Polymers based on oligo-aminoester monomers

Abstract

The invention relates to polymers that can be obtained by reacting oligo-aminoester monomers with at least one radically polymerizable monomer.

Description

[0001] Polymers based on oligoamino ester monomers

[0002] The present invention relates to polymers based on oligoamino ester monomers, their manufacturing processes and use as wetting and dispersing, thickening or defoaming additives.

[0003] A wide variety of different substances are known to be used today as wetting and dispersing agents for pigments and / or fillers.

[0004] High mechanical forces are necessary to introduce pigments and / or fillers into liquid media. However, after the dispersion process, the pigments and fillers tend to re-agglomerate due to mutual attraction, negating the previously invested dispersion effort and leading to serious application problems.

[0005] It is known to use dispersing agents to facilitate the incorporation of pigments and fillers.

[0006] For example, polymeric wetting and dispersing agents are known from the prior art. These contain, on the one hand, pigment-affine groups such as carboxyl, amino, or phenyl functionalities, and on the other hand, side chains that are soluble in the medium. Ideally, the pigment-affine groups should exhibit rapid orientation to the surface of the pigments and high permanence on it. The side chains ensure compatibility with the dispersing or coating medium and steric stabilization of the dispersed phase.

[0007] The chemical design of modern wetting and dispersing additives is characterized by their ability to stabilize a wide variety of inorganic and organic pigments. Nitrogen has been found to have a highly beneficial effect on the dispersion of aromatic particles. The need to adjust the nitrogen density has led to the development of two main classes of dispersing additives: (a) hyperdispersing additives and (b) nitrogen-functionalized comb copolymers. Hyperdispersing additives are characterized by a cross-linked, hyperbranched polymeric core with a three-dimensional structure and a large number of terminal functional groups to which numerous linear polymeric side chains are attached. Nitrogen-containing monomers are typically used to synthesize the cross-linked, hyperbranched core in order to achieve a high nitrogen density.Hydrophobic polymeric side chains are attached to the terminal functional groups to sterically stabilize the core structures. In previously known dispersing additives, the nitrogen density is controlled either by the number of polymeric side chains or by the molecular weight of the nitrogen-rich core.

[0008] Nitrogen density is the number of nitrogen atoms per total number of atoms in the dispersing additive. In polymer chemistry, this definition is understood as a number-averaged value.

[0009] Polyethyleneimines (PEIs) are often used as core structures in hyperdispersible additives. Polyethyleneimines are hyperbranched polyamines produced by homopolymerization of aziridine. Among organic polymers, PEIs have the highest possible nitrogen density, with amine numbers ranging from 1,000 mg KOH / g to 1,400 mg KOH / g. Commercially available PEIs have a molecular weight of approximately 1,000 g / mol to 2,000,000 g / mol and a distribution of primary amine groups between 25 mol% and 35 mol%, secondary amine groups between 35 mol% and 50 mol%, and tertiary amine groups between 20 mol% and 30 mol%.

[0010] For example, US patent 4,224,212 A describes a basic design for PEI-containing hyperdispersion additives in which PEI core structures are functionalized with at least two polyester side chains based on polyhydroxycarboxylic acids, such as 12-hydroxystearic acid. A disadvantage of these additives is that the entire nitrogen content of the dispersion additives is concentrated in the core, and the nitrogen density within the core structure cannot be adjusted.

[0011] EP 943 526 A1 describes non-PEI-based, amine hyperdispersants featuring cross-linked polyamidoamine core structures. This synthetic route allows for the adjustment of nitrogen density and the distribution of amine functional groups within the polyamidoamine core. Compared to established PEI-based dispersing additives, this publication offers flexible access to amine-containing core structures tailored to specific applications. However, a disadvantage of the described dispersing additives remains that nitrogen-containing functionalities are still restricted to the hyperbranched core.

[0012] Another important class of dispersing additives describes nitrogen-containing comb polymers. These are generally based on styrene-maleic anhydride (SMA) copolymers, in which an alternating backbone of styrene and maleic anhydride monomers is present in a 1:1 ratio, or an excess of styrene is used. These SMA copolymers are particularly well-suited because they possess carboxylic acid and aromatic groups that are beneficial for dispersion, and they can also be functionalized with nitrogen-containing compounds. However, the amount of SMA limits the amount of nitrogen and thus also the nitrogen density, as described in the following documents.

[0013] WO 2004 / 003029 describes the imidation of an SMA copolymer with A / ,A / - dimethylaminopropylamine and ammonium salts based thereon. A disadvantage of the described composition is the insufficient length of the side chains for steric stabilization and the presence of only a single nitrogenous group at the side chain end.

[0014] WO 2008 / 080580 covers comb polymers obtained by reacting SMA resins with polyalkylene oxide monoamines and amino alcohols, A / ,A / -disubstituted amines, or mono-hydroxy-terminated polyalkylene oxides or polyesters. The use of OH- or amine-functionalized polyalkylene oxides allows for the attachment of side chains of varying lengths. A disadvantage of the described compositions, however, is that only single nitrogen-containing functionalities per side chain can be realized. These are either in amidic or imic form directly bonded to the polymeric backbone or in the form of amino or ammonium groups at the ends of individual side chains.

[0015] Documents WO 2013 / 189568 and WO 2022 / 214502 describe further variants of such SMA-based comb polymers with grafted polyalkylene oxide monoamines and side chains with tertiary amine functionalities. The number of nitrogen functionalities is determined and limited solely by the chain length of the SMA comb copolymers and the proportion of maleic anhydride functionalities. Varying the density of the nitrogen-containing groups in the side chain is not possible.

[0016] In addition to nitrogen-containing hyperdispersive additives and comb polymers, linear, nitrogen-containing polymer structures are also mentioned as possible dispersive additives. For example, US 5,854,331 describes the cationically initiated homo- and copolymerization of oxazoline and oxazine derivatives to polyoxazolines and oxazines. A disadvantage of these dispersive additives is the uniform distribution of amidic groups along the polymer chain and the absence of side chains for steric stabilization.

[0017] The disadvantage of all dispersing additives known from the state of the art lies in the limited adjustability of the nitrogen density.

[0018] All of the nitrogen-containing dispersing additives listed above are used in a wide variety of applications in the paints and coatings industry, but it is desirable to further improve the dispersing effect in formulations containing pigments or particles.

[0019] In view of the large, almost unmanageable number of possible compound classes, the discovery of particularly effective specific structural parameters and corresponding copolymers for the purpose of producing dispersing additives represents a progress-accelerating and therefore inventive achievement.

[0020] The object of the present invention is therefore to provide novel polymers that allow a wide adjustability of the nitrogen density and are suitable as dispersing additives.

[0021] To solve the problem, polymers are proposed which can be obtained by reacting oligoaminoester monomers with at least one radical polymerizable monomer.

[0022] It has been found that the nitrogen density of the polymers according to the invention, namely at the side chains and at the backbone, can be individually adjusted. The preparation of oligoesteramide macromonomers is known from the publication Chem. Commun. 2015, 51, 16213, whereby these can subsequently be polymerized. However, the publication is silent on the properties of such homopolymerized oligoesteramide macromonomers.

[0023] Oligoaminoester monomers, oligomer and oligoesteramide macromonomers are used synonymously here.

[0024] It was not foreseeable that a copolymerization of the oligoaminoester monomers with different monomers would lead to polymers that vary in their nitrogen density and are suitable as a dispersing additive.

[0025] In this context, "different" is understood to mean that preferably radically polymerizable monomers are used, provided that they are not identical to the oligoaminoester monomers or preferably not identical to the oligoaminoester monomers according to formula M1.

[0026] Surprisingly, it was also found that the nitrogen density of the polymers according to the invention can be adjusted. On the one hand, the number of nitrogen atoms on the backbone can be increased, which is not possible with SMA-based comb copolymers, and on the other hand, the nitrogen density can also be increased by functionalizing the side chains with nitrogen-containing compounds. Furthermore, the side chains can conceivably be functionalized, e.g., with pigment-affine groups, in such a way that they ensure compatibility with the dispersing medium and steric stabilization of the dispersed phases.

[0027] Unless otherwise stated, where average values ​​are given below, they are numerical averages. Where measured values, parameters, or material properties are given below that are determined by measurement, they are measured values, parameters, or material properties measured at 25 °C and preferably at a pressure of 101,325 Pa (standard pressure), unless otherwise stated.

[0028] If number ranges are subsequently specified in the form "X to Y", where X and Y represent the limits of the number range, this is equivalent to stating "from at least X to and including Y", unless otherwise specified. Range specifications therefore include the range limits X and Y, unless otherwise stated.

[0029] Wherever molecules or molecular fragments have one or more stereocenters, or can be differentiated into isomers due to symmetries, or can be differentiated into isomers due to other effects, such as restricted rotation, all possible isomers are included in the present invention.

[0030] All formulas describe compounds or residues composed of repeating units, such as repeating fragments, blocks, or monomer units, which may exhibit a molecular weight distribution. The frequency of the repeating units is indicated by indices. The indices used in the formulas are to be considered statistical means (numerical means). The index numbers used, as well as the ranges of values ​​of the specified indices, are understood as means of the possible statistical distribution of the actual existing structures and / or their mixtures. The various fragments or repeating units of the compounds described in the formulas may be statistically distributed.Statistical distributions are structured block-wise with any number of blocks and any sequence, or they follow a randomized distribution. They can also be structured alternately, or form a gradient over the chain, if one exists. In particular, they can also form all mixed forms, in which groups of different distributions may follow one another. The following formulas include all permutations of repetition units.

[0031] Preferably, the oligoaminoester monomers are prepared by reacting (meth)acrylic acids and oxazolines or oxazines according to the formula Mi with

[0032] Ri = independently of each other, identical or different, a hydrogen or a methyl group; R2 = independently of each other, identical or different, a hydrogen, an alkyl group with 1 to 18 carbon atoms, or an aryl group with 6 to 18 carbon atoms.

[0033] R3 = independent of each other, the same or different, a hydrogen or - CH2CH(R1)COX1R 4I with R4 = independent of each other, the same or different, a hydrogen, an alkyl group with 1 to 18 C atoms, hydroxyl-functionalized alkyl groups with 1 to 18 C atoms, phosphate-containing groups with 1 to 18 C atoms, an aryl group, a CH2 aryl group with 6 to 18 C atoms, - (CHR5-CHR5-O) n R6 with n = 1 to 50, or independently of each other, identical or different, a dimethylethylamine, a diethylethylamine, a dimethylpropylamine, a diethylpropylamine and / or 1-(3-aminopropyl)imidazole, as well as quaternary structures thereof, preferably a hydrogen, R5 = independently of each other, identical or different, a hydrogen, an alkyl group with 1 to 4 C atoms or an aryl group with 6 C atoms,

[0034] Re = independently of each other, the same or different, a hydrogen atom, a saturated and / or unsaturated alkyl group with 1 to 50 carbon atoms, an aryl group or a CH2 aryl group with 6 to 18 carbon atoms, a phosphate group,

[0035] Xi = O, NH, preferably O, m = 0 to 50, preferably 0 to 10, n = 1 or 2, available.

[0036] The oligoaminoester monomers preferably exhibit a degree of polymerization (DP). n ) between 1 and 50, preferably between 1 and 20 and particularly preferably between 1 and 5, wherein the DP n according to the calculation formula: is calculated, where M n The degree of polymerization is determined using GPC (standard polystyrene, eluent: THF, PSSSECcurity 1260, column material: SDV 1000 / 10000 e). Within the scope of this invention, oligoaminoester monomer and macromonomer are to be understood as synonyms covering a degree of polymerization from 1 to 50.

[0037] The polymers according to the invention are preferably formed by reacting the oligoaminoester monomers (Mi) with at least one monomer selected from one or more of the monomers of the group consisting of alkyl(meth)acrylates and alkenyl(meth)acrylates of straight-chain, branched or cycloaliphatic mono-alcohols with 1 to 22 carbon atoms or of straight-chain or branched aromatic or mixed aromatic-aliphatic mono-alcohols with 1 to 22 carbon atoms, mono(meth)acrylates of oligomeric or polymeric ethers, (meth)acrylates of halogenated alcohols; oxirane-containing (meth)acrylates, styrene, substituted stymium, α-olefins, vinyl ethers, vinyl alcohol, vinyl acetate, allyl ethers; methacrylonitrile, acrylonitrile;Cycloaliphatic heterocycles containing vinyl groups with at least one A / atom as a ring member, vinyl esters of monocarboxylic acids with 1 to 20 carbon atoms, A / -alkyl and A / ,A / -dialyk-substituted acrylamides with straight-chain, branched or cycloaliphatic alkyl groups with 1 to 22 carbon atoms, unsaturated carboxylic anhydrides and their imides, amides, and / or esters, ethylene-unsaturated monomers with at least one carboxylic, phosphoric, phosphoric and / or sulfonic acid group and unsaturated fatty acids or mixtures thereof.

[0038] Preferably, the polymers comprise combinations of repeating units selected from the group consisting of

[0039]

[0040] •»»firm chain extension

[0041] — Connection to O in structural unit III with

[0042] Xi = an O or NH, preferably an O,

[0043] X2 = CH, NH, O and / or N, with the proviso that for five-membered aromatics X2 = -CH or NH or O and for six-membered aromatics X2 = CH or N,

[0044] X3= CH or N,

[0045] X4 = an O or NH, preferably an NH,

[0046] Ri = independently of each other, the same or different, a hydrogen or a methyl group; R2 = independently of each other, the same or different, a hydrogen, an alkyl group with

[0047] 1 to 18 carbon atoms or an aryl group with 6 to 18 carbon atoms,

[0048] R3 = independently of each other, the same or different, a hydrogen or - CH2CH(R1)COX1R4, with R4 = independently of each other, the same or different, a hydrogen, an alkyl group with 1 to 18 C atoms, hydroxyl-functionalized alkyl groups with 1 to 18 C atoms, phosphate-containing groups with 1 to 18 C atoms, an aryl group, a CH2-aryl group with 6 to 18 C atoms, -(CHRs-CHRs-O^Re with n = 1 to 50, or independently of each other, the same or different, a dimethylethylamine, a diethylethylamine, a dimethylpropylamine, a diethylpropylamine and / or 1-(3-Aminopropyl)imidazole, as well as quaternary structures thereof, preferably a hydrogen,

[0049] R5 = independent of each other, the same or different, a hydrogen atom, an alkyl group with 1 to 4 carbon atoms or an aryl group with 6 carbon atoms,

[0050] R6 = independently of each other, the same or different, a hydrogen atom, a saturated and / or unsaturated alkyl group with 1 to 50 C atoms, an aryl group or a CH2 aryl group with 6 to 18 C atoms, a phosphate group, m = 0 to 50, preferably 0 to 10, n = 1 or 2,

[0051] M = independently of each other, the same or different, a hydrogen, NH4, alkali or alkaline earth cation, preferably NH4, Na or K, wherein at least one repeating unit (III) is present.

[0052] Preferably, the polymers have oligoaminoester monomers according to the formula Mi, with the proviso that Mi is not present as part of the linear polymeric backbone.

[0053] Preferably, the acid groups of the polymers are esterified, amidated, neutralized, quaternized and / or alkoxylated.

[0054] The acid groups are particularly preferably esterified or amidated by reaction with at least one compound selected from the group of primary and secondary amines and alcohols (especially amines and alcohols based on polyoxyalkylenes).

[0055] It has surprisingly turned out that the pigment affinity of the polymers according to the invention can be increased preferably by amidation, esterification, quaternerization and / or alkoxylation, which can lead to improved dispersibility.

[0056] The use of the polymers according to the invention as wetting and dispersing additives, thickeners and defoamers also constitutes a further invention.

[0057] It is also conceivable that the homopolymerized oligoaminoester monomers could be used as dispersing additives, although these would need to be functionalized with further pigment-affine groups. This might require additional amidation, esterification, quaternerization, and / or alkoxylation.

[0058] A further object of the invention is a dispersion which contains a dispersing medium and dispersed particulate solid, which is preferably in the form of an inorganic filler, and / or in the form of an inorganic or organic pigment and / or in the form of carbon nanotubes and / or in the form of graphene, wherein 0.1 - 10.0 wt.%, preferably 0.3 to 4.5 wt.%, of the polymer according to the invention is used as a wetting and dispersing agent, based on the total weight of the dispersion.

[0059] Preferably, the dispersion according to the invention is in the form of an ink or coating material, in particular as a varnish.

[0060] The invention also relates to a process for producing the polymers, characterized by the following steps:

[0061] 1.) Provision of oligoaminoester monomers by reaction of (meth)acrylic acids and oxazolines or oxazines,

[0062] 2.) Polymerization of the oligoaminoester monomers with at least one monomer selected from one or more of the monomers of the group consisting of alkyl(meth)acrylates and alkenyl(meth)acrylates of straight-chain, branched or cycloaliphatic mono-alcohols with 1 to 22 carbon atoms or of straight-chain or branched aromatic or mixed aromatic-aliphatic mono-alcohols with 1 to 22 carbon atoms, mono(meth)acrylates of oligomeric or polymeric ethers, (meth)acrylates of halogenated alcohols; oxirane-containing (meth)acrylates, styrene, substituted stymium, α-olefins, vinyl ethers, vinyl alcohol, vinyl acetate, allyl ethers; methacrylonitrile, acrylonitrile;cycloaliphatic heterocycles having vinyl groups and at least one A / atom as a ring member, vinyl esters of monocarboxylic acids with 1 to 20 carbon atoms, A / -alkyl and A / , / V-dialkyl-substituted acrylamides with straight-chain, branched or cycloaliphatic alkyl groups with 1 to 22 carbon atoms, unsaturated carboxylic anhydrides and their imides, amides, and / or esters, ethylene-unsaturated monomers with at least one carboxylic, phosphoric, phosphoric and / or sulfonic acid group and unsaturated fatty acids or mixtures thereof, optionally 3.) reaction of the polymer with at least one compound selected from the group of primary and secondary amines and alcohols, preferably amines and alcohols based on polyoxyalkylenes, and;

[0063] 4.) Optional quaternization of the primary and secondary or tertiary amines by uncatalyzed, acid- or base- or metal-catalyzed reaction of halogenated or epoxidized compounds or compounds accessible by ring opening, as well as hydroxylamines accessible by oxidation, and subsequent neutralization with carboxylic, phosphoric and / or sulfonic compounds.

[0064] It has surprisingly turned out that the nitrogen density of the polymers can be adjusted in particular by the method according to the invention.

[0065] The conversion in step 2) is preferably carried out at a temperature between 70 °C and 130 °C, preferably 80 °C to 120 °C and particularly preferably 90 °C to 110 °C.

[0066] Preferably, the temperature is kept constant during the reaction in step 1) and step 2). This prevents gel formation, which is particularly important for large-scale industrial applications.

[0067] Preferably, the solvent is removed before step 3).

[0068] It is also preferred that the procedure be carried out in situ.

[0069] Preferably, the process according to the invention is carried out such that no free oxazolines or oxazines are present after step 1). To achieve this, the person skilled in the art can employ all measures known to them. Known measures include, for example, adjusting the molar ratio of (meth)acrylic acids to oxazolines or oxazines and / or optimizing the reaction time and / or the feed time of one or more reactants.

[0070] The following examples are provided solely to illustrate this invention to those skilled in the art and do not constitute any limitation of the claimed subject matter or method. Materials

[0071] Methoxyphenol (abbreviation: MEHQ; Sigma-Aldrich), Butyl acetate, technical grade (Brenntag), Acrylic acid, 99% (Sigma-Aldrich), 2-Ethyl-2-oxazoline, >98.0% (Sigma-Aldrich, TCI), 2-Phenyl-2-oxazoline, 99% (Sigma-Aldrich), 2-Methyl-2-oxazoline, 98% (Sigma-Aldrich, TCI), Styrene, >99.0% (Merk, Sigma-Aldrich), 2,2-Azodi(2-methylbutyronitrile) (Akzo), Butyl acrylate, =>99% (Sigma-Aldrich), Ammonia (Baker), Methoxypropyl acetate, technical grade (Brenntag)

[0072] Poly(ethylene glycol) methyl ether methacrylate (MPEG 500 MA) (M n500 g / mol), contains 200 ppm BHT as an inhibitor and 100 ppm MEHQ as an inhibitor, N,D-Dimethyl-1,3-propanediamine 99% (DMAPA), Methacrylic acid 2-(dimethylamino)ethyl ester 98% (DMAEMA), N-[3-(Dimethylamino)propyl]methacrylamide 99% (DMAPAA), Surfonamine L-207 (Huntsman),

[0073] 230% aqueous solution of H2O (Sigma-Aldrich)

[0074] - IPOX RD 24 (Ipox),

[0075] Benzoic acid => 99% (Sigma-Aldrich),

[0076] Defoamer: TEGO Foamex 812 (Evonik)

[0077] Aerosil 200 (Evonik)

[0078] Biocide: Parmetol K6 (Company)

[0079] Heliogen Blue L 7085 (BASF Color Index: PB 15:3) Irgalite Red 3773 (BASF Color Index: PR 48:2) Bayferrox 130 M (Lanxess Color Index: PR 101) analytical devices

[0080] GPC: In tetrahydrofuran as the mobile phase and an SDV column (1,000-10,000 μ porosity) as the immobile phase. Polystyrene (PS) was used for calibration.

[0081] NMR: Bruker Avance III 400 (av401): 1 H DMSO-d6, CDCh;

[0082] Bruker Avance Neo (Neo400): 13 C in CDCh

[0083] 1. Production of the polymer according to the invention

[0084] 1.1 Production of the oligoamino ester monomer

[0085] First, various oligoaminoester monomers (Table 1) were prepared.

[0086] In a four-necked flask, 10–20 wt% technical-grade butyl acetate, based on the total components, was placed and heated to 70°C (0.3: 100°C). Oxazolines and acrylic acid were then added simultaneously over 2 hours according to the quantities given in Table 1. The temperature was maintained at 70°C (0.3: 100°C) for 24 hours.

[0087] Table 1

[0088] The oligoaminoester monomer O1 exhibited the following characteristic parameters:

[0089] 1H (400 MHz, DMSO-d6): ö / ppm=12.5-12 (1 H, COOH), 8, 0-7, 8 (1 H, NH), 6, 4-5, 8 (3H, CH=CH2), 4, 3-3, 9 (2H, C(=O)O-CH2), 3, 8-3.4 (4H, CH2-N-CH2), 3, 4-3, 2 (2H, CH2-C(=O)O), 2, 1-1, 9 (3H, C(=O)-CH3).

[0090] GPC (THF vs. PS): M w =580 g / mol, M n =450 g / mol, D=1.3

[0091] The oligoaminoester monomer O2 exhibited the following characteristic parameters:

[0092] 1 H (400 MHz, DMSO-d6): ö / ppm=12.5-12 (1 H, COOH), 8, 0-7, 8 (1 H, NH), 6, 4-5, 8 (3H, CH=CH2), 4, 3-3, 9 (2H, C(=O)O-CH2), 3, 8-3.4 (4H, CH2-N-CH2), 3, 4-3, 2 (2H, CH2-C(=O)O), 2, 8-1, 9 (2H, C(=O)-CH2-CH3), 1,1-0, 8 (3H, C(=O)-CH2-CH3).

[0093] GPC (THF vs. PS): Mw=650 g / mol, M n =460 g / mol, D=1.4

[0094] The oligoaminoester monomer O3 exhibited the following characteristic parameters:

[0095] 1H (400 MHz, DMSO-d6): ö / ppm=13-12 (1 H, COOH), 8, 7-8, 4 (1 H, C(=O)-phenyl), 7, 9-7, 7 (1 H, NH), 7, 5-7, 2 (4H, C(=O)-phenyl), 6, 4-5, 8 (3H, CH=CH2), 4, 3-3, 9 (2H, C(=O)O-CH2), 3, 8-3, 4 (4H, CH2-N-CH2), 3, 4-3, 2 (2H, CH2-C(=O)O).

[0096] GPC (THF vs. PS): M w =400 g / mol, M n =330 g / mol, D=1,2 1.2 Reaction of the oligoaminoester monomer with radical polymerizable monomers to obtain the polymers according to the invention

[0097] First, 10–20 wt% butyl acetate, based on the total components, was added and heated to 100 °C. After reaching the reaction temperature, the oligoaminoester monomer from reaction step 1.1, a mixture consisting of monomer(s) according to the specifications in Table 2 (possibly 0–40 wt% butyl acetate depending on its state of matter and viscosity) and a solution of 1.0 wt% 2,2-azodi(2-methylbutyronitrile) in 5 wt% butyl acetate, was added dropwise over a period of 1–4 h. After addition, this mixture was kept at 100 °C for 2 h.

[0098] Table 2

[0099] The polymer KO1.1 exhibited the following characteristic parameters:

[0100] GPC (THF vs. PS): M w =3,000 g / mol, M n =1,600 g / mol, D=1.8

[0101] 1 H (400 MHz, DMSO-d6): ö / ppm=12, 4-12.1 (COOH), 8, 0-7, 5 (NH), 4, 5-3.0 (polyester), 2, 9-0, 7 (polymer backbone).

[0102] The polymer KO2.1 exhibited the following characteristic parameters:

[0103] GPC (THF vs. PS): M w =4,900 g / mol, M n =2,100 g / mol, D=2.3

[0104] 1 H (400 MHz, DMSO-d6): ö / ppm=12, 5-11.8 (COOH), 8, 0-7, 8 (NH), 7, 4-6, 4 (aromatic CH CH), 4.2- 3.0 (polyester), 2, 9-0, 7 (polymer backbone).

[0105] The polymer KO2.2 exhibited the following characteristic parameters:

[0106] GPC (THF vs. PS): M w =4,800 g / mol, M n =2,600 g / mol, D=1.9

[0107] 1 H (400 MHz, DMSO-d6): δ / ppm=12, 5-12.0 (COOH), 8, 0-7, 5 (NH), 4, 2-3.0 (polyester), 2, 9-0, 7 (polymer backbone).

[0108] The polymer KO2.3 exhibited the following characteristic parameters:

[0109] GPC (THF vs. PS): M w =18,000 g / mol, M n =4,600 g / mol, D=3.9

[0110] 1H (400 MHz, DMSO-d6): ö / ppm=12, 5-12.0 (COOH), 8, 0-7, 5 (NH), 7, 4-6, 4 (aromatic CH CH), 4.2- 3.0 (polyester), 2, 9-0, 7 (polymer backbone).

[0111] The polymer KO2.4 exhibited the following characteristic parameters:

[0112] GPC (THF vs. PS): M w =3,100 g / mol, M n =1,400 g / mol, D=2.2;

[0113] 1 H (400 MHz, DMSO-d6): ö / ppm=12, 5-12.0 (COOH), 8, 0-7, 6 (NH), 7, 3-6, 4 (aromatic CH CH ), 4.2- 3.0 (polyester), 2, 9-0, 7 (polymer backbone).

[0114] The polymer KO2.5 exhibited the following characteristic parameters:

[0115] GPC (THF vs. PS): M w =3,300 g / mol, M n =1,600 g / mol, D=2.1

[0116] 1 H (400 MHz, DMSO-d6): μ / ppm = 12.5–12.0 (COOH), 8.0–7.5 (NH), 7.4–6.4 (aromatic CH₃CH₄), 4.2–3.0 (polyester), 2.9–0.7 (polymer backbone). The polymer KO2.6 exhibited the following characteristic parameters:

[0117] GPC (THF vs. PS): M w =3,200 g / mol, M n =1,500 g / mol, D=2.1

[0118] 1 H (400 MHz, DMSO-d6): ö / ppm=12, 5-12.0 (COOH), 8, 0-7, 5 (NH), 7, 4-6, 4 (aromatic CH CH ), 4.2- 3.0 (polyester), 2, 9-0, 7 (polymer backbone).

[0119] The polymer KO2.7 exhibited the following characteristic parameters:

[0120] GPC (THF vs. PS): M w =8,400 g / mol, M n =3,300 g / mol, D=2.5

[0121] 1 H (400 MHz, DMSO-d6): ö / ppm=12, 4-12.1 (COOH), 7, 9-7, 5 (NH), 7, 4-6, 4 (aromatic CH CH ), 4.2- 3.0 (polyester), 2, 9-0, 7 (polymer backbone).

[0122] The polymer KO2.8 exhibited the following characteristic parameters:

[0123] GPC (THF vs. PS): M w =11,500 g / mol, M n =4,300 g / mol, D=2.7

[0124] 1 H (400 MHz, DMSO-d6): δ / ppm=12, 4-12.1 (COOH), 7, 9-7, 5 (NH), 4, 2-3.0 (polyester), 2, 9-0, 7 (polymer backbone).

[0125] The polymer KO2.9 exhibited the following characteristic parameters:

[0126] 1 H (400 MHz, DMSO-d6): ö / ppm= 7, 9-7, 6 (NH), 7.4-6, 5 (aromatic CH), 4, 2-3.0 (polyester), 2, 9-0, 7 (polymer backbone).

[0127] The polymer KO2.10 exhibited the following characteristic parameters:

[0128] 1 H (400 MHz, DMSO-d6): ö / ppm= 7, 9-7, 6 (NH), 7.4-6, 5 (aromatic CH), 4, 2-3.0 (polyester), 2, 9-0, 7 (polymer backbone).

[0129] The polymer KO2.11 exhibited the following characteristic parameters:

[0130] 1 H (400 MHz, DMSO-d6): ö / ppm= 8, 0-7, 6 (NH), 7.4-6, 5 (aromatic CH), 4, 2-3.0 (polyester), 2, 9-0, 7 (polymer backbone).

[0131] The polymer KO2.12 exhibited the following characteristic parameters:

[0132] GPC (in THF vs. PS): M w =4,400 g / mol, M n =2,100 g / mol, D=2.1 ;

[0133] 1H (400 MHz, DMSO-d6): μ / ppm = 12.5–12.0 (COOH), 7.9–7.5 (NH), 7.4–6.4 (aromatic CH), 4.2–3.0 (polyester), 2.9–0.7 (polymer backbone). The polymer KO2.13 exhibited the following characteristic parameters:

[0134] GPC (in THF vs. PS): M w =5,100 g / mol, M n =2,200 g / mol, D=2.3

[0135] 1 H (400 MHz, DMSO-d6): ö / ppm=12, 5-12.0 (COOH), 8, 0-7, 5 (NH), 7, 4-5, 8 (aromatic CH), 4, 2-3.0 (polyester), 2, 9-0, 7 (polymer backbone).

[0136] The polymer KO3.1 exhibited the following characteristic parameters:

[0137] GPC (THF vs. PS): M w =5,400 g / mol, M n =2,200 g / mol, D=2.5;

[0138] 1 H (400 MHz, DMSO-d6): δ / ppm=12, 5-12.0 (COOH), 8, 8-8, 2 (aromatic CH oxazoline), 8, 0-7, 5 (NH), 7, 5-7.0 (aromatic CH oxazoline), 4, 5-3.0 (polyester), 2, 9-0, 7 (polymer backbone).

[0139] The inventive method thus makes it possible to produce a wide variety of polymers in which the number and length of the side chains determine the amount of nitrogen in the polymer and thus tailor-made dispersants can be produced.

[0140] 1.3 Post-modification of the polymer according to the invention

[0141] For the subsequent post-modification, the solvent was removed from the product obtained after reaction step 1.2.

[0142] In a four-necked flask, a quantity of the polymer according to the invention from reaction step 1.2, as specified in Table 3, and at least one reagent 1 and / or 2 from Table 3 were placed and heated to 160 °C (K 2.3 and K 2.13; 120 °C) and held for 4 h. The post-modified polymer was transferred to a container at 100 °C and characterized. The analytical results confirmed the desired structure.

[0143] Table 3

[0144] The post-modified polymer K1.1 according to the invention exhibited the following characteristic parameters: GPC in THF versus PS: M w = 8,200 g / mol, M n =2,400 g / mol, D=3.4

[0145] 1 H (400 MHz, DMSO-d6): ö / ppm=12.5-12 (COOH), 8, 0-7, 8 (NH), 4, 2-3.0 (polyether, polyester), 2, 9-0, 7 (polymer backbone).

[0146] The post-modified polymer K2.1 according to the invention exhibited the following characteristic parameters:

[0147] GPC in THF against PS: M w =11,600 g / mol, M n =2,500 g / mol, D=4.6

[0148] 1 H (400 MHz, DMSO-d6): μ / ppm = 12.5–12 (COOH), 8.0–7.8 (NH), 7.4–6.4 (aromatic CH3CH3), 4.2–3.0 (polyether, polyester), 2.9–0.7 (polymer backbone). The post-modified polymer K2.2 according to the invention exhibited the following characteristic parameters:

[0149] GPC in THF against PS: M w =9,400 g / mol, M n =3,600 g / mol, D=2.6

[0150] 1H (400 MHz, CDCI3): δ / ppm=7.4-6.4 (NH), 4, 2-3.0 (polyether, polyester), 2, 9-0, 7 (polymer backbone).

[0151] The post-modified polymer K2.3 according to the invention exhibited the following characteristic parameters:

[0152] GPC in THF against PS: M w =10,200 g / mol, M n =1,300 g / mol, D=7.8

[0153] 1 H (400 MHz, DMSO-d6): ö / ppm=8.0-7.7 (NH), 7, 4-6, 5 (aromatic CH), 4, 2-3.0 (polyether, polyester), 2, 9-0, 7 (polymer backbone).

[0154] The post-modified polymer K2.4 according to the invention exhibited the following characteristic parameters:

[0155] GPC in THF against PS: M w =13,000 g / mol, M n =2,500 g / mol, D=5.2

[0156] 1 H (400 MHz, DMSO-d6): ö / ppm=12.5-12 (COOH), 8, 0-7, 7 (NH), 7, 3-6, 5 (aromatic CH), 4, 2-3.0 (polyether, polyester), 2, 9-0, 7 (polymer backbone).

[0157] The post-modified polymer K2.5 according to the invention exhibited the following characteristic parameters:

[0158] GPC in THF against PS: M w =15,200 g / mol, M n =2,400 g / mol, D=6.4

[0159] 1 H (400 MHz, DMSO-d6): ö / ppm=12.5-12 (COOH), 8, 0-7, 7 (NH), 7, 6-6, 5 (aromatic CH), 4, 2-3.0 (polyether, polyester), 2, 9-0, 7 (polymer backbone).

[0160] The post-modified polymer K2.6 according to the invention exhibited the following characteristic parameters:

[0161] GPC in THF against PS: M w =10,200 g / mol, M n =2,100 g / mol, D=4.8

[0162] 1 H (400 MHz, DMSO-d6): μ / ppm = 12.5–12 (COOH), 8.0–7.6 (NH), 7.5–6.3 (aromatic CH), 4.2–3.0 (polyether, polyester), 2.9–0.7 (polymer backbone). The post-modified polymer K2.7 according to the invention exhibited the following characteristic parameters:

[0163] GPC in THF against PS: M w =17,500 g / mol, M n=3,000 g / mol, D=5.8

[0164] 1 H (400 MHz, DMSO-d6): ö / ppm=12.5-12 (COOH), 8, 0-7, 6 (NH), 7, 4-6, 3 (aromatic CH), 4, 2-3.0 (polyether, polyester), 2, 9-0, 7 (polymer backbone).

[0165] The post-modified polymer K2.8 according to the invention exhibited the following characteristic parameters:

[0166] GPC in THF against PS: M w =21,800 g / mol, M n =3,900 g / mol, D=5.6

[0167] 1 H (400 MHz, DMSO-d6): ö / ppm=12.5-12 (COOH), 8, 0-7, 6 (NH), 4, 2-3.0 (polyether, polyester), 2, 9-0, 7 (polymer backbone).

[0168] The post-modified polymer K2.9 according to the invention exhibited the following characteristic parameters:

[0169] GPC (in THF / TEA against PS): M w =70,600 g / mol, M n =2,600 g / mol, D=27.2

[0170] 1 H (400 MHz, DMSO-d6): ö / ppm=8.0-7.6 (NH), 7, 4-6, 5 (aromatic CH), 4, 2-3.0 (polyether, polyester), 2, 9-0, 7 (polymer backbone).

[0171] The post-modified polymer K2.10 according to the invention exhibited the following characteristic parameters:

[0172] GPC (in THF / TEA against PS): M w =26,700 g / mol, M n =2,900 g / mol, D=9.2

[0173] 1 H (400 MHz, DMSO-d6): ö / ppm=8.0-7.6 (NH), 7, 5-6, 5 (aromatic CH), 4, 2-3.0 (polyether, polyester), 2, 9-0, 7 (polymer backbone).

[0174] The post-modified polymer K2.11 according to the invention exhibited the following characteristic parameters:

[0175] GPC (in THF / TEA against PS): M w =50,800 g / mol, M n =3,700 g / mol, D=13.7

[0176] 1 H (400 MHz, DMSO-d6): μ / ppm = 8.0–7.6 (NH), 7.5–6.5 (Aromat CH), 4.2–3.0 (Polyether, Polyester), 2.9–0.7 (Polymer backbone). The post-modified polymer K2.12 according to the invention exhibited the following characteristic

[0177] Parameters on:

[0178] GPC in THF against PS: M w=17,900 g / mol, M n =4,800 g / mol, D=3.7

[0179] 1 H (400 MHz, DMSO-d6): ö / ppm=12.5-12 (COOH), 8, 0-7, 6 (NH), 7, 4-6, 3 (aromatic CH), 4, 2-3.0 (polyether, polyester), 2, 9-0, 7 (polymer backbone).

[0180] The post-modified polymer K2.13 according to the invention exhibited the following characteristic parameters:

[0181] GPC in THF against PS: M w =17,900 g / mol, M n =4,800 g / mol, D=3.7

[0182] 1 H (400 MHz, DMSO-d6): ö / ppm=12.5-12 (COOH), 8, 0-7, 6 (NH), 7, 4-6, 3 (aromatic CH), 4, 2-3.0 (polyether, polyester), 2, 9-0, 7 (polymer backbone).

[0183] The post-modified polymer K2.14 according to the invention exhibited the following characteristic parameters:

[0184] GPC in THF against PS: M w =21,600 g / mol, M n =6,200 g / mol, D=3.5

[0185] 1H (400 MHz, DMSO-d6): ö / ppm=12.5-12 (COOH), 8, 0-7, 6 (NH), 7, 5-6.0 (aromatic CH), 4, 2-3.0 (polyether, polyester), 2, 9-0, 7 (polymer backbone).

[0186] The post-modified polymer K2.15 according to the invention exhibited the following characteristic parameters:

[0187] GPC in THF against PS: M w =25,000 g / mol, M n =8,100 g / mol, D=3.1

[0188] 1 H (400 MHz, DMSO-d6): ö / ppm=12.5-12 (COOH), 8, 0-7, 6 (NH), 7, 5-6.0 (aromatic CH), 4, 2-3.0 (polyether, polyester), 2, 9-0, 7 (polymer backbone).

[0189] The post-modified polymer K3.1 according to the invention exhibited the following characteristic parameters:

[0190] GPC in THF against PS: M w =11,100 g / mol, M n =1,900 / mol, D=5.8

[0191] 1H (400 MHz, DMSO-d6): μ / ppm = 12.5–12 (COOH), 8.7–8.2 (aromatic CH₃ oxazoline), 8.0–7.8 (NH₃), 7.6–7.1 (aromatic CH₃ oxazoline), 4.2–3.0 (polyether, polyester), 2.9–0.7 (polymer backbone). 1.4 Quaternization of the post-modified polymer according to the invention (variant Q1)

[0192] For the quaternization of variant Q1, several post-modified polymers according to the invention were used as examples. A post-modified polymer according to the invention from Table 3 was weighed out and heated to 95 °C. After reaching the reaction temperature, reagent 3 from Table 4 was added dropwise. The material was held at reaction temperature for 2 h. The product was filled at approximately 95 °C and made available for further use.

[0193] Table 4

[0194] 1.5 Quaternization of the post-modified polymer according to the invention (variant Q2)

[0195] For the quaternization of variant Q2, several post-modified polymers according to the invention were used as examples. A post-modified polymer according to the invention from Table 3 and 1–10 wt% benzoic acid according to Table 5 were weighed out and heated to 120 °C. After reaching the reaction temperature, reagent 4 was added dropwise according to the values ​​in Table 5. The mixture was held at reaction temperature for 4 h. The product was filled into containers at 100 °C and made available for further use. Table 5

[0196] The synthesis of the polymers shows that the nitrogen density can be successfully increased by varying the oligomer from 1.1 as well as the post-modifications.

[0197] 2. Application-related tests

[0198] 2.1 Production of the pigment preparations according to the invention and comparison preparations for checking the viscosity

[0199] First, a selection of the polymers produced in Tables 3-5 was made for application-related testing regarding pigment stability, color strength, and compatibility in coating applications. The selection of polymers is compiled in Table 6. An aqueous pigment preparation was then produced using the polymer according to the formulations listed in Table 7. For comparison, pigment preparations with wetting and dispersing additives from existing patents were also prepared.

[0200] VD1 and VD2 were produced as comparative examples based on the following writings:

[0201] VD1: US5225456A1, Example 1 (page 5)

[0202] VD2: W02008080580A2, Polymer 4 (page 34) Table 6

[0203] A polymer from Table 6 was placed in a 250 mL wide-mouth glass vial with the other liquid components from Table 7. It was briefly homogenized by hand using a metal spatula, and then the pigment from Table 7 was added by weight. Dispersal was carried out after the addition of 250 g of glass beads (d = 2.5–2.8 mm) in a Lau Scandex shaker for 2 h (Bayferrox 130 M: 1 h).

[0204] Table 7 Viscosity measurement of the preparations:

[0205] The Haake RheoStress 1 rheometer was used for the rheological viscosity profiles. Measurement parameters: cone / plate C35 / 2°, 23°C, multiple measurement points in the range of 1–1000 1 / s. The viscosity was evaluated at 100 1 / s.

[0206] Storage stability

[0207] The pigment preparations were stored in an oven at 50°C. After one, two, and four weeks of storage, the preparations were cooled to room temperature and visually assessed for sedimentation and homogeneity. All samples showed a homogeneous and stable pigment preparation without sedimentation, so the rheological viscosity profile was subsequently determined as described above.

[0208] 2.2 Tinted coating material

[0209] For the production of the tinted coating material, an aqueous, satin-gloss polyurethane lacquer, white, from Chemische Werke Kluthe GmbH, product name CONTIPUR® SATIN, was used as a base coat. Table 8 shows the mixing ratios between the base coat and the pigment preparation.

[0210] Table 8

[0211] First, the basecoat and pigment preparation were weighed into a 60ml PP screw-top container. Using the Hauschild Speed ​​Mixer DAC 150.1 FVZ, the basecoat and pigment preparation were mixed and homogenized for 1 minute at 2,000 rpm. The resulting tinted coatings were then used for further application tests, including a rub-out test to determine compatibility.

[0212] For the "rub-out test," the tinted coating materials were applied to a test substrate using a 150 µm squeegee from Leneta. After a 5-minute drying time, the "rub-out test" was performed. This test involves mixing the applied coating with a friction tool, such as a gloved finger, using medium pressure in circular motions. The goal is to avoid both the coating being completely pushed away from the substrate and the coating film tearing.

[0213] After the coating has dried, the color values ​​are determined on the area of ​​the "rub-out" test as well as on an adjacent area not subjected to the "rub-out" test. The AE (Delta E) is calculated from both values. This difference in color coordinates is a measure of the quality of the pigment stabilization.

[0214] Color intensity

[0215] The colorimetric values ​​for determining the color intensity were also determined using an X-Rite SP 62 spectrometer. The standard color values ​​X, Y, and Z are determined, and the color intensity F is calculated using the following formula:

[0216] > (ioo-y) r — - 2

[0217] 2 Y

[0218] Y = is the reflectance of the wavelength of maximum absorption

[0219] 3. Application-related assessment

[0220] The pigment preparations and tinted base materials were prepared using the pigments Heliogen Blue L 7085, Irgalite Red 3773, and Bayferrox 130 M and tested using the application-related evaluation described in Section 2. An acrylate dispersion additive (VD 1) for the acrylate-based chemistry and a dispersion additive based on SMA chemistry (VD 2) were selected as comparison systems and evaluated separately. The results are listed below in tabular form. The following equation was used as the basis for the relative color strength:

[0221] F (oxazoline comb copolymer) rel. F [%] = ■ 100%

[0222] FV er gleichsdisperser greed additive

[0223] Due to the chemical nature of the comparative dispersing additives based on acrylate (VD 1) and SMA (VD 2), the comb copolymers listed in Table 6 are each compared with the acrylate system (entries 1–9) or the SMA system (entries 10–12) and evaluated separately. The application-related results are summarized in Tables 10–15.

[0224] The following points should be considered when evaluating the results: The higher the relative color strength, the greater the efficiency of the pigment used. A low AE* value is desirable, as this indicates better compatibility of the pigment preparation with the basecoat. The lower the viscosity of the pigment preparation, the more fluid and processable it becomes; therefore, low viscosity values ​​are preferred. Furthermore, the viscosity of the pigment preparation after storage (4 weeks, 50 °C) should hardly differ from the value at room temperature (immediately after preparation). The smaller the deviation from high viscosity values, the more efficient the stabilizing effect of the wetting and dispersing additive. A decrease in viscosity is also acceptable and is explained by subsequent wetting effects.However, a very strong increase in viscosity indicates an unstable pigment preparation, which should be well known to those skilled in the art. Table 10.

[0225] Acrylate system: The pigment Heliogen Blue L 7085 yielded stable pigment preparations with the polymers from Table 10 with viscosities <150 mPa*s (100 1 / s, room temperature). These were comparable to or even better than the reference example VD1. Furthermore, the relative color strengths (rel. F in %) were superior to VD1 for all polymer additions. Compatibility (AE*) also improved.

[0226] Table 11 SMA system: The pigment Heliogen Blue L 7085 yielded stable pigment preparations with the polymers from Table 11 with viscosities <270 mPa*s (100 1 / s, room temperature) and represented an improvement compared to VD 2. Furthermore, the relative color strength (rel. F in %) and the compatibility (AE*) for entry Q1.2.12 were better than for VD 2. Entry Q2.2.13 showed comparable relative color strength (rel. F in %) to VD 2, but the viscosity of the pigment preparation and the compatibility (AE*) exceeded those of VD 2.

[0227] Table 12 Acrylate system: The pigment Irgalite Red 3773 yielded predominantly stable pigment preparations with the polymers from Table 12. It should be noted that the comparison dispersion additive VD 1 itself already exhibited very high viscosity values ​​and showed instabilities after storage. In contrast, polymers Q2.2.9 and Q2.2.11 showed particularly stable pigment preparations with good storage stability. Furthermore, the relative color strengths (rel. F in %) were better for all polymer additions than for VD 1. Table 13

[0228] SMA system: The pigment Irgalite Red 3773 yielded stable pigment preparations with the polymers from Table 13 with viscosities <600 mPa*s (100 1 / s, room temperature). Compared to VD 2, the viscosities were slightly increased, but the relative color strengths (rel. F in %) and the compatibility (AE*) were better than with VD 2.

[0229] Table 14: Tinted coating material with Bayferrox 130 M

[0230] Acrylate system: The pigment Bayferrox 130 M showed predominantly stable pigment preparations with the polymers from Table 12 with viscosities <600 mPa*s (100 1 / s, room temperature). In addition, the relative color strengths (rel. F in %) were improved for all polymer additions compared to VD 1.

[0231] Table 15

[0232] SMA system: The pigment Bayferrox 130 M showed that the pigment preparations achieved more stable pigment preparations after storage with the polymers from Table 13 compared to VD 2, while the relative color strengths (rel. F in %) as well as the compatibility (AE*) were comparable to the results at VD 2.

[0233] Based on the application-related tests carried out, it was determined that the dispersion properties according to the invention are present with regard to improved color strength and / or the compatibility of the color pigment.

Claims

Patent claims 1. Polymers obtainable by reacting oligoaminoester monomers with at least one radical polymerizable monomer.

2. Polymers according to claim 1, characterized in that the oligoaminoester monomers are obtainable by reacting (meth)acrylic acids and oxazolines or oxazines, according to formula Mi with Ri = independently of each other, same or different, a hydrogen or a methyl group, R 2 = independently of each other, the same or different, a hydrogen atom, an alkyl group with 1 to 18 carbon atoms or an aryl group with 6 to 18 carbon atoms, Ra = independent of each other, the same or different, a hydrogen or - CH2CH( R I)COXI R 4, with R4 = independent of each other, the same or different, a hydrogen atom, an alkyl group with 1 to 18 carbon atoms, hydroxyl-functionalized alkyl groups with 1 to 18 carbon atoms, phosphate-containing groups with 1 to 18 carbon atoms, an aryl group, a CH2 aryl group with 6 to 18 carbon atoms, -(CH R s-CH R 5-O) n R 6 with n = 1 to 50, or independently of each other, identical or different, a dimethylethylamine, a diethylethylamine, a dimethylpropylamine or a diethylpropylamine and / or 3-aminopropylimidazole, as well as quaternary structures thereof, preferably a hydrogen atom, Rs = independent of each other, the same or different, a hydrogen atom, an alkyl group with 1 to 4 carbon atoms or an aryl group with 6 carbon atoms, Rs = independently of each other, the same or different, a hydrogen atom, a saturated and / or unsaturated alkyl group with 1 to 50 carbon atoms, an aryl group or a CH2 aryl group with 6 to 18 carbon atoms, a phosphate group, Xi = O, NH, preferably O, m = 0 to 50, preferably 0 to 10, n = 1 or 2.

3. Polymers according to claim 2, characterized in that the oligoaminoester monomers have a degree of polymerization (DP). n ) between 1 and 50, preferably between 1 and 20, and particularly preferably between 1 and 5, wherein the DP n according to the calculation formula: Dp _ _ M n (0Ugomer) _ n M Meth) Acrylic acid) + M(Oxazoline / Oxazine) is calculated, where M n is determined using GPC (standard polystyrene, eluent: THF, PSSSECcurity 1260, column material: SDV 1000 / 10000Ä).

4. Polymers according to one of the preceding claims, characterized in that they comprise oligoaminoester monomers according to the formula Mi, with the proviso that Mi is not present as part of the linear polymeric backbone.

5. Polymers according to one of the preceding claims, characterized in that the oligoaminoester monomers (Mi) are combined with at least one monomer selected from one or more of the monomers of the group consisting of alkyl(meth)acrylates and alkenyl(meth)acrylates of straight-chain, branched or cycloaliphatic mono-alcohols with 1 to 22 carbon atoms or of straight-chain or branched aromatic or mixed aromatic-aliphatic mono-alcohols with 1 to 22 carbon atoms, mono(meth)acrylates of oligomeric or polymeric ethers, (Meth)acrylates of halogenated alcohols, oxirane-containing (meth)acrylates, styrene, substituted styrenes, α-olefins, vinyl ethers, vinyl alcohol, vinyl acetate, (meth)allyl ethers; methacrylonitrile, acrylonitrile; cycloaliphatic heterocycles containing vinyl groups with at least one / V atom as a ring member, vinyl esters of monocarboxylic acids with 1 to 20 carbon atoms, / V-alkyl and / V, / V-dialky-substituted acrylamides with straight-chain, branched or cycloaliphatic alkyl groups with 1 to 22 carbon atoms, unsaturated carboxylic anhydrides and their imides, amides, and / or esters, ethylene-unsaturated monomers with at least one carboxylic, phosphoric, phosphoric and / or sulfonic acid group and unsaturated fatty acids or mixtures thereof are reacted.

6. Polymers according to any of the preceding claims, comprising combinations of repeating units selected from the group consisting of Chain extension — Connection to O in structural unit III with Xi = an O or NH, preferably an O, X2 = CH, NH, O and / or N, with the proviso that for five-membered aromatics X2 = -CH or NH or O and for six-membered aromatics X2 = CH or N, X3= CH or N, Ri = independently of each other, same or different, a hydrogen or a methyl group, R2 = independently of each other, the same or different, a hydrogen atom, an alkyl group with 1 to 18 carbon atoms or an aryl group with 6 to 18 carbon atoms, R3 = independently of each other, the same or different, a hydrogen or - CH2CH(RI)COXIR4, with R4 = independently of one another, identical or different, a hydrogen, an alkyl group with 1 to 18 carbon atoms, hydroxyl-functionalized alkyl groups with 1 to 18 carbon atoms, phosphate-containing groups with 1 to 18 carbon atoms, an aryl group, a CH2 aryl group with 6 to 18 carbon atoms, -(CHRs-CHRs-OJnRe with n = 1 to 50, or independently of one another, identical or different, a dimethylethylamine, a diethylethylamine, a dimethylpropylamine or a diethylpropylamine and / or 1-(3-aminopropyl)imidazole, as well as quaternary structures thereof, preferably a hydrogen, Rs = independent of each other, the same or different, a hydrogen atom, an alkyl group with 1 to 4 carbon atoms or an aryl group with 6 carbon atoms, Re = independently of each other, the same or different, a hydrogen atom, a saturated and / or unsaturated alkyl group with 1 to 50 C atoms, an aryl group or a CH2 aryl group with 6 to 18 C atoms, a phosphate group, m = 0 to 50, preferably 0 to 10, n = 1 or 2, M = independently of one another, identical or different, hydrogen, NH4, alkali or alkaline earth metals, preferably NH4, Na or K, wherein they have at least one repeating unit (III).

7. Polymers according to one of the preceding claims, characterized in that the acid groups of the Kamm copolymers are esterified or amidated, quaternized, neutralized or alkoxylated.

8. Polymers according to claim 6, characterized in that the acid groups are esterified or amidated by reaction with at least one compound selected from the group of primary and secondary amines and alcohols (especially amines and alcohols based on polyoxyalkylenes).

9. Use of the polymers according to any of the preceding claims as wetting and dispersing additives, thickeners and defoamers.

10. Dispersion comprising a dispersing medium and dispersed particulate solid, preferably in the form of an inorganic filler, and / or in the form of an inorganic or organic pigment and / or in the form of carbon nanotubes and / or in the form of graphene, wherein 0.1 - 10 wt.%, preferably 0.3 to 4.5 wt.%, of the polymer according to any one of claims 1 to 8 is used as a wetting and dispersing agent, based on the total weight of the dispersion.

11. Dispersion according to claim 10, which is in the form of an ink or coating material, in particular a varnish.

12. Process for the production of the polymers, characterized by the following steps: 1.) Provision of oligoaminoester monomers by reaction of (meth)acrylic acids and oxazolines or oxazines, 2.) Polymerization of the oligoaminoester monomers with at least one monomer selected from one or more of the monomers of the group consisting of alkyl(meth)acrylates and alkenyl(meth)acrylates of straight-chain, branched or cycloaliphatic mono-alcohols with 1 to 22 carbon atoms or of straight-chain or branched aromatic or mixed aromatic aliphatic mono-alcohols with 1 to 22 carbon atoms, mono(meth)acrylates of oligomeric or polymeric ethers, (meth)acrylates of halogenated alcohols; oxirane-containing (meth)acrylates, styrene, substituted styrenes, α-olefins, vinyl ethers, vinyl alcohol, vinyl acetate, allyl ethers; methacrylonitrile, acrylonitrile; cycloaliphatic heterocycles containing vinyl groups with at least one / V atom as a ring member, vinyl esters of monocarboxylic acids with 1 to 20 carbon atoms, / V-alkyl and A / . / V-Dialkyl-substituted acrylamides with straight-chain, branched or cycloaliphatic alkyl groups with 1 to 22 carbon atoms, unsaturated carboxylic anhydrides and their imides, amides, and / or esters, ethylene-unsaturated monomers with at least one carboxylic, phosphoric, phosphoric and / or sulfonic group and unsaturated fatty acids or mixtures thereof, optional. 3.) Reaction of the polymer with at least one compound selected from the Group of primary and secondary amines and alcohols, preferably amines and alcohols based on polyoxyalkylenes, and 4.) Optional quaternization of the primary and secondary or tertiary amines by uncatalyzed, acid- or base- or metal-catalyzed reaction of halogenated or epoxidized compounds or compounds accessible by ring opening, as well as hydroxylamines accessible by oxidation, and subsequent neutralization with carboxylic, phosphoric and / or sulfonic compounds.

13. Method according to claim 12, characterized in that the reaction in step 2) is carried out at a temperature between 70 °C and 130 °C, preferably 80 °C to 120 °C and particularly preferably 90 °C to 110 °C.

14. Method according to one of claims 12 or 13, characterized in that the temperature is kept constant during the reaction in step 1) and in step 2).

15. Method according to one of the preceding claims, characterized in that the solvent is removed before step 3).

16. Method according to one of the preceding claims, characterized in that the method is carried out in-situ.

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