Amine-modified polymers, controlled free radical polymerization for their preparation and implementation thereof

Abstract

The present invention relates to amine-modified polymers and methods for their preparation. The invention also relates to the use of said polymers as dispersants in ink and coating compositions. Polyacrylate polymers are obtained by controlled free radical polymerization of a mixture comprising at least one acrylate monomer. Post-modification of polyacrylate polymers results in amine-modified polymers that provide improved viscosity parameters without sacrificing the advantages of a well-defined polymer structure.

Description

Field of the Invention

[0001] The present invention relates to an amine-modified polymer useful as a dispersant in ink and coating compositions. Background of the Invention

[0003] Pigments, the main components of coating and ink compositions, are usually dispersed in finely divided form to ensure uniformity of color and related properties (such as gloss) throughout the composition. However, it is well known that pigments such as carbon black tend to reaggregate over time, thereby leading to non-uniformity, loss of gloss or jetness properties and an unfavorable increase in viscosity in the composition. Therefore, dispersants, i.e. polymers that ensure stable pigment distribution throughout the composition, are key components in modern ink and coating compositions.

[0004] Controlled free radical polymerization (CFRP) is a tool to tailor the microstructure of polymers (e.g., block copolymers) in a way that is conducive to dispersing and stabilizing pigments. Furthermore, the combination of CFRP with subsequent post-modification of the resulting polymers enables the introduction of useful chemical moieties that contribute to solubility and overall functionality. A large number of different polymer materials are available through one CFRP process for use in water-based or solvent-based high-solids systems.

[0005] Although the concept of post-modification of classically produced polymers is known and described, for example, in DE 4308773, it has not been widely used because polymer analogous reactions are generally much more difficult to control than their low molecular weight analogs. US 10 / 623685 proposes post-modification of classically produced acrylate polymers for use as dispersants.

[0006] Due to the polymeric nature of the substrate, post-modification reactions are slow and often incomplete unless drastic reaction conditions such as high temperatures or highly reactive reagents are used. However, these measures often result in less defined polymer structures caused by chain scission and cross-coupling reactions, leading to broadening of the molecular weight distribution, branching and gel formation. Another fundamental problem in polymer analogous reactions is that the reaction is usually not carried out to completion, and it is very difficult and expensive, if not impossible, to purify the resulting modified polymer from unconverted reagents or unwanted by-products. In order to be applicable in industry, functional reproducibility is a key criterion. Therefore, post-modification of polymers has not been widely used due to the uncertainty of the resulting products.

[0007] In view of the above, it is an object of the present invention to obtain polymers that are easy to produce and provide improved properties (such as viscosity) while being formulated as dispersants in ink and coating compositions without interfering with basic functions (such as gloss or jetness). SUMMARY OF THE INVENTION

[0009] It has surprisingly been found that post-modification of polyacrylate polymers, particularly transamidization, produces amine-modified polymers that offer improved viscosity parameters without sacrificing the advantages of well-defined polymer structure, such as jetness.

[0010] Accordingly, a main aspect of the present invention relates to a polymer obtained by reacting the following components

[0011] i) at least one polyacrylate P1 obtained by controlled free radical polymerization of a mixture M1 in the presence of a1 or a2, the mixture M1 comprising at least one acrylate monomer selected from C1-C6 alkyl acrylates, C1-C6 alkyl methacrylates, hydroxy C1-C6 alkyl acrylates and hydroxy C1-C6 alkyl methacrylates,

[0012] Where a1 is at least one of the formula R 21 R 22 NOX(I) is a nitroxyl ether and a2 is at least one of the formula R 21 R 22 The stable nitroxyl radical of NO·(II);

[0013] R 21 and R 22 are independently selected from substituted or unsubstituted straight or branched C1-C 18 Alkyl, where R 21 and R 22 Together with the nitrogen atom to which they are attached, they form an unsubstituted or substituted 5- to 10-membered aliphatic ring containing 1 to 3 heteroatoms selected from nitrogen and oxygen, and X is selected from -CH2-phenyl, -CH3CH-phenyl, -(CH3)2C-phenyl, -(C5-C6 cycloalkyl)2C-CN, -(CH3)2CCN, -CH2CH=CH2, -CH3CH-CH=CH2, -(C1-C4 alkyl)CR 20 -C(O)-phenyl, -(C1-C4)alkyl-CR 20 -C(O)-(C1-C4)alkoxy, -(C1-C4)alkyl-CR 20 -C(O)-(C1-C4)alkyl, -(C1-C4)alkyl-CR 20 -C(O)-N-di(C1-C4)alkyl, -(C1-C4)alkyl-CR 20 -C(O)-NH(C1-C4)alkyl and -(C1-C4)alkyl-CR 20 -C(O)-NH2, where R 20 is hydrogen or (C1-C4)alkyl,

[0014] and

[0015] ii) a mixture M2 comprising at least one alcohol W selected from W1 and W2 and at least one amine Z selected from Z1 and Z2;

[0016] in,

[0017] W1 is R 1 -OH, where R 1 is a substituted or unsubstituted straight or branched C8-C 36 alkyl;

[0018] W2 is at least one of the formula B-(OA) n -OH polyether alcohol, wherein A is a substituted or unsubstituted straight chain or branched C1-C4 alkylene, and B is selected from a substituted or unsubstituted straight chain or branched C1-C 22 Alkyl, substituted or unsubstituted C1-C 24 Alkyl aryl and substituted or unsubstituted C1-C 24 dialkylaryl, n is an integer in the range of ≥1 to ≤150;

[0019] Z1 is NH2-R 11 -NR 12 R 13 , Z2 is NH2-R 11 -Y,

[0020] Where R 11 is a substituted or unsubstituted straight or branched C1-C 12 Alkylene;

[0021] R 12 and R 13 are independently selected from hydrogen and substituted or unsubstituted straight or branched C1-C 12 Alkyl, or

[0022] R 12 and R 13 Together with the nitrogen atom to which they are attached, they form an unsubstituted or substituted 3- to 12-membered ring containing 1 to 3 heteroatoms selected from nitrogen and oxygen;

[0023] and

[0024] Y is a 5- or 6-membered N-containing heterocyclic ring containing 1 or 2 nitrogen atoms and 0 or 1 oxygen atoms.

[0025] In another aspect, the present invention provides a method for preparing the polymer, comprising at least the following steps:

[0026] a. polymerizing a mixture M1 comprising at least one acrylate monomer in the presence of a1 or a2;

[0027] Where a1 is at least one of the formula R 21 R22 NOX(I) is a nitroxyl ether and a2 is at least one of the formula R 21 R 22 The stable nitroxyl radical of NO·(II) 21 and R 22 are independently selected from substituted or unsubstituted straight or branched C1-C 18 Alkyl, where R 21 and R 22 Together with the nitrogen atom to which they are attached, they form an unsubstituted or substituted 5- to 10-membered aliphatic ring containing 1 to 3 heteroatoms selected from nitrogen and oxygen, and X is selected from -CH2-phenyl, -CH3CH-phenyl, -(CH3)2C-phenyl, -(C5-C6 cycloalkyl)2C-CN, -(CH3)2CCN, -CH2CH=CH2, -CH3CH-CH=CH2, -(C1-C4 alkyl)CR 20 -C(O)-phenyl, -(C1-C4)alkyl-CR 20 -C(O)-(C1-C4)alkoxy, -(C1-C4)alkyl-CR 20 -C(O)-(C1-C4)alkyl, -(C1-C4)alkyl-CR 20 -C(O)-N-di(C1-C4)alkyl, -(C1-C4)alkyl-CR 20 -C(O)-NH(C1-C4)alkyl and -(C1-C4)alkyl-CR 20 -C(O)-NH2, where R 20 is hydrogen or (C1-C4)alkyl; and

[0028] b. modifying the polyacrylate obtained in step a. by transesterification using at least one alcohol (W) selected from W1 and W2 and transamide using at least one amine (Z) selected from Z1 and Z2;

[0029] Where W1 is R 1 -OH, where R 1 is a substituted or unsubstituted straight or branched C8-C 36 alkyl;

[0030] W2 is at least one of the formula B-(OA) n -OH polyether alcohol, wherein A is a substituted or unsubstituted straight chain or branched C1-C4 alkylene, and B is selected from a substituted or unsubstituted straight chain or branched C1-C 22 Alkyl, substituted or unsubstituted C1-C 24 Alkyl aryl or substituted and unsubstituted C1-C 24 dialkylaryl, n is an integer in the range of ≥1 to ≤150;

[0031] Z1 is NH2-R 11 -NR 12 R 13 , Z2 is NH2-R 11 -Y,

[0032] Where R 11 is a substituted or unsubstituted straight or branched C1-C 12 Alkylene;

[0033] R 12 and R 13 are independently selected from hydrogen and substituted or unsubstituted straight or branched C1-C 12 Alkyl, or R 12 and R 13 Together with the nitrogen atom to which they are attached, they form an unsubstituted or substituted 3- to 12-membered ring containing 1 to 3 heteroatoms selected from nitrogen and oxygen;

[0034] Y is a 5- or 6-membered N-containing heterocyclic ring containing 1 or 2 nitrogen atoms and 0 or 1 oxygen atoms.

[0035] In still another aspect, the present invention provides a coating composition comprising the polymer.

[0036] In still another aspect, the present invention provides an ink composition comprising the polymer.

[0037] In another aspect, the present invention provides use of the polymer as a dispersant in a coating composition or an ink composition. DETAILED DESCRIPTION OF THE INVENTION

[0039] Before describing the present compositions and formulations of the present invention, it is to be understood that the present invention is not limited to the particular compositions and formulations described, as such compositions and formulations may, of course, vary. It is also to be understood that the terminology used herein is not intended to be limiting, as the scope of the present invention is limited only by the appended claims.

[0040] In addition, ranges specified throughout this specification also include endpoint values, i.e., a range of 10 to 50 means that both 10 and 50 are included in the range. For the avoidance of doubt, the applicant is entitled to any equivalents under applicable law. In addition, the values ​​selectable within the range do not need to be only integers, such as 12, 14, 45, 48, etc., but may also be non-integer values, such as 12.5, 14.2, 45.2, 48.5, etc.

[0041] In the following paragraphs, different aspects of the present invention are defined in more detail. Each aspect defined in this way can be combined with any other aspect, unless clearly indicated to the contrary. In particular, any feature indicated as being preferred or advantageous can be combined with any other feature indicated as being preferred or advantageous.

[0042] "One embodiment" or "an embodiment" mentioned throughout this specification refers to a particular element, structure or feature described in connection with the embodiment being included in at least one embodiment of the present invention. Therefore, the phrase "in one embodiment" or "in one embodiment" appearing in various places in this specification does not necessarily refer to the same embodiment, but may refer to the same embodiment. In addition, the terms "preferably", "more preferably", "even more preferably", "most preferably" and "particularly" or similar terms used below are used in conjunction with optional elements, rather than limiting the possibilities for selection. Therefore, the elements introduced by these terms are optional elements and are not intended to limit the scope of the claims in any way.

[0043] In addition, specific elements, structures or features can be combined in one or more embodiments in any suitable manner as apparent to those skilled in the art from this disclosure. In addition, although some embodiments described herein include some elements contained in other embodiments and do not include other elements, as will be appreciated by those skilled in the art, the combination of elements of different embodiments is intended to be within the scope of the present invention and constitutes different embodiments. For example, in the appended claims, any claimed embodiment can be used in any combination.

[0044] In addition, it should be noted that the terms "at least one", "one or more" or similar expressions indicating that a feature or element may exist once or more than once are usually used only once when introducing the corresponding feature or element. Subsequently, in most cases, when referring to the corresponding feature or element, the words "at least one" or "one or more" are not repeated, although in fact the corresponding feature or element may exist once or more than once.

[0045] As mentioned above, it is necessary to have a polymer that can serve as a dispersant for a coating or ink composition. The post-modification of a polymer is a way to introduce an attractive chemical moiety. However, as mentioned above, this strategy has not been widely used due to many shortcomings. Recently, EP 1 861 429 describes the post-modification of homopolymers and copolymers prepared by controlled radical polymerization. The polymer obtained by the CFRP method is post-modified by transesterification in the presence of alcohol. The post-modification carried out by transamide exchange is not disclosed in EP 1 861429.

[0046] Further studies in this direction led to the surprising discovery that dual post-modification of CFRP polymers in the presence of alcohols and amines yields amine-modified polymers capable of improving dispersant properties (eg, viscosity) while maintaining essential pigment parameters (eg, jetness).

[0047] Accordingly, one aspect of the present invention is embodiment 1, which relates to a polymer obtained by reacting the following components

[0048] i) at least one polyacrylate P1 obtained by controlled free radical polymerization of a mixture M1 in the presence of a1 or a2, the mixture M1 comprising at least one acrylate monomer selected from C1-C6 alkyl acrylates, C1-C6 alkyl methacrylates, hydroxy C1-C6 alkyl acrylates and hydroxy C1-C6 alkyl methacrylates,

[0049] Where a1 is at least one of the formula R 21 R 22 NOX(I) is a nitroxyl ether and a2 is at least one of the formula R 21 R 22 The stable nitroxyl radical of NO·(II);

[0050] R 21 and R 22 are independently selected from substituted or unsubstituted straight or branched C1-C 18 Alkyl, where R 21 and R 22 Together with the nitrogen atom to which they are attached, they form an unsubstituted or substituted 5- to 10-membered aliphatic ring containing 1 to 3 heteroatoms selected from nitrogen and oxygen, and X is selected from -CH2-phenyl, -CH3CH-phenyl, -(CH3)2C-phenyl, -(C5-C6 cycloalkyl)2C-CN, -(CH3)2CCN, -CH2CH=CH2, -CH3CH-CH=CH2, -(C1-C4 alkyl)CR 20 -C(O)-phenyl, -(C1-C4)alkyl-CR 20 -C(O)-(C1-C4)alkoxy, -(C1-C4)alkyl-CR 20 -C(O)-(C1-C4)alkyl, -(C1-C4)alkyl-CR 20 -C(O)-N-di(C1-C4)alkyl, -(C1-C4)alkyl-CR 20 -C(O)-NH(C1-C4)alkyl and -(C1-C4)alkyl-CR 20 -C(O)-NH2, where R 20 is hydrogen or (C1-C4)alkyl,

[0051] and

[0052] ii) a mixture M2 comprising at least one alcohol W selected from W1 and W2 and at least one amine Z selected from Z1 and Z2;

[0053] in,

[0054] W1 is R 1 -OH, where R 1 is a substituted or unsubstituted straight or branched C8-C36 alkyl;

[0055] W2 is at least one of the formula B-(OA) n -OH polyether alcohol, wherein A is a substituted or unsubstituted straight chain or branched C1-C4 alkylene, and B is selected from a substituted or unsubstituted straight chain or branched C1-C 22 Alkyl, substituted or unsubstituted C1-C 24 Alkyl aryl and substituted or unsubstituted C1-C 24 dialkylaryl, n is an integer in the range of ≥1 to ≤150;

[0056] Z1 is NH2-R 11 -NR 12 R 13 , Z2 is NH2-R 11 -Y,

[0057] Where R 11 is a substituted or unsubstituted straight or branched C1-C 12 Alkylene;

[0058] R 12 and R 13 are independently selected from hydrogen and substituted or unsubstituted straight or branched C1-C 12 Alkyl, or

[0059] R 12 and R 13 Together with the nitrogen atom to which they are attached, they form an unsubstituted or substituted 3- to 12-membered ring containing 1 to 3 heteroatoms selected from nitrogen and oxygen;

[0060] Y is a 5- or 6-membered N-containing heterocyclic ring containing 1 or 2 nitrogen atoms and 0 or 1 oxygen atoms.

[0061] Another aspect of the present invention is embodiment 2, which relates to a controlled radical polymerization method for preparing a polymer according to embodiment 1, comprising at least the following steps:

[0062] a. polymerizing a mixture M1 comprising at least one acrylate monomer in the presence of a1 or a2;

[0063] Where a1 is at least one of the formula R 21 R 22 NOX(I) is a nitroxyl ether and a2 is at least one of the formula R 21 R 22 The stable nitroxyl radical of NO·(II) 21 and R 22 are independently selected from substituted or unsubstituted straight or branched C1-C 18 Alkyl, where R 21 and R22 Together with the nitrogen atom to which they are attached, they form an unsubstituted or substituted 5- to 10-membered aliphatic ring containing 1 to 3 heteroatoms selected from nitrogen and oxygen, and X is selected from -CH2-phenyl, -CH3CH-phenyl, -(CH3)2C-phenyl, -(C5-C6 cycloalkyl)2C-CN, -(CH3)2CCN, -CH2CH=CH2, -CH3CH-CH=CH2, -(C1-C4 alkyl)CR 20 -C(O)-phenyl, -(C1-C4)alkyl-CR 20 -C(O)-(C1-C4)alkoxy, -(C1-C4)alkyl-CR 20 -C(O)-(C1-C4)alkyl, -(C1-C4)alkyl-CR 20 -C(O)-N-di(C1-C4)alkyl, -(C1-C4)alkyl-CR 20 -C(O)-NH(C1-C4)alkyl and -(C1-C4)alkyl-CR 20 -C(O)-NH2, where R 20 is hydrogen or (C1-C4)alkyl; and

[0064] b. modifying the polyacrylate obtained in step a. by transesterification using at least one alcohol (W) selected from W1 and W2 and transamide using at least one amine (Z) selected from Z1 and Z2;

[0065] Where W1 is R 1 -OH, where R 1 is a substituted or unsubstituted straight or branched C8-C 36 alkyl;

[0066] W2 is at least one of the formula B-(OA) n -OH polyether alcohol, wherein A is a substituted or unsubstituted straight chain or branched C1-C4 alkylene, and B is selected from a substituted or unsubstituted straight chain or branched C1-C 22 Alkyl, substituted or unsubstituted C1-C 24 Alkyl aryl or substituted and unsubstituted C1-C 24 dialkylaryl, n is an integer in the range of ≥1 to ≤150;

[0067] Z1 is NH2-R 11 -NR 12 R 13 , Z2 is NH2-R 11 -Y,

[0068] Where R 11 is a substituted or unsubstituted straight or branched C1-C 12 Alkylene;

[0069] R 12 and R 13 are independently selected from hydrogen and substituted or unsubstituted straight or branched C1-C 12 Alkyl, or R 12 and R 13 Together with the nitrogen atom to which they are attached, they form an unsubstituted or substituted 3- to 12-membered ring containing 1 to 3 heteroatoms selected from nitrogen and oxygen;

[0070] Y is a 5- or 6-membered N-containing heterocyclic ring containing 1 or 2 nitrogen atoms and 0 or 1 oxygen atoms.

[0071] In the present invention, the term "controlled free radical polymerization" or "CRFP" as used herein refers to a process for making defined oligomeric homopolymers and copolymers, including block and graft copolymers, by controlled or "living" growth of polymer chains. The process enables enhanced control of polydispersity and the production of polymers within a narrow molecular weight range. Here, the process involves the use of an initiator of the partial general formula R'R"NOX. In this polymerization process, free radical species R'R"NO· and ·X are generated, ·X being a free radical capable of polymerizing ethylene-containing monomer units, such as tert-butyl or cyanoisopropyl radicals.

[0072] The term "alkyl" as used herein refers to an acyclic saturated aliphatic group, including a straight chain or branched alkyl saturated hydrocarbon group, which is composed of the general formula C n H 2n+1 It represents and where n is the number of carbon atoms, such as 1, 2, 3, 4, etc.

[0073] For the purposes of the present invention, an unsubstituted straight-chain C1-C 18 The alkyl group is preferably selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl; more preferably selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl; still more preferably selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl and nonyl; most preferably selected from the group consisting of ethyl, propyl, butyl, pentyl, hexyl and heptyl; in particular selected from the group consisting of ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl.

[0074] In a preferred embodiment, the unsubstituted branched C1-C 18The alkyl group is preferably selected from the group consisting of isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, 3-methylhexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1-butyl, 2,3-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, 2,3-dimethyl-2-pentyl, butyl and 3,3-dimethyl-2-butyl, 1-methyl-2-ethyl-hexyl, 2-propyl-heptyl, 2-butyl-octyl, 2-pentyl-nonyl, 2-hexyl-decyl, isohexyl, isoheptyl, isooctyl, isononyl, isodecyl, isododecyl, isotetradecyl, isohexadecyl and isooctyl, more preferably selected from 2-ethyl-hexyl, 2-propyl-heptyl, 2-butyl-octyl, 2-pentyl-nonyl, 2-hexyl-decyl, isohexyl, isoheptyl, isooctyl, isononyl, isodecyl and isododecyl.

[0075] In a preferred embodiment, the substituted straight or branched C1-C 18 Alkyl refers to a C1-C1 substituted functional group selected from hydroxy, alkoxy, C(=O)-R4, CN, C(=O)-OR4, C(=O)-NR5, NR5 and SR4. 18 a branched or straight chain saturated hydrocarbon group of carbon atoms, wherein R4 and R5 are independently selected from hydrogen, a substituted or unsubstituted straight chain or branched C1-C 18 Alkyl, substituted or unsubstituted straight chain or branched C2-C 18 Alkenyl, substituted or unsubstituted C5-C 18 Cycloalkyl, substituted or unsubstituted C5-C 12 Cycloalkenyl, substituted or unsubstituted C6-C 18 Aryl and substituted or unsubstituted C7-C 18 Arylalkyl.

[0076] In a preferred embodiment, the substituted straight or branched C1-C 18 Alkyl refers to a C1-C 18a branched or straight chain saturated hydrocarbon group having 10 carbon atoms, wherein the functional group is selected from hydroxyl, alkoxy, C(=O)-R4, CN, C(=O)-OR4, C(=O)-NR5, NR5 and SR4,Preferably, the group consisting of 1-hydroxymethyl, 1-methoxymethyl, 1-hydroxyethyl, 1-hydroxypropyl, 1-hydroxybutyl, 1-hydroxypentyl, 1-hydroxyhexyl, 1-hydroxyheptyl, 1-hydroxyoctyl, 1-hydroxynonyl, 1-hydroxydecyl, 1-hydroxyundecyl, 1-hydroxydodecyl, 1-methoxymethyl, 1-methoxyethyl, 1-methoxypropyl, 1-methoxybutyl, 1-methoxypentyl, 1-methoxyhexyl, 1-methoxyheptyl, 1-methoxyoctyl, 1-methoxynonyl, 1-methoxydecyl, 1-methoxyundecyl, 1-methoxydodecyl, 1-hydroxytridecyl, 1-hydroxytetradecyl, 1-hydroxypentadecyl, 1-hydroxyhexadecyl, 1-hydroxyheptadecyl, 1-hydroxyoctadecyl 2-methoxypropyl, 2-methoxybutyl, 2-methoxypentyl, 2-methoxyhexyl, 2-methoxyheptyl, 2-methoxyoctyl, 2-methoxynonyl, 2-methoxydecyl, 2-methoxyundecyl, 2-methoxydodecyl, 2-methoxytridecyl, 2-methoxytetradecyl, 2-methoxypentadecyl, 2-methoxyhexadecyl, 2-methoxyheptadecyl, 2-methoxyoctadecyl, 1-acetoxymethyl, 1-acetoxyethyl, 1-acetoxypropyl, 1-acetoxybutyl, 1-acetoxypentyl, 1-acetoxyhexyl, 1-acetoxyheptyl, 1-acetoxyoctyl, 1-acetoxynonyl, 1-acetoxydecyl, 1-acetoxyethyl, 1-acetoxypropyl, 1-acetoxybutyl, 1-acetoxypentyl, 1-acetoxyhexyl, 1-acetoxyheptyl, 1-acetoxyoctyl, 1-acetoxynonyl, 1-acetoxydecyl, 1-acetoxy undecyl, 1-acetoxydodecyl, 1-acetoxytridecyl, 1-acetoxytetradecyl, 1-acetoxypentadecyl, 1-acetoxyhexadecyl, 1-acetoxyheptadecyl, 1-acetoxyoctadecyl, 1-cyanomethyl, 1-cyanoethyl, 1-cyanopropyl, 1-cyanobutyl, 1-cyanopentyl, 1-cyanohexyl, 1-cyanoheptyl, 1-cyanooctyl, 1-cyanononyl, 1-cyanodecyl, 1-cyanoundecyl, 1-cyanododecyl, 1-cyanododecyl, 1-cyanotridecyl, 1-cyanotetradecyl, 1-cyanopentadecyl, 1-cyanohexadecyl, 1-cyanoheptadecyl, 1-cyanooctadecyl, 2-cyanopropyl, 2-cyanobutyl, 2-cyanopentyl, 2 -cyanohexyl, 2-cyanoheptyl, 2-cyanooctyl, 2-cyanononyl, 2-cyanodecyl, 2-cyanoundecyl, 2-cyanododecyl, 2-cyanotridecyl, 2-cyanotetradecyl, 2-cyanopentadecyl, 2-cyanohexadecyl, 2-cyanoheptadecyl, 2-cyanooctadecyl, 2-cyanooctadecyl, 1-sulfonylmethyl, 1-sulfonylethyl, 1-sulfonylpropyl, 1-sulfonylbutyl, 1-sulfonylpentyl, 1-sulfonylhexyl, 1-sulfonylheptyl, 1-sulfonyloctyl, 1-sulfonylnonyl, 1-sulfonyldecyl, 1-sulfonylundecyl and 1-sulfonyldodecyl, 1-sulfonyltridecyl, 1-sulfonyltetradecyl, 1-sulfonylpentadecyl, 1-sulfonylhexadecyl, 1-sulfonylheptadecyl and 1-sulfonyloctadecyl. ,

[0077] In a preferred embodiment of the present invention, the at least one acrylate monomer in Embodiment 1 or Embodiment 2 is selected from C1-C6 alkyl esters of acrylic acid, preferably C2-C5 alkyl esters of acrylic acid.

[0078] In a more preferred embodiment of the present invention, the at least one acrylate monomer in embodiment 1 or embodiment 2 is selected from n-butyl acrylate, methyl acrylate and ethyl acrylate.

[0079] In a more preferred embodiment of the present invention, the at least one acrylate monomer in Embodiment 1 or Embodiment 2 is selected from n-butyl (meth)acrylate, methyl (meth)acrylate and ethyl (meth)acrylate.

[0080] In a most preferred embodiment of the present invention, the at least one acrylate monomer in embodiment 1 or embodiment 2 is n-butyl (meth)acrylate.

[0081] In a preferred embodiment of the present invention, the at least one acrylate monomer in Embodiment 1 or Embodiment 2 is selected from hydroxy C1-C6 alkyl acrylates, preferably hydroxy C2-C5 alkyl acrylates.

[0082] In a most preferred embodiment of the present invention, the at least one acrylate monomer in embodiment 1 or embodiment 2 is 4-hydroxybutyl acrylate.

[0083] In a preferred embodiment of the present invention, the at least one acrylate monomer in embodiment 1 or embodiment 2 is selected from hydroxy C1-C6 alkyl methacrylates, preferably hydroxy C2-C5 alkyl methacrylates.

[0084] In a most preferred embodiment of the present invention, the at least one acrylate monomer in embodiment 1 or embodiment 2 is 4-hydroxybutyl methacrylate.

[0085] In a preferred embodiment of the present invention, the structural unit NOX or NO· in embodiment 1 or embodiment 2 may be part of a cyclic ring system or be substituted to form an acyclic structure.

[0086] In a more preferred embodiment of the invention, the structural unit NOX or NO· in embodiment 1 or embodiment 2 is part of a 5- or 6-membered heterocyclic ring, optionally with additional nitrogen or oxygen atoms in the ring system.

[0087] In a more preferred embodiment of the present invention, the formula R in Embodiment 1 or Embodiment 2 21 R 22 The nitroxyl ether of NOX is a compound of formula (Ic), (Id) or (Ie),

[0088]

[0089] in,

[0090] R is hydrogen, C1-C2-C3-C1-C2-C1 ... 18 An alkyl group, a cyanoethyl group, a benzoyl group, a glycidyl group, a monovalent group of an aliphatic carboxylic acid having 2 to 18 carbon atoms, a monovalent group of an alicyclic carboxylic acid having 7 to 15 carbon atoms, or a monovalent group of an α,β-unsaturated carboxylic acid having 3 to 5 carbon atoms, or a monovalent group of an aromatic carboxylic acid having 7 to 15 carbon atoms;

[0091] R 101 It is C1-C 12 Alkyl, C5-C7 cycloalkyl, C7-C8 aralkyl, C2-C 18 Alkanoyl, C3-C5 alkenoyl or benzoyl;

[0092] R 102 is a C1-C2- 18 alkyl, C5-C7 cycloalkyl, C2-C8 alkenyl, or a glycidyl group, a group of the formula -CH2CH(OH)-Z, or a group of the formula -CO-Z or -CONH-Z,

[0093] wherein Z is hydrogen, methyl or phenyl;

[0094] G6 is hydrogen and

[0095] G6 is hydrogen or C1-C4 alkyl,

[0096] G1 and G3 are methyl and G2 and G4 are ethyl or propyl, or G1 and G2 are methyl and G3 and G4 are ethyl or propyl;

[0097] X is selected from -CH2-phenyl, CH3CH-phenyl, (CH3)2C-phenyl, (C5-C6 cycloalkyl)2CCN, (CH3)2CCN,

[0098]

[0099] -CH2CH=CH2、CH3CH-CH=CH2(C1-C4 alkyl)CR 20 -C(O)-phenyl, (C1-C4)alkyl-CR 20 -C(O)-(C1-C4)alkoxy, (C1-C4)alkyl-CR 20 -C(O)-(C1-C4)alkyl, (C1-C4)alkyl-CR 20-C(O)-N-di(C1-C4)alkyl, (C1-C4)alkyl-CR 20 -C(O)-NH(C1-C4)alkyl, (C1-C4)alkyl-CR 20 -C(O)-NH2, where R 20 It is hydrogen or (C1-C4) alkyl.

[0100] In another preferred embodiment of the present invention, the formula R in Embodiment 1 or Embodiment 2 21 R 22 The nitroxyl ether of NOX is a compound of formula (If), (Ig), (Ih), (Ii), (Ij) or (Ik),

[0101]

[0102] in,

[0103] R 201 , R 202 , R 203 and R 204 Independently of each other, C1-C 18 Alkyl, C3-C 18 Alkenyl, C3-C 18 Alkynyl, OHYDROGEN, halogen or group -OC(O)-R 205 Substituted C1-C 18 Alkyl, C3-C 18 Alkenyl, C3-C 18 Alkynyl, substituted by at least one O atom and / or NR 205 C2-C 18 Alkyl, C3-C 12 Cycloalkyl or C6-C 10 Aryl, or R 201 and R 202 and / or R 203 and R 204 Together with the carbon atom to which it is attached, it forms a C3-C12 cycloalkyl group; R 205 , R 206 and R 207 are independently hydrogen, C1-C 18 Alkyl or C6-C 10 Aryl; R 208 It is hydrogen, OHYDROGEN, C1-C 18 Alkyl, C3-C 18 Alkenyl, C3-C 18 Alkynyl, substituted by one or more OHYDROGEN, halogen or the group -OC(O)-R 205 Substituted C1-C 18 Alkyl, C3-C18 Alkenyl, C3-C 18 Alkynyl, substituted by at least one O atom and / or NR 205 C2-C 18 Alkyl, C3-C 12 Cycloalkyl or C6-C 10 Aryl, C7-C9 phenylalkyl, C5-C 10 Heteroaryl, -C(O)-C1-C 18 Alkyl, -OC1-C 18 Alkyl or -COOC1-C 18 Alkyl; R 209 , R 210 , R 211 and R 212 are independently hydrogen, phenyl or C1-C 18 Alkyl; X is selected from -CH2-phenyl, CH3CH-phenyl, (CH3)2C-phenyl, (C5-C6 cycloalkyl)2CCN, (CH3)2CCN,

[0104]

[0105] -CH2CH=CH2、CH3CH-CH=CH2(C1-C4 alkyl)CR 20 -C(O)-phenyl, (C1-C4)alkyl-CR 20 -C(O)-(C1-C4)alkoxy, (C1-C4)alkyl-CR 20 -C(O)-(C1-C4)alkyl, (C1-C4)alkyl-CR 20 -C(O)-N-di(C1-C4)alkyl, (C1-C4)alkyl-CR 20 -C(O)-NH(C1-C4)alkyl, (C1-C4)alkyl-CR 20 -C(O)-NH2, where R 20 It is hydrogen or (C1-C4) alkyl.

[0106] In a more preferred embodiment of the present invention, the formula R in Embodiment 1 or Embodiment 2 21 R 22 The nitroxyl ethers of NOX are compounds of formula (If), (Ig), (Ih), (Ii), (Ij) and (Ik), R 201 , R 202 , R 203 and R 204 At least two of the groups are ethyl, propyl or butyl, and the rest are methyl; or R 201 and R 202 or R 203 and R 204Together with the attached carbon atom it forms a C5-C6 cycloalkyl group, and one of the remaining substituents is ethyl, propyl or butyl.

[0107] In a most preferred embodiment of the present invention, X in Embodiment 1 or Embodiment 2 is CH3CH-phenyl.

[0108] In another preferred embodiment of the present invention, the at least one formula R in embodiment 1 or embodiment 2 21 R 22 The nitroxyl ether of NOX is a compound of formula III,

[0109]

[0110] in,

[0111] G 11 , G 12 , G 13 and G 14 are independently C1-C4 alkyl, or G 11 and G 12 Together with G 13 and G 14 Together, or G 11 and G 12 Together or G 13 and G 14 Together they are pentamethylene; G 15 and G 16 Each independently represents hydrogen or C1-C4 alkyl;

[0112] X is as defined above;

[0113] k is 1, 2, 3, or 4;

[0114] Y is O or NR 302 Or when k is 1 and R 301 When Y represents an alkyl or aryl group, it is also a direct bond; R 302 is hydrogen, C1-C 18 Alkyl or phenyl;

[0115] If k is 1,

[0116] In a more preferred embodiment of the present invention, R in Embodiment 1 or Embodiment 2 301 is hydrogen, straight or branched C1-C 18 Alkyl, C3-C 18 Alkenyl or C3-C 18 Alkynyl, which may be unsubstituted or substituted by one or more OHYDROGEN, C1-C8 alkoxy, carboxyl, C1-C8 alkoxycarbonyl; C5-C 12 Cycloalkyl or C5-C12 Cycloalkenyl; phenyl, C7-C9 phenylalkyl or naphthyl, which may be unsubstituted or substituted by one or more C1-C8 alkyl, halogen, OH, C1-C8 alkoxy, carboxyl, C1-C8 alkoxycarbonyl; -C(O)-C1-C 36 An alkyl group, or an acyl moiety of an α,β-unsaturated carboxylic acid having 3 to 5 carbon atoms or an acyl moiety of an aromatic carboxylic acid having 7 to 15 carbon atoms;

[0117] -SO3-Q + 、-PO(OQ + )2, -P(O)(OC1-C8alkyl2)2, -P(O)(OH2)2, -SO2-OHYDROGEN, -SO2-C1-C8alkyl, -CO-NH-C1-C8alkyl, -CONH2, COO-C1-C8alkyl2, COOH or Si(Me)3, wherein Q + Yes H + , ammonium or alkali metal cations;

[0118] If k is 2,

[0119] R in Embodiment 1 or Embodiment 2 301 It is C1-C 18 Alkylene, C3-C 18 Alkenylene or C3-C 18 Alkyne groups, which may be unsubstituted or substituted by one or more OHYDROGEN, C1-C8 alkoxy, carboxyl, C1-C8 alkoxycarbonyl; or xylene; or R 301 is a diacyl group of an aliphatic dicarboxylic acid having 2 to 36 carbon atoms or a diacyl group of an alicyclic or aromatic dicarboxylic acid having 8 to 14 carbon atoms;

[0120] If k is 3,

[0121] R in Embodiment 1 or Embodiment 2 301 is a trivalent radical of an aliphatic, alicyclic or aromatic tricarboxylic acid;

[0122] And if k is 4,

[0123] R in Embodiment 1 or Embodiment 2 301 It is a tetravalent radical of an aliphatic, alicyclic or aromatic tetracarboxylic acid.

[0124] In another preferred embodiment of the present invention, G in Embodiment 1 or Embodiment 2 16 is hydrogen and G 15 is hydrogen or C1-C4 alkyl, especially methyl, G 11 and G 12 is methyl and G13 and G 14 It is ethyl or propyl.

[0125] In a more preferred embodiment of the present invention, the formula R in embodiment 1 or embodiment 2 21 R 22 The nitroxyl ether of NOX is a compound of formula (Ia)

[0126]

[0127] in,

[0128] G 1 , G 2 , G 3 , G 4 are independently C1-C6 alkyl, or G 1 and G 2 or G 3 and G 4 , or G 1 and G 2 and G 3 and G 4 Together they form C5-C 12 Cycloalkyl;

[0129] G 5 , G 6 are independently hydrogen, C1-C 18 Alkyl, phenyl, naphthyl or the group COOC1-C 18 alkyl;

[0130] X is selected from -CH2-phenyl, CH3CH-phenyl, (CH3)2C-phenyl, (C5-C6 cycloalkyl)2CCN, (CH3)2CCN, -CH2CH=CH2, CH3CH-CH=CH2(C1-C4 alkyl)CR 20 -C(O)-phenyl, (C1-C4)alkyl-CR 20 -C(O)-(C1-C4)alkoxy, (C1-C4)alkyl-CR 20 -C(O)-(C1-C4)alkyl, (C1-C4)alkyl-CR 20 -C(O)-N-di(C1-C4)alkyl, (C1-C4)alkyl-CR 20 -C(O)-NH(C1-C4)alkyl, (C1-C4)alkyl-CR 20 -C(O)-NH2, where R 20 is hydrogen or (C1-C4)alkyl,

[0131] * indicates chemical valence.

[0132] In a preferred embodiment of the present invention, the formula R in Embodiment 1 or Embodiment 2 21 R 22 The nitroxyl ether of NOX is a compound of formula (Ia) wherein G 1 , G 2 , G 3 , G 4 are independently C1-C4 alkyl, or G 1 and G 2 or G 3 and G 4 , or G 1 and G 2 and G 3 and G 4 Together they form C5-C 12 Cycloalkyl.

[0133] In another preferred embodiment of the present invention, the formula R in Embodiment 1 or Embodiment 2 21 R 22 The nitroxyl ether of NOX is a compound of formula (Ia) wherein G 1 , G 2 , G 3 , G 4 are independently C1-C4 alkyl.

[0134] In a preferred embodiment of the present invention, the formula R in Embodiment 1 or Embodiment 2 21 R 22 The nitroxyl ether of NOX is a compound of formula (Ia) wherein G 5 , G 6 are independently H or C1-C8 alkyl.

[0135] In another preferred embodiment of the present invention, the formula R in Embodiment 1 or Embodiment 2 21 R 22 The nitroxyl ether of NOX is a compound of formula (Ia) wherein G 5 , G 6 are independently H or C1-C3 alkyl.

[0136] In a preferred embodiment of the present invention, the formula R in Embodiment 1 or Embodiment 2 21 R 22 The nitroxyl ether of NOX is a compound of formula (Ia) wherein X is selected from -CH2-phenyl, CH3CH-phenyl or (CH3)2C-phenyl.

[0137] In another preferred embodiment of the present invention, the formula R in Embodiment 1 or Embodiment 2 21 R 22The nitroxyl ether of NOX is a compound of formula (Ia) wherein X is selected from CH3CH-phenyl.

[0138] In a more preferred embodiment of the present invention, the at least one nitroxyl ether in Embodiment 1 or Embodiment 2 is selected from the formula

[0139]

[0140]

[0141] In a most preferred embodiment of the present invention, the at least one nitroxyl ether in embodiment 1 or embodiment 2 is

[0142]

[0143] In a preferred embodiment of the present invention, the formula R in Embodiment 1 or Embodiment 2 21 R 22 The stable nitroxyl radical of NO· is the structural unit of formula (IIa)

[0144]

[0145] in,

[0146] G 1 , G 2 , G 3 , G 4 are independently C1-C6 alkyl, or G 1 and G 2 or G 3 and G 4 , or G 1 and G 2 and G 3 and G 4 Together they form C5-C 12 Cycloalkyl;

[0147] G 5 , G 6 are independently hydrogen, C1-C 18 Alkyl, phenyl, naphthyl or the group COOC1-C 18 alkyl;

[0148] X is selected from -CH2-phenyl, CH3CH-phenyl, (CH3)2C-phenyl, (C5-C6 cycloalkyl)2CCN, (CH3)2CCN, -CH2CH=CH2, CH3CH-CH=CH2(C1-C4 alkyl)CR 20 -C(O)-phenyl, (C1-C4)alkyl-CR 20-C(O)-(C1-C4)alkoxy, (C1-C4)alkyl-CR 20 -C(O)-(C1-C4)alkyl, (C1-C4)alkyl-CR 20 -C(O)-N-di(C1-C4)alkyl, (C1-C4)alkyl-CR 20 -C(O)-NH(C1-C4)alkyl, (C1-C4)alkyl-CR 20 -C(O)-NH2, where R 20 is hydrogen or (C1-C4)alkyl,

[0149] * indicates valence.

[0150] In a preferred embodiment of the present invention, the formula R in Embodiment 1 or Embodiment 2 21 R 22 The stable nitroxyl radical of NO· is a compound of formula (IIa), wherein G 1 , G 2 , G 3 , G 4 are independently C1-C4 alkyl, or G 1 and G 2 or G 3 and G 4 , or G 1 and G 2 and G 3 and G 4 Together they form C5-C 12 Cycloalkyl.

[0151] In another preferred embodiment of the present invention, the formula R in Embodiment 1 or Embodiment 2 21 R 22 The stable nitroxyl radical of NO· is a compound of formula (IIa), wherein G 1 , G 2 , G 3 , G 4 are independently C1-C4 alkyl.

[0152] In a preferred embodiment of the present invention, the formula R in Embodiment 1 or Embodiment 2 21 R 22 The stable nitroxyl radical of NO· is a compound of formula (IIa), wherein G 5 , G 6 are independently H or C1-C8 alkyl.

[0153] In another preferred embodiment of the present invention, the formula R in Embodiment 1 or Embodiment 2 21 R 22The stable nitroxyl radical of NO· is a compound of formula (IIa), wherein G 5 , G 6 are independently H or C1-C3 alkyl.

[0154] In a preferred embodiment of the present invention, the formula R in Embodiment 1 or Embodiment 2 21 R 22 The stable nitroxyl radical of NO· is a compound of formula (IIa), wherein X is selected from -CH2-phenyl, CH3CH-phenyl or (CH3)2C-phenyl.

[0155] In another preferred embodiment of the present invention, the formula R in Embodiment 1 or Embodiment 2 21 R 22 The stable nitroxyl radical of NO· is a compound of formula (IIa), wherein X is selected from CH3CH-phenyl.

[0156] In another preferred embodiment of the present invention, the at least one formula R in embodiment 1 or embodiment 2 21 R 22 The stable nitroxyl radical of NO· is a compound of formula III',

[0157]

[0158] in,

[0159] G 11 , G 12 , G 13 and G 14 are independently C1-C4 alkyl, or G 11 and G 12 Together with G 13 and G 14 Together, or G 11 and G 12 Together or G 13 and G 14 Together they are pentamethylene; G 15 and G 16 Each independently represents hydrogen or C1-C4 alkyl;

[0160] X is as defined above;

[0161] k is 1, 2, 3, or 4;

[0162] Y is O or NR 302 Or when k is 1 and R 301 When Y represents an alkyl or aryl group, it is also a direct bond; R 302 is hydrogen, C1-C 18 Alkyl or phenyl;

[0163] If k is 1,

[0164] In a more preferred embodiment of the present invention, R in Embodiment 1 or Embodiment 2 301 is hydrogen, straight or branched C1-C 18 Alkyl, C3-C 18 Alkenyl or C3-C 18 Alkynyl, which may be unsubstituted or substituted by one or more OHYDROGEN, C1-C8 alkoxy, carboxyl, C1-C8 alkoxycarbonyl; C5-C 12 Cycloalkyl or C5-C 12 Cycloalkenyl; phenyl, C7-C9 phenylalkyl or naphthyl, which may be unsubstituted or substituted by one or more C1-C8 alkyl, halogen, OH, C1-C8 alkoxy, carboxyl, C1-C8 alkoxycarbonyl; -C(O)-C1-C 36 An alkyl group, or an acyl moiety of an α,β-unsaturated carboxylic acid having 3 to 5 carbon atoms or an acyl moiety of an aromatic carboxylic acid having 7 to 15 carbon atoms;

[0165] -SO3-Q + 、-PO(OQ + )2, -P(O)(OC1-C8alkyl2)2, -P(O)(OH2)2, -SO2-OHYDROGEN, -SO2-C1-C8alkyl, -CO-NH-C1-C8alkyl, -CONH2, COO-C1-C8alkyl2, COOH or Si(Me)3, wherein Q + Yes H + , ammonium or alkali metal cations;

[0166] If k is 2,

[0167] R in Embodiment 1 or Embodiment 2 301 It is C1-C 18 Alkylene, C3-C 18 Alkenylene or C3-C 18 Alkyne groups, which may be unsubstituted or substituted by one or more OHYDROGEN, C1-C8 alkoxy, carboxyl, C1-C8 alkoxycarbonyl; or xylene; or R 301 is a diacyl group of an aliphatic dicarboxylic acid having 2 to 36 carbon atoms or a diacyl group of an alicyclic or aromatic dicarboxylic acid having 8 to 14 carbon atoms;

[0168] If k is 3,

[0169] R in Embodiment 1 or Embodiment 2 301 is a trivalent radical of an aliphatic, alicyclic or aromatic tricarboxylic acid;

[0170] If k is 4,

[0171] R in Embodiment 1 or Embodiment 2 301 It is a tetravalent radical of an aliphatic, alicyclic or aromatic tetracarboxylic acid.

[0172] In a more preferred embodiment of the present invention, the formula R in Embodiment 1 or Embodiment 2 21 R 22 The stable nitroxyl radical of NO· is a structural unit of formula (A'), (B') or (C'),

[0173]

[0174] in

[0175] R is hydrogen, C1-C2-C3-C1-C2-C1 ... 18 An alkyl group, a cyanoethyl group, a benzoyl group, a glycidyl group, a monovalent group of an aliphatic carboxylic acid having 2 to 18 carbon atoms, a monovalent group of an alicyclic carboxylic acid having 7 to 15 carbon atoms, or a monovalent group of an α,β-unsaturated carboxylic acid having 3 to 5 carbon atoms, or a monovalent group of an aromatic carboxylic acid having 7 to 15 carbon atoms;

[0176] R 101 It is C1-C 12 Alkyl, C5-C7 cycloalkyl, C7-C8 aralkyl, C2-C 18 Alkanoyl, C3-C5 alkenoyl or benzoyl;

[0177] R 102 is a C1-C2- 18 alkyl, C5-C7 cycloalkyl, C2-C8 alkenyl, or a glycidyl group, a group of the formula -CH2CH(OH)-Z, or a group of the formula -CO-Z or -CONH-Z,

[0178] wherein Z is hydrogen, methyl or phenyl;

[0179] G6 is hydrogen and

[0180] G6 is hydrogen or C1-C4 alkyl,

[0181] G1 and G3 are methyl and G2 and G4 are ethyl or propyl, or G1 and G2 are methyl and G3 and G4 are ethyl or propyl.

[0182] In another preferred embodiment of the present invention, the alkyl group in Embodiment 1 or Embodiment 2 may be linear or branched. Examples of the alkyl group having 1 to 18 carbon atoms in Embodiment 1 or Embodiment 2 are methyl, ethyl, propyl, isopropyl, butyl, 2-butyl, isobutyl, tert-butyl, pentyl, 2-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, t-octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl and octadecyl.

[0183] In another preferred embodiment of the present invention, the alkenyl group having 3 to 18 carbon atoms in embodiment 1 or embodiment 2 is a straight chain or branched chain group, for example, propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl, isododecenyl, oleyl, n-2-octadecenyl or n-4-octadecenyl.

[0184] In a more preferred embodiment of the present invention, the alkenyl group in embodiment 1 or embodiment 2 contains 3 to 12 carbon atoms, with a particularly preferred range containing 3 to 6 carbon atoms.

[0185] In another preferred embodiment of the invention, the alkynyl group having 3 to 18 carbon atoms is a straight-chain or branched group, for example propynyl, 2-butynyl, 3-butynyl, n-2-octynyl or n-2-octadecinyl. Preferred in embodiment 1 or embodiment 2 are alkynyl groups having 3 to 12, particularly preferably 3 to 6, carbon atoms.

[0186] In a more preferred embodiment of the present invention, the hydroxy-substituted alkyl group in Embodiment 1 or Embodiment 2 is hydroxypropyl, hydroxybutyl or hydroxyhexyl.

[0187] In a more preferred embodiment of the present invention, the halogen-substituted alkyl group in Embodiment 1 or Embodiment 2 is dichloropropyl, monobromobutyl or trichlorohexyl.

[0188] In a more preferred embodiment of the present invention, the C2-C 18 Alkyl is, for example, -CH2-CH2-O-CH2-CH3, -CH2-CH2-O-CH3- or -CH2-CH2-O-CH2-CH2CH2-O-CH2-CH3-. It is preferably derived from polyethylene glycol. In embodiment 1 or embodiment 2, the general description is -((CH Z ) a -O) b -H / CH3, wherein a is a number from 1 to 6, and b is a number from 2 to 10.

[0189] In a more preferred embodiment of the present invention, the at least one NR 205 C2-C 18 Alkyl groups are often described as -((CH2)a-NR 205 ) b -H / CH3, where a, b and R 205 As defined above.

[0190] In another more preferred embodiment of the present invention, C3-C in Embodiment 1 or Embodiment 2 12 Cycloalkyl is typically cyclopropyl, cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl or trimethylcyclohexyl.

[0191] In another more preferred embodiment of the present invention, C6-C 10 Aryl is, for example, phenyl or naphthyl, and also includes C1-C4 alkyl-substituted phenyl, C1-C4 alkoxy-substituted phenyl, hydroxyl, halogen or nitro-substituted phenyl. Examples of alkyl-substituted phenyl are ethylbenzene, toluene, xylene and isomers thereof, mesitylene or isopropylbenzene. In embodiment 1 or embodiment 2, halogen-substituted phenyl is, for example, dichlorobenzene or bromotoluene.

[0192] In a more preferred embodiment of the present invention, the alkoxy substituents in embodiment 1 or embodiment 2 are typically methoxy, ethoxy, propoxy or butoxy and the corresponding isomers thereof.

[0193] In a more preferred embodiment of the present invention, the C7-C9 phenylalkyl group in Embodiment 1 or Embodiment 2 is benzyl, phenethyl or phenylpropyl.

[0194] In a more preferred embodiment of the present invention, C5-C in Embodiment 1 or Embodiment 2 10 Heteroaryl is, for example, pyrrole, pyrazole, imidazole, 2,4-dimethylpyrrole, 1-methylpyrrole, thiophene, furan, furfural, indole, coumarone, oxazole, thiazole, isoxazole, isothiazole, triazole, pyridine, α-methylpyridine, pyridazine, pyrazine or pyrimidine.

[0195] In a more preferred embodiment of the present invention, R in embodiment 1 or embodiment 2 is a monovalent radical of a carboxylic acid, such as acetyl, propionyl, butyryl, valeryl, hexanoyl, stearoyl, lauroyl, acryloyl, methacryloyl, benzoyl, cinnamoyl or β-(3,5-di-tert-butyl-4-hydroxy-phenyl)propionyl.

[0196] In a more preferred embodiment of the present invention, the at least one stable nitroxyl radical in embodiment 1 or embodiment 2 is selected from the formula

[0197]

[0198] In a most preferred embodiment of the present invention, the at least one stable nitroxyl radical in embodiment 1 or embodiment 2 is

[0199]

[0200] In a preferred embodiment of the present invention, the reaction with at least one alcohol W in embodiment 1 or embodiment 2 is a transesterification reaction.

[0201] The term "ester exchange" refers to a reaction in which an alcohol radical in an ester group of a polymer or copolymer is replaced by another alcohol radical. The alcohol radical to be replaced is preferably methanol, ethanol, propanol or butanol. Typically, the ester exchange reaction is carried out at an elevated temperature, typically 70-200°C, by using a well-known catalyst, such as tetraisopropyl titanate, tetrabutyl titanate. Alkali metal or alkaline earth metal alkoxides, such as NaOMe or LiOMe, react the CFRP polymer with the corresponding alcohol. Typically, low-boiling product alcohols are removed from the ester exchange reaction mixture by distillation to change the reaction equilibrium. If necessary, catalyst residues can be removed by adsorption or extraction, or processed or deactivated by known methods, such as hydrolysis with water or acid. The choice of the substituted alcohol is important because the substituted alcohol controls the properties of the resulting copolymer.

[0202] The term "alcohol" as used herein refers to organic compounds carrying at least one hydroxyl functional group (C-OH) bonded to their aliphatic base structure. The alcohol is used to carry out the transesterification as mentioned above. Preferred alcohols are of formula B-(OA) n -OH, wherein A is a substituted or unsubstituted straight or branched C1-C4 alkylene group, and B is selected from a substituted or unsubstituted straight or branched C1-C 22 Alkyl, substituted or unsubstituted C1-C 24 Alkyl aryl and substituted or unsubstituted C1-C 24 Dialkylaryl, n is an integer in the range of ≥1 to ≤150. Particularly preferred are unsubstituted straight or branched C8-C 36 An example is iso-C 12 -C 15 Alcohol. Preferably, the alcohol is a primary alcohol or a secondary alcohol. Most preferably, it is a primary alcohol or an alcohol mixture. More preferably, the alcohol or alcohol mixture is non-volatile and has a boiling point or boiling range of at least 100°C, more preferably at least 200°C.

[0203] In another preferred embodiment of the present invention, the at least one alcohol in embodiment 1 or embodiment 2 is used in an amount of about 1 to about 70%.

[0204] In a more preferred embodiment of the present invention, the at least one alcohol in embodiment 1 or embodiment 2 is used in an amount of about 10 to about 60%.

[0205] In an even more preferred embodiment of the present invention, the at least one alcohol in embodiment 1 or embodiment 2 is used in an amount of about 30 to about 60%.

[0206] In a more preferred embodiment of the present invention, the at least one of the formula B-(OA) in embodiment 1 or embodiment 2 n Polyether alcohols containing -OH are polyether alcohols having an average molecular weight (M) in the range of ≥100 to ≤1000 g / mol, as determined in accordance with DIN 55672-1. n ) of methoxy polyethylene glycol.

[0207] In a more preferred embodiment of the present invention, the polyether alcohols in embodiment 1 or embodiment 2 have an average molecular weight (M) in the range of ≥200 to 800≤g / mol as determined according to DIN 55672-1. n ) of methoxy polyethylene glycol.

[0208] In a further preferred embodiment of the present invention, the polyether alcohol in embodiment 1 or embodiment 2 has an average molecular weight (M) in the range of ≥300 to ≤700 g / mol as determined according to DIN 55672-1. n ) of methoxy polyethylene glycol.

[0209] In a most preferred embodiment of the present invention, the polyether alcohol in embodiment 1 or embodiment 2 has an average molecular weight (M) of about 500 g / mol as determined in accordance with DIN 55672-1. n ) of methoxy polyethylene glycol.

[0210] In another preferred embodiment of the present invention, the at least one alcohol W in embodiment 1 or embodiment 2 is of the formula B-(OA) n -OH polyether alcohol, wherein A is a substituted or unsubstituted straight chain or branched C1-C4 alkylene, and B is selected from a substituted or unsubstituted straight chain or branched C1-C 20 Alkyl, substituted or unsubstituted C1-C 20 Alkyl aryl and substituted or unsubstituted C1-C 20 In the dialkylaryl group, n is an integer in the range of ≥1 to ≤120.

[0211] In another preferred embodiment of the present invention, the at least one alcohol W in embodiment 1 or embodiment 2 is of the formula B-(OA) n-OH polyether alcohol, wherein A is a substituted or unsubstituted straight chain or branched C1-C4 alkylene, and B is selected from a substituted or unsubstituted straight chain or branched C1-C 15 Alkyl, substituted or unsubstituted C1-C 15 Alkyl aryl and substituted or unsubstituted C1-C 15 In the dialkylaryl group, n is an integer in the range of ≥1 to ≤100.

[0212] In a more preferred embodiment of the present invention, the at least one alcohol W in embodiment 1 or embodiment 2 is of the formula B-(OA) n -OH polyether alcohol, wherein A is a substituted or unsubstituted straight chain or branched C1-C4 alkylene, and B is selected from a substituted or unsubstituted straight chain or branched C1-C 10 Alkyl, substituted or unsubstituted C1-C 10 Alkyl aryl and substituted or unsubstituted C1-C 10 In the dialkylaryl group, n is an integer in the range of ≥1 to ≤80.

[0213] In a still more preferred embodiment of the present invention, the at least one alcohol W in embodiment 1 or embodiment 2 is of the formula B-(OA) n -OH polyether alcohol, wherein A is a substituted or unsubstituted straight chain or branched C2-C3 alkylene group, B is selected from a substituted or unsubstituted straight chain or branched C1-C4 alkyl group, and n is an integer in the range of ≥1 to ≤50.

[0214] In another more preferred embodiment of the present invention, the at least one alcohol W in embodiment 1 or embodiment 2 is of formula B-(OA) n -OH polyether alcohol, wherein A is ethylene or propylene, B is selected from substituted or unsubstituted straight or branched C1-C4 alkyl, and n is an integer in the range of ≥1 to ≤50.

[0215] In a preferred embodiment of the present invention, the at least one alcohol in Embodiment 1 or Embodiment 2 is an unsubstituted straight or branched C8-C 36 Alkyl monoalcohol.

[0216] In a more preferred embodiment of the present invention, the at least one alcohol in embodiment 1 or embodiment 2 is an unsubstituted straight or branched chain C 10 -C 25 Alkyl monoalcohol.

[0217] In a further more preferred embodiment of the present invention, the at least one alcohol in embodiment 1 or embodiment 2 is an unsubstituted linear or branched C 12 -C 22 Alkyl monoalcohol.

[0218] In a preferred embodiment of the present invention, the compound R 1 -OH is selected from nonan-1-ol, nonan-2-ol, dodecan-1-ol, decan-1-ol and decan-2-ol.

[0219] In a preferred embodiment of the present invention, the at least one alcohol is compound R 1 -OH, where R 1 is a substituted or unsubstituted straight chain or branched C 15 -C 40 alkyl.

[0220] In a preferred embodiment of the present invention, the at least one alcohol is compound R 1 -OH, where R 1 is a substituted or unsubstituted straight chain or branched C 10 -C 34 alkyl.

[0221] In a preferred embodiment of the present invention, the at least one alcohol is compound R 1 -OH, where R 1 is a substituted or unsubstituted straight chain or branched C 12 -C 30 alkyl.

[0222] In a preferred embodiment of the present invention, the at least one alcohol is compound R 1 -OH, where R 1 is a substituted or unsubstituted straight chain or branched C 10 -C 28 alkyl.

[0223] In a preferred embodiment of the present invention, the at least one alcohol is compound R 1 -OH, where R 1 is a substituted or unsubstituted straight or branched C8-C 25 alkyl.

[0224] The term "amid exchange" refers to a reaction involving the aminolysis of a polyacrylate, wherein the acrylate is reacted with at least one amine NH2-R as described herein. 11 -NR 12 R 13 (Z1) or NH2-R 11-Y(Z2) reaction to produce the corresponding amide. The alcohol radical to be replaced is preferably methanol, ethanol, propanol or butanol. Typically, the reaction is carried out at an elevated temperature, typically 70-180°C, by reacting the CFRP polymer with the corresponding amine in the absence or presence of a well-known catalyst, such as tetraisopropyl titanate, tetrabutyl titanate, an alkali metal or alkaline earth metal alkoxide, such as NaOMe or LiOMe. Typically, the low-boiling product alcohol is removed from the reaction mixture by distillation to change the reaction equilibrium. If necessary, the catalyst residue can be removed by adsorption or extraction, or processed or deactivated by known methods, such as hydrolysis with water or acid. The choice of the amine used for substitution is important because the amine used for substitution controls the properties of the resulting copolymer. It is also noted that the reacted carboxyl group in acrylic acid self-catalyzes the reaction, so the presence of a catalyst is optional for the reaction.

[0225] In a preferred embodiment of the present invention, the at least one amine in Embodiment 1 or Embodiment 2 is used in an amount of about 1 to about 50%.

[0226] In an even more preferred embodiment of the present invention, the at least one amine of Embodiment 1 or Embodiment 2 is used in an amount of about 5 to about 40%.

[0227] In a more preferred embodiment of the present invention, the at least one amine in embodiment 1 or embodiment 2 is used in an amount of about 10 to about 30%.

[0228] In another preferred embodiment of the present invention, R in Embodiment 1 or Embodiment 2 11 It is an unsubstituted straight or branched C1-C8 alkylene group.

[0229] In a more preferred embodiment of the present invention, R in Embodiment 1 or Embodiment 2 11 It is an unsubstituted straight or branched C1-C7 alkylene group.

[0230] In a more preferred embodiment of the present invention, R in Embodiment 1 or Embodiment 2 11 It is an unsubstituted straight or branched C1-C6 alkylene group.

[0231] In another preferred embodiment of the present invention, R in Embodiment 1 or Embodiment 2 11 Selected from -CH2-, -CH2CH2-, -CH2CH2CH2- and -CH2CH2CH2CH2-.

[0232] In a preferred embodiment of the present invention, R in Embodiment 1 or Embodiment 2 11 is an unsubstituted straight or branched C1-C8 alkylene group; R 12 and R13 It is an unsubstituted straight or branched C1-C8 alkyl group.

[0233] In a more preferred embodiment of the present invention, R in Embodiment 1 or Embodiment 2 11 is an unsubstituted straight or branched C1-C6 alkylene group; R 12 and R 13 It is an unsubstituted straight or branched C1-C6 alkyl group.

[0234] In a preferred embodiment of the present invention, R in Embodiment 1 or Embodiment 2 12 and R 13 Independently selected from hydrogen and substituted or unsubstituted linear or branched C1-C8 alkyl, which may be the same or different.

[0235] In a more preferred embodiment of the present invention, R 12 and R 13 Independently selected from methyl, ethyl, propyl and isopropyl.

[0236] In a more preferred embodiment of the present invention, R 12 and R 13 is an unsubstituted straight or branched C1-C8 alkyl group, which together with the nitrogen atom to which they are attached form an unsubstituted or substituted 3- to 6-membered ring containing 1 or 2 heteroatoms selected from nitrogen and oxygen.

[0237] In another preferred embodiment of the present invention, R in Embodiment 1 or Embodiment 2 12 and R 13 Together with the nitrogen atom to which they are attached, they form a 6-membered ring containing 1 to 2 heteroatoms.

[0238] In a more preferred embodiment of the present invention, R 12 and R 13 Together with the nitrogen atom to which they are attached they form a pyrrolidinyl, piperidinyl or morpholinyl group.

[0239] In another more preferred embodiment of the present invention, Y is a 5- or 6-membered N-containing heterocyclic ring containing 1 or 2 nitrogen atoms.

[0240] In another more preferred embodiment of the present invention, Y is selected from imidazolyl and pyridyl.

[0241] In another preferred embodiment of the present invention, the at least one amine in embodiment 1 or embodiment 2 is an aliphatic diamine selected from 2-(diethylamino)ethylamine, 3-(dimethylamino)propylamine, 3-(diethylamino)propylamine or 1-diethylamino-4-aminopentane.

[0242] In another preferred embodiment of the present invention, the at least one amine in embodiment 1 or embodiment 2 is a heterocyclic amine selected from N-(3-aminopropyl)imidazole, N-(3-aminopropyl)morpholine or N-(2-aminoethyl)-piperidine.

[0243] In another preferred embodiment of the present invention, the at least one amine in embodiment 1 or embodiment 2 is a saturated or unsaturated aliphatic amine containing 6 to 22 carbon atoms.

[0244] In a more preferred embodiment of the present invention, the at least one amine in embodiment 1 or embodiment 2 is a saturated or unsaturated aliphatic amine selected from 2-ethylhexylamine, oleylamine or stearylamine.

[0245] In yet another preferred embodiment of the present invention, the at least one amine in embodiment 1 or embodiment 2 is an alicyclic amine containing 2 to 6 carbon atoms.

[0246] In a more preferred embodiment of the present invention, the at least one amine in Embodiment 1 or Embodiment 2 is selected from 3-(dimethylamino)-1-propylamine, 1-(3-aminopropyl)imidazole, 4-(aminomethyl)pyridine, 1-(2-aminoethyl)piperidine, 3-morpholinepropylamine and combinations thereof.

[0247] In an alternative preferred embodiment of the present invention, the mixture M1 in embodiment 1 or embodiment 2 further comprises at least one ethylenically unsaturated monomer to obtain a polyacrylate P1 which is subsequently reacted with the mixture M2 in step ii).

[0248] In a more preferred embodiment of the present invention, the polyacrylate P1 in embodiment 1 or embodiment 2 is a random copolymer.

[0249] In a more preferred embodiment of the present invention, the polyacrylate P1 in embodiment 1 or embodiment 2 is a block copolymer.

[0250] In an alternative preferred embodiment of the present invention, the mixture M2 in embodiment 1 or embodiment 2 further comprises at least one ethylenically unsaturated monomer to obtain a polyacrylate P2, which is subsequently reacted with the mixture M2 in step ii).

[0251] In a more preferred embodiment of the present invention, the polyacrylate P1 in embodiment 1 or embodiment 2 is further reacted with at least one ethylenically unsaturated monomer to obtain the polyacrylate P2, which is subsequently reacted in step ii) with the mixture M2.

[0252] In a more preferred embodiment of the present invention, the polyacrylate P2 in embodiment 1 or embodiment 2 is a gradient block copolymer.

[0253] In a more preferred embodiment of the present invention, the at least one ethylenically unsaturated monomer in embodiment 1 or embodiment 2 is selected from C5-C 20 Vinyl aromatic compounds, ethylenically unsaturated nitriles, acrylamides, vinyl halides, C1-C 10 Vinyl ethers of alcohols and C2-C8 aliphatic hydrocarbons having one or two double bonds.

[0254] In a further more preferred embodiment of the present invention, the at least one ethylenically unsaturated monomer in embodiment 1 or embodiment 2 is selected from C7-C 18 Vinyl aromatics, ethylenically unsaturated nitriles, acrylamides, vinyl halides, vinyl ethers of C2-C8 alcohols and C4-C6 aliphatic hydrocarbons having one or two double bonds.

[0255] In a further more preferred embodiment of the present invention, the at least one ethylenically unsaturated monomer in embodiment 1 or embodiment 2 is selected from C9-C 15 Vinyl aromatics, ethylenically unsaturated nitriles, acrylamides, vinyl halides, vinyl ethers of C3-C7 alcohols and C4-C6 aliphatic hydrocarbons having one or two double bonds.

[0256] The term "vinyl" as used herein refers to one of the olefinic functional groups, also known as "ethenyl".

[0257] The term "aromatic" as used herein refers to one of the unsaturated cyclic, planar molecules having a ring with resonant bonds. Examples of aromatic groups are, in particular, pyridyl, benzyl, phenyl, naphthyl, anthracenyl, phenanthrenyl, naphthacene, The aromatic molecules may also be interrupted by heteroatoms selected from oxygen or nitrogen. These are preferably selected from pyridyl, imidazolyl, bipyridyl, etc. In addition, the aromatic radicals may be substituted, depending on the number and size of their ring systems, with one or more (e.g. 1, 2, 3, 4, 5 or more than 5) substituents. These are preferably independently selected from alkyl, alkoxy, cycloalkyl, cycloalkyloxy, heterocycloalkyl, aryl, aryloxy, arylthio, heteroaryl, halogen, hydroxy, shoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, coohydrogens, carboxylates, so3hydrogenates, sulfonates, ne 5 E 6 , nitro and cyano, among which E 5 and E 6 Each is independently hydrogen, alkyl, cycloalkyl, cycloalkoxy, polycyclic, polycyclicoxy, heterocycloalkyl, aryl, aryloxy or heteroaryl.

[0258] In a preferred embodiment of the present invention, the at least one ethylenically unsaturated monomer in embodiment 1 or embodiment 2 comprises monomers which are at least free of primary or secondary ester bonds.

[0259] In a preferred embodiment of the present invention, the at least one ethylenically unsaturated monomer is selected from isoprene, 1,3-butadiene, α-C5-C18-olefins, 4-vinyl-pyridine or pyridine -ion, 2-vinyl-pyridine or pyridine -ion, vinyl-imidazole or imidazoline ions, dimethylacrylamide, 3-dimethylaminopropylmethacrylamide, styrene, α-methylstyrene, p-methylstyrene, p-tert-butyl-styrene and compounds of the formula CH2=C(Ra)-(C=Z)-Rb, wherein Ra is hydrogen or methyl, Rb is NH2, O-(Me+), unsubstituted C1-C18-alkoxy, C2-C100-alkoxy interrupted by at least one nitrogen and / or oxygen atom or C1-C18 alkoxy substituted with hydroxyl, unsubstituted C1-C18 alkylamino, di(C1-C18 alkyl)-amino, hydroxy-substituted C1-C18 alkylamino or hydroxy-substituted di(C1-C18 alkyl)amino, -O-CH2-CH2-N(CH3)2 or -O-CH2-CH2-N+H(CH3)2An-;

[0260] An- is the anion of a monovalent organic or inorganic acid;

[0261] Me is a monovalent metal atom or an ammonium ion;

[0262] Z is oxygen or sulfur.

[0263] In another preferred embodiment of the present invention, R in Embodiment 1 or Embodiment 2 b is a C2-C interrupted by at least one O atom 100 Alkoxy groups having the formula

[0264]

[0265] Where Rc is C1-C 25 Alkyl, phenyl or C1-C 18 Alkyl-substituted phenyl, Rd is hydrogen or methyl, v is a number from 1 to 50. These monomers are derived from nonionic surfactants, for example by acrylation of the corresponding alkoxylated alcohols or phenols. The repeating units may be derived from ethylene oxide, propylene oxide, a mixture of the two or hydrogen.

[0266] In another preferred embodiment of the present invention, the ethylenically unsaturated monomer in embodiment 1 or embodiment 2 is selected from the formula CH2=C(R a )-(C=Z)-Rb A compound wherein R a is hydrogen or methyl, R b NH2, O-(Me+), unsubstituted C1-C 18 Alkoxy, C2-C 100 Alkoxy or hydroxy substituted C1-C 18 Alkoxy, unsubstituted C1-C 18 Alkylamino, di(C1-C 18 Alkyl)-amino, hydroxy substituted C1-C 18 Alkylamino or hydroxy substituted di(C1-C 18 alkyl)amino, -O-CH2-CH2-N(CH3)2 or -O-CH2-CH2-N + H(CH3)2An - ;

[0267] An- is the anion of a monovalent organic or inorganic acid;

[0268] Me is a monovalent metal atom or an ammonium ion;

[0269] Z is oxygen or sulfur.

[0270] In another preferred embodiment of the present invention, the ethylenically unsaturated monomer in embodiment 1 or embodiment 2 is selected from the formula CH2=C(R a )-(C=Z)-R b A compound wherein R a is hydrogen or methyl, R b NH2, O-(Me+), unsubstituted C1-C 10 Alkoxy, C2-C 50 Alkoxy or hydroxy substituted C1-C 10 Alkoxy, unsubstituted C1-C 18 Alkylamino, di(C1-C 10 Alkyl)-amino, hydroxy substituted C1-C 10 Alkylamino or hydroxy substituted di(C1-C 10 alkyl)amino, -O-CH2-CH2-N(CH3)2 or -O-CH2-CH2-N + H(CH3)2An - ;

[0271] An- is the anion of a monovalent organic or inorganic acid;

[0272] Me is a monovalent metal atom or an ammonium ion;

[0273] Z is oxygen or sulfur.

[0274] In a preferred embodiment of the present invention, the at least one ethylenically unsaturated monomer is selected from 4-vinyl-pyridine or pyridine -ion, 2-vinyl-pyridine or pyridine -ion, vinyl-imidazole or imidazoline -ion, dimethylacrylamide, 3-dimethylaminopropylmethacrylamide, styrene, α-methylstyrene, p-methylstyrene and p-tert-butyl-styrene.

[0275] In a more preferred embodiment of the present invention, the at least one ethylenically unsaturated monomer in embodiment 1 or embodiment 2 is selected from C6-C 15 Vinyl aromatic compounds, preferably C6-C 10 Vinyl aromatic compounds.

[0276] In a more preferred embodiment of the present invention, the at least one ethylenically unsaturated monomer in embodiment 1 or embodiment 2 is selected from 4-vinyl-pyridine, vinyltoluene, α- and p-methylstyrene, α-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and styrene.

[0277] In a further more preferred embodiment of the present invention, the ethylenically unsaturated monomer in embodiment 1 or embodiment 2 is selected from 4-vinyl-pyridine or pyridine -ion, 2-vinyl-pyridine or pyridine -ion ​​and vinyl-imidazole or imidazoline -ion.

[0278] In a most preferred embodiment of the present invention, the ethylenically unsaturated monomer in embodiment 1 or embodiment 2 is 4-vinyl-pyridine or pyridine -ion.

[0279] In a most preferred embodiment of the present invention, the at least one ethylenically unsaturated monomer in embodiment 1 or embodiment 2 is 4-vinyl-pyridine.

[0280] In a preferred embodiment of the present invention, the at least one ethylenically unsaturated nitrile in embodiment 1 or embodiment 2 is selected from acrylonitrile and methacrylonitrile.

[0281] In a preferred embodiment of the present invention, the at least one vinyl ether in embodiment 1 or embodiment 2 is selected from vinyl methyl ether and vinyl isobutyl ether.

[0282] In a preferred embodiment of the present invention, the vinyl halide in embodiment 1 or embodiment 2 is selected from at least one ethylenically unsaturated compound substituted with chlorine, fluorine or bromine, preferably vinyl chloride and vinylidene chloride.

[0283] In a preferred embodiment of the present invention, the at least one ethylenically unsaturated monomer in embodiment 1 or embodiment 2 is selected from C2-C8 aliphatic hydrocarbons, preferably C3-C7 aliphatic hydrocarbons.

[0284] The term "C2-C8 aliphatic hydrocarbon" refers to a hydrocarbon having 2 to 8 carbon atoms and one or two olefinic double bonds. In a most preferred embodiment of the present invention, the C2-C8 aliphatic hydrocarbon in embodiment 1 or embodiment 2 is selected from butadiene, isoprene, chloroprene, ethylene and propylene.

[0285] In a preferred embodiment of the present invention, the at least one ethylenically unsaturated monomer in embodiment 1 or embodiment 2 is selected from C1-C 10 Vinyl ethers of aliphatic hydrocarbons, preferably vinyl ethers of C2-C8 aliphatic hydrocarbons.

[0286] In another preferred embodiment of the present invention, the ethylenically unsaturated monomer in Embodiment 2 is selected from ethylene, propylene, n-butene, isobutylene, styrene, substituted styrene, conjugated dienes, acrolein, vinyl acetate, vinyl pyrrolidone, vinyl imidazole, maleic anhydride, (alkyl) acrylic anhydride, (alkyl) acrylic acid salt, (alkyl) acrylic ester, (alkyl) acrylonitrile, (alkyl) acrylamide, vinyl halide or vinylidene halide.

[0287] In another preferred embodiment of the present invention, the ethylenically unsaturated monomer in embodiment 1 or embodiment 2 is styrene, substituted styrene, methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, tert-butyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, dimethylaminoethyl acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide or dimethylaminopropyl-methacrylamide.

[0288] In another preferred embodiment of the present invention, the at least one acrylate monomer in embodiment 1 or embodiment 2 is, for example, styrene, a C1-C8 alkyl ester of acrylic acid or methacrylic acid, such as n-butyl acrylate or n-butyl methacrylate, acrylonitrile or methacrylonitrile, in particular styrene, acrylonitrile and n-butyl acrylate.

[0289] In another preferred embodiment of the present invention, the particularly preferred at least one acrylate monomer in embodiment 1 or embodiment 2 is styrene / acrylonitrile, styrene / butyl acrylate, styrene / methyl methacrylate and styrene / butyl methacrylate.

[0290] In a more preferred embodiment of the present invention, the polymer is obtained by reacting the following components

[0291] i) at least one polyacrylate P1 obtained by controlled free radical polymerization of a mixture M1 in the presence of a1 or a2, the mixture M1 comprising at least one acrylate monomer selected from C1-C6 alkyl acrylates, C1-C6 alkyl methacrylates, hydroxy C1-C6 alkyl acrylates and hydroxy C1-C6 alkyl methacrylates,

[0292] Where a1 is at least one of the formula R 21 R 22 NOX(I) is a nitroxyl ether and a2 is at least one of the formula R 21 R 22 The stable nitroxyl radical of NO·(II);

[0293] R21 and R22 are independently selected from substituted or unsubstituted straight or branched C1-C18 alkyl groups, wherein R21 and R22 together with the nitrogen atom to which they are attached form an unsubstituted or substituted 5- to 10-membered aliphatic ring containing 1 to 3 heteroatoms selected from nitrogen and oxygen, and X is selected from -CH2-phenyl, -CH3CH-phenyl, -(CH3)2C-phenyl, -(C5-C6 cycloalkyl)2C-CN, -(CH3)2CCN, -CH2CH=CH2, -CH3CH-CH=CH2, -(C1-C4 alkyl) CR20-C(O)-phenyl, -(C1-C4)alkyl-CR20-C(O)-(C1-C4)alkoxy, -(C1-C4)alkyl-CR20-C(O)-(C1-C4)alkyl, -(C1-C4)alkyl-CR20-C(O)-N-di(C1-C4)alkyl, -(C1-C4)alkyl-CR20-C(O)-NH(C1-C4)alkyl and -(C1-C4)alkyl-CR20-C(O)-NH2, wherein R20 is hydrogen or (C1-C4)alkyl;

[0294] reacting a polyacrylate P1 with at least one ethylenically unsaturated monomer to obtain a polyacrylate P2,

[0295] Make P2 and

[0296] ii) reacting a mixture M2 comprising at least one alcohol W selected from W1 and W2 and at least one amine Z selected from Z1 and Z2;

[0297] in,

[0298] W1 is R1-OH, wherein R1 is a substituted or unsubstituted linear or branched C8-C36 alkyl group;

[0299] W2 is at least one of the formula B-(OA)n -OH, wherein A is a substituted or unsubstituted straight or branched C1-C4 alkylene group, B is selected from a substituted or unsubstituted straight or branched C1-C22 alkyl group, a substituted or unsubstituted C1-C24 alkylaryl group and a substituted or unsubstituted C1-C24 dialkylaryl group, and n is an integer in the range of ≥1 to ≤150;

[0300] Z1 is NH2-R11-NR12R13, Z2 is NH2-R11-Y,

[0301] Wherein R11 is a substituted or unsubstituted straight or branched C1-C12 alkylene group;

[0302] R12 and R13 are independently selected from hydrogen and substituted or unsubstituted linear or branched C1-C12 alkyl, or

[0303] R12 and R13 together with the nitrogen atom to which they are attached form an unsubstituted or substituted 3- to 12-membered ring containing 1 to 3 heteroatoms selected from nitrogen and oxygen;

[0304] Y is a 5- or 6-membered N-containing heterocyclic ring containing 1 or 2 nitrogen atoms and 0 or 1 oxygen atoms.

[0305] In a more preferred embodiment of the present invention, the polymer is obtained by reacting the following components

[0306] i) at least one polyacrylate P1 obtained by controlled free radical polymerization of a mixture M1 in the presence of a1 or a2, the mixture M1 comprising at least one acrylate monomer selected from C1-C6 alkyl acrylates, C1-C6 alkyl methacrylates, hydroxy C1-C6 alkyl acrylates and hydroxy C1-C6 alkyl methacrylates,

[0307] Where a1 is at least one of the formula R 21 R 22 NOX(I) is a nitroxyl ether and a2 is at least one of the formula R 21 R 22 The stable nitroxyl radical of NO·(II);

[0308] R21 and R22 are independently selected from substituted or unsubstituted straight or branched C1-C18 alkyl groups, wherein R21 and R22 together with the nitrogen atom to which they are attached form an unsubstituted or substituted 5- to 10-membered aliphatic ring containing 1 to 3 heteroatoms selected from nitrogen and oxygen, and X is selected from -CH2-phenyl, -CH3CH-phenyl, -(CH3)2C-phenyl, -(C5-C6 cycloalkyl)2C-CN, -(CH3)2CCN, -CH2CH=CH2, -CH3CH-CH=CH2, -(C1-C4 alkyl) CR20-C(O)-phenyl, -(C1-C4)alkyl-CR20-C(O)-(C1-C4)alkoxy, -(C1-C4)alkyl-CR20-C(O)-(C1-C4)alkyl, -(C1-C4)alkyl-CR20-C(O)-N-di(C1-C4)alkyl, -(C1-C4)alkyl-CR20-C(O)-NH(C1-C4)alkyl and -(C1-C4)alkyl-CR20-C(O)-NH2, wherein R20 is hydrogen or (C1-C4)alkyl;

[0309] The polyacrylate P1 is reacted with a 20 Vinyl aromatic compounds, ethylenically unsaturated nitriles, acrylamides, vinyl halides, C1-C 10 The vinyl ether of an alcohol and at least one ethylenically unsaturated monomer of a C2-C8 aliphatic hydrocarbon having one or two double bonds are reacted to obtain a polyacrylate P2,

[0310] Make P2 and

[0311] ii) reacting a mixture M2 comprising at least one alcohol W selected from W1 and W2 and at least one amine Z selected from Z1 and Z2;

[0312] in,

[0313] W1 is R1-OH, wherein R1 is a substituted or unsubstituted linear or branched C8-C36 alkyl group;

[0314] W2 is at least one of the formula B-(OA) n -OH, wherein A is a substituted or unsubstituted straight or branched C1-C4 alkylene group, B is selected from a substituted or unsubstituted straight or branched C1-C22 alkyl group, a substituted or unsubstituted C1-C24 alkylaryl group and a substituted or unsubstituted C1-C24 dialkylaryl group, and n is an integer in the range of ≥1 to ≤150;

[0315] Z1 is NH2-R11-NR12R13, Z2 is NH2-R11-Y,

[0316] Wherein R11 is a substituted or unsubstituted straight or branched C1-C12 alkylene group;

[0317] R12 and R13 are independently selected from hydrogen and substituted or unsubstituted linear or branched C1-C12 alkyl, or

[0318] R12 and R13 together with the nitrogen atom to which they are attached form an unsubstituted or substituted 3- to 12-membered ring containing 1 to 3 heteroatoms selected from nitrogen and oxygen;

[0319] Y is a 5- or 6-membered N-containing heterocyclic ring containing 1 or 2 nitrogen atoms and 0 or 1 oxygen atoms.

[0320] In a more preferred embodiment of the present invention, the polymer in embodiment 1 or embodiment 2 is obtained by reacting the following components

[0321] i) at least one polyacrylate P1 obtained by controlled free-radical polymerization of a mixture M1 comprising at least one acrylate monomer selected from C2-C5 alkyl acrylates, C2-C5 alkyl methacrylates, hydroxy C2-C5 alkyl acrylates and hydroxy C2-C5 alkyl methacrylates in the presence of a1 or a2,

[0322] Where a1 is at least one of the formula R 21 R 22 NOX(I) is a nitroxyl ether and a2 is at least one of the formula R 21 R 22 The stable nitroxyl radical of NO·(II);

[0323] R 21 and R 22 are independently selected from substituted or unsubstituted straight or branched C1-C 18 Alkyl, where R 21 and R 22 Together with the nitrogen atom to which they are attached, they form an unsubstituted or substituted 5- to 10-membered aliphatic ring containing 1 to 3 heteroatoms selected from nitrogen and oxygen, and X is selected from -CH2-phenyl, -CH3CH-phenyl, -(CH3)2C-phenyl, -(C5-C6 cycloalkyl)2C-CN, -(CH3)2CCN, -CH2CH=CH2, -CH3CH-CH=CH2, -(C1-C4 alkyl)CR 20 -C(O)-phenyl, -(C1-C4)alkyl-CR 20 -C(O)-(C1-C4)alkoxy, -(C1-C4)alkyl-CR 20 -C(O)-(C1-C4)alkyl, -(C1-C4)alkyl-CR 20 -C(O)-N-di(C1-C4)alkyl, -(C1-C4)alkyl-CR 20-C(O)-NH(C1-C4)alkyl and -(C1-C4)alkyl-CR 20 -C(O)-NH2, where R 20 is hydrogen or (C1-C4)alkyl,

[0324] and

[0325] ii) a mixture comprising at least one alcohol W selected from W1 and W2 and at least one amine Z selected from Z1 and Z2;

[0326] in,

[0327] W1 is R 1 -OH, where R 1 is a substituted or unsubstituted straight chain or branched C 10 -C 34 alkyl;

[0328] W2 is at least one of the formula B-(OA) n -OH polyether alcohol, wherein A is a substituted or unsubstituted straight chain or branched C1-C4 alkylene, and B is selected from a substituted or unsubstituted straight chain or branched C1-C 20 Alkyl, substituted or unsubstituted C1-C 20 Alkyl aryl and substituted or unsubstituted C1-C 20 dialkylaryl, n is an integer in the range of 7 to 48;

[0329] Z1 is NH2-R 11 -NR 12 R 13 , Z2 is NH2-R 11 -Y,

[0330] Where R 11 is a substituted or unsubstituted straight or branched C1-C 10 Alkylene;

[0331] R 12 and R 13 are independently selected from hydrogen and substituted or unsubstituted straight or branched C1-C 10 Alkyl, or

[0332] R 12 and R 13 Together with the nitrogen atom to which they are attached, they form an unsubstituted or substituted 3- to 12-membered ring containing 1 to 3 heteroatoms selected from nitrogen and oxygen;

[0333] Y is a 5- or 6-membered N-containing heterocyclic ring containing 1 or 2 nitrogen atoms or it may additionally contain oxygen atoms.

[0334] In another more preferred embodiment of the present invention, the polymer in embodiment 1 or embodiment 2 is obtained by reacting the following components

[0335] i) at least one polyacrylate P1 obtained by controlled free-radical polymerization of a mixture M1 comprising at least one acrylate monomer selected from C2-C5 alkyl acrylates, C2-C5 alkyl methacrylates, hydroxy C2-C5 alkyl acrylates and hydroxy C2-C5 alkyl methacrylates in the presence of a1 or a2,

[0336] Where a1 is at least one of the formula R 21 R 22 NOX(I) is a nitroxyl ether and a2 is at least one of the formula R 21 R 22 The stable nitroxyl radical of NO·(II);

[0337] R 21 and R 22 are independently selected from substituted or unsubstituted straight or branched C1-C 18 Alkyl, where R 21 and R 22 Together with the nitrogen atom to which they are attached, they form an unsubstituted or substituted 5- to 10-membered aliphatic ring containing 1 to 3 heteroatoms selected from nitrogen and oxygen, and X is selected from -CH2-phenyl, -CH3CH-phenyl, -(CH3)2C-phenyl, -(C5-C6 cycloalkyl)2C-CN, -(CH3)2CCN, -CH2CH=CH2, -CH3CH-CH=CH2, -(C1-C4 alkyl)CR 20 -C(O)-phenyl, -(C1-C4)alkyl-CR 20 -C(O)-(C1-C4)alkoxy, -(C1-C4)alkyl-CR 20 -C(O)-(C1-C4)alkyl, -(C1-C4)alkyl-CR 20 -C(O)-N-di(C1-C4)alkyl, -(C1-C4)alkyl-CR 20 -C(O)-NH(C1-C4)alkyl and -(C1-C4)alkyl-CR 20 -C(O)-NH2, where R 20 is hydrogen or (C1-C4)alkyl,

[0338] The polyacrylate P1 is reacted with a C6-C 10 At least one ethylenically unsaturated monomer of a vinyl aromatic compound, an ethylenically unsaturated nitrile, an acrylamide, a vinyl halide, a vinyl ether of a C2-C9 alcohol and a C3-C7 aliphatic hydrocarbon having one or two double bonds is reacted to obtain a polyacrylate P2,

[0339] Make P2 and

[0340] ii) reacting a mixture comprising at least one alcohol W selected from W1 and W2 and at least one amine Z selected from Z1 and Z2;

[0341] in,

[0342] W1 is R 1 -OH, where R 1 is a substituted or unsubstituted straight chain or branched C 10 -C 34 alkyl;

[0343] W2 is at least one of the formula B-(OA) n -OH polyether alcohol, wherein A is a substituted or unsubstituted straight chain or branched C1-C4 alkylene, and B is selected from a substituted or unsubstituted straight chain or branched C1-C 20 Alkyl, substituted or unsubstituted C1-C 20 Alkyl aryl and substituted or unsubstituted C1-C 20 dialkylaryl, n is an integer in the range of 7 to 48;

[0344] Z1 is NH2-R 11 -NR 12 R 13 , Z2 is NH2-R 11 -Y,

[0345] Where R 11 is a substituted or unsubstituted straight or branched C1-C 10 Alkylene;

[0346] R 12 and R 13 are independently selected from hydrogen and substituted or unsubstituted straight or branched C1-C 10 Alkyl, or

[0347] R 12 and R 13 Together with the nitrogen atom to which they are attached, they form an unsubstituted or substituted 3- to 12-membered ring containing 1 to 3 heteroatoms selected from nitrogen and oxygen;

[0348] Y is a 5- or 6-membered N-containing heterocyclic ring containing 1 or 2 nitrogen atoms and 0 or 1 oxygen atoms.

[0349] In a further more preferred embodiment of the present invention, the polymer in embodiment 1 or embodiment 2 is obtained by reacting the following components

[0350] i) at least one polyacrylate P1 obtained by controlled free radical polymerization of a mixture M1 comprising at least one acrylate monomer selected from C1-C6 alkyl esters of acrylic acid in the presence of a1 or a2, wherein a1 is at least one compound of the formula R 21 R 22 NOX(I) is a nitroxyl ether and a2 is at least one of the formula R 21 R 22 The stable nitroxyl radical of NO·(II);

[0351] R 21 and R 22 are independently selected from substituted or unsubstituted straight or branched C1-C 18 Alkyl, where R 21 and R 22 Together with the nitrogen atom to which they are attached, they form an unsubstituted or substituted 5- to 10-membered aliphatic ring containing 1 to 3 heteroatoms selected from nitrogen and oxygen, and X is selected from -CH2-phenyl, -CH3CH-phenyl, -(CH3)2C-phenyl, -(C5-C6 cycloalkyl)2C-CN, -(CH3)2CCN, -CH2CH=CH2, -CH3CH-CH=CH2, -(C1-C4 alkyl)CR 20 -C(O)-phenyl, -(C1-C4)alkyl-CR 20 -C(O)-(C1-C4)alkoxy, -(C1-C4)alkyl-CR 20 -C(O)-(C1-C4)alkyl, -(C1-C4)alkyl-CR 20 -C(O)-N-di(C1-C4)alkyl, -(C1-C4)alkyl-CR 20 -C(O)-NH(C1-C4)alkyl and -(C1-C4)alkyl-CR 20 -C(O)-NH2, where R 20 is hydrogen or (C1-C4)alkyl,

[0352] and

[0353] ii) a mixture comprising at least one alcohol W selected from W2 and at least one amine Z selected from Z1;

[0354] in,

[0355] W2 is the formula B-(OA) n -OH polyether alcohol, wherein A is ethylene or propylene, B is selected from substituted or unsubstituted linear or branched C1-C4 alkyl, and n is an integer in the range of ≥1 to ≤50;

[0356] Z1 is NH2-R 11 -NR 12 R 13,

[0357] Where R 11 is a substituted or unsubstituted straight or branched C1-C 12 Alkylene;

[0358] R 12 and R 13 are independently selected from hydrogen and substituted or unsubstituted straight or branched C2-C 10 alkyl groups, which may be the same or different, or R 12 and R 13 Together with the nitrogen atom to which they are attached, they form a 3- to 12-membered ring containing 1 to 3 heteroatoms selected from nitrogen and oxygen,

[0359] Y is a 5- or 6-membered N-containing heterocyclic ring containing 1 or 2 nitrogen atoms and 0 or 1 oxygen atoms.

[0360] In another even more preferred embodiment of the present invention, the polymer in embodiment 1 or embodiment 2 is obtained by reacting the following components

[0361] i) at least one polyacrylate P1 obtained by controlled free radical polymerization of a mixture M1 comprising at least one acrylate monomer selected from C1-C6 alkyl esters of acrylic acid in the presence of a1 or a2, wherein a1 is at least one compound of the formula R 21 R 22 NOX(I) is a nitroxyl ether and a2 is at least one of the formula R 21 R 22 The stable nitroxyl radical of NO·(II);

[0362] R 21 and R 22 are independently selected from substituted or unsubstituted straight or branched C1-C 18 Alkyl, where R 21 and R 22 Together with the nitrogen atom to which they are attached, they form an unsubstituted or substituted 5- to 10-membered aliphatic ring containing 1 to 3 heteroatoms selected from nitrogen and oxygen, and X is selected from -CH2-phenyl, -CH3CH-phenyl, -(CH3)2C-phenyl, -(C5-C6 cycloalkyl)2C-CN, -(CH3)2CCN, -CH2CH=CH2, -CH3CH-CH=CH2, -(C1-C4 alkyl)CR 20 -C(O)-phenyl, -(C1-C4)alkyl-CR 20 -C(O)-(C1-C4)alkoxy, -(C1-C4)alkyl-CR 20 -C(O)-(C1-C4)alkyl, -(C1-C4)alkyl-CR 20-C(O)-N-di(C1-C4)alkyl, -(C1-C4)alkyl-CR 20 -C(O)-NH(C1-C4)alkyl and -(C1-C4)alkyl-CR 20 -C(O)-NH2, where R 20 is hydrogen or (C1-C4)alkyl,

[0363] The polyacrylate P1 is reacted with a 20 at least one ethylenically unsaturated monomer of a vinyl aromatic compound is reacted to obtain a polyacrylate P2,

[0364] Make P2 and

[0365] ii) reacting a mixture comprising at least one alcohol W selected from W2 and at least one amine Z selected from Z1;

[0366] in,

[0367] W2 is the formula B-(OA) n -OH polyether alcohol, wherein A is ethylene or propylene, B is selected from substituted or unsubstituted linear or branched C1-C4 alkyl, and n is an integer in the range of ≥1 to ≤50;

[0368] Z1 is NH2-R 11 -NR 12 R 13 ,

[0369] Where R 11 is a substituted or unsubstituted straight or branched C1-C 12 Alkylene;

[0370] R 12 and R 13 are independently selected from hydrogen and substituted or unsubstituted straight or branched C2-C 10 alkyl groups, which may be the same or different, or R 12 and R 13 Together with the nitrogen atom to which they are attached, they form a 3- to 12-membered ring containing 1 to 3 heteroatoms selected from nitrogen and oxygen,

[0371] Y is a 5- or 6-membered N-containing heterocyclic ring containing 1 or 2 nitrogen atoms and 0 or 1 oxygen atoms.

[0372] In another more preferred embodiment of the present invention, the polymer in embodiment 1 or embodiment 2 is obtained by reacting the following components

[0373] i) at least one polyacrylate P1 obtained by controlled free radical polymerization of a mixture M1 comprising at least one acrylate monomer selected from C2-C5 alkyl esters of acrylic acid in the presence of a1 or a2, wherein a1 is at least one monomer of the formula R 21 R 22 NOX(I) is a nitroxyl ether and a2 is at least one of the formula R 21 R 22 The stable nitroxyl radical of NO·(II);

[0374] R 21 and R 22 are independently selected from substituted or unsubstituted straight or branched C1-C 18 Alkyl, where R 21 and R 22 Together with the nitrogen atom to which they are attached, they form an unsubstituted or substituted 5- to 10-membered aliphatic ring containing 1 to 3 heteroatoms selected from nitrogen and oxygen, and X is selected from -CH2-phenyl, -CH3CH-phenyl, -(CH3)2C-phenyl, -(C5-C6 cycloalkyl)2C-CN, -(CH3)2CCN, -CH2CH=CH2, -CH3CH-CH=CH2, -(C1-C4 alkyl)CR 20 -C(O)-phenyl, -(C1-C4)alkyl-CR 20 -C(O)-(C1-C4)alkoxy, -(C1-C4)alkyl-CR 20 -C(O)-(C1-C4)alkyl, -(C1-C4)alkyl-CR 20 -C(O)-N-di(C1-C4)alkyl, -(C1-C4)alkyl-CR 20 -C(O)-NH(C1-C4)alkyl and -(C1-C4)alkyl-CR 20 -C(O)-NH2, where R 20 is hydrogen or (C1-C4)alkyl,

[0375] and

[0376] ii) a mixture comprising at least one alcohol W selected from W2 and at least one amine Z selected from Z1;

[0377] in,

[0378] W2 is the formula B-(OA) n -OH polyether alcohol, wherein A is ethylene or propylene, B is selected from substituted or unsubstituted linear or branched C1-C4 alkyl, and n is an integer in the range of ≥1 to ≤50;

[0379] Z1 is NH2-R 11 -NR 12 R 13,

[0380] Where R 11 is a substituted or unsubstituted straight or branched C1-C 10 Alkylene;

[0381] R 12 and R 13 are independently selected from hydrogen and substituted or unsubstituted straight or branched C2-C 10 alkyl groups, which may be the same or different, or R 12 and R 13 Together with the nitrogen atom to which they are attached, they form a 4- to 10-membered ring containing 1 to 3 heteroatoms selected from nitrogen and oxygen,

[0382] Y is a 5- or 6-membered N-containing heterocyclic ring containing 1 or 2 nitrogen atoms.

[0383] In another more preferred embodiment of the present invention, the polymer in embodiment 1 or embodiment 2 is obtained by reacting the following components

[0384] i) at least one polyacrylate P1 obtained by controlled free radical polymerization of a mixture M1 comprising at least one acrylate monomer selected from C2-C5 alkyl esters of acrylic acid in the presence of a1 or a2, wherein a1 is at least one monomer of the formula R 21 R 22 NOX(I) is a nitroxyl ether and a2 is at least one of the formula R 21 R 22 The stable nitroxyl radical of NO·(II);

[0385] R 21 and R 22 are independently selected from substituted or unsubstituted straight or branched C1-C 18 Alkyl, where R 21 and R 22 Together with the nitrogen atom to which they are attached, they form an unsubstituted or substituted 5- to 10-membered aliphatic ring containing 1 to 3 heteroatoms selected from nitrogen and oxygen, and X is selected from -CH2-phenyl, -CH3CH-phenyl, -(CH3)2C-phenyl, -(C5-C6 cycloalkyl)2C-CN, -(CH3)2CCN, -CH2CH=CH2, -CH3CH-CH=CH2, -(C1-C4 alkyl)CR 20 -C(O)-phenyl, -(C1-C4)alkyl-CR 20 -C(O)-(C1-C4)alkoxy, -(C1-C4)alkyl-CR 20 -C(O)-(C1-C4)alkyl, -(C1-C4)alkyl-CR 20 -C(O)-N-di(C1-C4)alkyl, -(C1-C4)alkyl-CR20 -C(O)-NH(C1-C4)alkyl and -(C1-C4)alkyl-CR 20 -C(O)-NH2, where R 20 is hydrogen or (C1-C4)alkyl,

[0386] The polyacrylate P1 is reacted with a C6-C 10 at least one ethylenically unsaturated monomer of a vinyl aromatic compound is reacted to obtain a polyacrylate P2,

[0387] Make P2 and

[0388] ii) reacting a mixture comprising at least one alcohol W selected from W2 and at least one amine Z selected from Z1;

[0389] in,

[0390] W2 is the formula B-(OA) n -OH polyether alcohol, wherein A is ethylene or propylene, B is selected from substituted or unsubstituted linear or branched C1-C4 alkyl, and n is an integer in the range of ≥1 to ≤50;

[0391] Z1 is NH2-R 11 -NR 12 R 13 ,

[0392] Where R 11 is a substituted or unsubstituted straight or branched C1-C 10 Alkylene;

[0393] R 12 and R 13 are independently selected from hydrogen and substituted or unsubstituted straight or branched C2-C 10 alkyl groups, which may be the same or different, or R 12 and R 13 Together with the nitrogen atom to which they are attached, they form a 4- to 10-membered ring containing 1 to 3 heteroatoms selected from nitrogen and oxygen,

[0394] Y is a 5- or 6-membered N-containing heterocyclic ring containing 1 or 2 nitrogen atoms.

[0395] In a preferred embodiment of the present invention, the controlled radical polymerization in embodiment 1 or embodiment 2 is carried out in the presence of the at least one acrylate monomer and the at least one ethylenically unsaturated monomer.

[0396] In a preferred embodiment of the present invention, the polymer in embodiment 1 or embodiment 2 has a polydispersity index of 1.0 to 2.2, more preferably 1.1 to 1.9, most preferably 1.1 to 1.5.

[0397] In a preferred embodiment of the present invention, the polymers in embodiment 1 or embodiment 2 have an amine number in the range of about ≥10 to ≤200 mg KOH / g, preferably ≥50 to ≤150 mg KOH / g, more preferably ≥80 to ≤120 mg KOH / g, as determined according to DIN 53176:2002-11.

[0398] In a preferred embodiment of the present invention, the weight ratio of the at least one alcohol W in embodiment 1 or embodiment 2 to the at least one amine Z is in the range of about 0.1:1 to 10:1, preferably in the range of about 0.2:1 to 8:1, more preferably in the range of about 0.5:1 to 6:1, and even more preferably in the range of about 1:1 to 5:1.

[0399] In a preferred embodiment of the present invention, the method of embodiment 2 further comprises heating the mixture M1 of step a. at a temperature of about 70-200°C, preferably about 80-190°C, more preferably about 90-180°C, still more preferably about 110-160°C, more preferably about 110-150°C.

[0400] In a preferred embodiment of the present invention, the molar ratio of the at least one acrylate monomer in Embodiment 2 to a1 or a2 is in the range of about 1:1 to 70:1, preferably in the range of about 10:1 to 60:1, and more preferably in the range of about 20:1 to 50:1.

[0401] In a preferred embodiment of the present invention, the first polymerization step in embodiment 2 is carried out in a1, that is, at least one 21 R 22 The reaction was carried out in the presence of a nitroxyl ether of NOX(I).

[0402] In another preferred embodiment of the present invention, the first polymerization step in embodiment 2 is carried out in a2, i.e., at least one 21 R 22 The reaction is carried out in the presence of stable nitroxyl free radical NO·(II).

[0403] In a preferred embodiment of the present invention, the transesterification in Embodiment 2 preferably comprises removing the C1-C6 alcohol by-product by distillation.

[0404] In a preferred embodiment of the present invention, the at least one acrylate monomer in Embodiment 2 is selected from C1-C6 alkyl or hydroxyalkyl esters of acrylic acid or methacrylic acid.

[0405] In a preferred embodiment of the present invention, the polyacrylate P1 of step a. in embodiment 2 is further reacted with at least one ethylenically unsaturated monomer and then modified in step b.

[0406] In a preferred embodiment of the present invention, the mixture M1 of step a. in embodiment 2 further comprises at least one ethylenically unsaturated monomer and is then modified in step b.

[0407] In a preferred embodiment of the present invention, the at least one acrylate monomer in Embodiment 2 is selected from

[0408]

[0409]

[0410] Among them - and R a has the meaning as defined above, R e is methyl, benzyl or benzoylbenzyl,

[0411] An - Preferably Cl - Br - or -O3S-O-CH3,

[0412] Me + It is an alkali metal cation or an ammonium cation.

[0413] In another preferred embodiment of the present invention, the at least one acrylate monomer in embodiment 2 is also a silicone functional (meth)acrylate.

[0414] In a preferred embodiment of the present invention, the polyacrylate P1 of step a. in embodiment 2 is further reacted with at least one ethylenically unsaturated monomer and then modified in step b.

[0415] In a preferred embodiment of the present invention, at least one ethylenically unsaturated monomer in Embodiment 2 is selected from C5-C 20 Vinyl aromatic compounds, ethylenically unsaturated nitriles, acrylamides, vinyl halides, C1-C 10 Vinyl ethers of alcohols and C2-C8 aliphatic hydrocarbons having one or two double bonds.

[0416] In a preferred embodiment of the present invention, the monomers in step a) of embodiment 2 may be selected from isoprene, 1,3-butadiene, α-C5-C 18 Olefins, 4-vinyl-pyridine or pyridine -ion, 2-vinyl-pyridine or pyridine -ion, vinyl-imidazole or imidazoline -ion, dimethylacrylamide, 3-dimethylaminopropylmethacrylamide, styrene, α-methylstyrene, p-methylstyrene, p-tert-butyl-styrene or a compound of formula CH2=C(Ra)-(C=Z)-Rb, wherein Ra is hydrogen or C1-C4 alkyl, Rb is NH2, O - (Me + ), unsubstituted C1-C 18 Alkoxy, C2-C 100 Alkoxy or hydroxy substituted C1-C 18 Alkoxy, unsubstituted C1-C 18 Alkylamino, di(C1-C 18 Alkyl)amino, hydroxy substituted C1-C 18 Alkylamino or hydroxy substituted di(C1-C 18 alkyl)amino, -O-CH2-CH2-N(CH3)2 or -O-CH2-CH2-N + H(CH3)2An - ;

[0417] An - It is the anion of a monovalent organic or inorganic acid;

[0418] Me is a monovalent metal atom or an ammonium ion,

[0419] Z is oxygen or sulfur.

[0420] In another preferred embodiment of the present invention, step a of the process of embodiment 2 is carried out twice and a block copolymer is obtained, wherein in the first or second free-radical polymerization step, the monomer or monomer mixture contains 50 to 100% by weight of C1-C6 alkyl or hydroxyalkyl ester of acrylic acid or methacrylic acid, based on the total monomers, and in the second or first free-radical polymerization step, respectively, the ethylenically unsaturated monomer does not contain primary or secondary ester bonds.

[0421] In another preferred embodiment of the present invention, when a block polymer is prepared by the method of embodiment 2, a block copolymer is prepared, preferably, in the first polymerization step, the monomer or monomer mixture contains 50 to 100% by weight of a C1-C6 alkyl or hydroxyalkyl ester of acrylic acid or methacrylic acid, based on the total monomers, and in the second polymerization step, the ethylenically unsaturated monomer is 4-vinyl-pyridine or pyridine -ion, 2-vinyl-pyridine or pyridine -ion, vinyl-imidazole or imidazoline -ion, dimethylacrylamide, 3-dimethylaminopropylmethacrylamide, styrene, α-methylstyrene, p-methylstyrene or p-tert-butyl-styrene.

[0422] In another preferred embodiment of the present invention, the block polymer prepared by the method of Embodiment 2 is a gradient block polymer.

[0423] In another preferred embodiment of the present invention, the polymer prepared by the method of embodiment 2 is prepared by controlled radical polymerization (CFRP). A similar method using stable nitroxyl radicals as control agents has been described by Solomon et al. in US 4,581,429. These are the steps defined under a1) and a2) herein. A free radical polymerization method carried out by controlled or "living" growth of polymer chains, which produces defined oligomeric homopolymers and copolymers, including block and graft copolymers. The use of initiators of the partial general formula R'R"NOX is disclosed. In this polymerization method, free radical species R'R"NO· and ·X are generated. Here, ·X is a free radical capable of polymerizing ethylene-containing monomer units, such as tert-butyl or isocyanopropyl radicals.

[0424] In another preferred embodiment of the present invention, the polymer prepared by the method of embodiment 2 relates to a1, wherein the nitroxyl ether is cleaved between the OX bonds according to the structure outlined above. The regulating fragment in formula (I) corresponds to the ON fragment and the initiating fragment (In) corresponds to the C-centered group of the group X.

[0425] In another preferred embodiment of the present invention, the polymer prepared by the process of embodiment 2 relates to a2, wherein the free radical initiator is preferably an azo compound, a peroxide, a perester or a hydroperoxide.

[0426] In a more preferred embodiment of the present invention, the polymer prepared by the method of embodiment 2 relates to a2, wherein the preferred free radical source is selected from 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 1,1'-azobis(1-cyclohexanecarbonitrile), 2,2'-azobis(isobutyramide) dihydrate, 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, dimethyl-2,2'-azobisisobutyrate, 2-(carbamoylazo)isobutyronitrile, 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(2-methylpropane), 2,2'-azobis(N,N'-dimethyleneisobutyramidine), free base or hydrochloric acid salt, 2,2'-azobis(2-amidinopropane), free base or hydrochloride, 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide} or 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide; acetyl peroxysulfonyl cyclohexane, diisopropyl peroxydicarbonate, tert-amyl perneodecanoate, tert-butyl perneodecanoate, perpivalic acid tert-butyl ester, tert-amyl perpivalate, bis(2,4-dichlorobenzoyl) peroxide, diisononanoyl peroxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, bis(2-methylbenzoyl) peroxide, disuccinic acid peroxide, diacetyl peroxide, dibenzoyl peroxide, tert-butyl per2-ethylhexanoate, bis-(4-chlorobenzoyl) peroxide, tert-butyl perisobutyrate, tert-butyl permaleate permaleinate), 1,1-bis(tert-butylperoxy)3,5,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, tert-butyl peroxyisopropyl carbonate, tert-butyl perisononanoate, 2,5-dimethylhexane 2,5-dibenzoate, tert-butyl peracetate, tert-amyl perbenzoate, tert-butyl perbenzoate, 2,2-bis(tert-butylperoxy)butane, 2,2-bis(tert-butylperoxy)propane, diisopropyl peroxide, 2,5-dimethylhexane-2,5-di-tert-butyl Peroxide, 3-tert-butylperoxy-3-phenylphthalide, di-tert-amyl peroxide, α,α'-bis(tert-butylperoxyisopropyl)benzene, 3,5-bis(tert-butylperoxy)3,5-dimethyl1,2-dioxolane, di-tert-butyl peroxide, 2,5-dimethylhexyne-2,5-di-tert-butyl peroxide, 3,3,6,6,9,9-hexamethyl-1,2,4,5-tetraoxacyclononane, p-menthane hydroperoxide, pinane hydroperoxide, mono-α-diisopropylbenzene hydroperoxide, isopropylbenzene hydroperoxide and tert-butyl hydroperoxide.

[0427] In another preferred embodiment of the present invention, the free radical source in Embodiment 2 is preferably present in an amount of 0.01 mol % to 30 mol %, more preferably in an amount of 0.1 mol % to 20 mol %, and most preferably in an amount of 0.5 mol % to 10 mol %, based on the monomer or monomer mixture.

[0428] In another preferred embodiment of the present invention, the at least one alcohol (W) and the at least one amine (Z) described in embodiment 2 are added together.

[0429] In yet another preferred embodiment of the present invention, the transesterification and transamide conversion in Embodiment 2 are carried out simultaneously.

[0430] In another preferred embodiment of the present invention, the modification of the polyacrylate obtained in step b. in embodiment 2 is carried out in a stepwise manner.

[0431] In yet another preferred embodiment of the present invention, step b. in embodiment 2 involves modifying the polyacrylate obtained in step a. by transesterification using at least one alcohol (W) selected from W1 and W2, followed by transamidation using at least one amine (Z) selected from Z1 and Z2.

[0432] In another preferred embodiment of the present invention, step b. in embodiment 2 involves modifying the polyacrylate obtained in step a. by amide transamidation using at least one amine (Z) selected from Z1 and Z2, followed by ester transamidation using at least one alcohol (W) selected from W1 and W2.

[0433] In another preferred embodiment of the present invention, the molar ratio of the free radical source to the nitroxyl radical in Embodiment 2 may be 1:10 to 10:1, preferably 1:5 to 5:1, and more preferably 1:2 to 2:1.

[0434] In another preferred embodiment of the invention, the polymers or copolymers according to embodiment 1 or embodiment 2 can also be prepared in a controlled manner by atom transfer radical polymerization (ATRP). This type of polymerization is described, for example, in WO 96 / 30421.

[0435] In another preferred embodiment of the present invention, the polymer or copolymer in embodiment 1 or embodiment 2 preferably has a polydispersity index of 1.0 to 2.2, more preferably 1.1 to 1.9, most preferably 1.1 to 1.5.

[0436] In a more preferred embodiment of the present invention, the initiator compound in embodiment 2 is present in an amount of 0.01 mol% to 30 mol%, more preferably 0.1 mol% to 20 mol%, and most preferably 0.1 mol% to 10 mol%, based on the monomer or monomer mixture. When a monomer mixture is used, the mol% is calculated based on the average molecular weight of the mixture.

[0437] Yet another aspect of the present invention is a coating composition comprising the polymer of embodiment 1 obtained by the method of embodiment 2.

[0438] In a preferred embodiment of the present invention, the coating composition is selected from an ink, a lacquer or a pigment composition.

[0439] Still another aspect of the present invention is an ink composition comprising the polymer of Embodiment 1 obtained by the method of Embodiment 2.

[0440] In a preferred embodiment of the present invention, the ink or coating composition further comprises a particulate solid material selected from the group consisting of a pigment, a filler, a liquid diluent and combinations thereof.

[0441] In a preferred embodiment of the present invention, the ink or coating composition has a viscosity in the range of about ≥200 to ≤4000 mPa.s, preferably in the range of ≥350 to ≤3500 mPa.s, more preferably in the range of ≥450 to ≤3000 mPa.s, determined according to DIN 53019-1:2008-09.

[0442] In a preferred embodiment of the present invention, the ink or coating composition has a blackness in the range of 150 to 500, preferably in the range of 200 to 450, preferably in the range of 220 to 420, even more preferably in the range of 250 to 400 as determined according to DIN 55979.

[0443] In a preferred embodiment of the present invention, the polymer has a weight percentage in the range of about 1 to 10%, preferably in the range of about 2 to 9%, more preferably in the range of about 3 to 8%, and even more preferably in the range of about 4 to 8%, based on the ink or coating composition.

[0444] In a preferred embodiment of the present invention, the polymer / pigment weight ratio is in the range of about 0.1:1 to 1.5:1, preferably in the range of about 0.3:1 to 1.3:1, more preferably in the range of about 0.6:1 to 1.2:1, and even more preferably in the range of about 0.7:1 to 1.1:1.

[0445] Yet another aspect of the present invention is the use of the polymer according to embodiment 1 as a dispersant in a coating composition or an ink composition.

[0446] The present invention provides one or more of the following advantages:

[0447] 1) The polymers of the present invention can be used as a dispersant as part of an ink or coating composition.

[0448] 2) The polymer of the present invention does not interfere with the original properties of the dye / pigment, thereby ensuring high blackness.

[0449] 3) The polymers of the present invention ensure low viscosity in ink or coating compositions when used as dispersants.

[0450] 4) The polymers of the present invention, when used as dispersants, enable aqueous processability of ink or coating compositions, thereby improving their compliance with environmental and safety regulations.

[0451] 5) The polymers of the present invention are compatible with common ink or coating ingredients and thus have no unwanted negative interactions with said ingredients.

[0452] The following list of embodiments is provided to further illustrate the present disclosure, but is not intended to limit the present disclosure to the specific embodiments listed below.

[0453] 1. A polymer obtained by reacting the following components

[0454] i) at least one polyacrylate P1 obtained by controlled free radical polymerization of a mixture M1 in the presence of a1 or a2, the mixture M1 comprising at least one acrylate monomer selected from C1-C6 alkyl acrylates, C1-C6 alkyl methacrylates, hydroxy C1-C6 alkyl acrylates and hydroxy C1-C6 alkyl methacrylates,

[0455] Where a1 is at least one of the formula R 21 R 22 NOX(I) is a nitroxyl ether and a2 is at least one of the formula R 21 R 22 The stable nitroxyl radical of NO·(II);

[0456] R 21 and R 22 independently selected from substituted or unsubstituted straight or branched C5-C 18 Alkyl, where R 21 and R 22Together with the nitrogen atom to which they are attached, they form an unsubstituted or substituted 5- to 10-membered aliphatic ring containing 1 to 3 heteroatoms selected from nitrogen and oxygen, and X is selected from -CH2-phenyl, -CH3CH-phenyl, -(CH3)2C-phenyl, -(C5-C6 cycloalkyl)2C-CN, -(CH3)2CCN, -CH2CH=CH2, -CH3CH-CH=CH2, -(C1-C4 alkyl)CR 20 -C(O)-phenyl, -(C1-C4)alkyl-CR 20 -C(O)-(C1-C4)alkoxy, -(C1-C4)alkyl-CR 20 -C(O)-(C1-C4)alkyl, -(C1-C4)alkyl-CR 20 -C(O)-N-di(C1-C4)alkyl, -(C1-C4)alkyl-CR 20 -C(O)-NH(C1-C4)alkyl and -(C1-C4)alkyl-CR 20 -C(O)-NH2, where R 20 is hydrogen or (C1-C4)alkyl,

[0457] and

[0458] ii) a mixture M2 comprising at least one alcohol W selected from W1 and W2 and at least one amine Z selected from Z1 and Z2;

[0459] in,

[0460] W1 is R 1 -OH, where R 1 is a substituted or unsubstituted straight or branched C8-C 36 alkyl;

[0461] W2 is at least one of the formula B-(OA) n -OH polyether alcohol, wherein A is a substituted or unsubstituted straight chain or branched C1-C4 alkylene, and B is selected from a substituted or unsubstituted straight chain or branched C1-C 22 Alkyl, substituted or unsubstituted C1-C 24 Alkyl aryl and substituted or unsubstituted C1-C 24 dialkylaryl, n is an integer in the range of ≥1 to ≤150;

[0462] Z1 is NH2-R 11 -NR 12 R 13 , Z2 is NH2-R 11 -Y,

[0463] Where R 11 is a substituted or unsubstituted straight or branched C1-C 12Alkylene;

[0464] R 12 and R 13 are independently selected from hydrogen and substituted or unsubstituted straight or branched C1-C 12 Alkyl, or

[0465] R 12 and R 13 Together with the nitrogen atom to which they are attached, they form an unsubstituted or substituted 3- to 12-membered ring containing 1 to 3 heteroatoms selected from nitrogen and oxygen;

[0466] Y is a 5- or 6-membered N-containing heterocyclic ring containing 1 or 2 nitrogen atoms and 0 or 1 oxygen atoms.

[0467] 2. The polymer according to embodiment 1, wherein the at least one acrylate monomer is selected from n-butyl acrylate, methyl acrylate, ethyl acrylate, n-butyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate and 4-hydroxybutyl acrylate.

[0468] 3. A polymer according to embodiment 1 or 2, wherein the at least one 21 R 22 The nitroxyl ether of NOX is a compound of formula (Ia),

[0469]

[0470] Among them, G 1 , G 2 , G 3 , G 4 are independently substituted or unsubstituted straight or branched C1-C6 alkyl, or G 1 and G 2 or G 3 and G 4 , or G 1 and G 2 and G 3 and G 4 Together they form substituted or unsubstituted C5-C 12 Cycloalkyl;

[0471] G 5 , G 6 are independently selected from hydrogen, substituted or unsubstituted straight or branched C1-C 18 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl and -C(O)-O-C1-C 18 alkyl;

[0472] X is selected from -CH2-phenyl, -CH3CH-phenyl, -(CH3)2C-phenyl, -(C5-C6 cycloalkyl)2C-CN, -(CH3)2CCN, -CH2CH=CH2, -CH3CH-CH=CH2, -(C1-C4 alkyl)CR 20 -C(O)-phenyl, -(C1-C4)alkyl-CR 20 -C(O)-(C1-C4)alkoxy, -(C1-C4)alkyl-CR 20 -C(O)-(C1-C4)alkyl, -(C1-C4)alkyl-CR 20 -C(O)-N-di(C1-C4)alkyl, -(C1-C4)alkyl-CR 20 -C(O)-NH(C1-C4)alkyl and -(C1-C4)alkyl-CR 20 -C(O)-NH2, where R 20 is hydrogen or (C1-C4)alkyl,

[0473] wherein phenyl, alkyl, alkoxy and cycloalkyl are in each case unsubstituted or substituted, alkyl and alkoxy are in each case straight-chain or branched,

[0474] * indicates chemical valence.

[0475] 4. A polymer according to embodiment 1 or 2, wherein the at least one 21 R 22 The stable nitroxyl radical of NO· is the structural unit of formula (IIa),

[0476]

[0477] Among them, G 1 , G 2 , G 3 , G 4 are independently substituted or unsubstituted straight or branched C1-C6 alkyl, or G 1 and G 2 or G 3 and G 4 , or G 1 and G 2 and G 3 and G 4 Together they form substituted or unsubstituted C5-C 12 Cycloalkyl;

[0478] G 5 , G 6 are independently selected from hydrogen, substituted or unsubstituted straight or branched C1-C 18 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl and -C(O)-O-C1-C18 alkyl;

[0479] * indicates chemical valence.

[0480] 5. The polymer according to any one of embodiments 1 to 4, wherein the at least one nitroxyl ether is

[0481]

[0482] 6. The polymer according to any of embodiments 1 to 5, wherein the polyacrylate P1 is further reacted with at least one ethylenically unsaturated monomer to obtain the polyacrylate P2, which is subsequently reacted in step ii) with the mixture M2.

[0483] 7. The polymer according to embodiment 6, wherein the polyacrylate P2 is a gradient block copolymer.

[0484] 8. The polymer according to any of embodiments 1 to 5, wherein the mixture M1 further comprises at least one ethylenically unsaturated monomer to obtain a polyacrylate P1 which is subsequently reacted in step ii) with the mixture M2.

[0485] 9. The polymer according to embodiment 8, wherein the polyacrylate P1 is a random copolymer.

[0486] 10. The polymer according to any one of embodiments 6 to 9, wherein the at least one ethylenically unsaturated monomer is selected from C5-C 20 Vinyl aromatic compounds, ethylenically unsaturated nitriles, acrylamides, vinyl halides, C1-C 10 Vinyl ethers of alcohols and C2-C8 aliphatic hydrocarbons having one or two double bonds.

[0487] 11. The polymer according to any one of embodiments 6 to 10, wherein the at least one ethylenically unsaturated monomer does not contain any primary or secondary ester bonds.

[0488] 12. The polymer according to any one of embodiments 6 to 11, wherein the at least one ethylenically unsaturated monomer is selected from isoprene, 1,3-butadiene, α-C5-C 18 -olefin, 4-vinyl-pyridine or pyridine -ion, 2-vinyl-pyridine or pyridine -ion, vinyl-imidazole or imidazoline ions, dimethylacrylamide, 3-dimethylaminopropylmethacrylamide, styrene, α-methylstyrene, p-methylstyrene, p-tert-butyl-styrene and compounds of the formula CH2=C(R a )-(C=Z)-R b A compound wherein R a is hydrogen or methyl, R bNH2, O-(Me+), unsubstituted C1-C 18 -alkoxy, C2-C 100 -alkoxy or hydroxy substituted C1-C 18 Alkoxy, unsubstituted C1-C 18 Alkylamino, di(C1-C 18 Alkyl)-amino, hydroxy substituted C1-C 18 Alkylamino or hydroxy substituted di(C1-C 18 alkyl)amino, -O-CH2-CH2-N(CH3)2 or -O-CH2-CH2-N + H(CH3)2A n - ;

[0489] A n - is the anion of a monovalent organic or inorganic acid;

[0490] Me is a monovalent metal atom or an ammonium ion;

[0491] Z is oxygen or sulfur.

[0492] 13. The polymer composition according to any one of embodiments 6 to 12, wherein the at least one ethylenically unsaturated monomer is selected from 4-vinyl-pyridine or pyridine -ion, 2-vinyl-pyridine or pyridine -ion, vinyl-imidazole or imidazoline -ion, dimethylacrylamide, 3-dimethylaminopropylmethacrylamide, styrene, α-methylstyrene, p-methylstyrene and p-tert-butyl-styrene.

[0493] 14. A polymer according to any one of embodiments 1 to 13, wherein R 1 is a substituted or unsubstituted straight chain or branched C 10 -C 34 alkyl.

[0494] 15. The polymer according to any one of embodiments 1 to 14, wherein the compound R 1 -OH is selected from nonan-1-ol, nonan-2-ol, dodecan-1-ol, decan-1-ol and decan-2-ol.

[0495] 16. The polymer according to any one of embodiments 1 to 13, wherein A is ethylene or propylene, B is selected from substituted or unsubstituted linear or branched C1-C4 alkyl, and n is an integer in the range of ≥1 to ≤50.

[0496] 17. The polymer according to any one of embodiments 1 to 13, wherein the at least one compound of formula B-(OA)n The polyether alcohols containing -OH are polyether alcohols having a number average molecular weight (M) in the range of ≥100 to ≤1000 g / mol, as determined in accordance with DIN 55672-1. n ) of methoxy polyethylene glycol.

[0497] 18. The polymer according to embodiment 17, wherein the at least one compound of formula B-(OA) n The polyether alcohols containing -OH are polyether alcohols having a number average molecular weight (M) in the range of ≥200 to 800 ≤ g / mol, as determined in accordance with DIN 55672-1. n ) of methoxy polyethylene glycol.

[0498] 19. A polymer according to any one of embodiments 1 to 18, wherein R 11 It is an unsubstituted straight or branched C1-C8 alkylene group.

[0499] 20. A polymer according to any one of embodiments 1 to 19, wherein R 11 Selected from -CH2-, -CH2CH2-, -CH2CH2CH2- and -CH2CH2CH2CH2-.

[0500] 21. A polymer according to any one of embodiments 1 to 20, wherein R 12 and R 13 is an unsubstituted straight or branched C1-C8 alkyl group, or together with the nitrogen atom to which they are attached, forms an unsubstituted or substituted 3- to 6-membered ring containing 1 or 2 heteroatoms selected from nitrogen and oxygen.

[0501] 22. A polymer according to any one of embodiments 1 to 21, wherein R 12 and R 13 Independently selected from methyl, ethyl, propyl and isopropyl.

[0502] 23. A polymer according to any one of embodiments 1 to 22, wherein R 11 is an unsubstituted straight chain C1-C8 alkylene group, R 12 and R 13 are independently selected from methyl, ethyl, propyl and isopropyl, or R 12 and R 13 Together with the nitrogen atom to which they are attached they form a pyrrolidinyl, piperidinyl or morpholinyl group.

[0503] 24. The polymer according to any one of embodiments 1 to 23, wherein Y is selected from imidazolyl and pyridyl.

[0504] 25. The polymer according to any of embodiments 1 to 24, having an amine value in the range of about ≧10 to ≦200 mg KOH / g as determined according to DIN 53176:2002-11.

[0505] 26. The polymer according to any one of embodiments 1 to 25, wherein the weight ratio of the at least one alcohol W to the at least one amine Z is in the range of about 0.1:1 to 10:1.

[0506] 27. A controlled radical polymerization process for preparing a polymer according to embodiments 1 to 26, comprising at least the following steps:

[0507] a. polymerizing a mixture M1 comprising at least one acrylate monomer in the presence of a1 or a2;

[0508] Where a1 is at least one of the formula R 21 R 22 NOX(I) is a nitroxyl ether and a2 is at least one of the formula R 21 R 22 The stable nitroxyl radical of NO·(II) 21 and R 22 independently selected from substituted or unsubstituted straight or branched C5-C 18 Alkyl, where R 21 and R 22 Together with the nitrogen atom to which they are attached, they form an unsubstituted or substituted 5- to 10-membered aliphatic ring containing 1 to 3 heteroatoms selected from nitrogen and oxygen, and X is selected from -CH2-phenyl, -CH3CH-phenyl, -(CH3)2C-phenyl, -(C5-C6 cycloalkyl)2C-CN, -(CH3)2CCN, -CH2CH=CH2, -CH3CH-CH=CH2, -(C1-C4 alkyl)CR 20 -C(O)-phenyl, -(C1-C4)alkyl-CR 20 -C(O)-(C1-C4)alkoxy, -(C1-C4)alkyl-CR 20 -C(O)-(C1-C4)alkyl, -(C1-C4)alkyl-CR 20 -C(O)-N-di(C1-C4)alkyl, -(C1-C4)alkyl-CR 20 -C(O)-NH(C1-C4)alkyl and -(C1-C4)alkyl-CR 20 -C(O)-NH2, where R 20 is hydrogen or (C1-C4)alkyl; and

[0509] b. modifying the polyacrylate obtained in step a. by transesterification using at least one alcohol (W) selected from W1 and W2 and transamide using at least one amine (Z) selected from Z1 and Z2;

[0510] Where W1 is R 1 -OH, where R 1 is a substituted or unsubstituted straight or branched C8-C 36 alkyl;

[0511] W2 is at least one of the formula B-(OA) n -OH polyether alcohol, wherein A is a substituted or unsubstituted straight chain or branched C1-C4 alkylene, and B is selected from a substituted or unsubstituted straight chain or branched C1-C 22 Alkyl, substituted or unsubstituted C1-C 24 Alkyl aryl or substituted and unsubstituted C1-C 24 dialkylaryl, n is an integer in the range of ≥1 to ≤150;

[0512] Z1 is NH2-R 11 -NR 12 R 13 , Z2 is NH2-R 11 -Y,

[0513] Where R 11 is a substituted or unsubstituted straight or branched C1-C 12 Alkylene;

[0514] R 12 and R 13 are independently selected from hydrogen and substituted or unsubstituted straight or branched C1-C 12 Alkyl, or R 12 and R 13 Together with the nitrogen atom to which they are attached, they form an unsubstituted or substituted 3- to 12-membered ring containing 1 to 3 heteroatoms selected from nitrogen and oxygen;

[0515] Y is a 5- or 6-membered N-containing heterocyclic ring containing 1 or 2 nitrogen atoms and 0 or 1 oxygen atoms.

[0516] 28. The method according to embodiment 27, wherein the at least one 21 R 22 The nitroxyl ether of NOX is a compound of formula (Ia),

[0517]

[0518] Among them, G 1 , G 2 , G 3 , G 4are independently substituted or unsubstituted straight or branched C1-C6 alkyl, or G 1 and G 2 or G 3 and G 4 , or G 1 and G 2 and G 3 and G 4 Together they form substituted or unsubstituted C5-C 12 Cycloalkyl;

[0519] G 5 , G 6 are independently selected from hydrogen, substituted or unsubstituted straight or branched C1-C 18 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl and -C(O)-O-C1-C 18 alkyl;

[0520] X is selected from -CH2-phenyl, -CH3CH-phenyl, -(CH3)2C-phenyl, -(C5-C6 cycloalkyl)2C-CN, -(CH3)2CCN, -CH2CH=CH2, -CH3CH-CH=CH2, -(C1-C4 alkyl)CR 20 -C(O)-phenyl, -(C1-C4)alkyl-CR 20 -C(O)-(C1-C4)alkoxy, -(C1-C4)alkyl-CR 20 -C(O)-(C1-C4)alkyl, -(C1-C4)alkyl-CR 20 -C(O)-N-di(C1-C4)alkyl, -(C1-C4)alkyl-CR 20 -C(O)-NH(C1-C4)alkyl and -(C1-C4)alkyl-CR 20 -C(O)-NH2, where R 20 is hydrogen or (C1-C4)alkyl,

[0521] wherein phenyl, alkyl, alkoxy and cycloalkyl are in each case unsubstituted or substituted, alkyl and alkoxy are in each case straight-chain or branched,

[0522] * indicates valence.

[0523] 29. The method according to embodiment 27, wherein the at least one 21 R 22 The stable nitroxyl radical of NO· is the structural unit of formula (IIa),

[0524]

[0525] Among them, G 1 , G2 , G 3 , G 4 are independently substituted or unsubstituted straight or branched C1-C6 alkyl, or G 1 and G 2 or G 3 and G 4 , or G 1 and G 2 and G 3 and G 4 Together they form substituted or unsubstituted C5-C 12 Cycloalkyl;

[0526] G 5 , G 6 are independently selected from hydrogen, substituted or unsubstituted straight or branched C1-C 18 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl and -C(O)-O-C1-C 18 alkyl;

[0527] * indicates chemical valence.

[0528] 30. The method according to any one of embodiments 27-29, wherein the at least one 21 R 22 The nitroxyl ether of NOX is

[0529]

[0530] 31. The process according to any of embodiments 27 to 30, wherein the polyacrylate P1 of step a. is further reacted with at least one ethylenically unsaturated monomer and then modified in step b.

[0531] 32. The process according to any of embodiments 27 to 30, wherein the mixture M1 of step a. further comprises at least one ethylenically unsaturated monomer and is then modified in step b.

[0532] 33. The method according to embodiment 31 or 32, wherein the at least one ethylenically unsaturated monomer is selected from C5-C 20 Vinyl aromatic compounds, ethylenically unsaturated nitriles, acrylamides, vinyl halides, C1-C 10 Vinyl ethers of alcohols and C2-C8 aliphatic hydrocarbons having one or two double bonds.

[0533] 34. The process according to any one of embodiments 31 to 33, wherein the at least one ethylenically unsaturated monomer does not contain any primary or secondary ester bonds.

[0534] 35. The method according to any one of embodiments 31 to 34, wherein the at least one ethylenically unsaturated monomer is selected from isoprene, 1,3-butadiene, α-C5-C 18 -olefin, 4-vinyl-pyridine or pyridine -ion, 2-vinyl-pyridine or pyridine -ion, vinyl-imidazole or imidazoline ions, dimethylacrylamide, 3-dimethylaminopropylmethacrylamide, styrene, α-methylstyrene, p-methylstyrene, p-tert-butyl-styrene and compounds of the formula CH2=C(R a )-(C=Z)-R b A compound wherein R a is hydrogen or methyl, R b NH2, O-(Me+), unsubstituted C1-C 18 -alkoxy, C2-C 100 -alkoxy or hydroxy substituted C1-C 18 Alkoxy, unsubstituted C1-C 18 Alkylamino, di(C1-C 18 Alkyl)-amino, hydroxy substituted C1-C 18 Alkylamino or hydroxy substituted di(C1-C 18 alkyl)amino, -O-CH2-CH2-N(CH3)2 and -O-CH2-CH2-N + H(CH3)2A n - ;

[0535] A n - is the anion of a monovalent organic or inorganic acid;

[0536] Me is a monovalent metal atom or an ammonium ion;

[0537] Z is oxygen or sulfur.

[0538] 36. The method according to any one of embodiments 27-35, wherein R 1 is a substituted or unsubstituted straight chain or branched C 10 -C 34 alkyl.

[0539] 37. The method according to any one of embodiments 27-36, wherein compound R 1 -OH is selected from nonan-1-ol, nonan-2-ol, dodecan-1-ol, decan-1-ol and decan-2-ol.

[0540] 38. The method according to any one of embodiments 27 to 37, wherein A is ethylene or propylene, B is selected from substituted or unsubstituted linear or branched C1-C4 alkyl, and n is an integer in the range of ≥1 to ≤50.

[0541] 39. The process according to any of embodiments 27-38, wherein the heating of the mixture M1 of step a. is carried out at a temperature of about 70-200°C.

[0542] 40. The method according to any one of embodiments 27 to 39, wherein the molar ratio of the at least one acrylate monomer to a1 or a2 is in the range of about 1:1 to 70:1.

[0543] 41. The process according to any one of embodiments 27 to 38, wherein the weight ratio of the at least one alcohol W to the at least one amine Z is in the range of about 0.1:1 to 10:1.

[0544] 42. A coating composition comprising the polymer according to any one of embodiments 1-26.

[0545] 43. An ink composition comprising the polymer according to any one of embodiments 1-26.

[0546] 44. The ink or coating composition according to embodiment 42 or 43, further comprising a particulate solid material selected from the group consisting of a pigment, a filler, a liquid diluent, and combinations thereof.

[0547] 45. The ink or coating composition according to any one of embodiments 42 to 44, wherein the ink or coating composition has a viscosity in the range of about ≧200 to ≦4000 mPa.s as determined according to DIN 53019-1:2008-09.

[0548] 46. ​​The ink or coating composition according to any one of embodiments 42 to 45, wherein the ink or coating composition has a jetness in the range of ≥150 to ≤500 as determined according to DIN 55979.

[0549] 47. The ink or coating composition according to any one of embodiments 42-46, wherein the polymer has a weight percentage in the range of about 1 to 10% based on the ink or coating composition.

[0550] 48. The ink or coating composition according to any one of embodiments 42-47, wherein the polymer / pigment weight ratio is in the range of about 0.1:1 to 1.5:1.

[0551] 49. Use of a polymer according to any of embodiments 1 to 26 as a coating composition or an ink or a dispersant in a coating composition.

[0552] While the invention has been described in terms of 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

[0553] The invention is illustrated in detail by the following non-limiting examples. More particularly, the test methods specified below are part of the general disclosure of the present application and are not limited to the specific examples.

[0554] Material

[0555] All chemicals used herein are commercially available from Sigma Aldrich, USA. For the present invention, commercial grade purity of the chemicals was found to be sufficient. However, as might be expected, further purification of the ingredients is expected to lead to improvements in plasticizer properties.

[0556] method

[0557] Amine value: The amine value was determined according to DIN 53176:2002-11.

[0558] Number average molecular weight (Mn) was determined by gel permeation chromatography (GPC) in tetrahydrofuran against polystyrene standards.

[0559] The polydispersity index was determined by means of gel permeation chromatography (GPC).

[0560] The OH value was determined according to ASTM E222-17.

[0561] Viscosity: Similar to DIN 53019-1:2008-09, using a Thermo-Haake RheoStress 600 device in CR mode at 22°C and 1 sec -1 The viscosity was measured at a shear rate of 1.5 % (Spindle CP50).

[0562] Gloss: The gloss of the resulting coatings was determined at an angle of 20° using a commercial reflectometer (Micro-Tri-Gloss reflectometer from BYK Gardner) in accordance with DIN 67530 / DIN EN ISO 2813:2012-10.

[0563] The blackness is measured according to DIN 55979.

[0564] Preparation of polyacrylates (P1) by controlled free radical polymerization - P1: Synthesis of linear polybutyl acrylate (BA)

[0565] Preparation of polyacrylates by controlled free radical polymerization of a mixture M1 containing acrylic esters. In a three-necked 1000 ml round-bottom flask equipped with a magnetic stirring bar, a cooler, a thermometer and a dropping funnel, 150.10 g of n-butyl acrylate (n-BA, acrylic ester monomer, 128.17 g / mol), 8.55 g of a compound of formula 1b (nitroxyl ether; 317.48 g / mol) and 122.13 g of methoxypropyl acetate (MPA; solvent) were added and the system was degassed three times with N2 / vacuum. Thereafter, polymerization was carried out at 135°C under N2 until a conversion of about 8 mol% was reached. 338.89 g of n-BA was slowly added to the reaction using a dropping funnel and polymerization was continued at 135°C under N2 until a conversion of about 48 mol%. Residual monomers and solvents were distilled off at 80°C and 12 mbar.

[0566] Analysis - Yield 47% (liquid). In addition, analysis was performed using gel permeation chromatography or GPC (tetrahydrofuran or THF, polystyrene or PS standards). The results are as follows - M n =7800 g / mol and polydispersity or PD = 1.27. 1 H-NMR analysis showed a degree of polymerization of 75.

[0567] Polyacrylate P2: Synthesis of Linear Block Copolymer Poly(n-BA-b-4VP)

[0568] The polyacrylate P1 can be further reacted with an ethylenically unsaturated monomer, such as 4-vinylpyridine, before reacting with the mixture M2. In a three-necked 500 ml round-bottom flask equipped with a magnetic stirring bar, a cooler and a thermometer, 214.18 g of P1, 70.90 g of 4-vinylpyridine (4-VP, ethylenically unsaturated monomer, 105.14 g / mol) and 79.70 g of MPA are added, and the system is degassed three times with N2 / vacuum, and polymerized at 125°C under N2 for 8 hours. Residual monomers and solvents are distilled off at 80°C and 12 mbar.

[0569] Yield 85% (liquid). In addition, GPC (THF, PS standard) was used for analysis. The results are as follows: n =8600 g / mol, PD = 1.24. 1 H-NMR analysis showed that the degree of polymerization was: P(BA-b-4VP) = 75-b-14. The product, P2, was used as an intermediate for further modification by transesterification and transamideization.

[0570] Modification of polyacrylates by transesterification and transamidation (P2)

[0571] After the above synthesis, the polyacrylates are modified in the presence of alcohols and amines (mixture M2). The following table 1 lists the polymers and their components amines and polyacrylates -

[0572] Table 1

[0573]

[0574] *MPEG-OH-methoxy-polyethylene glycol.

[0575] The synthesis details according to the composition mentioned in the above Table 1 are mentioned below.

[0576] Polymer synthesis

[0577] Embodiment 1:

[0578] 45 g of polyacrylate P2, 2.5 g of 3-(dimethylamino)-1-propylamine and 50 g of MPEG-OH (M n =500 g / mol) was dried at 120° C. under N2 gas for 3 hours. Then, three portions of 0.1 g of lithium tert-butoxide were added at 130° C. over 12 hours. Then, the mixture was heated to 150° C. to remove the n-butanol formed under vacuum over 12 hours. Finally, a yellow viscous dispersion with an amine value of 45 mg KOH / g was obtained. GPC showed an almost quantitative conversion of MPEG-OH.

[0579] Embodiment 2:

[0580] 45 g of polyacrylate P2, 5 g of 3-(dimethylamino)-1-propylamine and 50 g of MPEG-OH (M n =500 g / mol) was dried at 120° C. under N2 gas for 3 hours. Then, three portions of 0.1 g of lithium tert-butoxide were added at 130° C. over 12 hours. Then, the mixture was heated to 150° C. to remove the n-butanol formed under vacuum over 12 hours. Finally, a yellow viscous dispersion with an amine value of 56 mg KOH / g was obtained. GPC showed an almost quantitative conversion of MPEG-OH.

[0581] Embodiment 3:

[0582] 45 g of polyacrylate P2, 6 g of 1-(3-aminopropyl)imidazole and 50 g of MPEG-OH (M n=500 g / mol) was dried at 120° C. under N2 gas for 3 hours. Then, three portions of 0.1 g of lithium tert-butoxide were added at 130° C. over 12 hours. Then, the mixture was heated to 150° C. to remove the n-butanol formed under vacuum over 12 hours. Finally, a yellow viscous dispersion with an amine value of 58 mg KOH / g was obtained. GPC showed an almost quantitative conversion of MPEG-OH.

[0583] Embodiment 4:

[0584] 45 g of polyacrylate P2, 6 g of 4-(aminomethyl)pyridine and 50 g of MPEG-OH (M n =500 g / mol) was dried at 120° C. under N2 gas for 3 hours. Then, three portions of 0.1 g of lithium tert-butoxide were added at 130° C. over 12 hours. Then, the mixture was heated to 150° C. to remove the n-butanol formed under vacuum over 12 hours. Finally, a yellow viscous dispersion with an amine value of 60 mg KOH / g was obtained. GPC showed an almost quantitative conversion of MPEG-OH.

[0585] Embodiment 5:

[0586] 45 g of polyacrylate P2, 6 g of N-(2-aminoethyl)-piperidine and 50 g of MPEG-OH (M n =500 g / mol) was dried at 120° C. under N2 gas for 3 hours. Then, three portions of 0.1 g of lithium tert-butoxide were added at 130° C. over 12 hours. Then, the mixture was heated to 150° C. to remove the n-butanol formed under vacuum over 12 hours. Finally, a yellow viscous dispersion with an amine value of 58 mg KOH / g was obtained. GPC showed an almost quantitative conversion of MPEG-OH.

[0587] Embodiment 6:

[0588] 45 g of polyacrylate P2, 6 g of 3-morpholinepropylamine and 50 g of MPEG-OH (M n =500 g / mol) was dried at 120° C. under N2 gas for 3 hours. Then, three portions of 0.1 g of lithium tert-butoxide were added at 130° C. over 12 hours. Then, the mixture was heated to 150° C. to remove the n-butanol formed under vacuum over 12 hours. Finally, a yellow viscous dispersion with an amine value of 54 mg KOH / g was obtained. GPC showed an almost quantitative conversion of MPEG-OH.

[0589] Comparative Example (CP1): No Amide Exchange

[0590] Transesterification only - using MPEG-OH

[0591] In a 500 ml flask equipped with a magnetic stir bar and a dry ice acetone cooled distillation column, 92.8 g of P2 and 114.7 g of MPEG-OH (M n =550 g / mol). Subsequently, the system was dried by azeotropic distillation of xylene. Three portions of 0.36 g of tetra(isopropyl)orthotitanate were added at 190-205° C. over a period of 3 hours. The n-butanol formed was thereby distilled off under reduced pressure.

[0592] Yield: 187.7 g of poly(n-BA-MPEGA-b-4-VP) was obtained. n =17500 g / mol, PDI =1.6, OH value =0.05 meq / g. GPC showed almost quantitative conversion of MPEG-OH.

[0593] Therefore, the resulting comparative polymers, poly(n-BA-MPEGA-b-4-VP) or CP1, were used directly as dispersants without any further treatment with amines (ie, no transamidation was performed).

[0594] Performance Testing:

[0595] In order to determine the suitability of the polymers as dispersants, the above polymers were tested. In this regard, a resin-free pigment concentrate (pigment millbase) was prepared according to the formulation 1 mentioned below:

[0596] Formulation 1:- Preparation of pigment concentrate / pigment slurry

[0597] 1) Polymer (100% solids) 13.5g 2) MPA Solvent 61.5g 3) Butyl glycol 10 4) Pigment: Carbon Black FW 200 15g 5) 2.0mm glass beads 100g total 200g

[0598] Pigment slurry was dispersed by glass beads in Scandex Shaker for 4 hours. After this, the pigment slurry was filtered and stored at room temperature overnight. In addition, paint was prepared by mixing 2.0 grams of pigment slurry (as described above) into 8.0 grams of let-down systems (preparation 2) for 2 minutes at 2000rpm by Dispermat. This colored preparation was covered and applied on a glass substrate, and the blackness was measured from the back side (through glass) after solidification. The blackness and viscosity of the preparation are listed in the following table 2.

[0599] Table 2 - Pigment slurry viscosity (viscosity @ 1S -1 ) and blackness

[0600] Dispersants Viscosity* Blackness** Comparative polymer (CP1) 16500 308 Polymer of Example 2 2550 310 Polymer of Example 3 500 308 Polymer of Example 4 9500 312

[0601] *Viscosity in mPa.s

[0602] **Jet degree measured according to DIN 55979

[0603] It was observed that the performance of the dispersants was generally very good with low pigment paste viscosities (see Table 2 above). In addition, it should be noted that the polymers of the present invention, despite inducing a significant reduction in viscosity, did not interfere at all with the original properties of the dye / ink pigment (see the jetness values ​​in Table 2 above).

Claims

1. A polymer obtained by reacting the following components i) at least one polyacrylate P1 obtained by controlled free radical polymerization of a mixture M1 in the presence of a1 or a2, the mixture M1 comprising at least one acrylate monomer selected from n-butyl acrylate, methyl acrylate, ethyl acrylate, n-butyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate and 4-hydroxybutyl acrylate, Where a1 is at least one of the formula R 21 R 22 NOX(I) is a nitroxyl ether and a2 is at least one of the formula R 21 R 22 The stable nitroxyl radical of NO·(II); R 21 and R 22 independently selected from substituted or unsubstituted straight or branched C5-C 18 Alkyl, where R 21 and R 22 independently selected from substituted or unsubstituted straight or branched C5-C 18 Alkyl, where R 21 and R 22 Together with the nitrogen atom to which they are attached, they form an unsubstituted or substituted 5- to 10-membered aliphatic ring containing 1 to 3 heteroatoms selected from nitrogen and oxygen, and X is selected from -CH2-phenyl, -(CH3)CH-phenyl, -(CH3)2C-phenyl, -(C5-C6 cycloalkyl)2C-CN, -(CH3)2CCN, -CH2CH=CH2, -(CH3)CH-CH=CH2, -(C1-C4 alkyl)CR 20 -C(O)-phenyl, -(C1-C4 alkyl)CR 20 -C(O)-(C1-C4 alkoxy), -(C1-C4 alkyl)CR 20 -C(O)-(C1-C4 alkyl), -(C1-C4 alkyl)CR 20 -C(O)-N-di(C1-C4 alkyl), -(C1-C4 alkyl)CR 20 -C(O)-NH(C1-C4 alkyl) and -(C1-C4 alkyl)CR 20 -C(O)-NH2, where R 20 is hydrogen or C1-C4 alkyl, wherein the polyacrylate P1 is further reacted with at least one ethylenically unsaturated monomer to obtain the polyacrylate P2, which is subsequently reacted in step ii) with the mixture M2, and ii) a mixture M2 comprising at least one alcohol W selected from W1 and W2 and at least one amine Z selected from Z1 and Z2; in, W1 is R 1 -OH, where R 1 is a substituted or unsubstituted straight or branched C8-C 36 alkyl; W2 is at least one of the formula B-(OA) n -OH polyether alcohol, wherein A is a substituted or unsubstituted straight chain or branched C1-C4 alkylene, and B is selected from a substituted or unsubstituted straight chain or branched C1-C 22 Alkyl, substituted or unsubstituted C1-C 24 Alkyl aryl and substituted or unsubstituted C1-C 24 dialkylaryl, n is an integer in the range of ≥1 to ≤150; Z1 is NH2-R 11 -NR 12 R 13 , Z2 is NH2-R 11 -Y, Where R 11 is a substituted or unsubstituted straight or branched C1-C 12 Alkylene; R 12 and R 13 are independently selected from hydrogen and substituted or unsubstituted straight or branched C1-C 12 Alkyl, or R 12 and R 13 Together with the nitrogen atom to which they are attached, they form an unsubstituted or substituted 3- to 12-membered ring containing 1 to 3 heteroatoms selected from nitrogen and oxygen; Y is a 5- or 6-membered N-containing heterocyclic ring containing 1 or 2 nitrogen atoms and 0 or 1 oxygen atoms, wherein the polymer has an amine number, determined according to DIN 53176:2002-11, in the range of ≥10 to ≤200 mg KOH / g, Wherein the weight ratio of the at least one alcohol W to the at least one amine Z is in the range of 0.1:1 to 10:

1.

2. The polymer according to claim 1, wherein the at least one 21 R 22 The nitroxyl ether of NOX is a compound of formula (Ia), in, G 1 , G 2 , G 3 , G 4 are independently substituted or unsubstituted straight or branched C1-C6 alkyl, or G 1 and G 2 or G 3 and G 4 , or G 1 and G 2 and G 3 and G 4 Together they form substituted or unsubstituted C5-C 12 Cycloalkyl; G 5 , G 6 are independently selected from hydrogen, substituted or unsubstituted straight or branched C1-C 18 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl and -C(O)-O-C1-C 18 alkyl; X is selected from -CH2-phenyl, -(CH3)CH-phenyl, -(CH3)2C-phenyl, -(C5-C6 cycloalkyl)2C-CN, -(CH3)2CCN, -CH2CH=CH2, -(CH3)CH-CH=CH2, -(C1-C4 alkyl)CR 20 -C(O)-phenyl, -(C1-C4 alkyl)CR 20 -C(O)-(C1-C4 alkoxy), -(C1-C4 alkyl)CR 20 -C(O)-(C1-C4 alkyl), -(C1-C4 alkyl)CR 20 -C(O)-N-di(C1-C4 alkyl), -(C1-C4 alkyl)CR 20 -C(O)-NH(C1-C4 alkyl) and -(C1-C4 alkyl)CR 20 -C(O)-NH2, where R 20 is hydrogen or C1-C4 alkyl, wherein phenyl, alkyl, alkoxy and cycloalkyl are in each case unsubstituted or substituted, alkyl and alkoxy are in each case straight-chain or branched, * indicates chemical valence.

3. The polymer according to claim 1, wherein the at least one 21 R 22 The stable nitroxyl radical of NO· is the structural unit of formula (IIa), in, G 1 , G 2 , G 3 , G 4 are independently substituted or unsubstituted straight or branched C1-C6 alkyl, or G 1 and G 2 or G 3 and G 4 , or G 1 and G 2 and G 3 and G 4 Together they form substituted or unsubstituted C5-C 12 Cycloalkyl; G 5 , G 6 are independently selected from hydrogen, substituted or unsubstituted straight or branched C1-C 18 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl and -C(O)-O-C1-C 18 alkyl; * indicates valence.

4. The polymer according to claim 1, wherein the polyacrylate P2 is a gradient block copolymer.

5. The polymer according to any one of claims 1 to 4, wherein the at least one ethylenically unsaturated monomer is selected from the group consisting of C5-C 20 Vinyl aromatic compounds, ethylenically unsaturated nitriles, acrylamides, vinyl halides, C1-C 10 Vinyl ethers of alcohols and C2-C8 aliphatic hydrocarbons having one or two double bonds.

6. The polymer according to any one of claims 1 to 4, wherein the at least one ethylenically unsaturated monomer does not contain any primary or secondary ester bonds.

7. The polymer according to claim 5, wherein the at least one ethylenically unsaturated monomer does not contain any primary or secondary ester bonds.

8. The polymer according to any one of claims 1 to 4, wherein the at least one ethylenically unsaturated monomer is selected from the group consisting of isoprene, 1,3-butadiene, α-C5-C 18 -olefin, 4-vinyl-pyridine or pyridine -ion, 2-vinyl-pyridine or pyridine -ion, vinyl-imidazole or imidazoline -ion, dimethylacrylamide, 3-dimethylaminopropylmethacrylamide, styrene, α-methylstyrene, p-methylstyrene, p-tert-butyl-styrene and the formula CH2=C(R a )-(C=Z)-R b A compound wherein R a is hydrogen or methyl, R b NH2, O-(Me+), unsubstituted C1-C 18 Alkoxy, C2-C 100 Alkoxy or hydroxy substituted C1-C 18 Alkoxy, unsubstituted C1-C 18 Alkylamino, di(C1-C 18 Alkyl)amino, hydroxy substituted C1-C 18 Alkylamino or hydroxy substituted di(C1-C 18 alkyl)amino, -O-CH2-CH2-N(CH3)2 and -O-CH2-CH2-N + H(CH3)2A n - ; A n - is the anion of a monovalent organic or inorganic acid; Me is a monovalent metal atom or an ammonium ion; Z is oxygen or sulfur.

9. The polymer according to claim 8, wherein the at least one ethylenically unsaturated monomer is selected from 4-vinyl-pyridine or pyridine -ion, 2-vinyl-pyridine or pyridine -ion, vinyl-imidazole or imidazoline -ion, dimethylacrylamide, 3-dimethylaminopropylmethacrylamide, styrene, α-methylstyrene, p-methylstyrene and p-tert-butyl-styrene.

10. A polymer according to any one of claims 1 to 4, wherein R 1 is a substituted or unsubstituted straight chain or branched C 10 -C 34 alkyl.

11. A polymer according to claim 9, wherein R 1 is a substituted or unsubstituted straight chain or branched C 10 -C 34 alkyl.

12. The polymer according to any one of claims 1 to 4, wherein the compound R 1 -OH is selected from nonan-1-ol, nonan-2-ol, dodecan-1-ol, decan-1-ol and decan-2-ol.

13. The polymer according to claim 9, wherein the compound R 1 -OH is selected from nonan-1-ol, nonan-2-ol, dodecan-1-ol, decan-1-ol and decan-2-ol.

14. The polymer according to any one of claims 1 to 4, wherein A is ethylene or propylene, B is selected from substituted or unsubstituted linear or branched C1-C4 alkyl, and n is an integer in the range of ≥1 to ≤50.

15. The polymer according to any one of claims 1 to 4, wherein the at least one compound of formula B-(OA) n The polyether alcohols containing 2-hydroxy-1-hydroxy- ... n ) of methoxy polyethylene glycol.

16. A polymer according to any one of claims 1 to 4, wherein R 11 It is an unsubstituted straight or branched C1-C8 alkylene group.

17. A polymer according to any one of claims 1 to 4, wherein R 12 and R 13 is an unsubstituted straight or branched C1-C8 alkyl group, or R 12 and R 13 Together with the nitrogen atom to which they are attached, they form an unsubstituted or substituted 3- to 6-membered ring containing 1 or 2 heteroatoms selected from nitrogen and oxygen.

18. The polymer according to any one of claims 1 to 4, wherein Y is selected from imidazolyl and pyridyl.

19. The polymer according to any one of claims 1 to 4, wherein the polymer has an amine number determined according to DIN 53176:2002-11 in the range of ≧50 to ≦150 mg KOH / g.

20. A controlled radical polymerization process for preparing a polymer according to any one of claims 1 to 19, comprising the steps of: a. polymerizing a mixture M1 comprising at least one acrylate monomer in the presence of a1 or a2; Where a1 is at least one of the formula R 21 R 22 NOX(I) is a nitroxyl ether and a2 is at least one of the formula R 21 R 22 The stable nitroxyl radical of NO·(II); R 21 and R 22 independently selected from substituted or unsubstituted straight or branched C5-C 18 Alkyl, where R 21 and R 22 Together with the nitrogen atom to which they are attached, they form an unsubstituted or substituted 5- to 10-membered aliphatic ring containing 1 to 3 heteroatoms selected from nitrogen and oxygen, and X is selected from -CH2-phenyl, -(CH3)CH-phenyl, -(CH3)2C-phenyl, -(C5-C6 cycloalkyl)2C-CN, -(CH3)2CCN, -CH2CH=CH2, -(CH3)CH-CH=CH2, -(C1-C4 alkyl)CR 20 -C(O)-phenyl, -(C1-C4 alkyl)CR 20 -C(O)-(C1-C4 alkoxy), -(C1-C4 alkyl)CR 20 -C(O)-(C1-C4 alkyl), -(C1-C4 alkyl)CR 20 -C(O)-N-di(C1-C4 alkyl), -(C1-C4 alkyl)CR 20 -C(O)-NH(C1-C4)alkyl and -(C1-C4alkyl)CR 20 -C(O)-NH2, where R 20 is hydrogen or C1-C4 alkyl; and b. modifying the polyacrylate obtained in step a. by transesterification using at least one alcohol (W) selected from W1 and W2 and transamidation using at least one amine (Z) selected from Z1 and Z2; Where W1 is R 1 -OH, where R 1 is a substituted or unsubstituted straight or branched C8-C 36 alkyl; W2 is at least one of the formula B-(OA) n -OH polyether alcohol, wherein A is a substituted or unsubstituted straight chain or branched C1-C4 alkylene, and B is selected from a substituted or unsubstituted straight chain or branched C1-C 22 Alkyl, substituted or unsubstituted C1-C 24 Alkyl aryl and substituted or unsubstituted C1-C 24 dialkylaryl, n is an integer in the range of ≥1 to ≤150; Z1 is NH2-R 11 -NR 12 R 13 , Z2 is NH2-R 11 -Y, Where R 11 is a substituted or unsubstituted straight or branched C1-C 12 Alkylene; R 12 and R 13 are independently selected from hydrogen and substituted or unsubstituted straight or branched C1-C 12 Alkyl, or R 12 and R 13 Together with the nitrogen atom to which they are attached, they form an unsubstituted or substituted 3- to 12-membered ring containing 1 to 3 heteroatoms selected from nitrogen and oxygen; Y is a 5- or 6-membered N-containing heterocyclic ring containing 1 or 2 nitrogen atoms and 0 or 1 oxygen atoms; The polyacrylate P1 of step a. is reacted further with at least one ethylenically unsaturated monomer and then modified in step b.

21. The method according to claim 20, wherein the at least one 21 R 22 The nitroxyl ether of NOX is a compound of formula (Ia), in, G 1 , G 2 , G 3 , G 4 are independently substituted or unsubstituted straight or branched C1-C6 alkyl, or G 1 and G 2 or G 3 and G 4 , or G 1 and G 2 and G 3 and G 4 Together they form substituted or unsubstituted C5-C 12 Cycloalkyl; G 5 , G 6 are independently selected from hydrogen, substituted or unsubstituted straight or branched C1-C 18 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl and -C(O)-O-C1-C 18 alkyl; X is selected from -CH2-phenyl, -(CH3)CH-phenyl, -(CH3)2C-phenyl, -(C5-C6 cycloalkyl)2C-CN, -(CH3)2CCN, -CH2CH=CH2, -(CH3)CH-CH=CH2, -(C1-C4 alkyl)CR 20 -C(O)-phenyl, -(C1-C4 alkyl)CR 20 -C(O)-(C1-C4 alkoxy), -(C1-C4 alkyl)CR 20 -C(O)-(C1-C4 alkyl), -(C1-C4 alkyl)CR 20 -C(O)-N-di(C1-C4 alkyl), -(C1-C4 alkyl)CR 20 -C(O)-NH(C1-C4 alkyl), -(C1-C4 alkyl)CR 20 -C(O)-NH2, where R 20 is hydrogen or C1-C4 alkyl, wherein phenyl, alkyl, alkoxy and cycloalkyl are in each case unsubstituted or substituted, alkyl and alkoxy are in each case straight-chain or branched, * indicates valence.

22. The method according to claim 20, wherein the at least one 21 R 22 The stable nitroxyl radical of NO· is the structural unit of formula (IIa), in, G 1 , G 2 , G 3 , G 4 are independently substituted or unsubstituted straight or branched C1-C6 alkyl, or G 1 and G 2 or G 3 and G 4 , or G 1 and G 2 and G 3 and G 4 Together they form substituted or unsubstituted C5-C 12 Cycloalkyl; G 5 , G 6 are independently selected from hydrogen, substituted or unsubstituted straight or branched C1-C 18 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl and -C(O)-O-C1-C 18 alkyl; * indicates valence.

23. The process according to any one of claims 20 to 22, wherein the at least one ethylenically unsaturated monomer does not comprise any primary or secondary ester bonds.

24. The process according to any one of claims 20 to 22, wherein the at least one ethylenically unsaturated monomer is selected from the group consisting of isoprene, 1,3-butadiene, α-C5-C 18 -olefin, 4-vinyl-pyridine or pyridine -ion, 2-vinyl-pyridine or pyridine -ion, vinyl-imidazole or imidazoline ions, dimethylacrylamide, 3-dimethylaminopropylmethacrylamide, styrene, α-methylstyrene, p-methylstyrene, p-tert-butyl-styrene and compounds of the formula CH2=C(R a )-(C=Z)-R b A compound wherein R a is hydrogen or methyl, R b NH2, O-(Me+), unsubstituted C1-C 18 Alkoxy, C2-C 100 Alkoxy or hydroxy substituted C1-C 18 Alkoxy, unsubstituted C1-C 18 Alkylamino, di(C1-C 18 Alkyl)amino, hydroxy substituted C1-C 18 Alkylamino or hydroxy substituted di(C1-C 18 alkyl)amino, -O-CH2-CH2-N(CH3)2 and -O-CH2-CH2-N + H(CH3)2A n - ; A n - is the anion of a monovalent organic or inorganic acid; Me is a monovalent metal atom or an ammonium ion; Z is oxygen or sulfur.

25. The process according to any one of claims 20 to 22, wherein the process further comprises heating of the mixture M1 of step a. at a temperature of 70 to 200°C.

26. A coating composition comprising a polymer according to any one of claims 1 to 19.

27. An ink composition comprising a polymer according to any one of claims 1 to 19.

28. Use of a polymer according to any one of claims 1 to 19 as a dispersant in a coating composition or ink composition.

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