DE102008002254A1 - Monomer mixture, useful for preparing a polymer, which is useful to prepare a coating composition, preferably lacquers and aqueous dispersion, comprises a carbonyl group containing monomer and another carbonyl group containing monomer - Google Patents

Abstract

Monomer mixture comprises at least a carbonyl group containing monomer (I) and at least another carbonyl group containing monomer (II). Monomer mixture comprises at least a carbonyl group containing monomer of formula (CH 2=CH(R)-C(=O)-X 1>-Z-X 2>-C(=O)-R 1>) (I) and at least another carbonyl group containing monomer of formula (CH 2=CH(R)-C(=O)-X 1>-Z-X 2>-C(=O)-R 2>) (II). R : H or CH 3; X 1>, X 2>O or NR1a; R1a : H or a radical having 1-6C; Z : a connecting group, preferably OH; R 1>an unsaturated 9-25C-radical; and R 2>a saturated 9-25C-radical. Provided that: at least one of the X 1>and X 2>groups is NR 1>. Independent claims are included for: (1) a polymer comprising repetition units, which are derived from the monomer mixture; (2) a composition for the preparation of a coating comprising the polymer and an alkyd resin; and (3) the preparation of the monomer mixture comprising (a) reacting a fatty acid ester mixture with an amine and (b) subsequently reacting the obtained amide with a (meth)acrylate and/or (meth)acrylic acid.

Description

The The present invention relates to a monomer mixture and polymers, which are available from this monomer mixture. Farther The present invention is directed to coating compositions, comprising these polymers. Furthermore, the present invention relates Invention a process for the preparation of these monomers.

Coating agents, in particular paints are produced synthetically for a long time. Many of these coating compositions are based on so-called alkyd resins, those using polybasic acids, alcohols and fatty acids and / or fatty acid derivatives become. A special group of these alkyd resins form when exposed to oxygen cross-linked films, wherein cross-linking by oxidation with participation of unsaturated groups takes place. Many of these alkyd resins include organic solvents or dispersants to the resins in a thin layer on coating body to be able to apply. On the use of these solvents However, for reasons of environmental protection and the Occupational safety will be waived. Therefore, were appropriate Resins based on aqueous dispersions developed however, their storage stability is limited. Furthermore the water absorption of many alkyd resins is too high or their solvent resistance and their hardness too low. Accordingly, attempts were made undertook the above-mentioned classic alkyd-based paints to modify or replace.

For example, are off US 4,010,126 Compositions are known which comprise a modified with (meth) acrylate polymers alkyd resin, which is subsequently ßend used in an emulsion polymerization. The preparation of the compositions described is carried out over several steps, so that the described resins are very expensive to produce.

For example, a solution polymer-based vinyl monomer-based coating composition is disclosed in U.S. Pat DE-A-101 06 561 described. However, this composition comprises a high proportion of organic solvents.

Furthermore, aqueous dispersions based on (meth) acrylate polymers are also known. For example, the document describes DE-A-41 05 134 aqueous dispersions which can be used as binders in paints. However, the preparation of these binders is carried out over several stages, initially a solution polymer is produced, which is used after neutralization in an emulsion polymerization.

In addition, in DE-A-25 13 516 aqueous dispersions comprising polymers based on (meth) acrylates, wherein a part of the (meth) acrylates is derived from unsaturated alcohol radicals. A disadvantage of the described dispersions is in particular their complicated preparation, wherein the polymers based on (meth) acrylates are obtained by solution polymerization. In this case, these polymers have a high proportion of acid groups, which is in the range of 5 to 20 wt .-%, based on the solution polymer.

The publication DE-A-26 38 544 describes oxidatively drying aqueous dispersions which comprise emulsion polymers based on (meth) acrylates, some of the (meth) acrylates used being derived from unsaturated alcohol radicals. However, chain transfer agents have been used to prepare the emulsion polymers so that the emulsion polymer shows high solubility.

Furthermore, aqueous dispersions comprising oxidatively drying polymers in F.-B. Chen, G. Bufkin, "Crosslinkable Emulsion Polymers by Autooxidation II", Journal of Applied Polymer Science, Vol. 30, 4551-4570 (1985). explained. The polymers contain from 2 to 8% by weight of units derived from (meth) acrylates having unsaturated, long-chain alcohol radicals. The durability of these dispersions and the hardness of the coatings are not sufficient for many applications.

In addition, the document describes US 5,750,751 Polymers based on vinyl monomers, which can crosslink at room temperature. The polymers can be obtained both by solution polymerization and by emulsion polymerization. The monomer mixtures to be polymerized may include, inter alia, (meth) acrylates whose alcohol residues are modified by unsaturated fatty acids. The polymers obtained by solution and emulsion polymerization of modified (meth) acrylates show high solubility since chain transfer agents have been used. A disadvantage of the in US 5,750,751 However, the described coating compositions is that softening solvents must be added, which are to be avoided for environmental reasons.

An improvement in this regard is made by the teaching of the document EP-A-1 044 993 achieved. This document describes aqueous dispersions based on (meth) acrylates. The mixtures to be polymerized include (meth) acrylates which have been modified by unsaturated fatty acids. An essential aspect of this solution is the use of polymers having a particularly broad molecular weight distribution, wherein the number average molecular weight in the range of 300 to 3000 g / mol. However, a disadvantage of this system is that the films obtained are too soft for many applications.

Furthermore, the document describes WO 2006/013061 Dispersions comprising particles based on (meth) acrylates. The monomer mixtures used to prepare the particles include (meth) acrylates which have been modified by unsaturated fatty acids. However, the examples do not polymerize monomers comprising acid groups. Furthermore, the proportion of (meth) acrylates modified with unsaturated fatty acids is very high. A disadvantage of the in WO 2006/013061 The dispersions described are in particular their complex preparation and the high proportion of residual monomers. Furthermore, the coatings obtained from the dispersions show a low stability against some solvents.

In addition, dispersions are also known from the prior art which, in addition to polymers based on (meth) acrylates, may also comprise alkyd resins. For example, the document describes WO 98/22545 Polymers with units derived from (meth) acrylates with unsaturated alcohol radicals. These polymers can be used together with alkyd resins. However, solvents are used to prepare paints from the described polymers. Aqueous dispersions are in WO 98/22545 not described. Accordingly, these compositions suffer from the disadvantages set out above.

Furthermore, the Japanese document describes JP 59011376 Emulsion polymers based on (meth) acrylates. The dispersions have a solids content of about 40% to a dynamic viscosity of at least 200 mPas. A particle size is not mentioned in this document. Due to the high viscosity of the dispersion, however, it can be assumed that the emulsion polymers have a particle size below 40 nm. A disadvantage of the dispersions described in this document is their low storage life. In addition, it has been found that the coatings obtained do not have sufficient stability for all requirements compared to all solvents.

In addition, are out US 6,599,972 Coating compositions based on polymers are known, based on the (meth) acrylates whose alcohol residue is derived from unsaturated fatty acid derivatives. A disadvantage of the coating compositions explicitly set forth herein is their shelf life and the stability of the coatings obtainable from the described compositions.

In In view of the prior art, it is now the object of the present Invention to provide monomer mixtures, the can be processed into polymers with excellent properties. These characteristics include in particular features, by coating agents and coatings resulting from the coating agents are available, apparently.

Especially should the monomer mixtures become dispersions or polymers, For example, emulsion polymers can be processed, the one have very low residual monomer content.

Farther It was therefore an object of the present invention, a coating agent provide that a particularly long shelf life and durability. Furthermore, the hardness should be the coatings available from the coating agents are, can be varied over a wide range. In particular, should be particularly hard, scratch-resistant coatings can be obtained.

A Another object is to see polymers available through the use of coating agents without volatile organic solvents are available. The coatings obtainable from the aqueous dispersions should have a high weather resistance, in particular have a high UV resistance. About that In addition, those obtainable from the aqueous dispersions should Films have a low tackiness after a short time.

Farther should be those available from the polymers or monomer mixtures Coatings a particular high resistance to Have solvents. This should be stability against many different solvents be high.

Solved These and other not explicitly mentioned tasks that are however, from the contexts discussed hereinbefore can be readily deduced or deduced by monomer mixtures with all features of claim 1. Expedient Modifications of the monomer mixtures according to the invention are placed in subclaims under protection. Regarding a polymer, a composition for producing a coating and a method for producing a monomer mixture Claims 17, 20 and 22, respectively, are based on a solution lying tasks.

worin R Wasserstoff oder eine Methylgruppe, X¹ und X² unabhängig Sauerstoff oder eine Gruppe der Formel NR', worin R' Wasserstoff oder ein Rest mit 1 bis 6 Kohlenstoffatomen ist, mit der Maßgabe, dass mindestens einer der Gruppen X¹ und X² eine Gruppe der Formel NR' bedeutet, worin R' Wasserstoff oder ein Rest mit 1 bis 6 Kohlenstoffatomen darstellt, Z eine Verbindungsgruppe, und R¹ ein ungesättigter Rest mit 9 bis 25 Kohlenstoffatomen ist,
und mindestens ein Monomer B der allgemeinen Formel (II),

worin R Wasserstoff oder eine Methylgruppe, X¹ und X² unabhängig Sauerstoff oder eine Gruppe der Formel NR', worin R' Wasserstoff oder ein Rest mit 1 bis 6 Kohlenstoffatomen ist, mit der Maßgabe, dass mindestens einer der Gruppen X¹ und X² eine Gruppe der Formel NR' bedeutet, worin R' Wasserstoff oder ein Rest mit 1 bis 6 Kohlenstoffatomen darstellt, Z eine Verbindungsgruppe, und R² ein gesättigter Rest mit 9 bis 25 Kohlenstoffatomen ist.The present invention accordingly provides a monomer mixture comprising at least one monomer A of the general formula (I)

wherein R is hydrogen or a methyl group, X ¹ and X ^{2 are} independently oxygen or a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, with the proviso that at least one of the groups X ¹ and X ² a group of the formula NR 'in which R' is hydrogen or a radical having 1 to 6 carbon atoms, Z is a linking group, and R ^{1 is} an unsaturated radical having 9 to 25 carbon atoms,
and at least one monomer B of the general formula (II),

wherein R is hydrogen or a methyl group, X ¹ and X ^{2 are} independently oxygen or a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, with the proviso that at least one of the groups X ¹ and X ² a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, Z is a linking group, and R ^{2 is} a saturated radical having 9 to 25 carbon atoms.

Furthermore, the measures according to the invention make it possible, inter alia, to achieve the following advantages:
The monomer mixtures according to the invention can be processed into polymers, coating compositions and coatings which have a very low residual monomer content.

The hardness of the coatings obtainable from coating compositions according to the invention, which in turn are based on the polymers or monomer mixtures, can be varied over a wide range. According to a preferred modification, in particular particularly hard, scratch-resistant coatings can be obtained according to the invention. The coatings obtainable from the coating compositions of the present invention show a surprisingly high solvent resistance, which is particularly evident in tests with methyl isobutyl ketone (MIBK), ammonia solutions or ethanol. Thus, the coatings obtained, in particular in experiments according to the furniture test DIN 68861-1 an excellent classification.

Coating agents, those using the monomer mixtures according to the invention generally do not need any volatile organic solvent. About that In addition, the coating compositions of the invention a high storage stability, a high durability and a very good shelf life. In particular, hardly occurs an aggregate formation on.

The from the coating compositions of the invention available coatings show high weather resistance, in particular a high UV resistance. Furthermore the available from the coating compositions films after a short time a little stickiness.

The Inventive monomer mixtures, polymers and coating can be inexpensively in large Create scale. The invention Coating agents are environmentally friendly and safe and processed and produced without much effort. Here, the coating compositions of the invention a very high shear stability.

worin R Wasserstoff oder eine Methylgruppe, X¹ und X² unabhängig Sauerstoff oder eine Gruppe der Formel NR', worin R' Wasserstoff oder ein Rest mit 1 bis 6 Kohlenstoffatomen ist, mit der Maßgabe, dass mindestens einer der Gruppen X¹ und X² eine Gruppe der Formel NR' bedeutet, worin R' Wasserstoff oder ein Rest mit 1 bis 6 Kohlenstoffatomen darstellt, Z eine Verbindungsgruppe, und R¹ ein ungesättigter Rest mit 9 bis 25 Kohlenstoffatomen ist.Monomer mixture comprises at least one monomer A of the general formula (I)

wherein R is hydrogen or a methyl group, X ¹ and X ^{2 are} independently oxygen or a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, with the proviso that at least one of the groups X ¹ and X ² a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, Z is a linking group, and R ^{1 is} an unsaturated radical having 9 to 25 carbon atoms.

worin R Wasserstoff oder eine Methylgruppe, X' Sauerstoff oder eine Gruppe der Formel NR', worin R' Wasserstoff oder ein Rest mit 1 bis 6 Kohlenstoffatomen, Z eine Verbindungsgruppe, R' Wasserstoff oder ein Rest mit 1 bis 6 Kohlenstoffatomen und R¹ ein ungesättigter Rest mit 9 bis 25 Kohlenstoffatomen ist.According to a preferred embodiment, the monomer mixture comprises at least one monomer A of the general formula (III)

wherein R is hydrogen or a methyl group, X 'is oxygen or a group of the formula NR', wherein R 'is hydrogen or a radical having 1 to 6 carbon atoms, Z is a linking group, R' is hydrogen or a radical having 1 to 6 carbon atoms and R ¹ unsaturated group having 9 to 25 carbon atoms.

Of the Term "radical having 1 to 6 carbon atoms" stands for a group having 1 to 6 carbon atoms. It includes aromatic and heteroaromatic groups as well as alkyl, Cycloalkyl, alkoxy, cycloalkoxy, alkenyl, alkanoyl, alkoxycarbonyl groups as well as heteroalipatic groups. The mentioned Groups are branched or unbranched. Furthermore you can these groups are substituents, especially halogen atoms or hydroxy groups exhibit.

Preferably the radicals R 'are alkyl groups. Among the preferred Alkyl groups include the methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 2-methylpropyl, tert-butyl group.

The Group Z preferably stands for a connection group, 1 to 10, preferably 1 to 5 and most preferably 2 to 3 carbon atoms. These include in particular linear or branched, aliphatic or cycloaliphatic radicals, such as a methylene, ethylene, propylene, iso-propylene, n-butylene, iso-butylene, t-butylene or cyclohexylene group, wherein the ethylene group is particularly preferred.

The group R ¹ in formula (I) is an unsaturated radical having 9 to 25 carbon atoms. These groups include in particular alkenyl, cycloalkenyl, alkenoxy, cycloalkenoxy, alkenoyl and heteroalipatic groups. Furthermore, these groups may have substituents, in particular halogen atoms or hydroxyl groups. The preferred groups include, in particular, alkenyl groups, such as, for example, the nonenyl, decenyl, undecenyl, dodecyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl -, docosenyl, octanediazyl, nonanediazyl, decanediazyl, undecanedienyl, dodecanedienyl, tridecandienyl, tetradecan-diene-yl , Pentadecanediazyl, hexadecanediazyl, heptadecanediazyl, octadecanediazyl, nonadecanediazyl, eicosanedienyl, heneicosanedienyl, Docosanedienyl, tricosan-diene-yl and / or heptadecan-triene-yl group.

The preferred monomers A according to formula (I) or (III) include, but are not limited to, heptadecenyloyloxy-2-ethyl (meth) acrylamide, heptadecan-dien-yloyloxy-2-ethyl- (meth) acrylamide, heptadecan-triene-yloyloxy- 2-ethyl (meth) acrylamide, heptadecenyloyloxy-2-ethyl (meth) acrylamide, (meth) acryloyloxy-2-ethyl-palmitoleic acid amide, (meth) acryloyloxy-2-ethyl-oleic acid amide, (meth) acryloyloxy-2-ethyl -osilicic acid amide, (meth) acryloyloxy-2-ethyl-cetolenic acid amide, (meth) acryloyloxy-2-ethyl-erucic acid amide, (meth) acryloyloxy-2-ethyl-linoleic acid amide, (meth) acryloyloxy-2-ethyl-linolenic acid amide, (meth) acryloyloxy-2-propyl-palmitoleic acid amide, (meth) acryloyloxy-2-propyl-oleic acid amide, (meth) acryloyloxy-2-propyl-icosenoic acid amide, (meth) acryloyloxy-2-propyl-cetolenic acid amide, (meth) acryloyloxy-2-propyl-amide erucic acid amide, (meth) acryloyloxy-2-propyl-linoleic acid amide and (meth) acryloyloxy-2-propyl-linolenic acid amide.

The Notation (meth) acrylic stands for acrylic and methacrylic radicals, where methacrylic radicals are preferred. Particularly preferred monomers A according to formula (I) or (III) are methacryloyloxy-2-ethyl-oleic acid amide, Methacryloyloxy-2-ethyl-linolenic acid amide and / or methacryloyloxy-2-ethyl-linolenic acid amide.

According to one particular embodiment of the present invention can the monomers A according to formula (I) an iodine number in Range of 50 to 300 g of iodine / 100 g, more preferably in the range from 100 to 200 g of iodine / 100 g.

Particular advantages can be achieved in particular by virtue of the fact that at least some of the monomers A according to formula (I) have exactly one double bond in the unsaturated radical R ¹ . According to another aspect of the present invention, at least a portion of the monomers A of the formula (I) may have two or more double bonds in the unsaturated group R ¹ . Preferably mixtures of the monomers A can be used, whereby these mixtures can contain both monomers A with exactly one double bond in the remainder of R ¹ as well as monomers A with two or more double bonds in the remainder of R ¹ . Here, the weight ratio of the monomers A of the formula (I) which have exactly one double bond in the unsaturated radical R ¹ to the monomers A of the formula (I) which have two or more double bonds in the unsaturated radical R ^{1 can be} in the range of 100 : 1 to 1:10, more preferably in the range of 10: 1 to 1: 5.

The monomers A according to formula (I) or (III) can be obtained in particular by multi-stage processes. In a first step, for example, one or more unsaturated fatty acids or fatty acid esters can be reacted with an amine, for example, ethylenediamine, ethanolamine, propylenediamine or propanolamine, to form an amide. In a second step, the hydroxy group or the amine group of the amide is reacted with a (meth) acrylate, for example methyl (meth) acrylate, to obtain the monomers of the formula (I) or (III). Valuable information on the preparation of these monomers can be found, inter alia, in the example of the present application. For the preparation of monomers in which X ^{1 is} a group of the formula NR ', in which R' is hydrogen or a radical having 1 to 6 carbon atoms, and X ^{2 is} oxygen, an alkyl (meth) acrylate, for example methyl ( meth) acrylate, reacted with one of the abovementioned amines to give a (meth) acrylamide having a hydroxy group in the alkyl radical, which is subsequently reacted with an unsaturated fatty acid to form monomers of the formula A. Transesterification of alcohols with (meth) acrylates or the preparation of (meth) acrylic acid amides are further in CN 1355161 . DE 21 29 425 filed on 14.06.71 with the German Patent Office with application number P2129425.7, DE 34 23 443 filed on 26.06.84 with the German Patent Office with the application number P3423443.8 or EP-A-0 534 666 submitted on 16.09.92 to the European Patent Office with the application number EP 92308426.3 with the reaction conditions described in these references as well as the catalysts set forth therein, etc. being included in this application for purposes of disclosure. Furthermore, these reactions are in "Synthesis of Acrylic Esters by Transesterification", J. Haken, 1967 described.

in this connection can be obtained intermediates, for example carboxamides, have the hydroxy groups in the alkyl radical to be purified. According to a particular embodiment of the present Invention can obtained intermediates without consuming Purification to the monomers A according to formula (I) be implemented.

To the preferred unsaturated fatty acids which for the preparation of the present monomers A according to formula (I) may include undecylenic acid, Palmitoleic acid, oleic acid, elaidic acid, Vaccenic acid, icosenoic acid, cetoleic acid, Erucic acid, nervonic acid, linoleic acid, Linolenic acid, arachidonic acid, timnodonic acid, Clupanodonic acid and / or cervonic acid. These acids may also be preferred as esters of alcohols with 1 to 4 carbon atoms, for example as ethyl, propyl, butyl and in particular methyl esters are used.

To the preferred amines for the reaction of the fatty acid or of the fatty acid ester include in particular ethylenediamine, Ethanolamine, propanolamine and propylenediamine.

Advantages that are not obvious to those skilled in the art can be achieved by a monomer mixture having at least 2, preferably at least 5 wt .-% and particularly preferably at least 10 wt .-% of monomers A having 17 to 21 carbon atoms in the unsaturated radical R ¹ , based on the total weight of the monomer mixture.

worin R Wasserstoff oder eine Methylgruppe, X¹ und X² unabhängig Sauerstoff oder eine Gruppe der Formel NR', worin R' Wasserstoff oder ein Rest mit 1 bis 6 Kohlenstoffatomen ist, mit der Maßgabe, dass mindestens einer der Gruppen X¹ und X² eine Gruppe der Formel NR' bedeutet, worin R' Wasserstoff oder ein Rest mit 1 bis 6 Kohlenstoffatomen darstellt, Z eine Verbindungsgruppe, und R² ein gesättigter Rest mit 9 bis 25 Kohlenstoffatomen ist.In addition to at least one of the monomers A described above, a monomer mixture according to the invention comprises at least one monomer B of the general formula (II)

wherein R is hydrogen or a methyl group, X ¹ and X ^{2 are} independently oxygen or a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, with the proviso that at least one of the groups X ¹ and X ² a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, Z is a linking group, and R ^{2 is} a saturated radical having 9 to 25 carbon atoms.

worin R Wasserstoff oder eine Methylgruppe, X¹ Sauerstoff oder eine Gruppe der Formel NR', worin R' Wasserstoff oder ein Rest mit 1 bis 6 Kohlenstoffatomen, Z eine Verbindungsgruppe, R' Wasserstoff oder ein Rest mit 1 bis 6 Kohlenstoffatomen und R² ein gesättigter Rest mit 9 bis 25 Kohlenstoffatomen ist.Preferably, the monomer mixture comprises at least one monomer B according to the general formula (IV)

wherein R is hydrogen or a methyl group, X ^{1 is} oxygen or a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, Z is a linking group, R 'is hydrogen or a radical having 1 to 6 carbon atoms and R ² saturated group having 9 to 25 carbon atoms.

The Groups R 'and Z shown in formula (II) have previously been related with the monomers A according to formula (I), so that for the description of the monomers B according to formula (II) to which reference is made.

The group R ² in formula (II) or (IV) is a saturated radical having 9 to 25 carbon atoms. These groups include in particular alkyl, cycloalkyl, alkoxy, cycloalkoxy, alkanoyl, alkoxycarbonyl and heteroaliphatic groups. Furthermore, these groups may have substituents, in particular halogen atoms or hydroxyl groups. The preferred groups include in particular alkyl groups, such as the nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, docosyl Group.

To the preferred monomers B according to formula (II) or (IV) include inter alia pentadecyloyloxy-2-ethyl (meth) acrylamide, Heptadecyloyloxy-2-ethyl (meth) acrylamide, (meth) acryloyloxy-2-ethyl-lauric acid amide, (Meth) acryloyloxy-2-ethyl-myristic acid amide, (meth) acryloyloxy-2-ethyl-palmitic acid amide, (Meth) acryloyloxy-2-ethyl-stearic acid amide, (meth) acryloyloxy-2-propyl-lauric acid amide, (meth) acryloyloxy-2-propyl-myristic acid amide, (Meth) acryloyloxy-2-propyl-palmitic acid amide and (meth) acryloyloxy-2-propyl-stearic acid amide.

Especially preferred monomers B according to formula (II) or (IV) include methacryloyloxy-2-ethyl-palmitic acid amide and methacryloyloxy-2-ethyl-stearic acid amide.

According to a particular modification of the present invention, monomers B according to formula (II) which have 15 or 17 carbon atoms in the radical R ² are preferably used.

Preferably, 2 or more monomers B of the formula (II) are used in the monomer mixture, which differ in the number of carbon atoms in the radical R ² . In this case, preference is given to mixtures which contain both monomers B according to formula (II) which have 15 and also 17 carbon atoms in the radical R ² . The weight ratio of the monomers B of the formula (II) having 15 carbon atoms in the saturated radical R ² to the monomers B of the formula (II) having 17 carbon atoms in the saturated radical R ² is preferably in the range of 100: 1 to 1:10, more preferably in the range of 10: 1 to 1: 2.

According to a particular embodiment of the present invention, the monomer mixture may have at least 0.5, preferably at least 1 wt .-% and particularly preferably at least 3 wt .-% of monomers B having 11 to 17 carbon atoms in the saturated radical R ² , based on the total weight the monomer mixture.

monomers B of formula (II) or (IV) may be similar Be prepared as the previously set forth monomers A according to formula (I), but with saturated fatty acids or fatty acid esters be used. Among the preferred fatty acids include including capric, lauric, myristic, Palmitic acid, margaric acid, arachidic acid, Behenic acid, lignoceric acid, cerotic acid and stearic acid. These acids can preferably also as esters of alcohols having 1 to 4 carbon atoms, for example as ethyl, propyl, butyl and especially methyl esters be used.

monomer mixtures the monomers A according to formula (I) and monomers B according to formula (II), can by Mixing of monomers A and monomers B can be obtained. Prefers these mixtures can still be obtained by that a fatty acid mixture or a fatty acid ester mixture, which unsaturated and saturated fatty acids or fatty acid esters, in the manner outlined above with an amine and then with a (meth) acrylate or reacted with a (meth) acrylamide having a hydroxy group in the alkyl radical becomes.

The Weight ratio of the monomers A to the monomers B is not critical in itself. Surprising advantages can be however, if the weight ratio of the monomers A to the monomers B in the range of 100: 1 to 1:10, preferably in the range of 10: 1 to 1: 3, and more preferably in the range of 3: 1 to 1: 1.

Next The monomers of the formulas (I) and (II) set forth above can be a Inventive monomer mixture further monomers which are copolymerizable with the monomers A and B.

To These copolymerizable monomers are monomers with an acid group, monomers comprising ester groups C, which differ from the monomers of the formulas I or II, and styrenic monomers.

Containing acid groups Monomers are compounds which are preferably free-radical allow the above-described monomers A and B copolymerize. These include, for example, monomers with a sulfonic acid group, such as vinylsulfonic acid; Monomers with a phosphonic acid group, such as vinylphosphonic and unsaturated Carboxylic acids, such as methacrylic acid, Acrylic acid, fumaric acid and maleic acid. Particularly preferred are methacrylic acid and acrylic acid. The acid group-containing monomers can be used individually or as a mixture of two, three or more acid group-containing monomers be used.

To belonging to the preferred ester groups comprising monomers C. in particular (meth) acrylates derived from the monomers A or B distinguish fumarates, maleates and / or vinyl acetate. The term (meth) acrylates includes methacrylates and acrylates as well as mixtures of both. These monomers are well known.

These include in particular (meth) acrylates having 1 to 6 carbons in the alkyl radical, which are derived from saturated alcohols, such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate , n-butyl (meth) acrylate, tert-butyl (meth) acrylate and pentyl (meth) acrylate, hexyl (meth) acrylate;
Cycloalkyl (meth) acrylates such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate; and
(Meth) acrylates derived from unsaturated alcohols, such as 2-propynyl (meth) acrylate, allyl (meth) acrylate and vinyl (meth) acrylate.

Especially Preference is given to using mixtures which are methacrylates and acrylates include. Thus, in particular mixtures of methyl methacrylate and 2 to 6 carbon acrylates such as ethyl acrylate, butyl acrylate and hexyl acrylate.

In addition, these comonomers include, for example, (meth) acrylates having at least 7 carbon atoms in the alkyl radical, which are derived from saturated alcohols, such as 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, 2-tert-butylheptyl (meth) acrylate, octyl (meth) acrylate, 3-iso-propylheptyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, 5-methylundecyl (meth) acrylate, dodecyl (meth) acrylate, 2-methyldodecyl (meth) acrylate, tridecyl (meth) acrylate, 5-methyltridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, 2-methylhexadecyl (meth) acrylate, heptadecyl ( meth) acrylate, 5-iso-propylheptadecyl (meth) acrylate, 4-tert-butyloctadecyl (meth) acrylate, 5-ethyloctadecyl (meth) acrylate, 3-iso-propyloctadecyl (meth) acrylate, octadecyl (meth) acrylate, Nonadecyl (meth) acrylate, eicosyl (meth) acrylate, cetyleicosyl (meth) acrylate, stearyl eicosyl (meth) acrylate, docosyl (meth) acrylate and / or eicosyl tetratriacontyl (meth) acrylate; Cycloalkyl (meth) acrylates, such as 3-vinylcyclohexyl (meth) acrylate, bornyl (meth) acrylate, cycloalkyl (meth) acrylates, such as 2,4,5-tri-t-butyl-3-vinylcyclohexyl (meth) acrylate, 2, 3,4,5-tetra-t-butylcyclohexyl (meth) acrylate; heterocyclic (meth) acrylates such as 2 (1-imidazolyl) ethyl (meth) acrylate, 2 (4-morpholinyl) ethyl (meth) acrylate and 1 (2-methacryloyloxyethyl) -2-pyrrolidone; Nitrites of (meth) acrylic acid and other nitrogen-containing methacrylates such as N- (methacryloyloxyethyl) diisobutylketimine, N- (methacryloyloxyethyl) dihexadecylketimine, methacryloylamidoacetonitrile, 2-methacryloyloxyethylmethylcyanamide, cyanomethylmethacrylate; Aryl (meth) acrylates, such as benzyl (meth) acrylate or phenyl (meth) acrylate, wherein the aryl radicals may each be unsubstituted or substituted up to four times; (Meth) acrylates having two or more (meth) acrylic groups, glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetra- and polyethylene glycol di (meth) acrylate 1,3-butanediol (meth) acrylate, 1,4-butanediol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerol di (meth) acrylate; Dimethacrylates of ethoxylated bisphenol A; (Meth) acrylates having three or more double bonds, such as. As glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and dipentaerythritol penta (meth) acrylate.

The monomers C comprising ester groups furthermore include vinyl esters, such as vinyl acetate;
Maleic acid derivatives, such as, for example, maleic anhydride, esters of maleic acid, for example dimethyl maleate, methylmaleic anhydride; and fumaric acid derivatives such as dimethyl fumarate.

A Another preferred group of comonomers are styrene monomers, such as for example, styrene, substituted styrenes having an alkyl substituent in the side chain, such. As α-methylstyrene and α-ethylstyrene, substituted Styrenes with an alkyl substituent on the ring, such as vinyltoluene and p-methylstyrene, halogenated styrenes, such as monochlorostyrenes, Dichlorostyrenes, tribromostyrenes and tetrabromostyrenes.

In addition to the monomers set out above, polymers according to the invention which are obtained by the polymerization of monomer mixtures may comprise further monomers. These include, for example, heterocyclic vinyl compounds such as 2-vinylpyridine, 3-vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4-vinylpyridine, 2,3-dimethyl-5-vinylpyridine, vinylpyrimidine, vinylpiperidine, 9-vinylcarbazole, 3-vinylcarbazole, 4-vinylcarbazole, 1-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinylpyrrolidone, 2-vinylpyrrolidone, N-vinylpyrrolidine, 3-vinylpyrrolidine, N-vinylcaprolactam, N-vinylbutyrolactam, vinyloxolane, vinylfuran, vinylthiophene, Vinyl thiolane, vinyl thiazoles and hydrogenated vinyl thiazoles, vinyloxazoles and hydrogenated vinyloxazoles;
Maleimide, methylmaleimide;
Vinyl and isoprenyl ethers; and
Vinyl halides such as vinyl chloride, vinyl fluoride, vinylidene chloride and vinylidene fluoride.

Preferred monomer mixtures of the present invention include
0.1 to 50 wt .-%, preferably 0.5 to 30 wt .-% of monomer A;
0.1 to 50% by weight, preferably 0.5 to 30% by weight of monomer B;
From 30 to 95% by weight, preferably from 40 to 90% by weight, of monomers having ester groups C;
0 to 10 wt .-%, preferably 1 to 8 wt .-% monomer with an acid group,
0 to 50 wt .-% of styrene monomers and
From 0 to 50% by weight of further comonomers, the data referring in each case to the total weight of the monomers.

The Inventive monomer mixtures are used in particular for the preparation or modification of polymers. The polymerization can be done by any known manner. These include in particular free-radical, cationic or anionic polymerization, although variants of these polymerization, such as ATRP (= atom transfer radical polymerization), NMP process (nitroxides Mediated Polymerization) or RAFT (= Reversible Addition Fragmentation Chain Transfer) can be used.

The aforementioned monomers or monomer mixtures can for example by solution polymerizations, bulk polymerizations or emulsion polymerizations are reacted, wherein surprising Benefits achieved by a radical emulsion polymerization can be.

Methods of emulsion polymerization include, inter alia Ullmann's Encyclopedia of Industrial Chemistry, Fifth Edition explained. In general, an aqueous phase is prepared for this purpose, which may comprise, in addition to water, customary additives, in particular emulsifiers and protective colloids for stabilizing the emulsion.

To This aqueous phase are then monomers added and polymerized in the aqueous phase. In the preparation of homogeneous polymer particles in this case a monomer mixture over a time interval can be added continuously or batchwise.

The emulsion polymerization can be carried out, for example, as a mini or as a microemulsion, which is closer in Chemistry and Technology of Emulsion Polymerization, AM van Herk (editor), Blackwell Publishing, Oxford 2005 and J. O'Donnell, EW Kaler, Macromolecular Rapid Communications 2007, 28 (14), 1445-1454 being represented. A miniemulsion is customary characterized by the use of costabilizers or swelling agents, many of which use long-chain alkanes or alkanols. The droplet size in miniemulsions is preferably in the range of 0.05 to 20 microns. The droplet size in the case of microemulsions is preferably in the range below 1 μm, whereby particles below a size of 50 nm can be obtained in this way. Microemulsions often use additional surfactants, for example hexanol or similar compounds.

The Dispersing the monomer-containing phase in the aqueous Phase can be done by known means. These include in particular mechanical methods and the use of ultrasound.

at The preparation of homogeneous emulsion polymers may preferably a monomer mixture are used, the 10 to 40 wt .-% monomers A according to formula (I).

at Preparation of core-shell polymers may be the composition of Monomermischung be changed gradually, before change the composition preferably the polymerization up to one Sales of at least 80 wt .-%, more preferably at least 95 wt .-%, each based on the total weight of the used Monomermischung, polymerized. The tracking of reaction progress The polymerization in each step can be carried out in a known manner, for example carried out gravimetrically or by gas chromatography.

The Monomer mixture for producing the core preferably comprises 50 to 100% by weight of (meth) acrylates, more preferably a mixture of acrylates and methacrylates is used. After the production the core can be grafted onto this, preferably a monomer mixture or polymerized onto the core, the 15 to 40 wt .-% monomers A according to formula (I).

The Emulsion polymerization is preferably carried out at a temperature in the Range from 0 to 120 ° C, more preferably in the range from 30 to 100 ° C performed. It has become Polymersiationstemperaturen in the range of greater 60 to less than 90 ° C, conveniently in the range of greater than 70 to less than 85 ° C, preferably in the range from greater than 75 to less than 85 ° C, proved to be particularly favorable.

The initiation of the polymerization takes place with the customary for the emulsion polymerization initiators. Suitable organic initiators are, for example, hydroperoxides, such as tert-butyl hydroperoxide or cumene hydroperoxide. Suitable inorganic initiators are hydrogen peroxide and the alkali metal and the ammonium salts of peroxydisulfuric, in particular ammonium, sodium and potassium peroxodisulfate. Suitable redox initiator systems are, for example, combinations of tertiary amines with peroxides or sodium disulfite and alkali metal and the ammonium salts of peroxodisulfuric acid, in particular sodium and potassium peroxodisulfate. Further details can be found in the specialist literature, in particular H. Rauch-Puntigam, Th. Völker, "Acrylic and Methacrylic Compounds", Springer, Heidelberg, 1967 or Kirk-Othmer, Encyclopedia of Chemical Technology, Vol. 1, pp. 386ff, J. Wiley, New York, 1978 be removed. In the context of the present invention, the use of organic and / or inorganic initiators is particularly preferred.

The mentioned initiators can both individually and in Mixture be used. They are preferably in a crowd from 0.05 to 3.0 wt .-%, based on the total weight of the monomers the respective stage used. It is also possible to prefer the polymerization with a mixture of different polymerization initiators different Half-life perform to the radical flow in the course the polymerization and at different polymerization temperatures to keep constant.

The stabilization of the approach is preferably carried out by means of emulsifiers and / or protective colloids. Preferably, the emulsion is stabilized by emulsifiers to obtain a low dispersion viscosity. The total amount of emulsifier is preferably 0.1 to 15 wt .-%, in particular 1 to 10 wt .-% and particularly preferably 2 to 5 wt .-%, based on the total weight of the monomers used. According to a particular aspect of the present invention, a portion of the emulsifiers may be present during the poly be added.

• – Alkylsulfate, vorzugsweise solche mit 8 bis 18 Kohlenstoffatomen im Alkylrest, Alkyl- und Alkylarylethersulfate mit 8 bis 18 Kohlenstoffatomen im Alkylrest und 1 bis 50 Ethylenoxideinheiten;
• – Sulfonate, vorzugsweise Alkylsulfonate mit 8 bis 18 Kohlenstoffatomen im Alkylrest, Alkylarylsulfonate mit 8 bis 18 Kohlenstoffatomen im Alkylrest, Ester und Halbester der Sulfobernsteinsäure mit einwertigen Alkoholen oder Alkylphenolen mit 4 bis 15 Kohlenstoffatomen im Alkylrest; gegebenenfalls können diese Alkohole oder Alkylphenole auch mit 1 bis 40 Ethylenoxideinheiten ethoxyliert sein;
• – Phosphorsäureteilester und deren Alkali- und Ammoniumsalze, vorzugsweise Alkyl- und Alkylarylphosphate mit 8 bis 20 Kohlenstoffatomen im Alkyl- bzw. Alkylarylrest und 1 bis 5 Ethylenoxideinheiten;
• – Alkylpolyglykolether, vorzugsweise mit 8 bis 20 Kohlenstoffatomen im Alkylrest und 8 bis 40 Ethylenoxideinheiten;
• – Alkylarylpolyglykolether, vorzugsweise mit 8 bis 20 Kohlenstoffatomen im Alkyl- bzw. Alkylarylrest und 8 bis 40 Ethylenoxideinheiten;
• – Ethylenoxid/Propylenoxid-Copolymere, vorzugsweise Blockcopolymere, günstigerweise mit 8 bis 40 Ethylenoxid- bzw. Propylenoxideinheiten.

Particularly suitable emulsifiers are anionic or nonionic emulsifiers or mixtures thereof, in particular

• Alkyl sulfates, preferably those having 8 to 18 carbon atoms in the alkyl radical, alkyl and alkylaryl ether sulfates having 8 to 18 carbon atoms in the alkyl radical and 1 to 50 ethylene oxide units;
• Sulfonates, preferably alkyl sulfonates having 8 to 18 carbon atoms in the alkyl radical, alkylaryl sulfonates having 8 to 18 carbon atoms in the alkyl radical, esters and half-esters of sulfosuccinic acid with monohydric alcohols or alkylphenols having 4 to 15 carbon atoms in the alkyl radical; optionally, these alcohols or alkylphenols may also be ethoxylated with 1 to 40 ethylene oxide units;
• - Phosphorsäureteilester and their alkali metal and ammonium salts, preferably alkyl and alkylaryl phosphates having 8 to 20 carbon atoms in the alkyl or alkylaryl radical and 1 to 5 ethylene oxide units;
• - Alkylpolyglykolether, preferably having 8 to 20 carbon atoms in the alkyl radical and 8 to 40 ethylene oxide units;
• - Alkylarylpolyglykolether, preferably having 8 to 20 carbon atoms in the alkyl or alkylaryl radical and 8 to 40 ethylene oxide units;
• Ethylene oxide / propylene oxide copolymers, preferably block copolymers, desirably with 8 to 40 ethylene oxide or propylene oxide units.

The particularly preferred anionic emulsifiers include, in particular, fatty alcohol ether sulfates, diisooctyl sulfosuccinate, lauryl sulfate, C15 paraffin sulfonate, these compounds generally being usable as alkali metal salt, in particular as sodium salt. These compounds can be obtained commercially K1 from the companies Cognis GmbH, Cytec Industries, Inc. and Bayer AG in particular under the trade names Disponil.RTM ^® FES 32, Aerosol OT ^® 75, Texapon.RTM ^® K1296 and Statexan ^®.

Useful nonionic emulsifiers include tert-octylphenol ethoxylate having 30 ethylene oxide units and fatty alcohol polyethylene glycol ethers preferably having 8 to 20 carbon atoms in the alkyl group and 8 to 40 ethylene oxide units. These emulsifiers are available under the Triton ^® X 305 (Fluka), Tergitol ^® 15-S-7 (Sigma-Aldrich Co.), Marlipal ^® 1618/25 (Sasol Germany) and Marlipal ^® O 13/400 (Sasol Germany) commercial tradenames available.

Prefers may be mixtures of anionic emulsifier and nonionic Emulsifier can be used. Appropriately, the Weight ratio of anionic emulsifier to nonionic Emulsifier in the range of 20: 1 to 1:20, preferably 2: 1 to 1:10 and more preferably 1: 1 to 1: 5. There are mixtures, a sulfate, in particular a fatty alcohol ether sulfate, a lauryl sulfate, or a sulfonate, in particular a diisooctyl sulfosuccinate or a paraffin sulfonate anionic emulsifier and an alkylphenol ethoxylate or a fatty alcohol polyethylene glycol ether, each preferred 8 to 20 carbon atoms in the alkyl radical and 8 to 40 ethylene oxide units have proven particularly useful as a nonionic emulsifier.

Possibly The emulsifiers can also be mixed with protective colloids be used. Suitable protective colloids include u. a. partially hydrolyzed Polyvinyl acetates, polyvinylpyrrolidones, carboxymethyl, methyl, Hydroxyethyl, hydroxypropyl cellulose, starches, proteins, Poly (meth) acrylic acid, poly (meth) acrylamide, polyvinylsulfonic acids, Melamine formaldehyde sulfonates, naphthalene formaldehyde sulfonates, styrene-maleic acid and vinyl ether maleic acid copolymers. If protective colloids are used, this is preferably done in an amount of 0.01 to 1.0 wt .-%, based on the total amount of the monomers. The Protective colloids can be used before the start of the polymerization be submitted or added. The initiator can be submitted or be dosed. Furthermore, it is also possible to have a Part of the initiator to submit and the remainder metered.

Prefers the polymerization is carried out by heating the batch to the polymerization temperature and Addition of the initiator, preferably in aqueous solution, started. The dosages of emulsifier and monomers can be carried out separately or as a mixture. At the dosage mixtures of emulsifier and monomer are operated in such a way that Emulsifier and monomer upstream of the polymerization reactor Mixers are premixed. Preference is given to the radicals of emulsifier and monomer, which were not submitted, after the start of the Polymerization added separately. Preferably with the dosage 15 to 35 minutes after the start of the polymerization to be started.

Preferred emulsion polymers having a high content of insoluble polymers can be obtained in the manner set forth above, the reaction parameters for obtaining a high molecular weight being known. Thus, in particular, the use of molecular weight regulators ver be canceled.

The Adjustment of the particle radii can, inter alia, over the proportion of emulsifiers are influenced. The higher this proportion, especially at the beginning of the polymerization, the more smaller particles are obtained.

The available according to the method described above Polymers, in particular the preferably available emulsion polymers represent a further subject of the present invention.

Preferably For example, the emulsion polymer may contain from 2 to 60% by weight, especially preferably 10 to 50 wt .-% and most preferably 20 to 40 Wt .-%, based on the weight of the emulsion polymer, which is soluble in tetrahydrofuran (THF) at 20 ° C is. To determine the soluble fraction is an under Oxygen exclusion dried sample of the polymer in one 200 times the amount of solvent, by weight of the sample, stored at 20 ° C for 4 h. To the exclusion of the oxygen, the sample may, for example, under nitrogen or be dried under vacuum. Then the solution becomes from the insoluble portion, for example by filtration separated. After evaporation of the solvent, the Weight of the residue determined. For example, a 0.5 g sample of a vacuum dried emulsion polymer in 150 ml of THF are stored for 4 hours.

According to one Preferred modification of the present invention may be an emulsion polymer a swelling of at least 1000%, more preferably at least 1400% and most preferably at least 1600% in tetrahydrofuran (THF) at 20 ° C. The upper limit of swelling is not critical per se, with the swelling preferably at most 5000%, more preferably at most 3000%, and most especially preferably at most 2500%. For determination the swelling becomes a dried under exclusion of oxygen sample of the emulsion polymer at 20 ° C for 4 hours stored in a 200-fold amount of THF. As a result, the sample swells on. The thus swollen sample is from the protruding Solvent separated. Subsequently, the Solvent removed from the sample. For example, can a majority of the solvent at room temperature (20 ° C) are evaporated. Solvent residues can in the drying cabinet (140 ° C), this being in the Generally succeed within 1 hour. From the weight of through the sample of solvent and weight The dry sample results in the swelling. Furthermore results from the difference in the weight of the sample before the swelling experiment and the weight of the dried sample after the swelling experiment the soluble portion of the emulsion polymer.

Of the Particle radius of the emulsion polymers can be in a wide range lie. Thus, in particular emulsion polymers with a Particle radius in the range of 1 to 100 nm, preferably 5 to 59 nm be used. According to another aspect In the present invention, the radius of the particles is preferably in the range of 60 nm to 500 nm, more preferably 70 to 150 nm and most preferably 75 to 100 nm. The radius of the particles can be determined by PCS (Photon Correlation Spectroscopy) the data given refer to the d50 value (50% the particles are smaller, 50% are larger). For this For example, a Beckman Coulter N5 submicron particle size Analyzer can be used.

wobei x_n für den Massebruch (Gew.-%/100) des Monomeren n steht und Tg_n die Glasübergangstemperatur in Kelvin des Homopolymeren des Monomeren n bezeichnet. Weitere hilfreiche Hinweise kann der Fachmann dem Polymer Handbook 2nd Edition, J. Wiley & Sons, New York (1975) entnehmen, welche Tg-Werte für die geläufigsten Homopolymerisate angibt. Hierbei kann das Polymere ein oder mehrere unterschiedliche Glasübergangstemperaturen aufweisen. Diese Angaben gelten daher für ein Segment, das durch Polymerisation einer erfindungsgemäßen Monomermischung erhältlich ist.The glass transition temperature of the polymer of the invention is preferably in the range of -30 ° C to 70 ° C, more preferably in the range of -20 to 40 ° C and most preferably in the range of 0 to 25 ° C. The glass transition temperature can be influenced by the type and proportion of monomers used to make the polymer. In this case, the glass transition temperature Tg of the polymer can be determined in a known manner by means of differential scanning calorimetry (DSC). Furthermore, the glass transition temperature Tg can also be calculated approximately in advance by means of the Fox equation. To Fox TG, Bull. Physics Soc. 1, 3, page 123 (1956) applies:

where x _n is the mass fraction (wt .-% / 100) of monomer n and Tg _{n is} the glass transition temperature in Kelvin of the homopolymer of the monomer n denotes. Other helpful hints may be the Specialist in Polymer Handbook 2nd Edition, J. Wiley & Sons, New York (1975) which indicates Tg values for the most common homopolymers. In this case, the polymer may have one or more different glass transition temperatures. These data therefore apply to a segment which is obtainable by polymerization of a monomer mixture according to the invention.

The Architecture of the polymer is for many applications and Properties not critical. Accordingly, the Polymers, in particular the emulsion polymers random copolymers, Gradient copolymers, block copolymers and / or graft copolymers represent. Block copolymers or gradient copolymers can be For example, obtained by the monomer composition during the chain growth changed discontinuously. According to one preferred aspect of the present invention is the emulsion polymer a random copolymer in which the monomer composition is over the polymerization is substantially constant. Because the monomers however, may have different copolymerization parameters, can the exact composition across the polymer chain of the polymer vary.

The Polymer may be a homogeneous polymer, for example in an aqueous dispersion particles with an equal forming permanent composition. In this case, the polymer, which is preferably an emulsion polymer, from one or consist of several segments by polymerization of the invention Monomer mixtures are available.

According to one In another embodiment, the emulsion polymer may include Core-shell polymer, which is one, two, three or more Can have shells. Here forms the segment, which by Polymerization of the monomer mixture according to the invention is available, preferably the outermost shell of the core-shell polymer. The shell can be over covalent Bindings connected to the core or the inner shells. Furthermore, the shell can also be applied to the core or an inner shell be polymerized. In this embodiment, the Segment, which by polymerization of the monomer mixture according to the invention is available, often by suitable solvents separated from the core and isolated.

Preferably can the weight ratio of segment, which by Polymerization of the monomer mixture according to the invention is available to core in the range of 2: 1 to 1: 6, especially preferably 1: 1 to 1: 3.

Of the Core may preferably be formed from polymers containing 50 to 100 wt .-%, preferably 60 to 90 wt .-% comprises units which derived from (meth) acrylates. Preferred here are esters the (meth) acrylic acid whose alcohol residue is preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms and most preferably comprises 1 to 10 carbon atoms. These include in particular (meth) acrylates, which differ from derived saturated alcohols, such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate and pentyl (meth) acrylate, hexyl (meth) acrylate.

According to one particular embodiment of the present invention can for the production of the core, a mixture containing methacrylates and Acrylates includes. Thus, in particular mixtures of Methyl methacrylate and acrylates of 2 to 6 carbons, such as ethyl acrylate, Butyl acrylate and hexyl acrylate can be used.

About that In addition, the polymers of the core may have the abovementioned Comonomers include. According to a preferred modification the core can be networked. This networking can be through the use of monomers having two, three or more radically polymerizable Double bonds are achieved.

The shell of an emulsion polymer of the present invention obtainable by polymerization of a monomer mixture according to the invention may preferably comprise 15 to 50% by weight of units derived from monomers A of formula (I) having at least one double bond in the radical R ¹ .

According to one In particular, the core may preferably have a glass transition temperature in the range of -30 to 200 ° C, particularly preferred in the range of -20 to 150 ° C have. The shell the emulsion polymer of the invention, preferably by polymerization of the monomer mixture according to the invention is available, may preferably have a glass transition temperature in the range of -30 ° C to 70 ° C especially preferably in the range of -20 to 40 ° C and completely particularly preferably in the range of 0 to 25 ° C. According to a particular aspect of the present Invention can make the glass transition temperature of the core larger its than the glass transition temperature of the shell. expedient the glass transition temperature of the core can be at least 10 ° C, preferably at least 20 ° C above the glass transition temperature of Shell lie.

The iodine value of the polymers according to the invention is preferably in the range from 1 to 150 g of iodine per 100 g of polymer, more preferably in the range of 2 to 100 g of iodine per 100 g of polymer and most preferably 5 to 40 g of iodine per 100 g of polymer, measured according to DIN 53241-1 , In particular, the iodine value can also be measured by means of a dispersion according to the invention.

Suitably, the polymer may have an acid number in the range of 0.1 to 40 mg KOH / g, preferably 1 to 20 mg KOH / g and most preferably in the range of 2 to 10 mg KOH / g. The acid number can according to DIN EN ISO 2114 also be determined by means of a dispersion.

The hydroxyl number of the polymer may preferably be in the range from 0 to 200 mg KOH / g, more preferably 1 to 100 mg KOH / g and most preferably in the range from 3 to 50 mg KOH / g. The hydroxyl number can according to DIN EN ISO 4629 also be determined by means of a dispersion.

The by polymerization of the monomer mixture according to the invention available polymers can be isolated. According to a particular embodiment of the present Invention can be obtained by emulsion polymerization Dispersions are used as such as a coating agent.

Accordingly, aqueous dispersions are a further object of the present invention. The aqueous dispersions preferably have a solids content in the range from 10 to 70% by weight, particularly preferably from 20 to 60% by weight. The dispersion may expediently have a dynamic viscosity in the range from 0.1 to 180 mPas, preferably from 1 to 80 mPas and very particularly preferably from 10 to 50 mPas, measured according to DIN EN ISO 2555 at 25 ° C (Brookfield).

Farther can the aqueous according to the invention Dispersions in known manner with additives or other components provided to the properties of the coating composition to adapt to specific requirements. These additives include in particular drying aids, so-called siccatives, flow improvers, Pigments and dyes.

Preferably, the coating compositions of the invention have a minimum film-forming temperature of at most 50 ° C, more preferably at most 35 ° C and most preferably at most 25 ° C, according to DIN ISO 2115 can be measured.

The need coating material according to the invention no siccative, but this is an optional ingredient in may be included in the compositions. Especially Preferably, siccatives can be added to the aqueous dispersions become. These include in particular organometallic compounds, For example, metallic soaps of transition metals, such as for example, cobalt, manganese, lead, zirconium; Alkali or alkaline earth metals, such as lithium, potassium and calcium. Exemplary For example, cobalt naphthalate and cobalt acetate mentioned. The siccatives can be used individually or as a mixture, in particular mixtures, the cobalt, zirconium and lithium salts contain, are particularly preferred.

The aqueous dispersions of the present invention used in particular as a coating agent or as an additive become. These include in particular paints, impregnating agents, Adhesives and / or primers. Particularly preferred the aqueous dispersions for the production of paints or Impregnating agents for applications on wood and / or Serve metal.

The from the coating compositions of the invention available coatings show a high solvent resistance, in particular, only small amounts by solvent be released from the coating. Preferred coatings show in particular towards methyl isobutyl ketone (MIBK) a high resistance. So is the weight loss preferably not more than 50 after treatment with MIBK Wt .-%, preferably at most 35 wt .-%. The recording MIBK is preferably at most 300% by weight, particularly preferably at most 250% by weight, based on the Weight of the coating used. These values are at a Temperature of about 25 ° C and a contact time of at least 4 Hours measured, leaving a completely dried coating is measured. In this case, the drying takes place in the presence of oxygen, For example, air instead to allow networking.

The coatings obtained from the coating compositions of the invention show high mechanical resistance. The pendulum hardness is preferably at least 15 s, preferably at least 25 s, measured according to DIN ISO 1522.

The dispersions according to the invention can also be used in addition to the emulsion polymers parts included. These include in particular alkyd resins. Alkyd resins have long been known, and are generally understood to mean resins obtained by condensation of polybasic carboxylic acids and polyhydric alcohols, these compounds generally having long-chain alcohols (fatty alcohols), fatty acids or fatty acid-containing compounds, for example fats or oils are modified ( DIN 55945; 1968 ). For example, alkyd resins are used in Ullmann's Encyclopedia of Industrial Chemistry 5th edition set out on CD-ROM. In addition to these classic alkyd resins and resins can be used, which have similar properties. These resins are also characterized by a high content of groups derived from the long-chain alcohols (fatty alcohols), fatty acids or fatty acid-containing compounds described above, for example, fats or oils. However, these derivatives do not necessarily have polybasic carboxylic acids but can be obtained, for example, by reacting polyols with isocyanates. The usable alkyd resins may preferably be mixed or diluted with water.

For example, it is preferable to use alkyd resins modified with polymers obtainable by radical polymerization. Such resins are inter alia from the publications US 5,538,760 . US 6,369,135 and DE-A-199 57 161 known.

According to the documents US 5,538,760 and US 6,369,135 For example, modified alkyd resins can be obtained, inter alia, by polymerizing a monomer mixture in the presence of an alkyd resin. The weight ratio of monomer mixture to alkyd resin is preferably in the range from 100: 1 to 1: 4, preferably 5: 1 to 1: 1.

Particularly useful are, inter alia, in DE-A-199 57 161 described acrylate-modified alkyd resins. These alkyd resins have, besides an alkyd core, groups obtained by polymerization of (meth) acrylates.

Furthermore, alkyd resins are preferred, which according to the document US 5,096,959 are available. These alkyd resins are modified by cycloaliphatic polycarboxylic acid, with cyclohexanedicarboxylic acids and cyclopentanedicarboxylic acids in particular being suitable for the modification.

In addition, alkyd resins modified with polyethylene glycol can be used. A large number of patents describe the preparation of water-emulsifiable alkyd resins by modification with polyethylene glycol (PEG). In most processes, about 10 to 30% PEG are incorporated directly into the alkyd resin by transesterification or esterification (see, inter alia, US Pat U.S. Pat. No. 2,634,245 ; 2,853,459 ; 3,133,032 ; 3,223,659 ; 3,379,548 ; 3,437,615 ; 3,437,618 ; 10 3,442,835 ; 3,457,206 ; 3,639,315 ; the German Offenlegungsschrift 14 95 032 or the British Patent Publication Nos. 1,038,696 and no. 1,044,821 ).

Preferred alkyd resins which have been modified with polyethylene glycol are inter alia from the document EP-A-0 029 145 known. According to this document, a polyethylene glycol can first be reacted with epoxide-containing carboxylic acid. The reaction product thus obtained can then be used in the reaction mixture for the preparation of the alkyd resin. Preferred polyethylene glycols for modifying the alkyd resins have, for example, a number average molecular weight of 500 to 5000 g / mol.

Especially preferred polyethylene glycol modified alkyd resins be further modified with copolymers prepared by polymerization of methacrylic acid, unsaturated fatty acids and vinyl and / or vinylidene compounds are available. According to a particular aspect of the present Invention, these alkyd resins also with copolymers be modified by the inventive Monomer mixtures are available.

Also useful are alkyd resins modified with urethane groups. Such alkyd resins are inter alia in WO 2006/092211 and EP-A-1 533 342 explained.

Farther can the monomer mixtures of the invention also be used for the modification of alkyd resins.

following The present invention is intended to be illustrated by way of example and comparative examples be explained in more detail, without thereby a Restriction is to take place.

Example 1 (Preparation of a mixture of methacryloyloxy-2-ethyl-fatty acid amides)

In a four-necked round bottom flask equipped with a saber stirrer with mixing sleeve and stirring motor, nitrogen inlet, Equipped with a sump thermometer and a distillation bridge 206.3 g (0.70 mol) of fatty acid methyl ester mixture, 42.8 g (0.70 mol) of ethanolamine and 0.27 g (0.26%) submitted LiOH. The fatty acid methyl ester mixture comprised 6% by weight of saturated C12 to C16 fatty acid methyl ester, 2.5% by weight saturated C17 to C20 fatty acid methyl ester, 52 wt .-% monounsaturated C18 fatty acid methyl ester, 1.5% by weight monounsaturated C20 to C24 fatty acid methyl ester, 36 wt .-% polyunsaturated C18 fatty acid methyl ester, 2 wt .-% polyunsaturated C20 to C24 fatty acid methyl ester.

The Reaction mixture was heated to 150 ° C. Within After 2 h, 19.5 ml of methanol were distilled off. The obtained reaction product contained 86.5% fatty acid ethanolamides. The resulting reaction mixture was further processed without purification.

To the cooling was 1919 g (19.2 mol) of methyl methacrylate, 3.1 g LiOH and an inhibitor mixture consisting of 500 ppm hydroquinone monomethyl ether and 500 ppm phenothiazine added.

Under The reaction apparatus was stirred for 10 minutes with nitrogen rinsed. Thereafter, the reaction mixture was heated to boiling. The methyl methacrylate / methanol azeotrope was separated and then the head temperature gradually increased to 100 ° C. To Upon completion of the reaction, the reaction mixture was at about 70 ° C cooled and filtered.

At the Rotary evaporator became excess methylmethacrylate separated. It could be obtained 370 g of product.

Example 2

A obtained according to Example 1 monomer mixture, which various methacryloyloxy-2-ethyl-fatty acid amides included, was used to prepare a polymer dispersion.

First In a 2 l PE beaker, 180 g of butyl acrylate (BA), 156 g Methyl methacrylate (MMA), 60 g methacryloyloxy-2-ethyl-fatty acid amide mixture, 4 g of methacrylic acid (MAS), 1.2 g of ammonium peroxodisulfate (APS), 12.0 g of Disponil FES 32 (30%) and 359.18 g of water by means of Ultra-Turrax emulsified for 3 minutes at 4000 rpm.

In a 2 l glass reactor, which are tempered with a water bath could and was equipped with a paddle stirrer 230 g of water and 0.3 g of Disponil FES 32 (30% strength) initially charged, at 80 ° C. heated and dissolved with 0.3 g of ammonium peroxodisulfate (APS) in 10 g of water. 5 minutes after the APS addition was added the previously prepared emulsion within 240 minutes (interval: 3 minutes feed, 4 minutes break, 237 minutes remaining feed) added.

To Inlet end was stirred for 1 hr. At 80 ° C. It was then cooled to room temperature and the dispersion over Filtered VA screen mesh with 0.09 mm mesh size.

The produced emulsion had a solids content of 40 ± 1%, a pH of 5.6, a viscosity of 37 mPas and an r _N5 value of 70-75 nm.

The Properties of the coating composition thus obtained were determined examined by different methods. These were dried on Films tests for solvent resistance, the water absorption and hardness performed.

The Determination of solvent resistance was carried out using methyl isobutyl ketone (MIBK), taking a sample was swollen with MIBK at room temperature for 4 hours. Subsequently the sample was taken out of the solvent and excess Solvent removed. Subsequently, the Sample dried at 140 ° C for 1 hour. From the weight loss the proportion removed by the solvent is calculated the sample.

Of the Weight loss in ethanol reported in Table 1 became similar the experimental description set out above, but using determined by ethanol as a solvent.

to Determination of water absorption can be a test specimen untreated solid pine wood (dimensions: 45-50 mm × 45-50 mm × 17 mm). The test piece was coated and at room temperature given in water, leaving only the coated area in contact with water. From the weight gain of the specimen the water absorption is calculated.

The results obtained are shown in Table 1. Results of the obtained coating according to furniture test DIN 68861-1 are listed in Table 2.

Comparative Examples 1 and 2

To the Comparison, commercially available alkyd resins were investigated, wherein as Comparative Example 1 a commercially available from the company. Worlée under the name E150W available alkyd resin and was examined as Comparative Example 2 Xyladecor, which of the company ICI is sold commercially. The results obtained are set forth in Table 1.

Comparative Example 3

First In a 2 liter PE beaker, 206.8 g of butyl acrylate (BA), 165.2 g methyl methacrylate (MMA), 4 g methacrylic acid (MAS), 24 g acetoacetoxyethyl methacrylate (AAEMA), 1.2 g ammonium peroxodisulfate (APS), 12.0 g of Disponil FES 32 (30%) and 359.18 g of water by means of Ultra-Turrax emulsified for 3 minutes at 4000 rpm.

In a 2 l glass reactor, which are tempered with a water bath could and was equipped with a paddle stirrer 230 g of water and 0.3 g of Disponil FES 32 (30% strength) initially charged, at 80 ° C. heated and dissolved with 0.3 g of ammonium peroxodisulfate (APS) in 10 g of water. 5 minutes after the APS addition was added the previously prepared emulsion within 240 minutes (interval: 3 minutes feed, 4 minutes break, 237 minutes remaining feed) added.

To Inlet end was stirred for 1 hr. At 80 ° C. It was then cooled to room temperature and the dispersion over Filtered VA screen mesh with 0.09 mm mesh size.

The dispersions were equimolar to 6 wt.% AAEMA crosslinked with adipic dihydrazide (ADH). To this was added 100 g of dispersion with 6.54 g of 15% strength ADH solution with stirring and stirred for 30 min. The dried films were subjected to solvent resistance, water absorption and scratch resistance tests. Table 1: Results of property studies Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Pendulum hardness [s] 36.4 13.3 12.6 21.7 pencil hardness 3H <6B B - Weight loss in MIBK [%] 9.7 47.7 23.5 13.6 Weight loss in ethanol [%] 11.0 - 24.0 14.2 Water absorption after 24 h 9.7% 45.5% 25.2% 17.2% Table 2: Furniture test according to DIN 68861-1 Example 2 Comparative Example 3 Furniture test NH ₃ (10%) 1 h 3 1 16 h 3 1 Furniture test EtOH (48%) 1 h 5 2 16 h 4 1 Furniture test HOAc (15%) 1 h 5 5 16 h 4 1

The furniture test according to 68861-1 shows that a dispersion according to the invention leads to a coating which is very stable to a large number of different solvents. While the uncrosslinked polymer shows extremely low stability to ethanol, a coating according to the invention is stable to bases, acids and a polar solvent.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

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Claims (23)

Monomer mixture comprising at least one monomer A of the general formula (I)

wherein R is hydrogen or a methyl group, X ¹ and X ^{2 are} independently oxygen or a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, with the proviso that at least one of the groups X ¹ and X ² a group of the formula NR ', in which R' is hydrogen or a radical having 1 to 6 carbon atoms, Z is a connecting group, and R ^{1 is} an unsaturated radical having 9 to 25 carbon atoms, and at least one monomer B of the general formula (II) .

wherein R is hydrogen or a methyl group, X ¹ and X ^{2 are} independently oxygen or a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, with the proviso that at least one of the groups X ¹ and X ² a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, Z is a linking group, and R ^{2 is} a saturated radical having 9 to 25 carbon atoms. Monomer mixture according to claim 1, characterized in that the weight ratio the monomers A to the monomers B in the range of 100: 1 to 1:10 lies. Monomer mixture according to claim 1 or 2, characterized in that the monomers A according to formula (I) have an iodine value in the range of 50 to 300 g iodine / 100 g. Monomer mixture according to at least one of the preceding claims, characterized in that the monomer mixture comprises at least one monomer A of the general formula (III)

wherein R is hydrogen or a methyl group, X ^{1 is} oxygen or a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, Z is a linking group, R ^'is hydrogen or a radical having 1 to 6 carbon atoms and R ¹ is unsaturated radical having 9 to 25 carbon atoms, and at least one monomer B of the general formula (IV),

wherein R is hydrogen or a methyl group, X ^{1 is} oxygen or a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, Z is a linking group, R is hydrogen or a radical having 1 to 6 carbon atoms and R ^{2 is} a saturated The radical having 9 to 25 carbon atoms is included. Monomer mixture according to at least one of the preceding claims, characterized in that at least a part of the monomers A according to formula (I) has exactly one double bond in the unsaturated radical R ¹ . Monomer mixture according to at least one of the preceding claims, characterized gekennzeich net, that at least part of the monomers A according to formula (I) has two or more double bonds in the unsaturated radical R ¹ . Monomer mixture according to at least one of the preceding claims, characterized in that the weight ratio of the monomers A according to formula (I), which have exactly one double bond in the unsaturated radical R ¹ , to the monomers A according to formula (I), the two or more double bond in unsaturated radical R ^{1 is} in the range of 10: 1 to 1: 5. Monomer mixture according to at least one of the preceding claims, characterized in that the monomer mixture has at least 5 wt .-% of monomers A having 17 to 21 carbon atoms in the unsaturated radical R ¹ . Monomer mixture according to at least one of the preceding claims, characterized in that the monomer mixture has at least 1 wt .-% of monomers B having 11 to 17 carbon atoms in the saturated radical R ² . Monomer mixture according to at least one of the preceding claims, characterized in that the monomer mixture has monomers which react with the monomers A and B are copolymerizable. Monomer mixture according to claim 10, characterized in that the monomer mixture at least a monomer having an acid group. Monomer mixture according to claim 10 or 11, characterized in that the monomer mixture ester groups comprehensive monomers C, which are different from the monomers of the formulas I or II differ. Monomer mixture according to claim 12, characterized in that the monomer mixture comprises (meth) acrylates, Fumarates, maleates and / or vinyl acetate. Monomer mixture according to at least one of claims 10 to 13, characterized the monomer mixture comprises styrene monomers. Monomer mixture according to at least one of the preceding claims, characterized that the monomer mixture From 0.1 to 50% by weight of monomer A, 0.1 up to 50% by weight of monomer B, 30 to 95 wt .-% ester groups comprehensive Monomer C, 0 to 10% by weight of monomer with an acid group, 0 to 50 wt .-% styrene monomers and 0 to 50 wt .-% more comoners includes. Monomer mixture according to at least one of the preceding claims, characterized that the monomer mixture From 0.5 to 30% by weight of monomer A, 0.5 up to 30% by weight of monomer B, 40 to 90 wt .-% ester groups comprehensive Monomer C, 1 to 8% by weight of monomer with an acid group, 0 to 50 wt .-% styrene monomers and 0 to 50 wt .-% more comoners includes. Polymer comprising repeating units derived from a monomer mixture according to at least one of claims 1 to 16. Polymer according to claim 17, characterized characterized in that the polymer has a glass transition temperature ranging from -20 to 40 ° C. A polymer according to claim 17 or 18, characterized in that the polymer is an emulsion polymer is. Composition for producing a coating, characterized in that the composition is a polymer according to at least one of claims 17 to 19. Composition for producing a coating, characterized in that the composition comprises an alkyd resin. Process for the preparation of a monomer mixture according to at least one of the claims 1 to 16, characterized in that a fatty acid ester mixture reacted with an amine and then the resulting amide react with a (meth) acrylate and / or (meth) acrylic acid leaves. A method according to claim 22, characterized characterized in that the reaction of the resulting amide with a (Meth) acrylate in the presence of a base.