers containing formulas (IIp) and (IIq) to give polymer P:

[0226]

[0227] In a preferred embodiment, polymer P can be obtained as follows:

[0228] (a) Triethanolamine and polyethylene glycol (Mw = 200) are co-condensed to obtain an intermediate Q with a degree of polymerization in the range of 3-300, calculated based on its hydroxyl value or the amount of water collected during the condensation, wherein the triethanolamine and polyethylene glycol (Mw = 200) are co-condensed. w The molar ratio of (=200) is 7:3; and

[0229] (b) Intermediate Q is reacted with a mixture of glycidyl ethers containing formulas (IIp) and (IIq) to give polymer P:

[0230]

[0231] In a preferred embodiment, polymer P can be obtained as follows:

[0232] (a) Triethanolamine is subjected to self-condensation to obtain an intermediate Q with a degree of polymerization in the range of 3-300, calculated based on its hydroxyl value or the amount of water collected during the condensation process.

[0233] (b) Reaction of intermediate Q of formula (III) with a mixture of glycidyl ethers containing formulas (IIp), (IIq) and (IIr) yields polymer P:

[0234]

[0235] In a preferred embodiment, the dynamic surface tension of polymer P in a solution of butyl glycol and water (1:19) at a concentration of 0.5% by weight and at 100 ms was measured using a bubble tensiometer and was in the range of 25-35 mN / m.

[0236] Another aspect of the present invention relates to a method for preparing the polymer P of the present invention, the method comprising at least the following steps:

[0237] (i) subjecting at least one N-(hydroxyalkyl)amine of formula (I) to self-condensation at a temperature in the range of 180-220°C to obtain intermediate (Q), or

[0238] At least one N-(hydroxyalkyl)amine (I) is co-condensed with Z at a temperature in the range of 180-220°C, wherein Z is at least one compound selected from Z1, Z2 and Z3, to obtain intermediate (Q);

[0239] (ii) The at least one glycidyl ether (II) is added to intermediate (Q) at a temperature in the range of 100-160°C; and

[0240] (iii) The reaction mixture obtained in step (ii) is heated at a temperature in the range of 130-190°C to obtain the polymer.

[0241] Z, Z1, Z2, and Z3 are defined as above.

[0242] The weight ratio of the total amount of the at least one N-(hydroxyalkyl)amine of formula (I) used in step (i) to the total amount of the at least one glycidyl ether of formula (II) used in step (ii) is in the range of 1:10 to 10:1.

[0243] In a preferred embodiment, the method for preparing polymer P includes at least the following steps:

[0244] (i) The N-(hydroxyalkyl)amine of at least one formula (I) is subjected to self-condensation at a temperature in the range of 180-220°C to obtain intermediate (Q);

[0245] (ii) The at least one glycidyl ether (II) is added to intermediate (Q) at a temperature in the range of 100-160°C; and

[0246] (iii) The reaction mixture obtained in step (ii) is heated at a temperature in the range of 130-190°C to obtain the polymer;

[0247] The weight ratio of the total amount of the at least one N-(hydroxyalkyl)amine of formula (I) used in step (i) to the total amount of the at least one glycidyl ether of formula (II) used in step (ii) is in the range of 1:10 to 10:1.

[0248] In a preferred embodiment, the method for preparing polymer P includes at least the following steps:

[0249] (i) Co-condensing at least one N-(hydroxyalkyl)amine (I) with Z1 at a temperature in the range of 180-220°C to obtain intermediate (Q);

[0250] (ii) The at least one glycidyl ether (II) is added to intermediate (Q) at a temperature in the range of 100-160°C; and

[0251] (iii) The reaction mixture obtained in step (ii) is heated at a temperature in the range of 130-190°C to obtain the polymer;

[0252] Z1 is defined above.

[0253] The weight ratio of the total amount of the at least one N-(hydroxyalkyl)amine of formula (I) used in step (i) to the total amount of the at least one glycidyl ether of formula (II) used in step (ii) is in the range of 1:10 to 10:1.

[0254] In a preferred embodiment, the method for preparing polymer P includes at least the following steps:

[0255] (i) Co-condensing at least one N-(hydroxyalkyl)amine (I) with Z2 at a temperature in the range of 180-220°C to obtain intermediate (Q);

[0256] (ii) The at least one glycidyl ether (II) is added to intermediate (Q) at a temperature in the range of 100-160°C; and

[0257] (iii) The reaction mixture obtained in step (ii) is heated at a temperature in the range of 130-190°C to obtain the polymer;

[0258] Z2 is defined above.

[0259] The weight ratio of the total amount of the at least one N-(hydroxyalkyl)amine of formula (I) used in step (i) to the total amount of the at least one glycidyl ether of formula (II) used in step (ii) is in the range of 1:10 to 10:1.

[0260] In a preferred embodiment, the method for preparing polymer P includes at least the following steps:

[0261] (i) Co-condensing at least one N-(hydroxyalkyl)amine (I) with Z3 at a temperature in the range of 180-220°C to obtain intermediate (Q);

[0262] (ii) The at least one glycidyl ether (II) is added to intermediate (Q) at a temperature in the range of 100-160°C; and

[0263] (iii) The reaction mixture obtained in step (ii) is heated at a temperature in the range of 130-190°C to obtain the polymer;

[0264] Z3 is defined above.

[0265] The weight ratio of the total amount of the at least one N-(hydroxyalkyl)amine of formula (I) used in step (i) to the total amount of the at least one glycidyl ether of formula (II) used in step (ii) is in the range of 1:10 to 10:1.

[0266] In a preferred embodiment, the method for preparing polymer P includes at least the following steps:

[0267] (i) Co-condensing at least one N-(hydroxyalkyl)amine (I) with Z at a temperature in the range of 180-220°C, wherein Z is a mixture comprising two or more compounds selected from Z1, Z2 and Z3, to obtain intermediate (Q);

[0268] (ii) The at least one glycidyl ether (II) is added to intermediate (Q) at a temperature in the range of 100-160°C; and

[0269] (iii) The reaction mixture obtained in step (ii) is heated at a temperature in the range of 130-190°C to obtain the polymer;

[0270] Z, Z1, Z2, and Z3 are defined as above.

[0271] The weight ratio of the total amount of the at least one N-(hydroxyalkyl)amine of formula (I) used in step (i) to the total amount of the at least one glycidyl ether of formula (II) used in step (ii) is in the range of 1:10 to 10:1.

[0272] In a preferred embodiment, the method for preparing polymer P includes at least the following steps:

[0273] (i) Co-condensing at least one N-(hydroxyalkyl)amine (I) with Z at a temperature in the range of 180-220°C, wherein Z is a mixture comprising Z1 and Z2, to obtain intermediate (Q), wherein the amount of Z1 is in the range of 10-90% by weight and the amount of Z2 is in the range of 10-90% by weight, both based on the total weight of the mixture.

[0274] (ii) The at least one glycidyl ether (II) is added to intermediate (Q) at a temperature in the range of 100-160°C; and

[0275] (iii) The reaction mixture obtained in step (ii) is heated at a temperature in the range of 130-190°C to obtain the polymer;

[0276] Z, Z1, and Z2 are defined as above.

[0277] The weight ratio of the total amount of the at least one N-(hydroxyalkyl)amine of formula (I) used in step (i) to the total amount of the at least one glycidyl ether of formula (II) used in step (ii) is in the range of 1:10 to 10:1.

[0278] In a more preferred embodiment, the method for preparing polymer P includes at least the following steps:

[0279] (i) Co-condensing at least one N-(hydroxyalkyl)amine (I) with Z at a temperature in the range of 180-220°C, wherein Z is a mixture comprising Z1 and Z3, to obtain intermediate (Q), wherein the amount of Z1 is in the range of 10-90% by weight and the amount of Z3 is in the range of 10-90% by weight, both based on the total weight of the mixture.

[0280] (ii) The at least one glycidyl ether (II) is added to intermediate (Q) at a temperature in the range of 100-160°C; and

[0281] (iii) The reaction mixture obtained in step (ii) is heated at a temperature in the range of 130-190°C to obtain the polymer;

[0282] Z, Z1, and Z3 are defined as above.

[0283] The weight ratio of the total amount of the at least one N-(hydroxyalkyl)amine of formula (I) used in step (i) to the total amount of the at least one glycidyl ether of formula (II) used in step (ii) is in the range of 1:10 to 10:1.

[0284] In a more preferred embodiment, the method for preparing polymer P includes at least the following steps:

[0285] (i) Co-condensing at least one N-(hydroxyalkyl)amine (I) with Z at a temperature in the range of 180-220°C, wherein Z is a mixture comprising Z2 and Z3, to obtain intermediate (Q), wherein the amount of Z2 is in the range of 10-90% by weight and the amount of Z3 is in the range of 10-90% by weight, both based on the total weight of the mixture.

[0286] (ii) The at least one glycidyl ether (II) is added to intermediate (Q) at a temperature in the range of 100-160°C; and

[0287] (iii) The reaction mixture obtained in step (ii) is heated at a temperature in the range of 130-190°C to obtain the polymer;

[0288] Z, Z2, and Z3 are defined as above.

[0289] The weight ratio of the total amount of the at least one N-(hydroxyalkyl)amine of formula (I) used in step (i) to the total amount of the at least one glycidyl ether of formula (II) used in step (ii) is in the range of 1:10 to 10:1.

[0290] In a more preferred embodiment, the method for preparing polymer P includes at least the following steps:

[0291] (i) Co-condensing at least one N-(hydroxyalkyl)amine (I) with Z at a temperature in the range of 180-220°C, wherein Z is a mixture comprising Z1, Z2 and Z3, to obtain intermediate (Q), wherein the amount of Z1 is in the range of 10-50% by weight, the amount of Z2 is in the range of 10-50% by weight and the amount of Z3 is in the range of 10-50% by weight, all amounts based on the total weight of the mixture;

[0292] (ii) The at least one glycidyl ether (II) is added to intermediate (Q) at a temperature in the range of 100-160°C; and

[0293] (iii) The reaction mixture obtained in step (ii) is heated at a temperature in the range of 130-190°C to obtain the polymer;

[0294] Z, Z1, Z2, and Z3 are defined as above.

[0295] The weight ratio of the total amount of the at least one N-(hydroxyalkyl)amine of formula (I) used in step (i) to the total amount of the at least one glycidyl ether of formula (II) used in step (ii) is in the range of 1:10 to 10:1.

[0296] Condensation reaction

[0297] Step (i) involves a condensation reaction. The term "condensation" as used herein refers to a reaction in which two functional groups eliminate a small molecule, particularly underwater, by forming a covalent bond. The molecules of at least one N-(hydroxyalkyl)amine (I) can condense with each other via hydroxyl groups, resulting in the formation of ether bonds. Each N-tris(hydroxyalkyl)amine molecule (I) can form three ether bonds, and similarly, each N-di(hydroxyalkyl)amine molecule (I) can form two ether bonds. Furthermore, the two hydroxyalkyl chains attached to the nitrogen atom can condense intramolecularly with each other to form a morpholine structural moiety.

[0298] The molecule of at least one N-(hydroxyalkyl)amine (I) can condense with diol Z via a hydroxyl group, resulting in the formation of an ether bond. Similarly, the molecule of at least one N-(hydroxyalkyl)amine (I) can add to diols, polyoxyethylenes, and polyols, resulting in the formation of an ether bond.

[0299] The water formed during the condensation process is usually removed from the reaction using techniques familiar to skilled technicians, such as evaporating the water from the reaction, preferably by evaporating the water from the reaction under reduced pressure.

[0300] In a preferred embodiment, the self-condensation is carried out at a temperature in the range of 160-240°C, preferably 180-220°C. In a preferred embodiment, the self-condensation is carried out over a period of 1-24 hours, preferably 4-12 hours.

[0301] In a preferred embodiment, co-condensation is carried out at a temperature in the range of 160-240°C, preferably 180-220°C. In a preferred embodiment, co-condensation is carried out over a period of 1-24 hours, preferably 4-12 hours.

[0302] In a preferred embodiment, the weight ratio of at least one N-(hydroxyalkyl)amine of formula (I) to the amount of Z1 is in the range of 4:1 to 10:1, more preferably 1:1 to 10:1.

[0303] In a preferred embodiment, the weight ratio of at least one N-(hydroxyalkyl)amine of formula (I) to the amount of Z2 is in the range of 4:1 to 10:1, more preferably 1:1 to 10:1.

[0304] In a preferred embodiment, the weight ratio of at least one N-(hydroxyalkyl)amine of formula (I) to the amount of Z3 is in the range of 4:1 to 10:1, more preferably 1:1 to 10:1.

[0305] In a preferred embodiment, the weight ratio of at least one N-(hydroxyalkyl)amine of formula (I) to the amount of Z is in the range of 4:1 to 10:1, more preferably 1:1 to 10:1, wherein Z is a mixture of two or more compounds selected from Z1, Z2 and Z3.

[0306] Advantageously, the degree of condensation can be controlled by changing the temperature and time of the reaction.

[0307] In a preferred embodiment, step (i) further comprises adding at least one catalyst in an amount based on the at least one N-(hydroxyalkyl)amine of formula (I) in the range of 0.01-5% by weight, more preferably 0.05-4% by weight, most preferably 0.1-3% by weight, and even more preferably 0.2-2.0% by weight.

[0308] In a preferred embodiment, the at least one catalyst is an acid selected from phosphoric acid (H3PO3) and hypophosphoric acid (H3PO2), diphosphoric acid, sulfuric acid, trifluoromethanesulfonic acid and toluenesulfonic acid.

[0309] In a preferred embodiment, the at least one catalyst is a mixture of phosphoric acid and hypophosphoric acid.

[0310] In a preferred embodiment, the intermediate (Q) has:

[0311] a. Viscosity measured at 23°C in the range of 2000-110000 mPas according to ASTM-D7042;

[0312] and

[0313] b. Weight-average molecular weight (M) in the range of 2000-80000 g / mol w The number-average molecular weight (M) in the range of 1000-25000 g / mol n The polydispersity index (PDI) in the range of 1.0–3.0 was determined by gel permeation chromatography (HFIP).

[0314] In a preferred embodiment, the intermediate (Q) obtained by the self-condensation of triethanolamine has a viscosity in the range of 1,000-50,000 mPas, more preferably 1,500-25,000 mPas, and most preferably 2,000-10,000 mPas, as determined by ASTM-D7042 at 23°C.

[0315] In a preferred embodiment, the intermediate (Q) obtained by the self-condensation of triethanolamine has a hydroxyl value in the range of 400-1000 mg KOH / g, more preferably 550-900 mg KOH / g, as determined according to Part 2 of DIN 53240.

[0316] In a preferred embodiment, the intermediate (Q) obtained by the self-condensation of triethanolamine has a weight-average molecular weight (M) in the range of 2000-80000 g / mol. w The number-average molecular weight (M) in the range of 1000-25000 g / mol n The polydispersity index (PDI) in the range of 1.0–3.0 was determined by gel permeation chromatography (HFIP).

[0317] In a preferred embodiment, the intermediate (Q) obtained by the self-condensation of triisopropanolamine has a viscosity in the range of 10,000-110,000 mPas, more preferably 15,000-110,000 mPas, as determined by ASTM-D7042 at 23°C.

[0318] In a preferred embodiment, the intermediate (Q) obtained by the self-condensation of triisopropanolamine has a hydroxyl value in the range of 200-2000 mg KOH / g, more preferably 250-1500 mg KOH / g, and most preferably 300-1000 mg KOH / g, as determined according to Part 2 of DIN 53240.

[0319] In a preferred embodiment, the intermediate (Q) obtained by the self-condensation of triisopropanolamine has a weight-average molecular weight (M) in the range of 2000-80000 g / mol. w The number-average molecular weight (M) in the range of 1000-25000 g / mol n The polydispersity index (PDI) in the range of 1.0–3.0 was determined by gel permeation chromatography (HFIP).

[0320] Alkoxylation

[0321] In a preferred embodiment, step (ii) further comprises adding at least one catalyst in an amount ranging from 0.01 to 2.0% by weight, more preferably from 0.05 to 1.5% by weight, and most preferably from 0.1 to 1.0% by weight, based on the total weight of intermediate Q and glycidyl ether (II).

[0322] In a preferred embodiment, the at least one catalyst is selected from the following:

[0323] (i) Lewis acids selected from boron trifluoride, titanium tetrachloride, tin chloride, zirconium tetrachloride and their complexes;

[0324] and

[0325] (ii) Equation R 12 R 13 R 14 R 15 P + X - Season Salt, of which R 12 R 13 R 14 and R 15 Independently selected from substituted or unsubstituted linear or branched C1-C 10 Alkyl, substituted or unsubstituted C6-C 18 Aryl and substituted or unsubstituted linear or branched C7-C 18 Aryl alkyl group and X is a halide.

[0326] In the preferred embodiment, R 12 R 13 R 14 and R 15 Independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclohexyl, and benzyl. X is a halide selected from chlorides, bromides, and iodides.

[0327] In a preferred embodiment, the at least one catalyst is selected from boron trifluoride / benzylamine complex and ethyltriphenyl bromide.

[0328] The degree of alkoxylation of the polymer obtained by step (iii) of the method of the present invention depends on the amount of the at least one glycidyl ether used and the reaction conditions such as the reaction temperature.

[0329] In a preferred embodiment, step (iii) is performed at a temperature in the range of 130-190°C, more preferably 150-190°C.

[0330] In a preferred embodiment, step (iii) is performed within a time frame of 1-16 hours, preferably 2-8 hours.

[0331] In a preferred embodiment, step (iii) is carried out until the solids content of the reaction mixture is >95% by weight, as determined by a halogen dryer HR73 at 150°C.

[0332] Defoamer Composition

[0333] Another aspect of the present invention relates to the use of the polymer P of the present invention as an antifoaming agent.

[0334] In a preferred embodiment, the polymer P of the present invention can be used as a component of the defoamer composition.

[0335] Another aspect of the present invention relates to an antifoaming composition comprising the polymer P of the present invention.

[0336] In a preferred embodiment, the defoamer composition comprising the polymer P of the present invention is suitable for use as a defoamer in aqueous systems.

[0337] In a preferred embodiment, the amount of polymer P in the defoamer composition is in the range of 0.5-50% by weight, more preferably 1-20% by weight, even more preferably 3-15% by weight, and most preferably 4-7% by weight, based on the total weight of the defoamer composition.

[0338] In a preferred embodiment, the defoamer composition further comprises at least one additive selected from silicone oil, mineral oil, emulsifying agent, silica particles, and water.

[0339] In a preferred embodiment, the defoamer composition contains water as a carrier.

[0340] Compositions containing polymer P of the present invention can be used to control foam generated by any type of aqueous system with a surface tension lower than that of water, such as water-based personal care products (e.g., shampoos, facial cleansers, liquid hand soaps, etc.) as well as polymer latexes and latex paints.

[0341] Defoamer compositions can be used in aqueous systems in several ways. For example, the composition can be added to aqueous systems such as latex or latex paint to effectively eliminate or reduce the amount of foam generated by certain types of mechanical action such as mixing, pouring, application to a surface by brushing or rolling, and / or shaking.

[0342] In a preferred embodiment, the defoamer composition comprises a mixture of water and oil as a carrier.

[0343] In a preferred embodiment, the defoamer composition comprises an oil base as a carrier. This composition can be added to an aqueous system as part of a multi-component defoamer composition. The multi-component defoamer composition comprises a polymer P and a hydrophobic solid dispersed in the oil base. The hydrophobic solid is any solid insoluble in the carrier.

[0344] In a preferred embodiment, the oil base is at least one selected from mineral oil and silicone oil.

[0345] In a preferred embodiment, the mineral oil is at least one selected from paraffin oil, naphthenic oil, tall oil fatty acids and ethoxylated tall oil fatty acids, fatty alcohols and ethoxylated fatty alcohols, liquid polyoxypropylene, liquid polyoxyethylene and liquid poly(ethylene oxide-propylene oxide).

[0346] In a preferred embodiment, the silicone oil is at least one selected from modified polydimethylsiloxane, polysiloxane, and organopolysiloxane.

[0347] wetting agent

[0348] Another aspect of the invention relates to the use of the polymer P of the invention as a wetting agent.

[0349] Another aspect of the invention relates to a wetting composition comprising the polymer P of the invention and water.

[0350] In a preferred embodiment, the amount of polymer P in the wetting composition is in the range of 0.5-50% by weight, more preferably 1-20% by weight, even more preferably 3-15% by weight, and most preferably 4-7% by weight, based on the total weight of the wetting composition.

[0351] The wetting composition may further comprise a water-miscible organic solvent. Examples of such solvents include alcohols such as ethanol, n-propanol, isopropanol, or butyl diethylene glycol.

[0352] In a preferred embodiment, the wetting composition further comprises at least one additive selected from rheology modifiers, defoamers, pigment dispersants, UV filters, leveling agents, slip agents, antioxidants, free radical scavengers, biocides, and coalescing agents.

[0353] This wetting composition is prepared by mixing water, the polymer P of the present invention, and optionally other additives.

[0354] The water used can be fresh water, but seawater or formation water, i.e., more or less salt water, can also be used. One of the advantages of the wetting modifiers used in the method of the present invention is that they show good results in salt water.

[0355] In a preferred embodiment, the wetting composition is provided as a concentrated aqueous solution for direct use at the application site.

[0356] Coating composition

[0357] Another aspect of the invention relates to the use of the polymer P of the invention in coating compositions.

[0358] Another aspect of the present invention relates to a coating composition comprising the polymer P of the present invention.

[0359] In a preferred embodiment, the coating composition further comprises at least one additive selected from pigment dispersants, rheology modifiers, UV filters, defoamers, leveling agents, slip agents, substrate wetting agents, antioxidants, free radical scavengers, biocides, and coalescing agents.

[0360] Another aspect of the present invention relates to an article coated with the coating composition of the present invention.

[0361] Printing inks

[0362] Another aspect of the invention relates to the use of the polymer P of the invention in printing inks and / or printing varnishes.

[0363] Another aspect of the present invention relates to a printing ink or printing varnish comprising the polymer P of the present invention.

[0364] Printing ink is, in principle, any printing ink used in mechanical printing processes, that is, any printing ink in which the ink comes into contact with the substrate via a printing mold. Representative examples include printing inks used in offset printing, letterpress printing, flexographic printing, gravure printing, or screen printing. The term "printing ink" also includes printing varnish. Representative examples of printing molds include printing plates or circular molds, also known as sleeves. Printing varnish is similar to printing ink, except that it lacks a colorant.

[0365] In a preferred embodiment, the printing ink comprises at least one solvent, at least one colorant, at least one binder, and optionally other additives.

[0366] In a preferred embodiment, the printing ink contains water as a solvent.

[0367] In a preferred embodiment, the at least one adhesive is polymer P of the present invention. The printing ink optionally contains at least one adhesive other than polymer P.

[0368] The printing varnish does not contain colorants, but otherwise has the same composition as the printing inks mentioned above.

[0369] Printing inks and varnishes containing polymer P can be used to print on substrates also known as printing media, such as paper, cardboard, metal foil, and polymer films.

[0370] In a preferred embodiment, the printing ink or printing varnish containing the polymer P of the present invention is used to print on a substrate selected from metal foil and polymer film.

[0371] Printing inks or varnishes containing polymer P of the present invention can be used to print on various substrates.

[0372] In a preferred embodiment, the polymer film is selected from films of polyethylene, polypropylene, poly(4-methyl-1-pentene), and polystyrene. The polyethylene film is selected from films of high-density polyethylene (HDPE), low-density polyethylene (LDPE), and linear low-density polyethylene (LLDPE). In a preferred embodiment, the polymer film is selected from films of copolymers—those selected from ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, and styrene-butadiene copolymers. PVC or polycarbonate films may also be used. In a preferred embodiment, the polymer film is a polar material film and is selected from celluloid films, polyester films selected from polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, and polyamide films selected from PA6, PA12, PA6 / 66, PA6 / 12, and PA11 films.

[0373] In a more preferred embodiment, the substrate includes films of polyethylene, polypropylene, polystyrene, polyester, and polyamide.

[0374] In a preferred embodiment, the substrate includes a metal foil selected from aluminum foil, tin foil, titanium foil, copper foil, and gold foil.

[0375] Another aspect of the present invention relates to an article printed with the printing ink of the present invention.

[0376] This invention provides one or more of the following advantages:

[0377] 1) The polymers of the present invention can be used in a wide range of applications, such as components of wetting agent and defoamer compositions.

[0378] 2) Coating compositions containing the polymers of the present invention can be used to coat various substrates, including polymer sheets and metal surfaces.

[0379] 3) Defoamer compositions containing the polymers of the present invention can be used to prevent foaming in coating compositions.

[0380] The following provides a list of implementation schemes to further illustrate this disclosure, but it is not intended to limit this disclosure to the specific implementation schemes listed below.

[0381] 1. A polymer P that can be obtained as follows:

[0382] (a) Self-condensation of at least one N-(hydroxyalkyl)amine of formula (I):

[0383]

[0384] in

[0385] A1, A2, and A3 may be the same or different and are selected from unsubstituted linear or branched C1-C4 alkylene groups, R1, R 1* R2 and R 2* The same or different and selected from H, substituted or unsubstituted linear or branched C1-C4 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C6-C 18 Aryl and substituted or unsubstituted linear or branched C7-C 18 Aryl groups,

[0386] R3 is selected from H, substituted or unsubstituted linear or branched C1-C4 alkyl groups, substituted or unsubstituted C3-C6 cycloalkyl groups, and substituted or unsubstituted C6-C4 alkyl groups. 18 Aryl, substituted or unsubstituted linear or branched C7-C 18 Arane and Among them, R4 and R 4* The same or different and selected from H, substituted or unsubstituted linear or branched C1-C4 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C6-C 18 Aryl and substituted or unsubstituted linear or branched C7-C 18 Aryl group and # indicate the connection point with A3, yielding intermediate (Q);

[0387] Alternatively, at least one N-(hydroxyalkyl)amine of formula (I) can be co-condensed with Z, wherein Z is at least one compound selected from Z1, Z2, and Z3.

[0388] in

[0389] Z1 is at least one diol of the formula HO-R8-OH, wherein R8 is selected from substituted or unsubstituted linear or branched C2-C diols. 18 Alkylenes and substituted or unsubstituted C3-C6 cycloalkylenes, and

[0390] R8 may optionally be substituted with at least one linear or branched C1-C3 alkyl group and R8 may optionally be spaced by oxygen atoms.

[0391] Z2 is selected from polyoxyethylene, polyoxypropylene, and polytetramethylene ether glycol, and has a weight-average molecular weight (M). w ) is 100-1500 g / mol of polyoxyethylene, and

[0392] Z3 is formula R 11 (OH) m polyols, where m is an integer selected from 3 to 6 and R 11 Is it a linear or branched C3-C with m-valence substitution or no substitution? 10 Alkyl, substituted or unsubstituted C4-C 10 Cycloalkyl and substituted or unsubstituted linear or branched C7-C 10 Aryl alkyl groups;

[0393] Obtain the intermediate (Q); and

[0394] (b) React the intermediate (Q) obtained in step (a) with at least one glycidyl ether of formula (II):

[0395] in

[0396] R9 is a linear or branched C6-C that has been substituted or not substituted. 20 alkyl;

[0397] Wherein the ratio of the number of moles of hydroxyl groups in intermediate (Q) calculated based on its hydroxyl value in step (b) to the number of moles of glycidyl ethers of at least one formula (II) is in the range of 0.03:1 to 1:3; and

[0398] The amount of N-(hydroxyalkyl)amine of at least one formula (I) is in the range of 10-90% by weight and the amount of glycidyl ether of at least one formula (II) is in the range of 10-90% by weight, each based on the total weight of polymer P.

[0399] 2. The polymer P according to embodiment 1, wherein the at least one N-(hydroxyalkyl)amine of formula (I) is a mixture comprising N-(hydroxyalkyl)amines of formula (Ia) and / or (Ib):

[0400]

[0401] in

[0402] A5, A6, and A7 may be the same or different and are selected from unsubstituted C1-C4 alkylene groups.

[0403] R5, R 5* R6 and R6* The same or different and selected from H, substituted or unsubstituted linear or branched C1-C4 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C6-C 18 Aryl and substituted or unsubstituted linear or branched C7-C 18 Aryl groups,

[0404] R7 is selected from hydrogen, substituted or unsubstituted C1-C4 alkyl groups, substituted or unsubstituted C3-C6 cycloalkyl groups, and substituted or unsubstituted C6-C4 cycloalkyl groups. 18 Aryl and substituted or unsubstituted linear or branched C7-C 18 Aryl groups,

[0405] The amount of N-(hydroxyalkyl)amine in formula (Ia) is in the range of 70-100% by weight and the amount of N-(hydroxyalkyl)amine in formula (Ib) is in the range of 0-30% by weight, each based on the total weight of N-(hydroxyalkyl)amine in formula (I).

[0406] 3. The polymer P according to embodiment 1 or 2, wherein A1, A2 and A3 are the same or different and are selected from methylene, ethylene, n-propylene and isopropylene.

[0407] 4. The polymer P according to any one of embodiments 1-3, wherein A1, A2 and A3 are methylene groups.

[0408] 5. Polymer P according to any one of embodiments 1-4, wherein R1, R 1* R2 and R 2* Same or different and selected from H and methyl.

[0409] 6. Polymer P according to any one of embodiments 1-5, wherein R1, R 1* R2 and R 2* It's H.

[0410] 7. Polymer P according to any one of embodiments 1-6, wherein R1 and R2 are methyl and R 1* and R 2* It is hydrogen.

[0411] 8. Polymer P according to any one of embodiments 1-7, wherein R3 is Among them, R4 and R 4* Same or different and selected from H and methyl.

[0412] 9. Polymer P according to any one of embodiments 1-8, wherein R3 is -CH2OH.

[0413] 10. The polymer P according to any one of embodiments 1-9, wherein R9 is at least one selected from the group consisting of oxy, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, and octadecyl.

[0414] 11. The polymer P according to any one of embodiments 1-10 can be obtained by reacting the intermediate (Q) obtained in step (a) with at least one glycidyl ether of formula (II):

[0415]

[0416] It is obtained by reacting with at least one diglycidyl ether of formula (IIa):

[0417]

[0418] Where R 10 Is it a substituted or unsubstituted linear or branched C3-C? 20 Alkylene, substituted or unsubstituted C3-C6 cycloalkylene and substituted or unsubstituted C6-C 18 Aryl; and

[0419] The amount of diglycidyl ether of at least one formula (IIa) is in the range of 1-20% by weight relative to the amount of glycidyl ether of formula (II).

[0420] 12. According to any one of the embodiments 1-11, polymer P can be obtained as follows:

[0421] (a) Self-condensing at least one N-(hydroxyalkyl)amine of formula (I):

[0422]

[0423] in

[0424] R1, R 1* R2 and R 2′* Selected from H and methyl,

[0425] R3 is selected from H, methyl, and Among them, R4 and R 4* The same or different and selected from H and methyl; and

[0426] A1, A2, and A3 are identical and selected from methylene, ethylene, n-propylene, and isopropylene, yielding intermediate Q; and

[0427] (b) React the intermediate Q obtained in step (a) with at least one glycidyl ether of formula (II):

[0428]

[0429] in

[0430] R9 can be selected from alkyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, and octadecyl.

[0431] 13. The polymer P according to any one of embodiments 1-12, wherein the N-(hydroxyalkyl)amine of at least one formula (I) is triethanolamine.

[0432] 14. The polymer P according to any one of embodiments 1-12, wherein the at least one N-(hydroxyalkyl)amine of formula (I) is triisopropanolamine.

[0433] 15. Polymer P according to any one of embodiments 1-13 can be obtained as follows:

[0434] (a) Triethanolamine is subjected to self-condensation to obtain an intermediate Q with a degree of polymerization in the range of 3-300, calculated based on its hydroxyl value or the amount of water collected during the condensation process.

[0435] (b) Intermediate Q is reacted with a mixture of glycidyl ethers containing formulas (IIp) and (IIq) to give polymer P:

[0436]

[0437] 16. The polymer P according to any one of embodiments 1-13 can be obtained as follows:

[0438] (a) Triethanolamine is subjected to self-condensation to obtain an intermediate Q with a degree of polymerization in the range of 3-300, calculated based on its hydroxyl value or the amount of water collected during the condensation process.

[0439] (b) Intermediate Q is reacted with a mixture of glycidyl ethers containing formulas (IIp), (IIq), and (IIr) to give polymer P:

[0440]

[0441] 17. A method for preparing polymer P according to any one of embodiments 1-16, the method comprising at least the following steps:

[0442] (i) subjecting at least one N-(hydroxyalkyl)amine of formula (I) to self-condensation at a temperature in the range of 160-240°C to obtain intermediate (Q), or

[0443] At least one N-(hydroxyalkyl)amine (I) is co-condensed with Z1 or Z2 at a temperature in the range of 160-240°C to obtain intermediate (Q);

[0444] (ii) The at least one glycidyl ether (II) is added to intermediate (Q) at a temperature in the range of 100-160°C; and

[0445] (iii) The reaction mixture obtained in step (ii) is heated at a temperature in the range of 130-190°C to obtain the polymer;

[0446] Z1 and Z2 are defined as in any of embodiments 1-15, wherein the total weight ratio of the at least one N-(hydroxyalkyl)amine of formula (I) used in step (i) to the total weight ratio of the at least one glycidyl ether of formula (II) used in step (ii) is in the range of 1:10 to 10:1.

[0447] 18. The method according to embodiment 17, wherein step (i) further comprises adding at least one catalyst in an amount ranging from 0.1% to 5% by weight based on the amount of the at least one N-(hydroxyalkyl)amine of formula (I).

[0448] 19. The method according to embodiment 18, wherein the at least one catalyst is an acid selected from phosphoric acid, diphosphoric acid, sulfuric acid, trifluoromethanesulfonic acid and toluenesulfonic acid.

[0449] 20. The method according to any one of embodiments 17-19, wherein step (ii) further comprises adding at least one catalyst in an amount ranging from 0.1 to 2.0% by weight based on the total weight of intermediate Q and glycidyl ether (II).

[0450] 21. The method according to embodiment 20, wherein the at least one catalyst is selected from the following:

[0451] (i) Lewis acids selected from boron trifluoride, titanium tetrachloride, tin chloride, zirconium tetrachloride and their complexes;

[0452] and

[0453] (ii) Equation R 12 R 13 R 14 R 15 P + X - Season Salt, of which R 12 R 13 R 14 and R 15 Independently selected from substituted or unsubstituted linear or branched C1-C 10 Alkyl, substituted or unsubstituted C6-C 18 Aryl and substituted or unsubstituted linear or branched C7-C 18 Aryl alkyl group and X is a halide.

[0454] 22. The method according to embodiment 20 or 21, wherein the at least one catalyst is selected from boron trifluoride / benzylamine complex and ethyltriphenyl bromide.

[0455] 23. The method according to any one of embodiments 17-22, wherein the intermediate (Q) has:

[0456] a. Viscosity measured at 23°C in the range of 2000-110000 mPas according to ASTM-D7042;

[0457] and

[0458] b. Weight-average molecular weight (M) in the range of 2000-80000 g / mol w The number-average molecular weight (M) in the range of 1000-25000 g / mol n The polydispersity index (PDI) in the range of 1.0–3.0 was determined by gel permeation chromatography (HFIP).

[0459] 24. Use of polymer P as a wetting agent according to any one of embodiments 1-16.

[0460] 25. Use of polymer P according to any one of embodiments 1-16 in a coating composition.

[0461] 26. Use of polymer P as an antifoaming agent according to any one of embodiments 1-16.

[0462] 27. Use of polymer P according to any one of embodiments 1-16 in an antifoaming composition.

[0463] 28. An antifoaming composition comprising polymer P according to any one of embodiments 1-16.

[0464] 29. The defoamer composition according to embodiment 28 further comprises at least one additive selected from silicone oil, mineral oil, emulsifying agent, silica particles and water.

[0465] 30. A coating composition comprising polymer P according to any one of embodiments 1-16.

[0466] 31. The coating composition according to embodiment 30 further comprises at least one additive selected from pigment dispersants, rheology modifiers, UV filters, defoamers, leveling agents, slip agents, substrate wetting agents, antioxidants, free radical scavengers, biocides and coalescing agents.

[0467] 32. An article coated with a coating composition according to embodiment 30 or 31.

[0468] Although the invention has been described with respect to specific embodiments thereof, 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

[0469] 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.

[0470] Material

[0471] C3-C 18 The alkyl glycidyl ethers were purchased from Sigma-Aldrich Chemie GmbH and Fluka Chemie GmbH.

[0472] Boron trifluoride / benzylamine complex (CAS 696-99-1) was purchased from Apolda Laborchemie GmbH. Trialkyl bromide Phosphoric acid was obtained from Merck.

[0473] Used as a comparative composition 104E was purchased from Evonik GmBH.

[0474] Triethanolamine, triisopropanolamine, 1,6-hexanediol and PEG 200 were purchased from BASF SE.

[0475] 066 is a low-viscosity hexamethoxymethyl melamine resin;

[0476] 8300 is a rheology control acrylic emulsion for thermosetting water-based industrial metal, metal and glass coatings;

[0477] Ultra PX 4575 is a water-based dispersant;

[0478] SI 2250 is a silicone-based defoamer;

[0479] HS 1332 is a hydrophobically modified alkali-swellable emulsion (HASE);

[0480] MO NDW is a mineral oil-based defoamer;

[0481] Pro 770 is an acrylic emulsion polymer;

[0482] PU 1191 is an associative polyurethane thickener;

[0483] WE 3323 is a 100% active nonionic wetting agent, and

[0484] XL 50 is a nonionic surfactant.

[0485] Purchased from BASF SE.

[0486] AMP-90 TM It is 2-amino-2-methyl-1-propanol purchased from Angus Chemical Company. 2190 is titanium dioxide purchased from Kronos SE. 515 is a liquid organic corrosion inhibitor purchased from ICL Industrial SE for high-gloss (direct to metal) coating systems.

[0487] method

[0488] 1) Determination of solid content

[0489] The solids content of the reactants was measured by a Mettler-Toledo halogen dryer HR73 at 150°C by placing a 0.5g sample on the sample holder and heating the device until a constant weight was obtained at sensitivity level 3 (medium).

[0490] 2) Determination of Critical Aggregation Concentration (CAC)

[0491] The critical aggregation concentration was determined using a soap titration apparatus with a Du Nouy ring.

[0492] Prepare a 5% solution of the corresponding material and measure CAC.

[0493] The CAC value of the wetting agent is represented by a coordinate on the x-axis (concentration, log 10), where the slope of the static surface tension curve varies.

[0494] 3) Measurement of dynamic surface tension

[0495] The bubble lifetime was measured to be 0.03–10 s. Solutions or oil-in-water emulsions containing 0.25 wt% and 0.50 wt% wetting agents were prepared in softened water. The dynamic surface tension of a water / butyl glycol mixture (19 / 1) with a bubble lifetime of 0.03–10 s was measured using a surface tension meter (SITA). The surface tension of this mixture at a bubble lifetime of 100 ms was 35 mN / m.

[0496] Plot the resulting dynamic surface tension on a graph. The dynamic surface tension of this wetting agent is the value at a lifetime of 100 ms.

[0497] A1) Condensation of N-(hydroxyalkyl)amines

[0498] Polymerized N-(hydroxyalkyl)amines—polytriethanolamine (pTEOA) and polytriisopropanolamine (pTIPA)—were prepared to the OH values ​​shown in Table 1 by a method similar to that according to Example A of WO 2009 / 047269. In the method of the present invention, the condensation reaction is carried out at 200°C. Additionally, a distillation step may be optionally used.

[0499] Types of polytriethanolamine:

[0500] V: OH number = 880-885 mg KOH / g, viscosity at 23℃ = 2330 mPas

[0501] W: OH number = 690-695 mg KOH / g, viscosity at 23℃ = 3657 mPas

[0502] X: OH number = 630-635 mg KOH / g, viscosity at 23℃ = 4565 mPas

[0503] Y: OH number = 615-620 mg KOH / g, viscosity at 23℃ = 5450 mPas; GPC (HFIP)

[0504] Mn 4540 and Mw 8460 g / mol)

[0505] Z: OH number = 565-570 mg KOH / g, viscosity at 23℃ = 5600 mPas

[0506] Polytriisopropylamine type

[0507] M: OH number = 700-710 mg KOH / g, viscosity at 23℃ = 25200 mPas, GPC (HFIP)

[0508] Mn 3780 and Mw 4840 g / mol)

[0509] N: OH group = 490-500 mg KOH / g; viscosity at 23℃ = 102000 mPas; GPC (HFIP)

[0510] Mn 2550 and Mw 6180 g / mol)

[0511] A2) Co-condenses N-(hydroxyalkyl)amine with another monomer.

[0512] In a reactor equipped with an overhead stirrer, a nitrogen inlet, and a Dean-Stark condenser, N-(hydroxyalkyl)amine and glycol (polymer R or S) were added in the molar ratios shown in the examples below, followed by 3.2 mol% (relative to the total monomers) of 50% (aqueous) phosphoric acid. The mixture was slowly heated to 200°C while stirring and separating the resulting reaction water, until the target OH number was reached after several hours. The material was then used without further purification after cooling to RT.

[0513] R: OH number 355-365 mg KOH / g, triethanolamine (3.0 mol), 1,6-hexanediol (1.5 mol), viscosity at 23°C = 13800 mPas

[0514] S: OH number 290-300 mg KOH / g, triethanolamine (7.0 mol), polyethylene glycol 200 (3.0 mol), viscosity at 23℃ = 7067 mPas, GPC (HFIP) Mn 3000 and Mw 39770 g / mol)

[0515] B) Preparation of polymer P

[0516] General program G1

[0517] Preparation of alkylated polymerized N-(hydroxyalkyl)amine ethers under thermal conditions

[0518] The N-(hydroxyalkyl)amines polymerized as shown in Table 1 were added to a reactor equipped with a raised stirrer, nitrogen inlet, feed funnel, and cooler at room temperature, and the reactor was inertized. Heating was initiated, and when the internal temperature of the reaction mixture reached 150°C, glycidyl ethers as shown in Table 1 were added in several fractions (ampoules), each fraction being 10-20% by weight of the total feed mass, over a period of 2-4 hours. During the addition of the aliquots, the temperature of the reaction mixture increased due to the exothermic reaction, and the reaction mixture became turbid. The addition was carried out in a manner that the reactants were clarified and the reaction mixture was cooled back to 150°C before adding the next aliquot. After the addition was complete, the reactants were stirred at 170-180°C for at least 3 hours until the solids content reached >98% (measured by a halogen dryer HR73 at 150°C). After cooling, the product was obtained as a pale yellow viscous liquid. As a control method, 1 1H NMR showed complete conversion of the epoxide groups.

[0519] General Program G2

[0520] Alkyl-modified polyetheramines prepared using catalysts

[0521] The N-(hydroxyalkyl)amines polymerized as shown in Table 1 were added to a reactor equipped with a raised stirrer, nitrogen inlet, feed funnel, and cooler at room temperature, and the reactor was then inert. 0.5 wt% of catalyst (boron trifluoride / benzylamine, ethyltriphenyl bromide) was added. Tributylhexylbromination Or ethoxycarbonylmethyl (triphenyl) bromide The N-(hydroxyalkyl)amine was added to the reactor and the contents were heated to an internal temperature of 120°C.

[0522] When the internal temperature of the reaction mixture reaches 120°C, the glycidyl ethers shown in Table 1 are added in several fractions (ample samples) over a period of 2-4 hours, each fraction being 10-20% by weight. During the addition of the aliquots, the temperature of the reaction mixture rises due to the exothermic reaction and the reaction mixture becomes turbid. The addition is carried out in a manner that the reactants become clear and the reaction mixture is cooled back to 120-130°C before adding the next aliquot. After the addition is complete, the reactants are stirred at 150°C for at least 3 hours until the solids content reaches >98% (measured by a halogen dryer HR73 at 150°C). The product is obtained as a pale yellow viscous liquid after cooling. As a control method, 1 1H NMR showed complete conversion of the epoxide groups.

[0523] Examples 1-4, 6 and 9-13: Preparation of polymers P1-P4, P6 and P9-P13

[0524] Polymers P1-P4, P6, and P9-P13 were prepared using procedure G1. The amounts of glycidyl ether and polytriethanolamine W or X used in the preparation of polymers P1-P4, P6, and P9-P13 are provided in Table 1. Examples 5, 7, and 8: Preparation of polymers P5, P7, and P8

[0525] Polymers P5, P7, and P8 were prepared using procedure G2. The amounts of glycidyl ether D and polytriethanolamine W used to prepare polymers P5, P7, and P8 are provided in Table 1.

[0526] Examples 14-17: Preparation of polymers P14-P17

[0527] Polymers P14-P17 were prepared using procedure G1. The amounts of glycidyl ether D and polytriisopropanolamine M or N used to prepare polymers P14-P17 are provided in Table 1.

[0528] Examples 18-21: Preparation of polymer P18-21

[0529] Polymers P18-21 were prepared using procedure G1. The amounts of glycidyl ether D and polytrialkylamine-co-diol R or S used to prepare polymers P18-P21 are provided in Table 1.

[0530] Table 1: Preparation of polymers P1-P21

[0531]

[0532] *Glycidyl ether type:

[0533] A: C 16 Alkyl glycidyl ether CAS 15965-99-8

[0534] B: 2-Ethylhexyl glycidyl ether CAS 2461-15-6

[0535] C:C 8-10 Alkyl glycidyl ether CAS 68609-96-1

[0536] D:C 12-14 Alkyl glycidyl ether CAS 68609-97-2

[0537] E:C 13-15 Alkyl glycidyl ether CAS 146982-96-4

[0538] C) Comparative Example: Preparation of polymers C1-C3 containing C3 and C4 alkyl glycidyl ethers

[0539] For comparison, polymers C1-C3 were prepared using procedure G2. The amounts of glycidyl ethers F and G, and polytriethanolamine W and V used to prepare polymers C1-C3 are provided in Table 2.

[0540] Table 2: Preparation of polymers C1-C3

[0541]

[0542] **Glycidyl ether type:**

[0543] F: Allyl glycidyl ether CAS 106-92-3

[0544] G: Butyl glycidyl ether CAS 2426-08-6

[0545] B) Performance Testing:

[0546] The physical properties of the polymers of this invention, such as critical aggregation concentration and dynamic surface tension, were determined. The results are shown in Table 4.

[0547] The performance of the polymer of this invention as a wetting agent was evaluated by direct metal wetting. The results are shown in Tables 4 and 5.

[0548] In addition, the foaming behavior of the polymers of the present invention was evaluated and the results are shown in Tables 4 and 6.

[0549] The wetting properties and foaming behavior of the polymers of this invention are compared with the following benchmark / reference products.

[0550] · 104E

[0551] ·Hydropalat WE 3323

[0552] Lutensol XL 50

[0553] 1. Direct wetting of metal

[0554] Clean the steel plate surface with ethyl acetate and dry it. Apply an anti-corrosion coating to the dried surface by spraying. Protect G13F, then wipe evenly with a cotton cloth.

[0555] A series of water-based melamine coating compositions (Table 3) or water-based acrylic coating compositions (Table 4) comprising polymers P1-P17 of the present invention as wetting agents were prepared. The components of the coating compositions are provided in Tables 3 and 4. The coating compositions were prepared by mixing these components in a high-speed mixer at 2750 rpm for 2 minutes.

[0556] For comparison, a similar coating composition was prepared by replacing polymer P with a comparative wetting agent.

[0557] Apply each coating composition as an 80 μm thick layer to the steel plate surface using a scraper at 20 mm / s and allow the coated surface to air dry overnight. The next day, cure the coated surface in an oven at 80°C for 30 minutes.

[0558] Surface coverage is calculated after taking photos and producing black and white images.

[0559] Table 3: Aqueous Melamine System

[0560]

[0561] Table 4: Aqueous Dispersions

[0562]

[0563] 2. Bubble Behavior

[0564] Foam promotion was tested by adding 5% by weight of polymer P to water and shaking it thoroughly. Foam ratings were given from 1 (good, no foam) to 5 (poor, persistent foam).

[0565] The results are summarized in Tables 5, 6, and 7.

[0566] Table 5: Application Data

[0567]

[0568]

[0569] Table 6: Application Data

[0570]

[0571] Table 7: Application Data

[0572]

[0573] Application data of control polymers

[0574] The wetting properties and foaming behavior of polymers C1-C3 were analyzed and compared.

[0575] Wetting properties: Wetting properties were determined using compositions and procedures similar to those used for direct metal wetting (aqueous melamine system (Table 3)).

[0576] Foaming behavior: 0.5% by weight of the control polymer was added to 150g of the formulation in Table 3 in a 370ml glass jar and measured using a 4cm plate. Disperse at 5000 rpm for 3 minutes. Measure the density of the resulting formulation using a hydrometer flask.

[0577] The results are summarized in Table 8.

[0578] Table 8: Application data from the control trial

[0579]

Claims

1. A polymer P obtained as follows: (a) Self-condensation of at least one N-(hydroxyalkyl)amine of formula (I): Equation (I) in A1, A2, and A3 may be the same or different and are selected from unsubstituted linear or branched C1-C4 alkylene groups. R1, R1 2 and R2 Same or different and selected from H, substituted or unsubstituted linear or branched C1-C4 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C6-C 18 Aryl and substituted or unsubstituted linear or branched C7-C 18 Aryl groups, R3 is selected from H, substituted or unsubstituted linear or branched C1-C4 alkyl groups, substituted or unsubstituted C3-C6 cycloalkyl groups, and substituted or unsubstituted C6-C4 alkyl groups. 18 Aryl, substituted or unsubstituted linear or branched C7-C 18 Arane and Among them, R4 and R4 Same or different and selected from H, substituted or unsubstituted linear or branched C1-C4 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C6-C 18 Aryl and substituted or unsubstituted linear or branched C7-C 18 Aryl group and # indicate the connection point with A3, yielding intermediate (Q); Alternatively, at least one N-(hydroxyalkyl)amine of formula (I) can be co-condensed with Z, wherein Z is at least one compound selected from Z1, Z2, and Z3. in Z1 is at least one diol of the formula HO-R8-OH, wherein R8 is selected from substituted or unsubstituted linear or branched C2-C diols. 18 Alkylene and substituted or unsubstituted C3-C6 cycloalkylene, wherein R8 is optionally substituted with at least one linear or branched C1-C3 alkyl group and R8 is optionally spaced by oxygen atoms. Z2 is selected from polyoxyethylene, polyoxypropylene, polytetramethylene ether glycol and their copolymers, and has a weight-average molecular weight (M). w ) is 100-1500 g / mol of polyoxyethylene, and Z3 is formula R 11 (OH) m polyols, where m is an integer selected from 3 to 6 and R 11 Is it a linear or branched C3-C with m-valence substitution or no substitution? 10 Alkyl, substituted or unsubstituted C4-C 10 Cycloalkyl and substituted or unsubstituted linear or branched C7-C 10 Aryl alkyl groups; Obtain the intermediate (Q); and (b) React the intermediate (Q) obtained in step (a) with at least one glycidyl ether of formula (II): Equation (II) in R9 is a linear or branched C6-C that has been substituted or not substituted. 20 alkyl; Wherein the ratio of the number of moles of hydroxyl groups in intermediate (Q) calculated based on its hydroxyl value in step (b) to the number of moles of glycidyl ethers of at least one formula (II) is in the range of 0.03:1 to 1:3; and The amount of the N-(hydroxyalkyl)amine of at least one formula (I) is in the range of 10-90% by weight and the amount of the glycidyl ether of at least one formula (II) is in the range of 10-90% by weight, each based on the total weight of polymer P.

2. The polymer P according to claim 1, wherein the at least one N-(hydroxyalkyl)amine of formula (I) is a mixture comprising N-(hydroxyalkyl)amines of formula (Ia) and / or (Ib): Equation (Ia) Equation (Ib) in A5, A6, and A7 may be the same or different and are selected from unsubstituted C1-C4 alkylene groups. R5, R5 6 and R6 Same or different and selected from H, substituted or unsubstituted linear or branched C1-C4 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C6-C 18 Aryl and substituted or unsubstituted linear or branched C7-C 18 Aryl groups, R7 is selected from hydrogen, substituted or unsubstituted C1-C4 alkyl groups, substituted or unsubstituted C3-C6 cycloalkyl groups, and substituted or unsubstituted C6-C4 cycloalkyl groups. 18 Aryl and substituted or unsubstituted linear or branched C7-C 18 Aryl groups, The amount of N-(hydroxyalkyl)amine in formula (Ia) is in the range of 70-100% by weight and the amount of N-(hydroxyalkyl)amine in formula (Ib) is in the range of 0-30% by weight, each based on the total weight of N-(hydroxyalkyl)amine in formula (I).

3. The polymer P according to claim 1, wherein A1, A2 and A3 are the same or different and are selected from methylene, ethylene, n-propylene and isopropylene.

4. The polymer P according to claim 2, wherein A1, A2 and A3 are the same or different and are selected from methylene, ethylene, n-propylene and isopropylene.

5. The polymer P according to claim 1, wherein A1, A2 and A3 are methylene groups.

6. The polymer P according to claim 2, wherein A1, A2 and A3 are methylene groups.

7. The polymer P according to any one of claims 1-6, wherein R1, R1 2 and R2 Same or different and selected from H and methyl.

8. The polymer P according to any one of claims 1-6, wherein R1, R1 2 and R2 .

9. The polymer P according to any one of claims 1-6, wherein R1 and R2 are methyl and R1 2 hydrogen.

10. The polymer P according to any one of claims 1-6, wherein R3 is Among them, R4 and R4 Same or different and selected from H and methyl.

11. The polymer P according to claim 9, wherein R3 is Among them, R4 and R4 Same or different and selected from H and methyl.

12. The polymer P according to any one of claims 1-6, wherein R3 is -CH2OH.

13. The polymer P according to claim 9, wherein R3 is -CH2OH.

14. The polymer P according to any one of claims 1-6, wherein R9 is at least one selected from oxyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, and mixtures thereof.

15. The polymer P according to claim 13, wherein R9 is at least one selected from alkyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, and mixtures thereof.

16. The polymer P according to any one of claims 1-6, by reacting the intermediate (Q) obtained in step (a) with at least one glycidyl ether of formula (II): Equation (II) It is obtained by reacting with at least one diglycidyl ether of formula (IIa): Formula (IIa) Where R 10 Is it a substituted or unsubstituted linear or branched C3-C? 20 Alkylene, substituted or unsubstituted C3-C6 cycloalkylene and substituted or unsubstituted C6-C 18 Aryl; and The amount of at least one diglycidyl ether of formula (IIa) is in the range of 1-20% by weight relative to the amount of glycidyl ether of formula (II).

17. The polymer P according to claim 15, by reacting the intermediate (Q) obtained in step (a) with at least one glycidyl ether of formula (II): Equation (II) It is obtained by reacting with at least one diglycidyl ether of formula (IIa): Formula (IIa) Where R 10 Is it a substituted or unsubstituted linear or branched C3-C? 20 Alkylene, substituted or unsubstituted C3-C6 cycloalkylene and substituted or unsubstituted C6-C 18 Aryl; and The amount of at least one diglycidyl ether of formula (IIa) is in the range of 1-20% by weight relative to the amount of glycidyl ether of formula (II).

18. The polymer P according to any one of claims 1-6 is obtained as follows: (a) Self-condensing at least one N-(hydroxyalkyl)amine of formula (I): Equation (I) in R1, R1 2 and R 2' From H and methyl, R3 is selected from H, methyl, and Among them, R4 and R4 Same or different and selected from H and methyl; and A1, A2, and A3 are identical and selected from methylene, ethylene, n-propylene, and isopropylene. Obtain intermediate Q; and (b) React the intermediate Q obtained in step (a) with at least one glycidyl ether of formula (II): Equation (II) in R9 is selected from alkyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl and mixtures thereof.

19. The polymer P according to any one of claims 1-6, wherein the at least one N-(hydroxyalkyl)amine of formula (I) is triethanolamine.

20. The polymer P according to claim 18, wherein the at least one N-(hydroxyalkyl)amine of formula (I) is triethanolamine.

21. The polymer P according to any one of claims 1-6, wherein the at least one N-(hydroxyalkyl)amine of formula (I) is triisopropanolamine.

22. The polymer P according to claim 18, wherein the at least one N-(hydroxyalkyl)amine of formula (I) is triisopropanolamine.

23. The polymer P according to any one of claims 1-6 is obtained as follows: (a) Triethanolamine is subjected to self-condensation to obtain an intermediate Q with a degree of polymerization in the range of 3-300, calculated based on its hydroxyl value or the amount of water collected during the condensation process. (b) Intermediate Q is reacted with a mixture of glycidyl ethers containing formulas (IIp) and (IIq) to give polymer P: Equation (IIp) Equation (IIq).

24. The polymer P according to any one of claims 1-6 is obtained as follows: (a) Triethanolamine is subjected to self-condensation to obtain an intermediate Q with a degree of polymerization in the range of 3-300, calculated based on its hydroxyl value or the amount of water collected during the condensation process. (b) Intermediate Q is reacted with a mixture of glycidyl ethers containing formulas (IIp), (IIq), and (IIr) to give polymer P: Equation (IIp), Equation (IIq), Equation (IIr).

25. A method for preparing polymer P according to any one of claims 1-24, said method comprising at least the following steps: (i) subjecting at least one N-(hydroxyalkyl)amine of formula (I) to self-condensation at a temperature in the range of 160-240°C to obtain intermediate (Q), or At least one N-(hydroxyalkyl)amine (I) is co-condensed with Z at a temperature in the range of 160-240°C, wherein Z is at least one compound selected from Z1, Z2 and Z3, to obtain intermediate (Q); (ii) Adding the at least one glycidyl ether (II) to intermediate (Q) at a temperature in the range of 100-160°C; and (iii) Heating the reaction mixture obtained in step (ii) at a temperature in the range of 130-190°C to obtain the polymer; Wherein Z, Z1, Z2 and Z3 are as defined in claims 1-24, The total weight ratio of the at least one N-(hydroxyalkyl)amine of formula (I) used in step (i) to the total weight of the at least one glycidyl ether of formula (II) used in step (ii) is in the range of 1:10 to 10:

1.

26. The method of claim 25, wherein step (i) further comprises adding at least one catalyst in an amount ranging from 0.1% to 5% by weight based on the amount of the N-(hydroxyalkyl)amine of at least one formula (I).

27. The method of claim 26, wherein the at least one catalyst is an acid selected from phosphoric acid, diphosphoric acid, sulfuric acid, trifluoromethanesulfonic acid and toluenesulfonic acid.

28. The method of claim 25, wherein step (ii) further comprises adding at least one catalyst in an amount ranging from 0.1 to 2.0% by weight based on the total weight of intermediate Q and glycidyl ether (II).

29. The method of claim 26, wherein step (ii) further comprises adding at least one catalyst in an amount ranging from 0.1 to 2.0% by weight based on the total weight of intermediate Q and glycidyl ether (II).

30. The method of claim 27, wherein step (ii) further comprises adding at least one catalyst in an amount ranging from 0.1 to 2.0% by weight based on the total weight of intermediate Q and glycidyl ether (II).

31. The method of claim 28, wherein the at least one catalyst is selected from the group consisting of: (i) Lewis acids selected from boron trifluoride, titanium tetrachloride, tin chloride, zirconium tetrachloride, and their complexes; and (ii) Equation R 12 R 13 R 14 R 15 P + X - Season Salt, of which R 12 R 13 R 14 and R 15 Independently selected from substituted or unsubstituted linear or branched C1-C 10 Alkyl, substituted or unsubstituted C6-C 18 Aryl and substituted or unsubstituted linear or branched C7-C 18 Aryl alkyl group and X is a halide.

32. The method of claim 29, wherein the at least one catalyst is selected from the following: (i) Lewis acids selected from boron trifluoride, titanium tetrachloride, tin chloride, zirconium tetrachloride, and their complexes; and (ii) Equation R 12 R 13 R 14 R 15 P + X - Season Salt, of which R 12 R 13 R 14 and R 15 Independently selected from substituted or unsubstituted linear or branched C1-C 10 Alkyl, substituted or unsubstituted C6-C 18 Aryl and substituted or unsubstituted linear or branched C7-C 18 Aryl alkyl group and X is a halide.

33. The method of claim 30, wherein the at least one catalyst is selected from the group consisting of: (i) Lewis acids selected from boron trifluoride, titanium tetrachloride, tin chloride, zirconium tetrachloride, and their complexes; and (ii) Equation R 12 R 13 R 14 R 15 P + X - Season Salt, of which R 12 R 13 R 14 and R 15 Independently selected from substituted or unsubstituted linear or branched C1-C 10 Alkyl, substituted or unsubstituted C6-C 18 Aryl and substituted or unsubstituted linear or branched C7-C 18 Aryl alkyl group and X is a halide.

34. The method according to any one of claims 28-33, wherein the at least one catalyst is selected from boron trifluoride / benzylamine complex and ethyltriphenyl bromide. .

35. The method according to any one of claims 25-33, wherein the intermediate (Q) has: a. Viscosity measured at 23°C in the range of 2000–110000 mPas, according to ASTM-D7042; and b. Weight-average molecular weight (M) in the range of 2000-80000 g / mol w The number-average molecular weight (M) in the range of 1000-25000 g / mol n The polydispersity index (PDI) in the range of 1.0–3.0 was determined by gel permeation chromatography (HFIP).

36. The method of claim 34, wherein the intermediate (Q) has: a. Viscosity measured at 23°C in the range of 2000–110000 mPas, according to ASTM-D7042; and b. Weight-average molecular weight (M) in the range of 2000-80000 g / mol w The number-average molecular weight (M) in the range of 1000-25000 g / mol n The polydispersity index (PDI) in the range of 1.0–3.0 was determined by gel permeation chromatography (HFIP).

37. Use of polymer P according to any one of claims 1-24 as a wetting agent.

38. Use of the polymer P according to any one of claims 1-24 in a coating composition.

39. Use of polymer P according to any one of claims 1-24 as an antifoaming agent.

40. Use of the polymer P according to any one of claims 1-24 in an antifoaming composition.

41. An antifoaming composition comprising polymer P according to any one of claims 1-24.

42. The defoamer composition of claim 41 further comprises at least one additive selected from silicone oil, mineral oil, emulsifying agent, silica particles, wax and water.

43. A coating composition comprising polymer P according to any one of claims 1-24.

44. The coating composition of claim 43 further comprises at least one additive selected from pigment dispersants, rheology modifiers, UV filters, defoamers, leveling agents, slip agents, substrate wetting agents, antioxidants, free radical scavengers, biocides, and coalescing agents.

45. An article coated with a coating composition according to claim 43 or 44.

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