WO2012004160A1 - Composition for producing polymers, (meth)acrylic polymer, coating agent, and coating - Google Patents

Abstract

The invention relates to a composition for producing polymers comprising at least one monomer and at least one radical starter, wherein the radical starter is an azo compound, at least one monomer is an amide or an amide monomer, and at least one monomer is a (meth)acrylic monomer comprising at least one C-C double bond and 8 to 40 carbon atoms in the alkyl radical. The invention further relates to a (meth)acrylic polymer that can be obtained from the previously described composition, and to a coating agent. The invention further relates to a coating.

Description

 Composition for the production of polymers, (meth) acrylic polymer, coating agent and coating

The present invention relates to a composition for producing polymers and a (meth) acrylic polymer obtainable from the composition. In addition, the present invention is directed to a

Process for the preparation of polymers

Coating agent and a thereby obtainable

Coating.

Coating agents, in particular paints, have been produced synthetically for a long time. An important group of these agents is based on aqueous dispersions, many times

Include (meth) acrylate polymers. For example, the publication DE-A-41 05 134 describes aqueous dispersions which contain alkyl methacrylates as binders. Furthermore, such paints from US 5,750,751, EP-A-1 044 993, WO

2006/013061 and WO 2008/094503 known.

The coating compositions described above already show a good property spectrum. However, there is a permanent need to improve this property spectrum.

A particular disadvantage is that the previously stated

 Coating means partially insufficient for advanced claims processability. Accordingly, organic solvents must be added to the coating agents described in US 5,750,751. These

Solvents are for reasons of environmental protection too

avoid. An improvement in this regard is achieved by the teaching of document EP-A-1 044 993. This document

describes aqueous dispersions based on

(Metha) crylates. 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 which are particularly broad

Have 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, document WO 2006/013061 describes

Dispersions comprising particles based on (meth) acrylates. The ones used to make the particles

Monomer mixtures include (meth) acrylates which are characterized by

unsaturated fatty acids have been modified. Disadvantages of the dispersions described in WO 2006/013061 are

in particular their complex production and the high proportion of residual monomers. Furthermore, the

 Minimum film-forming temperatures are probably very high, since the coating compositions are described as microgels according to WO 2006/013061.

The set forth in WO 2008/094503

 Coating compositions have a very high

Minimum film forming temperature, based on the hardness of the coatings that can be obtained from these coating compositions.

In view of the state of the art, it is an object of the present invention to provide compositions which have become excellent polymers

Process properties. These properties include in particular features caused by coating agents and coatings consisting of the coating agents

are available, apparently.

In particular, the compositions should become

Dispersions or polymers, for example

Emulsion polymers, which can process a

have low residual monomer content.

Furthermore, it was therefore an object of the present

Invention to provide a coating agent which has a particularly long shelf life and durability. Furthermore, the hardness of the coatings obtainable from the coating compositions should be able to be varied over a wide range. In particular, should

particularly hard, scratch-resistant coatings can be obtained.

Another object is to see polymers for

To make available by their use

 Coating agents without volatile organic solvents are available. The from the aqueous dispersions

available coatings should have a high

 Weathering resistance, in particular have a high UV resistance. In addition, the films obtainable from the aqueous dispersions should have a low tackiness after a short time.

Furthermore, the from the coating agents

available coatings a high chemical resistance demonstrate. Here, a high stability compared to many different solvents and to bases and acids should be achieved. In particular, a very good resistance to methyl isobutyl ketone (MIBK) should be given.

The polymers and coating compositions obtainable from the compositions should in particular be a good one

Processability, which is particularly clear by a low minimum film-forming temperature, without thereby affecting the mechanical properties or the

Chemical resistance of the coatings obtainable from the coatings is adversely affected.

Another task can be seen in

To provide compositions for the production of polymers, (meth) polymers and coating compositions, which can be obtained very inexpensively and on an industrial scale.

These are solved as well as others not explicitly mentioned

Tasks, however, which are readily derivable or deducible from the contexts discussed hereinabove, by a composition for the manufacture of

Polymers with all features of patent claim 1.

Advantageous modifications of the invention

 Compositions are provided in subclaims under protection. With regard to a (meth) acrylic polymer, a process for producing polymers, a

Coating agent and a coating provide the claims 10, 12, 13 and 15, a solution to the underlying problems.

Accordingly, the subject of the present invention is a composition for the preparation of polymers at least one monomer and at least one radical initiator, which is characterized in that the radical initiator is an azo compound, at least one monomer is an amide or an amine monomer, and at least one monomer

Is (meth) acrylic monomer having in the alkyl group at least one C-C double bond and 8 to 40 carbon atoms.

Furthermore, the measures according to the invention make it possible, inter alia, to achieve the following advantages:

The compositions according to the invention can be added

Polymers, coating agents and coatings

process, which have a very low residual monomer content.

The hardness of the coatings consisting of inventive

Coating agents are available, which in turn are based on the polymers or compositions can be varied over a wide range. Surprisingly

In particular, mechanically stable coatings are obtained, which are characterized by a high elongation at break and / or a high tensile strength.

Furthermore, coatings that come from the

coating compositions according to the invention are available, based on the hardness and chemical resistance, a relatively low brittleness.

According to a preferred modification, in particular particularly hard, scratch-resistant coatings can be obtained according to the invention. From the coating agents of the The present invention obtainable coatings show a surprisingly high solvent resistance, which is particularly evident in experiments with methyl isobutyl ketone (MIBK), ammonia solutions or ethanol. Thus, the coatings obtained, in particular in tests according to the furniture test DIN 68861-1 an excellent classification.

The polymers obtainable from the compositions and

Coating agents show in particular a good

Processability, in particular by a low

Minimum film-forming temperature is clear, without affecting the mechanical properties or the

Chemical resistance of the coating agents

available coatings is adversely affected. With comparable chemical resistance or with comparable pendulum hardness of the coatings obtainable from the coatings or polymers coatings therefore show the

Coating agent or the polymers of the present

Invention a particularly low

Minimum film formation temperature. At comparable

 Minimum film-forming temperature of the coating compositions show the coatings obtainable from these improved chemical resistance and increased pendulum hardness.

Coating compositions using the

Compositions according to the invention are obtainable,

generally do not require volatile organic compounds

Solvent. In addition, the present invention

Coating agents a high storage stability, a high durability and a very good shelf life.

In particular, hardly any aggregate formation occurs. In relation to the performance show the

Coating an improved environmental impact. Preferred embodiments hardly show any release of organic compounds, in particular solvents, into the atmosphere. Furthermore, the coating compositions have an extremely low residual monomer content.

From the coating compositions of the invention

available coatings show a high

Weather resistance, in particular a high UV resistance. Furthermore, those from the

 Coating available films after a short time on a low stickiness.

The compositions, polymers and

 Coating agents can be inexpensively in large

Create scale. The coating compositions of the invention are environmentally friendly and safe and without large

Effort is processed and produced. Here, the coating compositions of the invention show a very high shear stability.

The composition according to the invention for the preparation of polymers comprises at least one (meth) acrylic monomer which has at least one double bond in the alkyl radical and 8 to 40

Having carbon atoms.

(Meth) acrylic monomers which in the alkyl radical at least one

Having double bond and having from 8 to 40 carbon atoms are esters or amides of (meth) acrylic acid whose alkyl radical has at least one carbon-carbon double bond and 8 to 40 carbon atoms. The spelling (Meth) acrylic acid means methacrylic acid and acrylic acid and mixtures thereof. The alkyl or alcohol or amide radical may preferably have 10 to 30 and more preferably 12 to 20 carbon atoms, this radical may include heteroatoms, in particular oxygen, nitrogen or sulfur atoms. The alkyl group may have one, two, three or more carbon-carbon double bonds. The

Polymerization conditions in which the (meth) acrylate polymer is prepared, are preferably chosen so that the largest possible proportion of the double bonds of the alkyl radical is maintained in the polymerization. This can be done for example by steric hindrance of the double bonds contained in the alcohol radical. Further points

at least a part, preferably all of the

Double bonds, which are contained in the alkyl radical of the (meth) acrylic monomer, a lower reactivity in a

radical polymerization as a (meth) acrylic group, so that in the alkyl radical preferably no further

 (Meth) acrylic groups are included.

The iodine value of the (meth) acrylic monomers to be used for the preparation of the (meth) acrylic polymers which are in the alkyl radical

has at least one double bond and 8 to 40 carbon atoms, is preferably at least 50, more preferably at least 100 and most preferably

at least 125 g of iodine / 100 g of (meth) acrylic monomer.

Such (meth) acrylic monomers generally correspond to the formula (I)

wherein the radical R is hydrogen or methyl, X

independently oxygen or a group of the formula NR ', in which R' is hydrogen or a radical having 1 to 6 carbon atoms, and R ¹ denotes a linear or branched radical having 8 to 40, preferably 10 to 30 and particularly preferably 12 to 20 carbon atoms, which has at least one CC double bond.

(Meth) acrylic monomers which in the alkyl radical at least one

Have double bond and 8 to 40 carbon atoms, for example, by esterification of (meth) acrylic acid,

Reaction of (meth) acryloyl halides and / or

(Meth) acrylic anhydride or transesterification of (meth) acrylates with alcohols containing at least one

Having double bond and 8 to 40 carbon atoms.

 Accordingly, (meth) acrylamides can be obtained by reaction with an amine. These reactions are

for example, in Ullmann's Encyclopedia of Industrial

Chemistry 5th edition on CD-ROM or F.-B. Chen, G. Bufkin, "Crosslinkable Emulsion Polymers by Autooxidation I", Journal of Applied Polymer Science, Vol. 30, 4571-4582 (1985).

Suitable alcohols include octenol, nonenol, decenol, undecenol, dodecenol, tridecenol, tetradecenol, pentadecenol, hexadecenol, heptadecenol, among others

Octadecenol, nonadecenol, ikosenol, docosenol, octadiene-ol, nonano-dien-ol, decadiene-ol, undecadiene-ol, dodecadiene-ol, trideca-diene-ol, tetradeca-diene-ol, Pentadeca-dien-ol,

Hexadeca-dien-ol, Heptadeca-dien-ol, Octadeca-dien-ol,

 Nonadeca-dien-ol, icosadien-ol and / or docosa-dien-ol.

These so-called fatty alcohols are partly commercially available or can be obtained from fatty acids, this reaction being carried out, for example, in F.-B. Chen, G. Bufkin, Journal of Applied Polymer Science, Vol. 30, 4571-4582

(1985).

Among the preferred (meth) acrylates by this

Octa-dienyl (meth) acrylate, octadeca-diene-yl (meth) acrylate, octadecanetrienyl (meth) acrylate, hexadecenyl (meth) acrylate,

Octadecenyl (meth) acrylate and hexadecadienyl (meth) acrylate.

In addition, (meth) acrylates which have at least one double bond and 8 to 40 carbon atoms in the alkyl radical can also be obtained by reacting unsaturated fatty acids with (meth) acrylates which are present in the alkyl radical, in particular

Alcohol radical reactive groups, can be obtained. The reactive groups include in particular hydroxy groups and epoxy groups. Accordingly, for example, hydroxyalkyl (meth) acrylates, such as

3-hydroxypropyl (meth) acrylate, 3, 4-

Dihydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2, 5-dimethyl-1, 6

hexanediol (meth) acrylate, 1, 10-decanediol (meth) acrylate; or epoxy group-containing (meth) acrylates, for example

Glycidyl (meth) acrylate can be used as starting materials for the preparation of the aforementioned (meth) acrylates.

Suitable fatty acids for reaction with the abovementioned (meth) acrylates are often commercially available and are obtained from natural sources. These 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.

Among the preferred (meth) acrylates by this

Methods available include, in particular

(Meth) acryloyloxy-2-hydroxypropyl linoleic acid ester,

(Meth) acryloyloxy-2-hydroxypropyl-linolenic acid ester

(Meth) acryloyloxy-2-hydroxypropyl-oleic acid ester.

The implementation of unsaturated fatty acids with

 (Meth) acrylates, the reactive groups in the alkyl radical,

in particular alcohol residue, is known per se and set forth, for example, in DE-A-41 05 134, DE-A-25 13 516, DE-A-26 38 544 and US 5,750,751.

According to a preferred embodiment, (meth) acrylic monomers of the general formula (II)

wherein R is hydrogen or a methyl group, X and X

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 signifies a group of the formula NR ', where R'

Is hydrogen or a radical having 1 to 6 carbon atoms, Z is a linking group, and R ^{2 is} an unsaturated radical having 9 to 25 carbon atoms are used. Surprising advantages can be continued by the

Use of a (meth) acrylic monomer 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

Connecting group, R ^'is hydrogen or a radical having 1 to 6 carbon atoms and R ^{2 is} an unsaturated radical having 9 to 25 carbon atoms, achieve.

The term "radical having 1 to 6 carbon atoms" represents a group having 1 to 6 carbon atoms and includes aromatic and heteroaromatic groups as well as

Alkyl, cycloalkyl, alkoxy, cycloalkoxy, alkenyl,

 Alkanoyl, alkoxycarbonyl and heteroaliphatic groups. The groups mentioned can be branched or unbranched. Furthermore, these groups can

Substituents, in particular halogen atoms or hydroxyl groups.

The radicals R 'are preferably alkyl groups. Preferred alkyl groups include methyl, ethyl,

Propyl, isopropyl, 1-butyl, 2-butyl, 2-methylpropyl or tert. Butyl group. The group Z preferably represents a linking group comprising 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, for example, 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 in formula (II) represents 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. To the

particularly preferred groups include alkenyl groups such as the nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl,

 Heneicosenyl, docosenyl, octadiene-yl, nona-dien-yl, decadienyl, undecanediazyl, dodeca-diene-yl, trideca-diene-yl, tetradeca- diene -yl, pentadeca-dien-yl, hexadeca-dien-yl, heptadeca-dien-yl, octadeca-dien-yl, nonadeca-dien-yl, eicosa-dien-yl, heneicosa-diene yl, docosa-dien-yl,

Tricosa-dien-yl and / or heptadeca-triene-yl group.

The preferred (meth) acrylic monomers of the formula (II) or (III) include heptadecenyloyloxy-2-ethyl (meth) acrylamide, heptadecadienyloxy-2-ethyl (meth) acrylamide, heptadeca- trienyloxy-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-icosenoic acid amide, (meth) acryloyloxy-2-ethyl-cetoleic 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 cetoleic acid amide,

(Meth) acryloyloxy-2-propyl-erucic acid amide, (meth) acryloyloxy-2-propyl-linoleic acid amide and (meth) acryloyloxy-2-propyllinolenic acid amide.

The notation (meth) acryl stands for acrylic and

Methacryl radicals, with methacrylic radicals are preferred.

 Particularly preferred monomers of the formula (II) or (III) are methacryloyloxy-2-ethyl-oleic acid amide, methacryloyloxy-2-ethyl-linolenic acid amide and / or methacryloyloxy-2-ethyl-linolenic acid amide.

The (meth) acrylic monomers of the formula (II) or (III) can be obtained in particular by multistage 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 amine group of the amide is reacted with a (meth) acrylate, for example

Methyl (meth) acrylate reacted to obtain the monomers of the formula (II) or (III). For the preparation of monomers in which X ^{1 is} a group of formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, and X ²

Represents oxygen, a corresponding first

Alkyl (meth) acrylate, for example methyl (meth) acrylate, with one of the aforementioned amines to a (meth) acrylamide with a hydroxy group in the alkyl radical are reacted, which is then reacted with an unsaturated fatty acid to a

(Meth) acrylic monomer according to formula (II) or (III) is reacted. Transesterifications of alcohols with (meth) acrylates or the preparation of (meth) acrylic acid amides are disclosed inter alia in CN 1355161, DE 21 29 425, DE 34 23 443 or EP-A-0 534 666, wherein the reaction conditions described in these publications and the ones stated therein

Catalysts, etc. for purposes of disclosure in these

Registration will be inserted. Furthermore, these reactions are described in "Synthesis of Acrylic Esters by Transesterification", J. Haken, 1967.

In this case, intermediates obtained, for example

Carboxylic acid amides which have hydroxy groups in the alkyl radical to be purified. According to a particular embodiment of the present invention, intermediates obtained can be reacted without expensive purification to the (meth) acrylic monomers of formula (II) or (III).

Furthermore, the (meth) acrylic monomers having 8 to 40, preferably 10 to 30 and particularly preferably 12 to 20 carbon atoms and at least one double bond in the

Alkyl radical, in particular monomers of the general formula (IV)

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, R ^{3 is} an alkylene group with 1 to 22 carbon atoms, Y is oxygen, sulfur or a group of the formula NR ", where R" is hydrogen or a radical having 1 to 6 carbon atoms, and R ^{4 is} an unsaturated radical having at least 8 carbon atoms and at least two double bonds ,

In formula (IV), the radical R is an alkylene group having 1 to 22 carbon atoms, preferably 1 to 10,

particularly preferably having 2 to 6 carbon atoms. The radical R ³ , according to a particular embodiment of the

present invention, an alkylene group having 2 to 4, particularly preferably 2 carbon atoms. Zu den

Alkylene groups having 1 to 22 carbon atoms

in particular the methylene, ethylene, propylene, isopropylene, n-butylene, isobutylene, t-butylene or

 Cyclohexylene group, wherein the ethylene group is particularly preferred.

The radical R ⁴ comprises at least two CC double bonds which are not part of an aromatic system. Preferably, the radical R ^{4 represents} a group with exactly 8 carbon atoms, which has exactly two double bonds. The radical R ⁴ preferably represents a linear hydrocarbon radical which has no heteroatoms. According to a special

Embodiment of the present invention, the radical R ⁴ in formula (IV) may comprise a terminal double bond. In a further variant of the present invention, the radical R ⁴ in formula (IV) can not comprise a terminal double bond. The double bonds contained in the radical R ⁴ can

preferably be conjugated. According to another

preferred embodiment of the present invention, the double bonds contained in the radical R ⁴ are not conjugated. Among the preferred radicals R ⁴ , the at least two

Include double bonds, include the octa-2, 7-dienyl group, octa-3, 7-dienyl group, Octa-4,7-dienyl, octa-5, 7-dienyl, octa-2, 4-dienyl, octa-2, 5-dienyl, octa-2, 6-dienyl, octa-3, 5-dienyl, octa 3, 6-dienyl group and octa-4, 6-dienyl group.

The (meth) acrylic monomers of the general formula (IV) include, inter alia, 2- [((2-E) octa-2,7-dienyl) methylamino] ethyl 2-methylprop-2-enoate, 2 - [( (2-Z) octa-2,7-dienyl) methylamino] ethyl-2-methylprop-2-enoate,

2- [((3-E) octa-3,7-dienyl) methylamino] ethyl 2-methylprop-2-enoate, 2- [((4-Z) octa-4,7-dienyl) methylamino] ethyl 2-methylprop-2-enoate, 2- [(octa-2, 6-dienyl) methylamino] ethyl 2-methylprop-2-enoate, 2- [(octa-2,4-dienyl) methylamino] ethyl-2- methylprop-2-enoate, 2- [(octa-3, 5-dienyl) methylamino] ethyl-2-methylprop-2-enoate, 2- [((2-E) octa-2, 7-dienyl) methylamino] ethyl (meth) acrylamide, 2- [((2-Z) octa-2,7-dienyl) methylamino] ethyl (meth) acrylamide,

2- [((3-E) octa-3,7-dienyl) methylamino] ethyl (meth) acrylamide, 2- [((4-Z) octa-4, 7-dienyl) methylamino] ethyl (meth) acrylic acid amide, 2- [(octa-2, 6-dienyl) methylamino] ethyl (meth) acrylamide, 2- [(octa-2, 4-dienyl) methylamino] ethyl (meth) acrylamide, 2- [(octa) 3, 5-dienyl) methylamino] ethyl (meth) acrylamide, 2- [((2-E) octa-2,7-dienyl) ethylamino] ethyl 2-methylprop-2-enoate,

2- [((2-Z) octa-2,7-dienyl) ethylamino] ethyl 2-methylprop-2-enoate, 2- [((3-E) octa-3,7-dienyl) ethylamino] ethyl 2-methylprop-2-enoate, 2- [((4-Z) octa-4,7-dienyl) ethylamino] ethyl 2-methylprop-2-enoate, 2- [(octa-2, 6-dienyl) ethylamino ] ethyl 2-methylprop-2-enoate, 2- [(octa-2, 4-dienyl) ethylamino] ethyl 2-methylprop-2-enoate, 2- [(octa-3, 5-dienyl) ethylamino] ethyl 2-methylprop-2-enoate, 2- [((2-E) octa-2,7-dienyl) methylamino] ethyl-prop-2-enoate, 2- [((2-Z) octa-2,7 - dienyl) methylamino] ethyl-prop-2-enoate, 2- [((3-E) octa-3,7-dienyl) methylamino] ethyl-prop-2-enoate, 2- [((4-Z) octa -4, 7-dienyl) methylamino] ethyl-prop-2-enoate, 2- [(octa-2, 6-dienyl) methylamino] ethyl-prop-2-enoate, 2- [(octa 2, 4-dienyl) methylamino] ethyl-prop-2-enoate, 2- [(octa-3, 5-dienyl) methylamino] ethyl-prop-2-enoate, 2 - ((2-E) octa-2, 7-dienyloxy) ethyl 2-methylprop-2-enoate, 2- ((2-Z) octa-2,7-dienyloxy) ethyl 2-methylprop-2-enoate, 2- ((3-E) Octa 3,7-dienyloxy) ethyl 2-methylprop-2-enoate, 2- ((4-Z) octa-4,7-dienyloxy) ethyl 2-methylprop-2-enoate, 2- (octa-2,6 - dienyloxy) ethyl 2-methylprop-2-enoate, 2- (octa-2, 4-dienyloxy) ethyl-2-methylprop-2-enoate, 2- (octa-3, 5-dienyloxy) ethyl-2-methylprop -2-enoate, 2- ((2-E) octa-2,7-dienyloxy) ethyl-prop-2-enoate, 2- ((2-Z) octa-2,7-dienyloxy) ethyl-prop-2 Enoate, 2- ((3-E) octa-3,7-dienyloxy) ethyl-prop-2-enoate, 2- ((4-Z) octa-4,7-dienyloxy) ethyl-prop-2-enoate , 2- (Octa-2, 6-dienyloxy) ethyl prop-2-enoate, 2- (octa-2,4-dienyloxy) ethyl prop-2-enoate and 2- (octa-3,5-dienyloxy) ethyl-prop-2-enoate.

The (meth) acrylic monomers of the formula (IV) set out above can be obtained in particular by processes in which (meth) acrylic acid or a (meth) acrylate, in particular

Methyl (meth) acrylate or ethyl (meth) acrylate is reacted with an alcohol and / or an amine. These reactions have been previously stated.

That with the (meth) acrylic acid or the (meth) acrylate

Reacted reactant can advantageously of the formula (V)

correspond,

 3 4

HX-R-YR (V), wherein X is oxygen or a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, R ^{3 is} an alkylene group having 1 to 22 carbon atoms, Y

Oxygen, sulfur or a group of the formula NR ", where R" is hydrogen or a radical having 1 to 6 carbon atoms, and R ^{4 is} an at least double unsaturated radical having at least 8 carbon atoms.

With regard to the meaning of preferred radicals R ', R ", R, and R ⁴ , reference is made to the description of the formula (IV)

Among the preferred starting materials according to formula (V) include

(Methyl (octa-2,7-dienyl) amino) ethanol, (ethyl (octa-2,7-dienyl) amino) ethanol, 2-octa-2,7-dienyloxyethanol,

 (Methyl (octa-2,7-dienyl) amino) ethylamine, (methyl (octa-3,7-dienyl) amino) ethanol, (ethyl (octa-3,7-dienyl) amino) ethanol, 2-octa-3 , 7-dienyloxyethanol, (methyl (octa-3,7-dienyl) amino) ethylamine, (methyl (octa-4, 7-dienyl) amino) ethanol, (ethyl (octa-4, 7-dienyl) amino) ethanol, 2-Octa-4,7-dienyloxyethanol, (methyl (octa-4, 7-dienyl) amino) ethylamine, (methyl (octa-5,7-dienyl) amino) ethanol, (ethyl (octa-5,7-dienyl ) amino) ethanol, 2-octa-5,7-dienyloxyethanol, (methyl (octa-5,7-dienyl) amino) ethylamine, (methyl (octa-2, 6-dienyl) amino) ethanol, (ethyl (octa) 2, 6-dienyl) amino) ethanol, 2-octa-2, 6-dienyloxyethanol, (methyl (octa-2, 6-dienyl) amino) ethylamine, (methyl (octa-2, 5-dienyl) amino) ethanol, (Ethyl (octa-2,5-dienyl) amino) ethanol, 2-octa-2,5-dienyloxyethanol, (methyl (octa-2, 5-dienyl) amino) ethylamine,

(Methyl (octa-2,4-dienyl) amino) ethanol, (ethyl (octa-2, 4-dienyl) amino) ethanol, 2-octa-2,4-dienyloxyethanol, (Methyl (octa-2,4-dienyl) amino) ethylamine, (methyl (octa-3, 6-dienyl) amino) ethanol, (ethyl (octa-3, 6-dienyl) amino) ethanol, 2-octa-3 , 6-dienyloxyethanol, (methyl (octa-3, 6-dienyl) amino) ethylamine, (methyl (octa-3, 5-dienyl) amino) ethanol, (ethyl (octa-3,5-dienyl) amino) ethanol, 2-octa-3,5-dienyloxyethanol, (methyl (octa-3, 5-dienyl) amino) ethylamine, (methyl (octa-4, 6-dienyl) amino) ethanol, (ethyl (octa-4,6-dienyl ) amino) ethanol, 2-octa-4, 6-dienyloxyethanol and (methyl (octa-4, 6-dienyl) amino) ethylamine. The educts of the formula (V) can be used individually or as a mixture.

The educts according to formula (V) can be obtained inter alia by known methods of telomerization of 1,3-butadiene. Herein, the term "telomerization" means the reaction of compounds with conjugated double bonds in the presence of nucleophiles, as set forth in the publications WO 2004/002931, WO 03/031379 and WO 02/100803

Process, in particular those used for the implementation

Catalysts and the reaction conditions, such as pressure and temperature, are included in the present application for disclosure purposes.

Preferably, the telomerization of 1,3-butadiene using metal compounds comprising metals of the 8th to 10th group of the Periodic Table of the Elements, as

Catalyst, with palladium compounds,

in particular Palladiumcarbenkomplexe, which are set forth in more detail in the above-mentioned documents, can be particularly preferably used.

As a nucleophile, especially dialcohols, such as

Ethylene glycol, 1, 2-propanediol, 1, 3-propanediol; Diamines, like Ethylenediamine, N-methylethylenediamine, Ν, Ν'-dimethylethylenediamine or hexamethylenediamine; or

Aminoalkanols such as aminoethanol, N-methylaminoethanol, ethylaminoethanol, aminopropanol, N-methylaminopropanol N-ethylaminopropanol can be used.

When using (meth) acrylic acid as the nucleophile, for example, octadienyl (meth) acrylates can be obtained, especially as (meth) acrylic monomers having 8 to 40

Carbon atoms are suitable.

The temperature at which the telomerization reaction

is carried out, is between 10 and 180 ° C, preferably between 30 and 120 ° C, more preferably between 40 and 100 ° C. The reaction pressure is 1 to 300 bar, preferably up to 120 bar, more preferably 1 to 64 bar and most preferably 1 to 20 bar.

The preparation of isomers from compounds having an octa-2,7-dienyl group can be accomplished by isomerization of the double bonds contained in the compounds having an octa-2,7-dienyl group.

The above-mentioned (meth) acrylic monomers having at least one double bond and 8 to 40 carbon atoms in the alkyl group may be used singly or as a mixture of two or more monomers.

The proportion of (meth) acrylic monomers in the alkyl radical

at least one double bond and having from 8 to 40 carbon atoms, in a composition according to the invention can vary over a wide range, wherein this proportion is preferably in the range of 0.1 to 60 wt .-%, more preferably 1 to 40 wt .-% and most preferably in the range of 2 to 20 wt .-%, based on the weight of the monomers.

The compositions of the invention comprise at least one amide or one amine monomer, wherein amine monomers

are preferred. The term monomer is understood here to mean a compound which is free-radically polymerizable, such that this compound has at least one carbon-carbon double bond. Accordingly, an amide or an amine monomer is an organic compound having at least one C-C double bond which additionally has an amine or an amide group. These monomers are known per se. In addition to olefinic compounds having an amine or amide group, such as N-allyl-N-methylacetamide or allylamine (3-amino-1-propene), these compounds include in particular unsaturated esters and ethers having an amine and / or amide group.

These include (meth) acrylates with a

Amine group in the alkyl radical, in particular

tert. Butylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopentyl (meth) acrylate and N, N-dibutylaminohexadecyl (meth) acrylate.

Furthermore, in particular amides of (meth) acrylic acid are preferred. These include, inter alia, (meth) acrylamide, N-methylol (meth) acrylamide and N, N-dimethylaminopropyl (meth) acrylamide. In addition, it is possible to use (meth) acrylates which are derived from saturated fatty acid amides, such as

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.

Particularly preferred amide or amine monomers are

in particular (meth) acrylic monomers which are an amide or an amine and in the alkyl radical at least one

Having double bond and 8 to 40 carbon atoms. These monomers include, but are not limited to, monomers of the formulas (II), (III) and (IV) set forth above

at least one of X ¹ , X ² , X or Y is a

represents nitrogen-containing group. These monomers have been previously set out, so reference is hereby made. According to a particular aspect of the present invention, the compositions for the preparation of polymers preferably comprise (meth) acrylic monomers of the general formula (IV) in which the radical Y denotes a group of the formula NR '', where R ''

Represents hydrogen or a radical having 1 to 6 carbon atoms.

According to a particular aspect of the present invention, the composition for the production of polymers

preferably from 0.1 to 60 wt .-%, more preferably 1 to 30 wt .-% and most preferably 5 to 20 wt .-% amide or an amine monomers, based on the weight of Monomers in the composition for the preparation of

Polymers.

In addition to the monomers set out above, a

composition according to the invention other monomers,

Also called comonomers below.

These copolymerizable monomers include, but are not limited to, monomers having an acid group, monomers A comprising ester groups, and styrenic monomers.

Acid group-containing monomers are compounds which are preferably free-radical with those set forth above

Copolymerize photoinitiator monomers. These include, for example, monomers having a sulfonic acid group, such as vinylsulfonic acid; Monomers with a

Phosphonic acid group, such as vinylphosphonic acid 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.

The preferred ester groups comprising monomers A include in particular (meth) acrylates which differ from the monomers described above, fumarates, maleates and / or vinyl acetate. The term (meth) acrylates include methacrylates and acrylates as well as mixtures of both. These monomers are well known. The comonomers mentioned include, among others

(Meth) acrylates having 1 to 10 carbon atoms in the alkyl radical which have no double bonds or heteroatoms in the alkyl radical.

The (meth) acrylates having 1 to 10 carbon atoms in the alkyl radical which have no double bonds or heteroatoms in the alkyl radical include, inter alia, (meth) acrylates having a linear or branched alkyl radical, such as, for example, methyl (meth) acrylate, ethyl (meth) acrylate,

n-propyl (meth) acrylate, iso-propyl (meth) acrylate,

n-butyl (meth) acrylate, iso-butyl (meth) acrylate,

tert. Butyl (meth) acrylate and pentyl (meth) acrylate,

Hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,

Heptyl (meth) acrylate, octyl (meth) acrylate, 3-iso-propylheptyl (meth) acrylate, nonyl (meth) acrylate,

Decyl (meth) acrylate; and cycloalkyl (meth) acrylates, such as

Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate,

Bornyl (meth) acrylate, norbornyl (meth) acrylate and

Isobornyl (meth) acrylate. The above-described (meth) acrylates having 1 to 10 carbon atoms in the alkyl group may be used singly or as a mixture.

Another class of comonomers are (meth) acrylates having at least 11 carbon atoms in the alkyl radical, which are derived from saturated alcohols and no heteroatoms in the

Alkyl radical, such as 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-isopropylheptadecyl (meth) acrylate,

4-tert. Butyl octadecyl (meth) acrylate,

5-ethyloctadecyl (meth) acrylate, 3-iso-propyloctadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate,

Cetyleicosyl (meth) acrylate, Stearyleicosyl (meth) acrylate,

Docosyl (meth) acrylate and / or

Eicosyltetratriacontyl (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, 1- (2-methacryloyloxyethyl) -2-pyrrolidone, 2- (3-oxazolidinyl) ethyl methacrylate;

Nitriles 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 in each case

unsubstituted or substituted up to four times; (Meth) acrylates with a hydroxy group in the alkyl radical,

in particular 2-hydroxyethyl (meth) acrylate, preferably 2-

Hydroxyethyl methacrylate (HEMA),

 Hydroxypropyl (meth) acrylate, for example 2-hydroxypropyl (meth) acrylate and 3-hydroxypropyl (meth) acrylate, preferably hydroxypropyl methacrylate (HPMA),

 Hydroxybutyl (meth) acrylate, preferably

 Hydroxybutyl methacrylate (HBMA),

 3,4-dihydroxybutyl (meth) acrylate,

2, 5-dimethyl-1,6-hexanediol (meth) acrylate,

 1, 10-decanediol (meth) acrylate,

 Glycerol mono (meth) acrylate and

polyalkoxylated derivatives of (meth) acrylic acid, in particular polypropylene glycol mono (meth) acrylate with 2 to 10,

preferably 3 to 6 propylene oxide units, preferably polypropylene glycol monomethacrylate with about 5

Propylene oxide units (PPM5), polyethylene glycol mono (meth) acrylate having 2 to 10, preferably 3 to 6

Ethylene oxide units, preferably polyethylene glycol monomethacrylate with about 5 ethylene oxide units (PEM5),

Polybutylene glycol mono (meth) acrylate,

Polyethylene glycol polypropyleneglycol mono (meth) acrylate;

 (Meth) acrylamides, in particular N-methylol (meth) acrylamide, N, -dimethylaminopropyl (meth) acrylamide, tert. Butylaminoethyl methacrylate, methacrylamide and acrylamide;

Glycerol carbonate methacrylate;

2-carbamoyloxyethyl methacrylate and

 (Meth) acrylates derived from saturated fatty acids, such as (meth) acryloyloxy-2-hydroxypropyl-palmitic acid ester,

(Meth) acryloyloxy-2-hydroxypropyl-stearic acid ester and

 (Meth) acryloyloxy-2-hydroxypropyl laurin ester.

Another class of comonomers make cross-linking

Monomers. These monomers have at least two

Double bonds with similar reactivity at one

radical polymerization. Belong to these

in particular (meth) acrylates derived from diols or

Derive higher alcohols, such.

 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 and

 Diurethane dimethacrylate; (Meth) acrylates having three or more double bonds, e.g. Glycerol tri (meth) acrylate,

 Trimethylolpropane tri (meth) acrylate,

 Pentaerythritol tetra (meth) acrylate and

Dipentaerythritol penta (meth) acrylate. The comonomers also include vinyl esters such as vinyl acetate, vinyl chloride, vinyl versatate, ethylene vinyl acetate, ethylene vinyl chloride;

 Maleic acid derivatives, such as maleic anhydride, esters of maleic acid, for example

 Maleic acid dimethyl ester, methylmaleic anhydride; and fumaric acid derivatives such as dimethyl fumarate.

Another group of comonomers are styrenic monomers, such as styrene, substituted styrenes with a

 Alkyl substituents in the side chain, such as. B.

 Methylstyrene and ethylstyrene, substituted styrenes with an alkyl substituent on the ring, such as vinyltoluene and p-butylstyrene.

Methylstyrene, halogenated styrenes, such as

Monochlorostyrenes, dichlorostyrenes, tribromostyrenes and

 Tetrabromostyrenes.

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, vinylthiolane,

 Vinylthiazoles and hydrogenated vinylthiazoles, vinyloxazoles and hydrogenated vinyloxazoles;

 Maleimide, methylmaleimide; Vinyl and isoprenyl ethers; and vinyl halides, such as vinyl chloride,

Vinyl fluoride, vinylidene chloride and vinylidene fluoride are further examples of comonomers. Surprising advantages in particular show compositions which preferably contain 1% by weight to 99% by weight, preferably 10% by weight to 95% by weight and very particularly preferably 20% by weight to 90% by weight of units. which are derived from (meth) acrylates having 1 to 10 carbon atoms in the alkyl radical which have no double bonds or heteroatoms in the alkyl radical, based on the weight of the monomers in the composition for the preparation of polymers.

Of particular interest are, in particular, compositions containing from 0 to 10% by weight, preferably from 0.5 to 8% by weight and more preferably from 1 to 5% by weight, of units derived from acid group-containing monomers on the weight of the monomers in the composition

Production of polymers.

According to a particular variant of the present invention, the composition according to the invention may comprise from 0 to 60% by weight, more preferably from 5 to 50% by weight and most preferably from 10 to 40% by weight of units derived from styrenic monomers, in particular from styrene , substituted styrenes having an alkyl substituent in the side chain, substituted styrenes having an alkyl substituent on the ring and / or halogenated styrenes are derived, based on the weight of the monomers in the composition of

Production of polymers.

In addition, compositions are preferred for the preparation of polymers which are a very small proportion of

(Meth) acrylates having two or more carbon-carbon double bonds having a reactivity identical to a (meth) acrylate group. According to a particular modification of the present invention the proportion of compounds having two or more (meth) acrylate groups is preferably at most 5% by weight, especially at most 2% by weight, particularly preferably at most

1 wt .-%, more preferably at most 0.5 wt .-% and very particularly preferably at most 0.1 wt .-% limited, based on the weight of the monomers in the composition of

Production of polymers.

The amount of monomers in the composition for producing the polymers can be in a wide range.

 Preferably, the composition comprises at least 10% by weight of monomers, preferably at least 20% by weight of monomers and most preferably at least 30% by weight of monomers. The upper limit results from the method with the

Composition is polymerized. At a

 Substance polymerization, the composition may consist of the said components, that is the

Composition consists of the monomers and the

Radical initiator. In a solution, emulsion or

Bead polymerization, the composition comprises a solvent or suspending agent.

As a further mandatory component includes a

Composition of the present invention at least one azo compound which can serve as a radical initiator, in particular for a radical polymerization.

Azo compounds are known in the art. These compounds comprise at least one group of the formula -N = N- (classic azo compounds) or -C = N- (azomethine)

Links . For example, suitable classical azo compounds can often correspond to the formula (VI) R ⁵ -N = NR (VI),

wherein R ⁵ and R ^{6 are} independently a group of 1 to 20 carbon atoms.

The radicals having 1 to 20 carbon atoms include, but are not limited to, (C 1 -C 20) alkyl, (C 2 -C 20) alkenyl, (C 2 -C 20) alkynyl, aryl or heterocyclyl, wherein the aryl - or heterocyclyl radicals may be unsubstituted or substituted and in said alkyl, alkenyl or alkynyl radicals one or more, preferably up to three non-adjacent

saturated carbon units may be replaced by heteroatom units, such as oxygen or sulfur, and further wherein 3 to 6 atoms of these optionally modified as above hydrocarbon radicals can form a cycle and these hydrocarbon radicals with or without the specified variations, optionally with a or more, preferably up to three, in the case of halogen up to the maximum number of identical or different radicals from the series hydroxy (-OH), carboxy (-COOH), formyl, cyano (- CN), sulfonate (SO ₃ H), Halogen, preferably fluorine, aryl,

Aryloxy, arylthio, (C3-C8) -cycloalkoxy, (C3-C8) -cycloalkylthio, heterocyclyl, heterocyclyloxy or (C1-C2) - alkoxycarbonyl may be substituted, wherein the

cycloaliphatic, aromatic or heterocyclic

Ring systems under the substituents just mentioned

unsubstituted or with up to three, in the case of fluorine also up to the maximum number of the same or different

Substituents may be provided.

The term "(C 1 -C 20) -alkyl" means an unbranched or branched hydrocarbon radical having 1 to 20 carbon atoms, such as. As the methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 2-methylpropyl or tert. Butyl radical; as well as B. the pentyl, 2-methylbutyl, 1, 1-dimethylpropyl, hexyl, heptyl, octyl, or the 1,1, 3, 3-tetramethylbutyl radical; , as well as z. The nonyl, 1-decyl, 2-decyl, undecyl, dodecyl, pentadecyl or eicosyl radical; the term "(C 2 -C 20) alkenyl" e.g. The vinyl, allyl, 2-methyl-2-propenyl or 2-butenyl group; as well as For example, the 2-pentenyl, 2-decenyl or the 2-eicosenyl group; by the term "(C 2 -C 20) -alkynyl", for example, the ethynyl, propargyl, 2-methyl-2-propynyl or 2-butynyl group; as well as The 2-pentynyl or the 2-decynyl group; the term "aryl" is an isocyclic aromatic radical having preferably 6 to 14, in particular 6 to 12, C atoms, for example phenyl, naphthyl or biphenylyl, preferably phenyl.

By the term "aryloxy" is meant, for. The phenoxy or 1- or 2-naphthyloxy group; by the term "arylthio" is meant z. B. the

Phenylthio or 1- or 2-naphthylthio group; the term "(C 3 -C 8) -cycloalkoxy" denotes a cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl group which is linked via an oxygen, and the term "(C 3 -C 8) -cycloalkylthio" a

Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,

Cycloheptyl or cyclooctyl group which is linked via a sulfur atom.

By the term "heterocyclyl" is meant a

heteroaromatic or heteroaliphatic ring system, wherein

"heteroaromatic ring system" means an aryl radical in which at least one CH group is replaced by N and 1 or at least two adjacent CH groups are replaced by S, NH or O, is understood, for. A residue of thiophene, furan, pyrrole, thiazole, oxazole, imidazole, isothiazole,

Isoxazole, pyrazole, 1, 3, 4-oxadiazole, 1, 3, 4-thiadiazole, 1,3,4-triazole, 1, 2, 4-oxadiazole, 1, 2, 4-thiadiatol, 1,2, 4- Triazole, 1, 2, 3-triazole, 1, 2, 3, 4-tetrazole, benzo [blthiophene, benzo [blfuran, indole, benzo [clthiophene, benzo [c] furan,

Isoindole, benzoxazole, benzothiazole, benzimidazole,

Benzisoxazole, benzisothiazole, benzopyrazole, benzothiadiazole, benzotriazole, dibenzofuran, dibenzothiophene, carbazole,

Pyridine, pyrazine, pyrimidine, pyridazine, 1, 3, 5-triazine, 1,2,4-triazine, 1, 2, 4, 5-triazine, quinoline, isoquinoline, quinoxaline, quinazoline, cinnoline, 1,8-naphthyridine, 1, 5-naphthyridine, 1, 6-naphthyridine, 1,1'-naphthyridine, phthalazine,

Pyridopyrimidine, purine, pteridine or 4H-quinolizine; the term "heteroaliphatic ring system" is replaced by a cycloalkyl radical in which at least one carbon unit is replaced by 0, S or a group NR "and R"

Hydrogen. (C 1 -C 4) -alkyl or aryl; the term "heterocyclyloxy" denotes one of the abovementioned heterocyclic radicals which are linked via an oxygen atom; and under (C 1 -C 2) -alkoxycarbonyl the methoxycarbonyl or ethoxycarbonyl group.

For example, preferred azo compounds include

2,2'-azobisisobutyronitrile (2,2'-azobis (isobutyronitrile)), 2,2'-azobis (2,4-dimethylvaleronitrile) and 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2, 2 'azobis (2, 4, 4 trimethylvaleronitrile), 1,1'-azobis (cyclooctanecarbonitrile), 1,1'-azobis (cyclohexanecarbonitrile), 2,2'-azobis (N, N'-dimethyleneisobutyramidine) and / or 2,2'-azobis (isobutyric acid methyl ester) ,

Particularly preferably used as azo compounds are: 2, 2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile) and / or 2,2'-azobis (isobutyronitrile) ,

According to a particular embodiment, water-soluble azo compounds can preferably be used, such as

for example, azobiscyanovaleric acid, 4- (phenylazo) benzoic acid, 2 (4-hydroxyphenylazo) benzoic acid, 2,2'-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} dihydrochloride, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride and 2,2'-azobis [2- (5-methyl-2 - imidazolin-2-yl) propane] dihydrochloride. Very particular preference is given to 2 azobis-cyanovaleric acid and

(Phenylazo) benzoic acid, 2 (4-hydroxyphenylazo) benzoic acid. The basic azo compounds set forth above can also be used as the free base. Furthermore, the

Azo compounds having an acid group such as azobiscyanovaleric acid, 4- (phenylazo) benzoic acid,

 2 (4-hydroxyphenylazo) benzoic acid also in the form of the salts, preferably as alkali metal salt, in particular as

Sodium salt can be used.

In addition to the classical azo compounds set out above, the scope of the present invention also includes

Azomethine compounds to the usable as radical starter compounds. To the preferred azomethine compounds In particular, compounds include the formula

(VII),

wherein the radicals R ⁷ , R ⁸ and R ^{9 are} independently a group having 1 to 20 carbon atoms.

Among the preferred azomethine compounds known as

Free radical initiators include, in particular, 4-hydroxy-5- (2-hydroxybenzylideneamino) -naphthalene-2, 7-disulfonic acid (azomethine-H), said compound

especially as sodium salt can be used.

The radical initiators mentioned can be used individually or as a mixture. Further details may 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, p. 386ff, J. Wiley, New York, 1978.

The proportion of radical initiator in the composition is preferably in the range of 0.05 to 10 wt .-%, in particular 0.1 to 5 wt .-% and most preferably 1 to 3 wt .-%, based on the weight of the monomers in the composition for the production of polymers.

In addition to the components mentioned can be an inventive

Composition comprise further ingredients. These include in particular solvents or water. The term of the solvent is to be understood here broadly. The preferred solvents include in particular aromatic hydrocarbons, such as toluene, xylene; Esters, in particular acetates, preferably butyl acetate, ethyl acetate, propyl acetate; Ketones, preferably ethyl methyl ketone, acetone, methyl isobutyl ketone or cyclohexanone; Alcohols, especially isopropanol, n-butanol, isobutanol; Ether, in particular

Glycol monomethyl ether, glycol monoethyl ether,

 Glycol monobutyl ether; Aliphatic, preferably pentane, hexane, cycloalkane and substituted cycloalkanes, for example cyclohexane; Mixtures of aliphatics and / or aromatics, preferably naphtha; Gasoline, biodiesel; but also

Plasticizers such as low molecular weight polypropylene glycols or phthalates.

According to a particularly preferred embodiment, the composition of the invention is an emulsion. 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 used

Monomers. According to a particular aspect of the present invention, a part of the emulsifiers may be used during the

Polymerization are added.

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 with 8 to 18

 Carbon atoms in the alkyl radical, alkylarylsulfonates having 8 to 18 carbon atoms in the alkyl radical, esters and

 Half ester of sulfosuccinic acid with monovalent

 Alcohols or alkylphenols with 4 to 15

 Carbon atoms in the alkyl radical; optionally, these alcohols or alkylphenols can also be from 1 to 40

 Be ethoxylated ethylene oxide units;

Phosphorsäurestsester and their alkali and

 Ammonium salts, preferably alkyl and alkylaryl phosphates having 8 to 20 carbon atoms in the alkyl or

 Alkylaryl group and 1 to 5 ethylene oxide units;

Alkyl polyglycol ethers, preferably with 8 to 20

 Carbon atoms in the alkyl radical and 8 to 40

 ethylene oxide units;

Alkylaryl polyglycol ethers, preferably with 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.

Particularly preferred anionic emulsifiers include, in particular, fatty alcohol ether sulfates,

Diisooctylsulfosuccinate, lauryl sulfate, C15 paraffin sulfonate, which compounds can generally be used as the alkali metal salt, in particular as the sodium salt. These

Compounds can be found in particular among the

 Tradenames Disponil® FES 32, Aerosol® OT 75,

Texapon® K1296 and Statexan® Kl from Cognis GmbH,

Cytec Industries, Inc. and Bayer AG. Useful nonionic emulsifiers include tert-octyl phenol ethoxylate with 30 ethylene oxide units and Fettalkoholpolyethylenglykolether which preferably 8 to 20 carbon atoms in the alkyl group and 8 to 40 have Ethyleno ^¬ oxide units. These emulsifiers are commercially available under the trade names Triton® X 305 (Fluka), Tergitol® 15-S (Sigma-Aldrich Co.), Marlipal® 1618/25 (Sasol Germany) and Marlipal® 0 13/400 (Sasol Germany) ,

Preference is given to using mixtures of anionic emulsifier and nonionic emulsifier. Conveniently, the weight ratio of anionic emulsifier to

nonionic emulsifier in the range from 20: 1 to 1:20, preferably 2: 1 to 1:10 and particularly preferably 1: 1 to 1: 5. In this case, mixtures containing a sulfate,

in particular a fatty alcohol ether sulfate, a lauryl sulfate, or a sulfonate, in particular a diisooctyl sulfosuccinate or a paraffin sulfonate as anionic emulsifier and an alkylphenol ethoxylate or a

Proven Fettalkoholpolyethylenglykolether each having preferably 8 to 20 carbon atoms in the alkyl group and 8 to 40 Ethyleno ^¬ oxide units as non-ionic emulsifier in particular.

Optionally, the emulsifiers can also be used in admixture with protective colloids. Suitable protective colloids include u. a. partially hydrolyzed polyvinyl acetates,

 Polyvinyl pyrrolidones, 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 from 0.01 to 1.0 wt .-%, based on the total amount of the monomers.

Surprising advantages can be achieved in particular by a

Emulsion can be achieved whose aqueous phase has a pH in the range of 4 to 9.5, particularly preferably 5 to 8. The pH value in this context is defined as the negative decadic logarithm of the activity of the oxonium ions (HsO ⁺ ). The pH can be determined at a temperature of 25 ° C by conventional titration, where it often sufficient to determine this size with electrical meters (pH meters).

Preference is therefore given in particular to compositions comprising a buffer. The preferred buffers include, in particular, carbonic acid or carbonate buffers, which preferably have a buffer range of from pH 6.2 to pH 8.6.

Furthermore, phosphate buffers with a preferred

Buffer range from pH 5.4 to pH 7.8, for example, buffers containing KH2 PO4 + Na2HPC> 4 can be used. Furthermore, buffers are preferred, the ammonia / ammonium and / or

Contain acetic acid / acetate. In addition, veronal acetate buffers according to Michaelis (pH 2.6 to 9.2), HEPES (4- (2-hydroxyethyl) -1-piperazineethanesulfonic acid) buffer (pH 6.8 to 8.2), PBS Buffer (pH 7.4), MES (2- (N-

Morpholino) ethanesulfonic acid) (pH 5.2 to 6.7), Tris-EDTA buffer (pH 7.4) and triethylammonium acetate buffer (pH 7).

In a further embodiment, compositions comprising an electrolyte are preferred. In this context, the term "electrolyte" denotes a salt, which is preferably derived from the buffers set forth above is, so in particular compositions are preferred which contain, for example, bicarbonates, acetates or phosphates.

The concentration of buffer and / or of electrolyte can be in a wide range. This should be the concentration

but not to a buffer and / or electrolyte

Coagulation of an emulsion. Surprising advantages arise in particular with a buffer and / or

Electrolyte concentration in the range of 0.01 to 0.5, particularly preferably 0.02 to 0.4 mol / 1, based on the

Total amount of buffer and / or electrolyte in the emulsion

The compositions according to the invention can be polymerized in particular by solution polymerizations, bulk polymerizations or emulsion polymerizations, with surprising advantages being achieved by a free-radical polymerization

Emulsion polymerizations can be achieved. These are set forth in Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition.

In addition to methods of classical radical polymerization can also be used related processes of controlled

radical polymerization, such as ATRP (= Atom Transfer Radical Polymerization), NMP (Nitroxide-mediated polymerization) or RAFT (= Reversible Addition Fragmentation Chain Transfer) can be used for the preparation of polymers. In general, in an emulsion polymerization, an aqueous phase is prepared which is customary in addition to water Additives, in particular emulsifiers and protective colloids for stabilizing the emulsion may include. Especially preferred are emulsions comprising buffers and / or electrolytes.

Monomers are then added to this aqueous phase and polymerized in the aqueous phase. at

Production of homogeneous polymer particles can in this case a

Monomermischung be added over a time interval continuously or batchwise.

The emulsion polymerization can be carried out, for example, as a micro-emulsion, which is closer in

Chemistry and Technology of Emulsion Polymerization, A.M. van Herk (editor), Blackwell Publishing, Oxford 2005 and J.

0 'Donneil, E.W. Kaier, Macromolecular Rapid Communications 2007, 28 (14), 1445-1454. A miniemulsion is commonly characterized by the use of costabilizers or swelling agents, often long-chain ones

 Alkanes or alkanols are used. The droplet size for miniemulsions is preferably in the range of 0.05 to 20 μm. The droplet size in the case of microemulsions is preferably in the range below 1 μm, in which case particles below a size of 50 nm can be obtained. In microemulsions are often additional

Surfactants, for example hexanol or similar compounds used.

The dispersing of the monomer-containing phase in the aqueous phase can be carried out by known means. These include in particular mechanical methods and the use of ultrasound.

In addition to homogeneous emulsion polymers, core-shell polymers can also be prepared. For this purpose, the composition of the monomer mixture can be changed stepwise, wherein prior to changing the composition, the polymerization is preferably up to a conversion of at least 80 wt .-%, particularly preferably at least 95 wt .-%, each based on the

Total weight of the monomer mixture used, is performed. Core-shell polymer here stands for a polymer which is prepared by a two- or multi-stage emulsion polymerization

was made without the core-shell construction

has been shown for example by electron microscopy. The tracking of the progress of the polymerization in each step may be carried out in a known manner, for example

carried out gravimetrically or by gas chromatography.

The monomer composition for producing the core preferably comprises 50 to 100% by weight of (meth) acrylates, wherein

particularly preferred is a mixture of acrylates and

Methacrylates is used. According to a particular aspect of the present invention, the weight ratio of acrylates to methacrylates in the core may be greater than or equal to 1, more preferably greater than or equal to 2. After the production of the core may be on these preferably a

Grafted onto the monomer or polymerized to the core, the 0.5 to 60 wt .-%, particularly preferably 2 to 30 wt .-%, in particular 5 to 20 wt .-% of (meth) acrylic monomer, which in the alkyl radical at least one Double bond and 8 to 40

Having carbon atoms, based on the weight of

Monomers includes.

The emulsion polymerization is preferably carried out at a

Temperature in the range of 0 to 120 ° C, more preferably in the range of 30 to 100 ° C performed. In this case, polymerization temperatures in the range from greater than 60 to less than 90 ° C., expediently in the range from greater than 70 to less than 85 ° C., preferably in the range from greater than 75 to less than 85 ° C., have proven to be particularly favorable.

The initiation of the polymerization takes place with

Radical starters, also called initiators, the one

Azo group or an azomethine group. These

Compounds have been previously set forth.

The initiators mentioned can be used both individually and in mixtures. They are preferably used in an amount of 0.05 to 3.0 wt .-%, based on the total weight of the monomers of each stage. It is also possible to carry out the polymerization with a mixture of different polymerization initiators having a different half-life, in order to control the free radical flow in the course of the polymerization and at different temperatures

Keep polymerization temperatures constant.

The stabilization of the approach is preferably carried out by means of emulsifiers and / or protective colloids. The protective colloids can be initially charged or added before the start of the polymerization. The initiator can be initially charged or added. Furthermore, it is also possible to submit a portion of the initiator and to meter in the remainder.

The polymerization is preferably carried out by heating the batch to the polymerization temperature and template and / or

Addition of the initiator, preferably in aqueous solution, started. In this case, a part of the monomers in the reactor submitted and the rest over a period of time

be dosed. As a rule, it is advantageous to polymerize the part of the monomers initially introduced in the reactor and only then to start the feed. Alternatively to the introduction of a defined amount of monomer, the feed may be interrupted for a few minutes after e.g. 1 - 5% of

Monomers are added. The dosages of emulsifier and monomers can be carried out separately or

preferably as a mixture, in particular as an emulsion in

Water .

The emulsion polymerization can be carried out in a wide pH range. Preferably, it is between 5 and 9.5. In a particular embodiment, the

 Polymerization at pH values between 6 and 9, in particular carried out between 6.5 and 8.5. Likewise, the dispersion after the polymerization to one for the application

preferred pH range can be adjusted. For pigmented coating systems, the range is generally 8 - 9 or above.

By polymerization of the invention

Compositions available polymers are new and therefore also subject of the present invention. These

 Polymers are distinguished in particular by an extremely high proportion of carbon-carbon double bonds in the polymer, based on the amount of (meth) acrylic monomers used, which have at least one C-C double bond and 8 to 40 carbon atoms in the alkyl radical.

The molecular weight of (meth) acrylic polymers according to the invention can be within a wide range. In general, the weight average molecular weight is usually at least 1000 g / mol, preferably at least 2000 g / mol and very particularly preferably at least 5000 g / mol. For example, according to a first aspect of the present invention

(Meth) acrylic polymers are used which have a relatively high molecular weight. These (meth) acrylic polymers can be obtained in particular by emulsion polymerization, these (meth) acrylic polymers, for example, a

Weight average molecular weight for example in

Range of 100000 to 10000000 g / mol, more preferably in the range of 200000 to 500000 g / mol.

 Emulsionspolymere are characterized in particular by a high environmental impact, since these often no

require organic solvents and can have a particularly low residual monomer content.

According to another aspect of the present invention, low molecular weight (meth) acrylic polymers may also be used. These (meth) acrylic polymers can

For example, show a weight average molecular weight in the range of 1000 to 150000 g / mol, in particular 4000 to 100000 g / mol, particularly preferably in the range of 5000 to 50,000 g / mol. Polymers with a low

Molecular weight is often in

 Coating compositions used with organic solvents. Coating compositions comprising organic solvents exhibit good processability over a wide temperature and humidity range. In relation to the performance show

 Coating compositions with these (meth) acrylic polymers improved environmental compatibility. Thus, extremely small amounts of organic solvents are released into the environment through evaporation, as the

Solvent content can be selected relatively low for a given workability. Also of particular interest are (meth) acrylic polymers which have a polydispersity index M _w / M _n in the range from 1 to 5, particularly preferably in the range from 2 to 3. The molecular weight can be determined by gel permeation chromatography (GPC) against a PMMA standard.

The glass transition temperature of the polymer (s) to be used according to the invention is preferably in the range from -30 ° C. to 70 ° C., more preferably in the range from -20 to 40 ° C. and very particularly preferably in the range from 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), for example according to DIN 53765. Furthermore, the glass transition temperature Tg can also be calculated approximately in advance by means of the Fox equation. After Fox T.G., Bull. Am. Physics Soc. 1, 3, page 123 (1956): - = ^ + ^ + ... + ^ -

Tg _Tgl Tg ₂ Tg _n where x _{n is} the mass fraction (% by weight / 100) of the monomer n and Tg _{n is} the glass transition temperature in Kelvin of

Homopolymers of the monomer n. Further helpful information can be found in the Polymer Handbook 2 ^nd Edition, J. Wiley & Sons, New York (1975), which gives Tg values for the most common homopolymers. Here, the polymer may have one or more different

Have glass transition temperatures. This information is therefore valid for a segment that is formed by polymerization of a

Mixture comprising at least one (meth) acrylic monomer having at least one double bond in the alkyl radical and 8 to 40

Having carbon atoms, preferably one

Monomer mixture according to the invention is available. The architecture of the (meth) acrylic polymer is for many

Applications and properties are not critical. Accordingly, the polymers, in particular the emulsion polymers, can be random copolymers, gradient copolymers,

Block copolymers and / or graft copolymers.

Block copolymers or gradient copolymers can be

For example, obtained by the one

Monomer composition during chain growth

changed discontinuously. According to a preferred aspect of the present invention, the emulsion polymer,

in particular the (meth) acrylic polymer is a statistical

A copolymer in which the monomer composition is substantially constant throughout the polymerization. However, since the monomers may have different copolymerization parameters, the exact composition may vary across the polymer chain of the polymer.

The polymer may be a homogeneous polymer which, for example, forms particles with a constant composition in an aqueous dispersion. In this case, the polymer, which is preferably an emulsion polymer, may consist of one or more segments obtainable by polymerization of a monomer mixture.

In another embodiment, the polymer may be a core-shell polymer which may have one, two, three, or more shells. The shell may be connected to the core or inner shells via covalent bonds. Furthermore, the shell can also be polymerized on the core or an inner shell. The outermost shell of preferred emulsion polymers may preferably comprise from 10 to 40% by weight, more preferably from 15 to% by weight, of (meth) acrylic monomers

are derived, which in the alkyl radical at least one

Double bond and having from 8 to 40 carbon atoms, comprise, based on the weight of the outermost shell.

The iodine value of preferred (meth) acrylic polymers is

preferably in the range of 1 to 300 g of iodine per 100 g

Polymer, preferably in the range of 2 to 250 g of iodine per 100 g of polymer, more preferably 5 to 100 g of iodine per 100 g

Polymer and most preferably 10 to 50 g of iodine per 100 g of polymer, measured in accordance with DIN 53241-1.

Suitably, the (meth) acrylic polymer may have an acid number in the range of 0 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 also be determined by dispersion according to DIN EN ISO 2114.

The hydroxyl number of the (meth) acrylic 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 be determined according to DIN EN ISO 4629.

The molecular weight of the polymers is initially uncritical within wide limits.

Are particularly hard and solvent resistant

Coating agent with good mechanical properties desired, as high a molecular weight may be helpful. Preferred emulsion polymers with a high

Proportion of polymers which are insoluble in THF can be obtained in the manner set forth above. The

 Reaction parameters to a high molecular weight too

received, are known. Thus, in particular, the use of molecular weight regulators can be dispensed with.

Coating compositions which are particularly easy and easy to process may also have lower molecular weight polymers, the

Solvent resistance and the hardness of these

Coatings reached a relatively high level.

Preferably, these polymers having a particularly good processability, a molecular weight below 1 000 000 g / mol, preferably below 500 000 g / mol and more preferably below 250 000 g / mol. The molecular weight can be determined by gel permeation chromatography (GPC) against a PMMA standard.

Polymers, in particular low molecular weight emulsion polymers, can be prepared by the addition of

Molecular weight regulators are obtained in the reaction mixture before or during the polymerization. Sulfur-free molecular weight regulators and / or

sulfur-containing molecular weight regulators are used.

The sulfur-free molecular weight regulators include, for example, but without limitation, dimeric methylstyrene (2,4 diphenyl-4-methyl-1-pentene), enol ethers aliphatic and / or cycloaliphatic aldehydes, terpenes, β-terpinene, terpinolene, 1,4-cyclohexadiene, 1,4-dihydronaphthalene, 1,4,5,8-tetrahydronaphthalene, 2,5-dihydrofuran, 2,5-dimethylfuran and / or 3,6 Dihydro-2H-pyran, preferred is dimeric methylstyrene.

As sulfur-containing molecular weight regulator can

preferably mercapto compounds, dialkyl sulfides,

Dialkyl disulfides and / or diaryl sulfides are used. The following polymerization regulators are given by way of example: di-n-butyl sulfide, di-n-octyl sulfide, diphenyl sulfide,

Thiodiglycol, ethylthioethanol, diisopropyl disulfide, di-n-butyl disulfide, di-n-hexyl disulfide, diacetyl disulfide,

Diethanol sulfide, di-t-butyl trisulfide and dimethyl sulfoxide. Preferably used as molecular weight regulators

 Compounds are mercapto compounds, dialkyl sulfides,

Dialkyl disulfides and / or diaryl sulfides. Examples of these compounds are ethyl thioglycolate, 2-

Ethylhexyl thioglycolate, cysteine, 2-mercaptoethanol, 1, 3-mercaptopropanol, 3-mercaptopropan-1,2-diol, 1,4-

Mercaptobutanol, mercaptoacetic acid, 3-mercaptopropionic acid, mercaptosuccinic acid, thioglycerol, thioacetic acid,

Thiourea and alkylmercaptans such as n-butylmercaptan, n-hexylmercaptan or n-dodecylmercaptan. Particularly preferably used polymerization regulators are mercapto alcohols and mercaptocarboxylic acids.

The molecular weight regulators are preferably used in amounts of 0.05 to 10, more preferably 0.1 to 5 wt .-%, based on the monomers used in the polymerization. Of course, mixtures of polymerization regulators can also be used in the polymerization.

In addition, polymerizations using molecular weight regulators to reduce the minimum Film forming temperature (MFT) of the polymers obtainable thereby can be used. According to this preferred

Embodiment, the proportion of molecular weight regulators may be such that the (meth) acrylic polymers or the coating compositions of the invention have a minimum film-forming temperature (MFT) of at most 60 ° C, more preferably at most 50 ° C and most preferably

at most 40 ° C, which can be measured according to DIN ISO 2115. The higher the proportion of molecular weight regulators, the lower the minimum film-forming temperature.

The adjustment of the particle radii can be influenced inter alia by the proportion of emulsifiers. The higher this proportion, especially at the beginning of the polymerization, the smaller the particles are obtained.

According to a particular embodiment, the

Emulsion polymer, in particular the (meth) acrylic polymer uncrosslinked or crosslinked so low that the in

 Tetrahydrofuran (THF) at 20 ° C soluble fraction is above 60 wt .-% based on the weight of the emulsion polymer. In a further preferred embodiment, the

Emulsion polymer has a content of 0 to 60 wt .-%, particularly preferably 5 to 50 wt .-% and most preferably 10 to 40 wt .-%, based on the weight of

Emulsion polymer which is soluble in THF at 20 ° C. To determine the soluble fraction is an under

Oxygen exclusion dried sample of the polymer in a 200-fold amount of solvent, based on the

 Weight of the sample, stored at 20 ° C for 4 h. To exclude the oxygen, the sample, for example, under

Nitrogen or dried under vacuum. Subsequently the solution is separated from the insoluble fraction, for example by filtration. After evaporation of the

Solvent, the weight of the residue is determined.

For example, a 0.5 g sample of a vacuum-dried emulsion polymer can be stored in 150 ml of THF for 4 hours.

Polymers of the invention may preferably have a relatively low minimum film-forming temperature, although they have a high molecular weight. In particular, these polymers can have a relatively high proportion of constituents which are dissolved in tetrahydrofuran (THF) at 20.degree

insoluble. Particular preference is given to polymers which have an insoluble fraction in THF of at least 10% by weight, preferably at least 15% by weight, measured according to the method set out above, a minimum film formation temperature, measured according to DIN ISO 2115, of at most 60 ° C., especially preferably at most 40 ° C and most preferably

not more than 20 ° C.

The particle radius of the emulsion polymers can be in a wide range. Thus, in particular emulsion polymers having a particle radius in the range of 10 to 500 nm, preferably 10 to 100 nm, particularly preferably 20 to 60 nm can be used. In particular, particle radii below 50 nm can be advantageous for the film formation and the

 Be coating properties. The radius of the particles can be determined by PCS (Photon Correlation Spectroscopy), the data given refer to the r50 value

(50% of the particles are smaller, 50% are larger). For example, a Beckman Coulter N5 Submicron Particle Size Analyzer may be used. Surprising advantages in particular show emulsion polymers having a high swelling factor. preferred

 Emulsion polymers, in particular (meth) acrylic polymers, exhibit a swelling factor of at least 1, in particular

at least 1.1, more preferably at least 1.2, and most preferably at least 1.5. For the determination of

Swelling factor is first the particle radius of the

Emulsion polymers in water (r _water ) measured by the method set out above. Subsequently, the emulsion polymers are swollen in a solvent / water mixture (THF / water = 90:10) and the particle size (microgels) quantified by measurement with the Coulter Nanosizer N5 (r _Lsgm .). For this purpose, a corresponding amount of tetrahydrofuran (THF) is customarily added to the dispersion to form a dispersion in the dispersion

Volume ratio of THF / water = 90:10 set. The measurement is carried out at 20 ° C, the dispersion is swollen after addition of the solvent (THF) for 5 minutes. The quotient of the particle volumes calculated from the obtained particle _radii (r _Lsgm . And ^ asser) is defined as swelling factor (QF):

High swelling factors in particular show emulsion polymers which have low crosslinking. Accordingly, in particular, emulsion polymers obtained from a monomer mixture having a low content of compounds having two or more (meth) acrylate groups show a high swelling factor.

Low swelling factors may in particular also be due to the fact that there is a high residual monomer content and / or a high content of low molecular weight oligomers which each transferred to the THF / water phase. As a result, swelling factors smaller than 1 can be measured.

The (meth) acrylic polymers set forth above can

be used in particular in coating compositions.

 Such coating compositions are also the subject of the present invention.

Of particular interest are in particular

Coating agent, preferably 40 to 80 wt .-%, particularly preferably 50 to 75 wt .-% of at least one

(Meth) acrylic polymer having units derived from (meth) acrylic monomers having at least one double bond and 8 to 40 carbon atoms in the alkyl radical.

The coating compositions of the invention do not require siccatives, but these may be included as an optional ingredient in the compositions. These include in particular organometallic compounds, such as metal soaps of transition metals, such as

Cobalt, manganese, lead, zirconium; Alkali or

Alkaline earth metals such as lithium, potassium and calcium. As an example, mention may be made of cobalt naphthalate and cobalt acetate. The siccatives can be used individually or as a mixture, with particular preference being given to mixtures containing cobalt, zirconium and lithium salts.

The proportion of siccatives in preferred coating compositions may preferably be in the range of 0.5 to 5 wt .-%, especially preferably in the range of 1 to 3 wt .-% based on the

Polymer content lie.

According to a particular aspect of the present invention, the coating agents may comprise solvents. These coating compositions can over a particularly wide

Temperature and humidity range are processed. The term of the solvent is to be understood here broadly. The preferred solvents include in particular

aromatic hydrocarbons, such as toluene, xylene; Esters, in particular acetates, preferably butyl acetate, ethyl acetate, propyl acetate; Ketones, preferably ethyl methyl ketone, acetone, methyl isobutyl ketone or cyclohexanone; Alcohols, especially isopropanol, n-butanol, isobutanol; Ether, in particular

Glycol monomethyl ether, glycol monoethyl ether,

 Glycol monobutyl ether; Aliphatic, preferably pentane, hexane, cycloalkane and substituted cycloalkanes, for example cyclohexane; Mixtures of aliphatics and / or aromatics, preferably naphtha; Gasoline, biodiesel; but also

Plasticizers such as low molecular weight polypropylene glycols or phthalates. The proportion of solvent in preferred

Coating agents may in particular be in the range from 0 to 50% by weight, more preferably in the range from 1 to 20% by weight.

A surprisingly good processability, moreover, show coating compositions whose solids content is preferably at least 50% by weight, more preferably at least 60% by weight. This information applies in particular to

Coating compositions comprising organic solvents.

According to a further embodiment, the

coating compositions according to the invention a relatively high Proportion of water, with aqueous dispersions being particularly preferred coating agents. 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. These coating compositions often comprise only a very small, preferably no fraction of organic

Solvents. Preferred aqueous dispersions comprise at most 5% by weight, more preferably at most 2% by weight, of volatile organic constituents (VOC), such as residual monomers or organic solvents. These coating compositions are therefore characterized by a particularly high

Environmental friendliness.

Furthermore, the coating compositions according to the invention may contain conventional additives, in particular UV stabilizers,

Flushing aids and biocides are included.

The dynamic viscosity of the coating agent is dependent on the solids content and may include a wide range. So this can be more than at high polymer content

10,000 mPas. A dynamic viscosity in the range from 10 to 4000 mPas, preferably from 10 to 1000 mPas and very particularly preferably from 10 to 500 mPas, measured according to DIN EN ISO 2555 at 25 ° C. (Brookfield), is usually expedient.

The (meth) acrylic polymers or the inventive

Coating agents preferably have a minimum film-forming temperature (MFT) of at most 60 ° C, more preferably at most 50 ° C, and most preferably

at most 40 ° C, which are measured according to DIN ISO 2115 can. Particularly preferred (meth) acrylic polymers or

Coating compositions of the invention exhibit a minimum film-forming temperature (MFT) in the range of -30 ° C to 15 ° C. Those available according to the present invention

(Meth) acrylic polymers display at these MFT values

surprisingly high molecular weight, for example a

Number average molecular weight> 5000 g / mol and very high iodine numbers, for example> 5 g iodine / 100 g (based on the polymer), so that the coatings obtainable thereby show excellent mechanical properties, which are reflected for example in a high pendulum hardness.

Furthermore, the present invention provides a method for producing a coating in which a coating composition of the invention is applied to a substrate and cured.

The coating composition of the invention can be applied by conventional application methods, in particular by roller application or spraying. Continue to be

Dipping method for applying the coating agent

suitable. The curing of the coating agent is carried out by drying and by oxidative crosslinking means

Atmospheric oxygen.

The present coating composition can be used in particular as a varnish, varnish, sealant, adhesive and printing ink

be used.

To the substrates, preferably with a

coating composition according to the invention can be provided include in particular wood, metals, especially iron and steel, and plastics.

Moreover, the present invention provides coated articles obtainable by a method according to the invention. The coating of this

Items characterized by an outstanding

Property spectrum.

From the coating compositions of the invention

available coatings show a high

Solvent resistance, in particular, only small amounts are dissolved by solvent from the coating. Preferred coatings show in particular

high resistance to methyl isobutyl ketone (MIBK). Thus, the weight loss after treatment with MIBK is preferably at most 50% by weight, preferably at most 35% by weight. The uptake of MIBK is preferably at most 1000 wt .-%, more preferably at most 600 wt .-%, based on the weight of the coating used. These values are measured at a temperature of about 25 ° C and an exposure time of at least 4 hours, whereby a completely dried coating is measured, which was crosslinked.

The coatings consisting of the inventive

Coating agents are obtained show a high

mechanical resistance. The pendulum hardness is preferably at least 15 s, preferably at least 25 s, measured in accordance with DIN ISO 1522. Inventive coatings show surprisingly good mechanical properties. Of particular interest are, in particular, coatings which have a nominal elongation at break of preferably at least 100%, particularly preferably at least 200%, measured in accordance with DIN EN ISO 527 Part 3.

In addition, coatings are furthermore preferred which have a tensile strength, measured in accordance with DIN EN ISO 527 Part 3, of at least 0.5 MPa, more preferably at least 2 MPa.

Furthermore, the present invention surprisingly

Coatings are available, which have a tensile strength of at least 1 MPa, more preferably at least 2 MPa, an elongation at break of at least 100%, more preferably at least 200%.

Furthermore, preferred coatings which are obtainable from the coating compositions of the invention have a surprisingly high adhesive strength, which can be determined in particular according to the cross-cut test. In particular, a classification of 0-1, especially

preferably from 0 according to the standard DIN EN ISO 2409 can be achieved.

Hereinafter, the present invention is based on

Examples are explained in more detail, without this being a restriction. Examples

Preparation of 2- [((2-E) octa-2,7-dienyl) methylamino] ethyl 2-methylprop-2-enoate

First, methyl (octa-2, 7-dienyl) aminoethanol

produced. To this was added 48 mg of PddvdsIMes (1,3-dimesitylimidazol-2-ylidene-palladium (0) -n ² , n ² , -l, l, 3,3-tetramethyl-1,3-divinyl-disiloxane 8.1 x 10 ^~5 mol) and 351 mg of 1,3-dimesityl-lH-imidazol-3-ium-methanesulfonate (8.7 x 10 ^{~ 4} mol) in a 1 L Schlenk flask under argon with 100 ml of MeOH and 185 ml of N-methylaminoethanol (173 g, 2.3 mol). The solution was stirred for half an hour and transferred under argon to a 2 liter stainless steel autoclave (Parr Instruments). The autoclave was cooled with dry ice, whereby 220 g of butadiene (4.1 mol) were condensed. The autoclave was opened

Room temperature heated, with nitrogen, a pressure of 20 bar was generated. The mixture was then stirred at 80 ° C for 20 h. After the end of the reaction, the autoclave was cooled, the pressure released and the reaction solution again transferred to a 1 L Schlenk flask. The product obtained was purified by vacuum distillation, the boiling point was about 60 ° C. There are obtained 349 g (93%) of product. The product was analyzed by NMR spectroscopy.

The obtained (methyl (octa-2, 7-dienyl) amino) ethanol was then reacted with methyl methacrylate to give [(octa-2,7-dienyl) methylamino] ethyl 2-methylprop-2-enoate.

To this was added 140.0 g (0.76 mol) of (E) -2- (methyl (octa-2,7-dienyl) amino) ethanol, 760.8 g (7.60 mol) of methyl methacrylate, 0.191 g (1000 ppm ) Hydroquinone monomethyl ether (HQME) and 0.191 g (1000 ppm) phenothiazine submitted. The mixture was then azeotropically dehydrated with methyl methacrylate. Then, the catalyst (2.80 g of tetraisopropyl titanate dissolved in 2.80 g of methyl methacrylate) was added.

The reaction mixture was heated to boiling. The

Methyl methacrylate / methanol azeotrope was separated, with the head temperature gradually increasing to 100 ° C. To

Termination of the reaction was briefly cooled, the catalyst precipitated by the addition of 20 ml of water and cooled with stirring to room temperature. After filtration, the excess methyl methacrylate was distilled off on a rotary evaporator.

Example 1 (BuA-MMA-OAEMA-MAS = 45-39-15-1 with

carbonate)

First, in a 1 l PE beaker, 90 g of butyl acrylate (BuA), 78 g of methyl methacrylate (MMA), 30 g of [(octa-2,7-dienyl) methylamino] ethyl 2-methylprop-2-enoate (octadienylmethyl -aminoethyl methacrylate; OAEMA), 2 g of methacrylic acid (MAS), 7.5 g of 4,4'-azobis (4-cyanovaleric acid) sodium salt (10%), 6 g of Disponil FES 32 (30%), 9 g of Triton X305, 0.3 g NaHCO ₃ , 0.63 g Na ₂ CO ₃ and 175.4 g water were emulsified by Ultra-Turrax for 3 minutes at 4000 rpm.

In a 1 1 glass reactor, which could be tempered with a water bath and was equipped with a paddle stirrer, 120 g of water and 0.15 g of Disponil FES 32 (30%) were introduced, heated to 80 ° C and with 7.5 g 4, 4 'azobis (4-cyanovaleric acid) sodium salt (10%) was added. 5 minutes After the initiator addition, the previously prepared emulsion was metered in within 240 minutes (interval: 3 minutes feed, 4 minutes break, 237 minutes residual feed). to

Dosing of the emulsion from a feed vessel, a Lewa piston metering pump, type HK with 5 mm piston was set to a capacity of 1.66 g / min used.

After the end of the feed was stirred at 80 ° C for 1 hr. It was then cooled to room temperature and the dispersion was filtered off via VA sieve mesh with a mesh size of 0.09 mm.

The emulsion prepared had a solids content of 40 ± 1%, a pH of 7.3, a viscosity of 10 mPas and an r _N5 value of 110 nm.

Subsequently, the swelling factor of the emulsion was determined. For this purpose, the particle radius of the

Emulsion polymers in water (r _water ) by PCS (Photon

Correlation spectroscopy) with a Beckman Coulter N5

Submicron Particle Size Analyzer, with the data given referring to the r50 value (50% of the particles are smaller, 50% are larger).

Subsequently, the emulsion polymers were in a

Solvent / water mixture (THF / water = 90:10) swollen and quantified the particle size (microgels) by measurement with the Coulter Nanosizer N5 (r _Lsgm .). For this purpose, an appropriate amount of tetrahydrofuran (THF) was added to the dispersion in order to adjust a volume ratio of THF / water = 90:10 in the dispersion. The measurement was carried out at 20 ° C, the dispersion was swollen after addition of the solvent (THF) for 5 minutes. The quotient of the calculated particle _radii (r _Lsgm and r _water )

Particle volumes are defined as swelling factor (QF):

The emulsion polymers showed a swelling factor of 1.15

Example 2 (BuA-MMA-OAEMA-MAS = 47.1-41.7-10.2-1 with

carbonate)

First, in a 1 liter PE beaker, 94.2 g

Butyl acrylate (BuA), 83.4 g methylmethacrylate (MMA), 20.4 g of [(octa-2, 7-dienyl) methylamino] ethyl-2-methylprop-2-enoate (OAEMA), 2 g of methacrylic acid (MAS), 7.5 g of 4,4'-azobis (4-cyanovaleric acid) sodium salt (10%), 6 g of Disponil FES 32 (30%), 9 g of Triton X305, 0.3 g of NaHCO ₃ , 0.63 g Na ₂ C0 ₃ and 175.4 g of water were emulsified by Ultra-Turrax at 4000 rpm for 3 minutes.

In a 1 1 glass reactor, which could be tempered with a water bath and was equipped with a paddle stirrer, 120 g of water and 0.15 g of Disponil FES 32 (30%) were introduced, heated to 80 ° C and with 7.5 g 4, 4 'azobis (4-cyanovaleric acid) sodium salt (10%) was added. 5 minutes after the initiator addition, the previously prepared emulsion was metered in within 240 minutes (interval: 3 minutes feed, 4 minutes break, 237 minutes residual feed). to

Dosing of the emulsion from a feed vessel, a Lewa piston metering pump, type HK with 5 mm piston was set to a capacity of 1.66 g / min used. After the end of the feed was stirred at 80 ° C for 1 hr. It was then cooled to room temperature and the dispersion was filtered through VA mesh with 0.09 mm mesh size.

The emulsion prepared had a solids content of 40 ± 1%, a pH of 7.2, a viscosity of 12 mPas and an _rN5 value of 105 nm.

The determination of the swelling factor according to the above

showed a value of 1.21.

Example 3 (BuA-MMA-OAEMA-MAS = 48.07-44.25-6.68-1 with

carbonate)

First, in a 1 liter PE beaker, 96.1 g

Butyl acrylate (BuA), 88.5 g methyl methacrylate (MMA), 13.4 g of [(octa-2, 7-dienyl) methylamino] ethyl 2-methylprop-2-enoate (OAEMA), 2 g of methacrylic acid (MAS), 7.5 g of 4,4'-azobis (4-cyanovaleric acid) sodium salt (10%), 6 g of Disponil FES 32 (30%), 9 g of Triton X305, 0.3 g of NaHCO ₃ , 0.63 g Na ₂ C0 ₃ and 175.4 g of water were emulsified by Ultra-Turrax at 4000 rpm for 3 minutes.

In a 1 1 glass reactor, which could be tempered with a water bath and equipped with a paddle stirrer, 120 g of water and 0.15 g of Disponil FES 32 (30%) were introduced, heated to 80 ° C and with 7.5 g 4, 4 'azobis (4-cyanovaleric acid) sodium salt (10%) was added. 5 minutes after the initiator addition, the previously prepared emulsion was added within 240 minutes (interval: 3 minutes feed, 4 minutes break, 237 minutes remaining feed). To dose the emulsion from a feed vessel was a

Lewa piston metering pump, type HK with 5 mm piston set to a capacity of 1.66 g / min. Used.

After the end of the feed was stirred at 80 ° C for 1 hr. It was then cooled to room temperature and the dispersion was filtered through VA mesh with 0.09 mm mesh size.

The emulsion prepared had a solids content of 40 ± 1%, a pH of 7.3, a viscosity of 12 mPas and an r _N5 value of 79 nm.

The determination of the swelling factor according to the above

This method gave a value of 2.7.

Example 4 (BuA-MMA-OAEMA-MAS = 45-39-15-1, with

Carbonate buffer and 0.1% controller based on polymer)

First, 90 g of butyl acrylate (BuA), 78 g of methyl methacrylate (MMA), 30 g of [(octa-2,7-dienyl) methylamino] ethyl-2-methylprop-2-enoate (OAEMA) were used in a 1 l PE beaker, 2 g

Methacrylic acid (MAS), 7.5 g of 4,4'-azobis (4-cyanovaleric acid) sodium salt (10%), 6 g of Disponil FES 32 (30%), 9 g of Triton X305, 0.3 g of NaHCO ₃ in 10 g water, 0.63 g Na ₂ C0 ₃ in 10 g water, 0.2 g regulator (2-

Ethylhexylthioglycolat) and 155.7 g of water emulsified by Ultra-Turrax for 3 minutes at 4000 rpm. In a 1 1 glass reactor, which could be tempered with a water bath and was equipped with a paddle stirrer, 120 g of water and 0.15 g of Disponil FES 32 (30%) were introduced, heated to 80 ° C and with 7.5 g 4, 4 'azobis (4-cyanovaleric acid) sodium salt (10%) was added. 5 minutes

After the initiator addition, the previously prepared emulsion was metered in within 240 minutes (interval: 3 minutes feed, 4 minutes break, 237 minutes residual feed). to

Dosing of the emulsion from a feed vessel was a Lewa piston metering pump, type HK with 5 mm piston set to a capacity of 1.58 g / min used.

After the end of the feed was stirred at 80 ° C for 1 hr. It was then cooled to room temperature and the dispersion was filtered off via VA sieve mesh with a mesh size of 0.09 mm.

The produced emulsion had a solids content of 40 ± 1%, a pH of 7.6, a viscosity of 11 mPas and an r _N5 value of 104 nm.

The determination of the swelling factor according to the above

showed a value of 1.62.

Example 5 (BuA-MMA-OAEMA-MAS = 45-39-15-1, with

Carbonate buffer and 0.5% controller based on polymer)

In a 1 l PE beaker, 90 g butyl acrylate (BuA), 78 g methyl methacrylate (MMA), 30 g [(octa-2,7- dienyl) methylamino] ethyl 2-methylprop-2-enoate (OAEMA), 2 g of methacrylic acid (MAS), 7.5 g of 4,4'-azobis (4-cyanovaleric acid) sodium salt (10%), 6 g of Disponil FES 32 (30%), 9 g Triton X305, 0, 3 g NaHCO ₃ in 10 g water, 0.63 ga ₂ CO ₃ in 10 g water, 1 g regulator (2-

Ethylhexylthioglycolat) and 156, 9 g of water emulsified by Ultra-Turrax for 3 minutes at 4000 rpm.

In a 1 1 glass reactor, which could be tempered with a water bath and was equipped with a paddle stirrer, 120 g of water and 0.15 g of Disponil FES 32 (30%) were introduced, heated to 80 ° C and with 7.5 g 4, 4 'azobis (4-cyanovaleric acid) sodium salt (10%) was added. 5 minutes after the initiator addition, the previously prepared emulsion was metered in within 240 minutes (interval: 3 minutes feed, 4 minutes break, 237 minutes residual feed). to

Dosing of the emulsion from a feed vessel was a Lewa piston metering pump, type HK with 5 mm piston set to a capacity of 1.59 g / min used.

After the end of the feed was stirred at 80 ° C for 1 hr. It was then cooled to room temperature and the dispersion was filtered through VA mesh with 0.09 mm mesh size.

The emulsion prepared had a solids content of 40 ± 1%, a pH of 7.3, a viscosity of 16 mPas and an _rN5 value of 92 nm.

The determination of the swelling factor according to the above

showed a value of 1.03. Example 6 (BuA-MMA-OAEMA-MAS

Acetic acid / acetate-buffer)

The above-outlined example 1 became essentially

repeated, but using a buffer based on acetic acid and acetate was used. Here, a 1: 1 mixture (molar) was used, wherein the molar concentration of

Acetic acid 0.1 mol / 1 and the molar concentration of acetate 0.1 mol / 1. The pH of the emulsion was 6.4.

Solvent resistance was determined using methyl isobutyl ketone (MIBK), with a sample (A) swollen with MIBK at room temperature for 4 hours. The sample was then removed from the solvent, excess solvent removed and the weight determined. Subsequently, the sample was dried for 1 hour at about 140 ° C (B). From the difference in weight between A and B, the fraction of the sample removed by the solvent is calculated. The swelling was calculated based on the weight of sample B freed from soluble fractions and will be referred to herein as "true swelling".

The resulting coating composition had a minimum film-forming temperature (MFT) of 9.5 ° C and a

Swelling factor of 1.151. The true swelling in MIBK after 4 hours was 286%, and the weight loss related to the sample released from soluble portions was 29.4%. Example 7 (BuA-MMA-OAEMA-MAS = 45-39-15-1

Dihydrogen phosphate / hydrogen phosphate buffer)

The above-outlined example 1 became essentially

repeated, but with a buffer based on

 Dihydrogen phosphate and hydrogen phosphate was used. Here, a 4: 1 mixture (molar) was used, wherein the molar concentration of dihydrogen phosphate was 0.02 mol / 1 and the molar concentration of hydrogen phosphate 0.005 mol / 1. The pH of the emulsion was 6.5.

The resulting coating composition had a minimum film-forming temperature (MFT) of less than 0 ° C and a swelling factor of 1.00. The true swelling in MIBK after 4 hours was 258% and the weight loss related to the sample released from soluble portions was 37.1%.

Example 8 (BuA-MMA-OAEMA-MAS = 45-39-15-1 with ammonia / ammonium buffer)

The above-outlined example 1 became essentially

repeated, but using a buffer based on ammonia and ammonium chloride was used. Here, a 1: 1 mixture (molar) was used, wherein the molar concentration of ammonia 0.1 mol / 1 and the molar concentration of

Ammonium chloride 0.1 mol / 1. The pH of the emulsion was 7.4.

The coating composition obtained had a minimum

Film Forming Temperature (MFT) of less than 0 ° C and a Swelling factor of 1.682. The true swelling in MIBK after 4 hours was 369%, and the weight loss related to the sample, which was freed from soluble portions, was 19.6%.

Claims

claims

A composition for the preparation of polymers comprising at least one monomer and at least one

 Radical starter, characterized in that the

 Radical initiator is an azo compound, at least one monomer is an amide or an amine monomer, and

 at least one monomer is a (meth) acrylic monomer having at least one C-C double bond and 8 to 40 carbon atoms in the alkyl radical.

A composition according to claim 1, characterized

 characterized in that the composition is an emulsion.

Composition according to claim 2, characterized

 characterized in that the aqueous phase of the emulsion has a pH in the range of 4 to 9.5.

Composition according to at least one of

 preceding claims, characterized in that the composition comprises at least one (meth) acrylic monomer which is an amide or an amine and in the

Alkyl has at least one double bond and 8 to 40 carbon atoms.

5. A composition according to claim 4, characterized in that at least one (meth) acrylic monomer corresponds to the general formula (II)

wherein R is hydrogen or a methyl group, X and X are independently oxygen or a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6

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

 Carbon atoms is used.

Composition according to at least one of

 preceding claims, characterized in that at least one (meth) acrylic monomer of the general

 Formula (IV) corresponds

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, R ^{3 is} a

Alkylene group having 1 to 22 carbon atoms, Y

Oxygen, sulfur or a group of the formula NR ", where R" is hydrogen or a radical having 1 to 6 carbon atoms, and R ^{4 is} an unsaturated radical Is radical having at least 8 carbon atoms and at least two CC double bonds.

Composition according to claim 6, characterized

 in that, in formula (IV), at least one of X and Y represents a group of the formula NR ", where R" is hydrogen or a radical having 1 to 6

 Represents carbon atoms.

8. Composition according to at least one of

 preceding claims, characterized in that at least one azo compound is selected from 2 azobis-cyanovaleric acid, 4- (phenylazo) benzoic acid and 2- (4-hydroxyphenylazo) benzoic acid.

9. Composition according to at least one of

 preceding claims, characterized in that the composition comprises at least one buffer.

(Meth) acrylic polymer obtainable by polymerization of a composition according to at least one of

 Claims 1 to 9.

(Meth) acrylic polymer according to claim 10, characterized

characterized in that the polymer is an emulsion polymer and the emulsion polymer has a swelling factor of at least 1.

12. A process for the preparation of polymers, characterized in that a composition according to any one of claims 1 to 9 is polymerized.

Coating composition comprising at least

 (Meth) acrylic polymer according to claim 10 or

14. Coating composition according to claim 13, characterized

 characterized in that the coating agent is an aqueous dispersion.

15. A coating obtainable with a coating composition according to claim 13 or 14.