EP2013252A2

EP2013252A2 - Copolymers of olefinically unsaturated monomers, process for their preparation and their use

Info

Publication number: EP2013252A2
Application number: EP07711382A
Authority: EP
Inventors: Dirk Schmelter; Horst HINTZE-BRÜNING
Original assignee: BASF Coatings GmbH
Current assignee: BASF Coatings GmbH
Priority date: 2006-03-24
Filing date: 2007-01-25
Publication date: 2009-01-14
Also published as: DE102006014088A1; US20090137715A1; WO2007110116A2; JP2009531479A; WO2007110116A3

Abstract

Copolymers (A) of olefinically unsaturated monomers (a) preparable by single-stage or multistage controlled free-radical copolymerization in an aqueous medium of (a1) at least one olefinically unsaturated monomer containing at least one chelate-forming group and (a2) at least one olefinically unsaturated monomer other than the olefinically unsaturated monomer (a1), selected from the group consisting of (a21) monomers of the general formula (I) R1R2C=CR3R4 (I) in which the R1, R2, R3 and R4 radicals are each independently hydrogen atoms or substituted or unsubstituted alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl or arylcycloalkyl radicals, with the proviso that at least two of the variables R1, R2, R3 and R4 are each substituted or unsubstituted aryl, arylalkyl or arylcycloalkyl radicals, especially substituted or unsubstituted aryl radicals; (a22) olefinically unsaturated terpene hydrocarbons and (a23) dimeric alpha-alkylvinylaromatics; process for their preparation and their use.

Description

Copolymers of olefinically unsaturated monomers, process for their preparation and their use

Field of the invention

The present invention relates to novel copolymers of olefinically unsaturated monomers. Moreover, the present invention relates to a novel process for the preparation of copolymers of olefinically unsaturated monomers. Not least, the present invention relates to the use of the novel copolymers of olefinically unsaturated monomers and the copolymers of olefinically unsaturated monomers prepared by the novel process.

State of the art

Copolymers of olefinically unsaturated monomers obtained by the controlled one- or multistage radical copolymerization of

at least one first olefinically unsaturated monomer and

- At least a second, different from the first olefinically unsaturated monomer, olefinically unsaturated monomer of general formula I.

R ¹ R ² C = CR ³ R ⁴ (I),

wherein the radicals R ¹ , R ² , R ³ and R ^{4 are} each independently

Are hydrogen atoms or substituted or unsubstituted alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl or arylcycloalkyl radicals, with the proviso that at least two of the variables R ¹ , R ² , R ³ and R ^{4 are} substituted or unsubstituted aryl, arylalkyl or arylcycloalkyl radicals, in particular substituted or unsubstituted aryl radicals;

can be produced in an aqueous medium, are known from German Patent Application DE 101 26 651 A1. They are used as emulsifiers in the production of pigmented powder coating suspensions (powder slurries). In this case, they are preferably introduced into the aqueous media of the powder coating suspensions via pigment pastes or pigment preparations. The pigment pastes or pigment preparations may have a particularly high content of nanoparticles, in particular hydrophilic, oxidic nanoparticles based on silica, alumina, zinc oxide, zirconium oxide and the polyacids and heteropolyacids of transition metals, preferably of molybdenum and tungsten. The nanoparticles have a primary particle size <50 nm.

Whether these known copolymers are able to act as crystallization inhibitors and dispersants towards barium sulfate nanoparticles, in particular to stabilize barium sulfate primary particles, is not apparent from the German patent application.

Object of the invention

It is an object of the present invention to find novel copolymers which can be prepared by the controlled radical copolymerization of olefinically unsaturated monomers and which are outstandingly suitable as dispersants for nanoparticles. In particular, they should be outstandingly suitable as crystallization inhibitors and / or dispersants for barium sulfate nanoparticles. Last but not least, they are ideal for the stabilization of barium sulfate primary particles.

In addition, it was an object of the present invention to find a novel process for the preparation of copolymers of olefinically unsaturated monomers by the controlled radical copolymerization in an aqueous medium, which can be carried out in a simple, safe and very reproducible manner.

The aqueous dispersions of the novel copolymers which can be prepared or prepared by the controlled radical copolymerization of olefinically unsaturated monomers should be capable of stably dispersing particularly large amounts of nanoparticles, in particular of barium sulfate nanoparticles.

The novel nanoparticle dispersions are said to be outstandingly suitable for the production of new, physically, thermally curable, actinic, thermally and actinic-curable materials, in particular new coating materials, adhesives and sealants and precursors of moldings and films. The new curable materials are intended to provide new, thermoplastic or thermoset materials, in particular new coatings, adhesive layers, seals, molded parts and films, with very good performance properties.

Inventive solution

Accordingly, the novel copolymers of (A) olefinically unsaturated monomers (a) were found, prepared by one or more stages controlled radical copolymerization in an aqueous medium of

(a1) at least one olefinically unsaturated monomer containing at least one chelating group, and

(a2) at least one olefinically unsaturated monomer other than the olefinically unsaturated monomer (a1) selected from the group consisting of

(a21) monomers of the general formula I

R ¹ R ² C = CR ³ R ⁴ (I),

wherein the radicals R ¹ , R ² , R ³ and R ^{4 are} each independently hydrogen or substituted or unsubstituted alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl or arylcycloalkyl radicals with the proviso that at least two of the variables R ¹ , R ² , R ³ and R ^{4 are} substituted or unsubstituted aryl,

Arylalkyl or arylcycloalkyl radicals, especially substituted or unsubstituted aryl radicals;

(a22) olefinically unsaturated terpene hydrocarbons; and

(a23) dimeric alpha-alkyl vinylaromatics.

The new copolymers (A) of olefinically unsaturated monomers (a) are referred to below as "copolymers (A) according to the invention". In addition, the novel process for the preparation of the novel copolymers (A) was found in which

(a1) at least one containing at least one chelating group, olefinically unsaturated monomer

(a21) monomers of the general formula I

R ¹ R ² C = CR ³ R ⁴ (I),

wherein R ¹ , R ² , R ³ and R ^{4 are} each independently hydrogen or substituted or unsubstituted alkyl, cycloalkyl,

Alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl or arylcycloalkyl radicals, with the proviso that at least two of the

Variables R ¹ , R ² , R ³ and R ^{4 represent} substituted or unsubstituted aryl,

(a22) olefinically unsaturated terpene hydrocarbons and

(a23) dimeric alpha-alkyl vinylaromatics;

in a aqueous medium controlled free-radical copolymerization.

The following is the new process for the preparation of the invention

Copolymers (A) referred to as "inventive method".

Last but not least, the novel use of the novel copolymers (A) and of the novel process according to the invention was prepared

Copolymers (A) found as a dispersant for nanoparticles, hereinafter referred to as

Is called "use according to the invention".

Other subjects of the invention will become apparent from the description. Advantages of the invention

In view of the prior art, it was surprising and unforeseeable for the skilled worker that the object on which the present invention was based could be achieved by the copolymers (A) according to the invention, the process according to the invention and the use according to the invention.

In particular, it was surprising that the novel copolymers (A) were outstandingly suitable as dispersants for nanoparticles. In particular, they were outstandingly suitable as crystallization inhibitors and / or dispersants for barium sulfate nanoparticles. Last but not least, they were outstandingly suitable for the stabilization of barium sulfate primary particles.

In addition, it was surprising that the process according to the invention could be carried out in a particularly simple, safe and very reproducible manner.

The resulting novel aqueous dispersions of the novel copolymers (A) were able to stably disperse particularly large amounts of nanoparticles, in particular of barium sulfate nanoparticles.

The resulting novel nanoparticle dispersions were eminently suitable for the production of new physical, thermal, actinic, thermally and actinic-curable materials, in particular new coating materials, adhesives and sealants, as well as precursors of molded parts and films.

The curable materials of the invention provided new, thermoplastic or thermoset materials, especially new coatings, adhesive layers, seals, moldings and films, with very good performance properties.

Detailed description of the invention

The novel copolymers (A) can be prepared by at least (a1) at least one, especially one, at least one, in particular a chelating group-containing, olefinically unsaturated monomer

(a2) at least one, in particular an olefinically unsaturated monomer other than the olefinically unsaturated monomer (a1), selected from the group consisting of

(a21) monomers of the general formula I

R ¹ R ² C = CR ³ R ⁴ (I),

wherein the radicals R ¹ , R ² , R ³ and R ^{4 are} each independently hydrogen or substituted or unsubstituted alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl or arylcycloalkyl radicals the proviso that at least two of the

Variables R ¹ , R ² , R ³ and R ^{4 are} substituted or unsubstituted aryl, arylalkyl or arylcycloalkyl radicals, in particular substituted or unsubstituted aryl radicals;

(a22) olefinically unsaturated terpene hydrocarbons and

(a23) dimeric alpha-alkyl vinylaromatics;

and optionally

(a3) at least one olefinically unsaturated monomer other than the monomers (a1) and (a2)

in a aqueous medium controlled free-radical copolymerization.

The olefinically unsaturated monomers (a1) contain at least one, in particular one, chelating group which is capable of forming so-called chelates (see Rompp Online, Georg Thieme Verlag, Stuttgart New York, 2005, "Chelates").

Preferably, the chelating group of the monomer (a1) is at least bidentate, in particular bidentate (compare Rompp Online 2005, "Chelates"). The chelating group preferably contains at least two, in particular two, atomic groups which act as electron donors. Through these atomic groups, the monomers (a1) are able to form coordination compounds with metal atoms or metal cations.

Groups of atoms are particularly preferably used, selected from the group consisting of carbonyl (> C = O), thiocarbonyl (> C = S), ether groups (- CH ₂ -O-CH ₂ -), thioether (-CH ₂ -S- CH ₂ -), primary, secondary and tertiary amino groups (> C-NR ⁵ ₂ ) with R = hydrogen atom or alkyl radical having 1 to 6 carbon atoms, primary and secondary imino groups (> C = NR ⁵ ) with R ⁵ = hydrogen atom or alkyl radical 1 to 6 carbon atoms, oxime groups (> C = NOH), imino ether groups (> C = NOR ⁶ ) with R ⁶ = alkyl radical having 1 to 10 carbon atoms or cycloalkyl radical having 4 to 10 carbon atoms, and primary, secondary and tertiary phosphine groups (-PR ⁷ ₂ ) where R ⁷ = hydrogen or alkyl of 1 to 6 carbon atoms, cycloalkyl of 4 to 10 carbon atoms or aryl of 6 to 10 carbon atoms.

Most preferably, the atomic groups are carbonyl groups (> C = O).

In particular, the chelating groups are 1, 3-dicarbonyl groups, especially acetoacetoxy groups (CH ₃ -C (O) -CH ₂ -C (O) -O-).

Preferably, the olefinically unsaturated groups of the monomers (a1) are selected from the group consisting of (meth) acrylate, ethacrylate, crotonate, cinnamate, vinyl ether, vinyl ester, dicyclopentadienyl, norbomenyl, isoprenyl, isopropenyl, Allyl or butenyl groups; Dicyclopentadienyl, norbomenyl, isoprenyl, isopropenyl, allyl or butenyl ether groups or dicyclopentadienyl, norbornyl, isoprenyl, isopropenyl, allyl or butenyl ester groups.

In particular, the olefinically unsaturated groups are (meth) acrylate groups.

Here and in the following, the term "(meth) acrylate groups" is used as a short version for "acrylate groups and / or methacrylate groups". In a monomer (a1), the chelating group or groups are linked to the olefinically unsaturated group or olefinically unsaturated groups via at least one covalent bond or via an at least divalent, especially divalent, linking group.

Preferably, in the monomer (a1), a chelating group is linked to an olefinically unsaturated group via a divalent linking group.

As divalent linking group, basically all divalent organic groups are considered, which are inert.

In the context of the present invention, "inert" means that the relevant divalent linking groups do not inhibit the controlled free-radical copolymerization in the preparation of the copolymers (A) according to the invention and have no undesirable side reactions before, during and after the preparation of the novel copolymers (A) z. B. decomposition reactions trigger.

Preferably, the divalent linking groups are groups which contain or consist of alkylene groups, cycloalkylene groups and / or arylene groups. Alkylene groups, particularly preferably alkylene groups having 2 to 6 carbon atoms, in particular 1, 2-ethylene groups, are preferably used.

Examples of particularly suitable monomers (a1) are 2- (acetoacetoxy) ethyl methacrylate and acrylate, in particular methacrylate, which is sold under the trademark Lonzamon® AAEMA by Lonza.

The amount of olefinically unsaturated monomer (a1) used in the controlled radical copolymerization can vary very widely and can therefore be perfectly adapted to the requirements of the individual case. The amount of (a1), in each case based on the sum of the monomers (a1) and (a2), is preferably from 1 to 99.9% by weight, preferably from 2 to 99% by weight, particularly preferably from 3 to 98% by weight .-% and in particular 5 to 97 wt .-%.

As monomers (a2) it is possible to use monomers (a21) of the general formula I. In the general formula I, the radicals R ¹ , R ² , R ³ and R ^{4 are} each independently hydrogen or substituted or unsubstituted alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl-arylalkyl or arylcycloalkyl radicals, with the proviso that at least two of the variables R ¹ , R ² , R ³ and R ^{4 are} substituted or unsubstituted aryl, arylalkyl or arylcycloalkyl radicals, in particular substituted or unsubstituted aryl radicals.

Examples of suitable alkyl radicals are methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, amyl, hexyl or 2-ethylhexyl.

Examples of suitable cycloalkyl radicals are cyclobutyl, cyclopentyl or cyclohexyl.

Examples of suitable alkylcycloalkyl radicals are methylenecyclohexane, ethylene cyclohexane or propane-1,3-diylcyclohexane.

Examples of suitable cycloalkylalkyl radicals are 2-, 3- or 4-methyl, -ethyl, -propyl or -butylcyclohex-1-yl.

Examples of suitable aryl radicals are phenyl, naphthyl or biphenylyl.

Examples of suitable alkylaryl radicals are benzyl or ethylene or propane-1, 3-diyl-benzene.

Examples of suitable cycloalkylaryl radicals are 2-, 3- or 4-phenylcyclohex-1-yl.

Examples of suitable arylalkyl radicals are 2-, 3- or 4-methyl, -ethyl, -propyl or -butylphen-1-yl.

Examples of suitable arylcycloalkyl radicals are 2-, 3- or 4-cyclohexylphen-1-yl.

The above-described radicals R ¹ , R ² , R ³ and R ⁴ may be substituted. For this purpose, electron-withdrawing or electron-shifting atoms or organic radicals can be used.

Examples of suitable substituents are halogen atoms, in particular chlorine and fluorine, nitrile groups, nitro groups, partially or completely halogenated, in particular chlorinated and / or fluorinated, alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, Cycloalkylaryl- arylalkyl and Arylcycloalkylreste, inclusive of the above exemplified, in particular tert-butyl; Aryloxy, alkyloxy and cycloalkyloxy, especially phenoxy, naphthoxy, methoxy, ethoxy, propoxy, butyloxy or cyclohexyloxy; Arylthio, alkylthio and cycloalkylthio radicals, in particular phenylthio, naphthylthio, methylthio, ethylthio, propylthio, butylthio or cyclohexylthio; hydroxyl groups; and / or primary, secondary and / or tertiary amino groups, in particular amino, N-methylamino, N-ethylamino, N-propylamino, N-phenylamino, N-cyclohexylamino, N, N-dimethylamino, N, N-diethylamino, N, N -Dipropylamino, N ₁ N- diphenylamino, N, N-dicyclohexylamino, N-cyclohexyl-N-methylamino or N-ethyl-N-methylamino.

Examples of monomers (a21) which are particularly preferably used according to the invention are diphenylethylene, dinaphthaleneethylene, cis- or trans-stilbene, vinylidene-bis (4-N, N-dimethylaminobenzene), vinylidene bis (4-aminobenzene) or vinylidene bis (4- nitrobenzene).

The monomers (a21) can be used individually or as a mixture of at least two monomers (a21).

With regard to the reaction procedure and the properties of the resulting copolymers (A), diphenylethylene (a21) is of very particular advantage and is therefore very particularly preferably used as monomer (a21) of general formula I.

Furthermore, monomers (a2) which can be used are olefinically unsaturated terpene hydrocarbons (a22).

The olefinically unsaturated terpene hydrocarbons (a22) are conventional and known, naturally occurring or synthetic compounds. Preferably, olefinically unsaturated terpene hydrocarbons are used which do not contain reactive functional groups, such as hydroxyl groups, amino groups or carbonyl groups.

Preferably, the olefinically unsaturated terpene hydrocarbon (a22) is selected from the group consisting of aeyclic diterpenes, monocyclic terpenes, bicyclic terpenes, acyclic sesquiterpenes, monocyclic sesquiterpenes, bicyclic sesquiterpenes, tricyclic sesquiterpenes, acyclic diterpenes, monocyclic diterpenes, and tricyclic diterpenes. More preferably, the terpene hydrocarbon (a22) is selected from the group consisting of acyclic monoterpenes, monocyclic terpenes and bicyclic terpenes.

Most preferably, the terpene hydrocarbon (a22) is selected from the group consisting of octimene, myrcene, the menthenes, the menthadienes, alpha-pinene and beta-pinene.

In particular, the menthadienes (a22) are selected from the group consisting of alpha-terpinene, beta-terpinene, gamma-terpinene, terpinolene, alpha-phellandrene, beta-phellandrene, limonene and dipentene.

Specifically, gamma-terpinene is used as the monomer (a22).

Suitable monomers (a2) are not least dimeric alpha-alkylvinylaromatics (a23) and preferably dimeric alpha-alkylstyrenes (a23), in particular dimeric alpha-methylstyrene (a23).

In the case of controlled free-radical copolymerization, the amount of monomers (a2) used can vary widely and thus be perfectly adapted to the requirements of the individual case. Preferably, the amount of (a2), based in each case on the sum of the monomers (a1) and (a2), is from 0.1 to 99% by weight, preferably from 1 to 98% by weight, particularly preferably from 2 to 97% by weight .-% and in particular 3 to 95 wt .-%.

The above-described olefinically unsaturated monomers (a1) and (a2) may be further copolymerized with at least one olefinically unsaturated monomer (a3) different therefrom. Preferably, at least two olefinically unsaturated monomers (a3) are used.

The structure of the olefinically unsaturated monomers (a3) can vary widely. It is essential that the olefinically unsaturated monomers (a3) are copolymerically free-radically copolymerizable with the olefinically unsaturated monomers (a1) and (a2) described above and do not cause any undesirable side reactions.

The olefinically unsaturated monomers (a3) may contain or be free from a wide variety of functional groups. If they contain functional groups, they may these do not undergo any undesired physical and chemical interactions with the chelating groups of the monomers (a1) and neither inhibit nor accelerate the controlled free-radical copolymerization. The person skilled in the art can therefore select suitable olefinically unsaturated monomers (a3) on the basis of their general knowledge in a simple manner, if appropriate with the aid of a few orienting experiments.

The olefinically unsaturated monomers (a3) serve to vary the profile of properties of the novel copolymers (A). Because of the large number of suitable olefinically unsaturated monomers (a3), the property profile of the copolymers (A) according to the invention can be varied very widely in a simple manner and adapted excellently to the requirements of the particular intended use, which is a very particular advantage of the novel copolymers (A).

Examples of suitable olefinically unsaturated monomers (a3) are known from German patent application DE 101 26 651 A1, pages 4 to 5, paragraphs [0024] and [0025].

The novel copolymers (A) are prepared in the context of the process according to the invention by the controlled radical copolymerization of the above-described olefinically unsaturated monomers (a1) and (a2) and optionally (a3), preferably (a1), (a2) and (a3) ,

Preferably, the olefinically unsaturated monomers (a1), (a2) and (a3) are used in amounts of, in each case based on (a1), (a2) and (a3),

From 1 to 30% by weight, preferably from 2 to 20% by weight and in particular from 5 to 15% by weight

(a1),

0.1 to 25 wt .-%, preferably 1 to 15 wt .-% and in particular 2 to 10 wt .-% (a2) and

From 45 to 98.9% by weight, preferably from 65 to 97% by weight and in particular from 75 to 93% by weight (a3)

used. The monomers (a1) and (a2) and optionally (a3) are reacted with one another in the presence of at least one free-radical initiator to give the copolymer (A). Examples of suitable initiators are: dialkyl peroxides, such as di-tert-butyl peroxide or dicumyl peroxide; Hydroperoxides, such as cumene hydroperoxide or tert-butyl hydroperoxide; Peresters, such as tert-butyl perbenzoate, tert-butyl perpivalate, tert-butyl per 3,5,5-trimethylhexanoate or tert-butylper-2-ethylhexanoate; Potassium, sodium or ammonium peroxodisulfate; Azodinitriles such as azobisisobutyronitrile; CC-cleaving initiators such as benzpinacol silyl ether; or a combination of a non-oxidizing initiator with hydrogen peroxide.

Preferably, comparatively large amounts of free-radical initiator are added, the proportion of initiator in the reaction mixture, based in each case on the total amount of monomers (a1) and (a2) and optionally (a3) and the initiator, preferably 0.5 to 50% by weight. %, more preferably 1 to 20 wt .-% and in particular 2 to 15 wt .-% is.

The weight ratio of initiator to monomers (a2) is preferably 4: 1 to 1: 4, more preferably 3: 1 to 1: 3 and especially 2: 1 to 1: 2. Further advantages result if the initiator is within the stated limits in the Excess is used.

Radical copolymerization is preferably carried out in customary and known devices, in particular stirred vessels, tubular reactors or Taylor reactors, the Taylor reactors being designed so that the conditions of the Taylor flow are fulfilled over the entire reactor length, even if the kinematic viscosity of the reaction medium due to the copolymerization strongly changes, in particular increases.

The copolymerization is carried out in an aqueous medium.

The aqueous medium contains essentially water. In this case, the aqueous medium in minor amounts organic solvents and / or other dissolved solid, liquid or gaseous organic and / or inorganic, low and / or high molecular weight substances, unless they affect the copolymerization in a negative way or even inhibit. In the context of the present invention, the term "minor amount" is to be understood as meaning an amount which expresses the aqueous character of the aqueous medium does not cancel. The aqueous medium may also be pure water.

Preferably, the copolymerization is carried out in the presence of at least one base. Particularly preferred are low molecular weight bases such as sodium hydroxide, potassium hydroxide, ammonia, diethanolamine, triethanolamine, mono-, di- and triethylamine, and / or dimethylethanolamine, in particular ammonia and / or di- and / or triethanolamine.

The copolymerization is advantageously carried out at temperatures above room temperature and below the lowest decomposition temperature of the monomers used in each case (a1) and (a2) and optionally (a3) is carried out, preferably using a temperature range of 10 to 15O ⁰ C, most preferably 70 to 12O ⁰ C and in particular 80 to 11O ⁰ C is selected.

When using particularly readily volatile monomers (a1) and (a2) and optionally (a3), the copolymerization under pressure, preferably from 1, 5 to 3,000 bar, preferably 5 to 1,500 and in particular 10 to 1000 bar are performed.

With regard to number-average and mass-average molecular weights M _n and M _w and the molecular weight distribution M _w / M _n , the novel copolymers (A) are not subject to any restrictions.

Advantageously, however, the copolymerization is conducted so that a molecular weight distribution M _w / M _n measured by gel permeation chromatography using polystyrene as a standard of <4, preferably <2 and in particular <1, 5 and in some cases also <1, 3 results ,

The molecular weights M _n and M _{w of} the copolymers (A) are controllable by the choice of the ratio of monomer (a1) and (a2) and optionally (a3) to radical initiator within wide limits. In particular, the content of monomer (a2) determines the molecular weight, and in such a way that the larger the proportion of monomer (a2), the lower the molecular weight obtained.

Preferably, the number average molecular weight M _{n is} from 1,000 to 100,000 daltons, preferably from 1,500 to 50,000 daltons and in particular from 2,000 to 25,000 daltons. In the novel process, the novel copolymers (A) are obtained in the form of finely divided dispersions, which are referred to below as "dispersions (A) according to the invention". The particle size of the dispersions (A) according to the invention can vary widely. Their average particle size d ₅₀ determined by photon correlation spectroscopy or laser diffraction is preferably from 1 nm to 500 μm.

The novel dispersions (A) can be supplied as such to the inventive use. However, the copolymers (A) according to the invention can be isolated from them by means of customary and known methods, for example freeze-drying, and be used in the form of liquid or solid resins (A). The form in which the novel copolymers (A) are used in accordance with the invention depends on the requirements of the individual case.

The copolymers (A) according to the invention and the dispersions (A) according to the invention can advantageously be used for all purposes which are customary and known for copolymers and dispersions.

However, they are preferably used as crystallization inhibitors and / or dispersants for nanoparticles, in particular in the preparation of dispersions of nanoparticles.

As nanoparticles, all customary and known nanoparticles can be used.

Preferably, they are selected from the group consisting of metals, compounds of

Metals and organic compounds, in particular compounds of metals selected.

Preferably, the metals are selected from the group consisting of ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, silver and gold.

Preferably, the metal compounds of the compounds of the metals of the second to fifth main group, the third to sixth and the first and second subgroup of the Periodic Table of the Elements and the lanthanides, and preferably from the group consisting of barium, boron, aluminum, gallium, silicon , Germanium, tin, arsenic, antimony, silver, zinc, titanium, zirconium, hafnium, vanadium, niobium, tantalum, molybdenum, tungsten and cerium. In particular, barium is used. The compounds of the metals are preferably oxides, hydrated oxides, sulfates, hydroxides or phosphates, in particular sulfates.

Examples of suitable organic compounds are lignins and starches.

In particular, barium sulfate nanoparticles are used.

The nanoparticles preferably have a primary particle size of <50 nm, preferably 5 to 50 nm, in particular 10 to 30 nm; measured by light scattering and / or laser diffraction methods.

With very particular advantage, the novel copolymers (A) and their dispersions (A) are used as crystallization inhibitors and dispersants in the preparation of deagglomerated barium sulfate nanoparticles by precipitation of barium ions with sulfate ions, as described, for example, in German patent application DE 10 2004 010 201 A1, Page 6, paragraph [0043], to page 7, paragraph [0050], described analogously used. "Deagglomerated" means that the average secondary particle size is at most 30% greater than the average primary particle size.

The dispersions of the barium sulfate nanoparticles according to the invention have a particularly high content of barium sulfate nanoparticles of up to 20% by weight, based on the dispersion.

The deagglomerated barium sulfate nanoparticles according to the invention can be isolated from their dispersions according to the invention, for example by freeze-drying, and stored and transported without problems until they are used further. It proves to be a very particular advantage of the invention deagglomerated barium sulfate nanoparticles that they can be particularly easily redispersed in water and / or organic solvents because of their content of copolymers of the invention (A).

Preferably, the content of the mixture of the deagglomerated barium sulfate nanoparticles according to the invention and the novel copolymers (A) of nanoparticles is from 10 to 90% by weight, preferably from 15 to 85% by weight and in particular from 20 to 80% by weight and (A) at 90 to 10 wt .-%, preferably 85 to 15 wt .-% and in particular 80 to 20 wt .-%, each based on the mixture. Preferably, the nanoparticles according to the invention described above, which contain the copolymers (A) according to the invention, in particular in the form of their dispersions or as isolated nanoparticles, are used for the production of physical, thermal, actinic and thermally and actinic radiation-curable materials of the invention.

In the context of the present invention, actinic radiation includes electromagnetic radiation such as near infrared (NiR), visible light, UV radiation, X-radiation or gamma radiation, in particular UV radiation, and corpuscular radiation such as electron radiation, beta radiation, alpha radiation, proton radiation and neutron radiation, in particular electron radiation, to understand.

The curable materials according to the invention are outstandingly suitable for the production of thermoplastic and thermoset materials.

The curable materials according to the invention are preferably used as coating materials, adhesives, sealants and precursors for moldings and films for the production of coatings according to the invention, adhesive layers, seals, molded parts and films.

In particular, the thermoplastic and thermoset, in particular thermoset, materials of the invention are coatings, moldings and films.

The coatings according to the invention are preferably highly scratch-resistant, pigmented and non-pigmented coatings, preferably transparent, in particular clear, clearcoats, moldings, in particular optical moldings, and self-supporting films.

Very particular preference is given to the coatings according to the invention highly scratch-resistant clearcoats and highly scratch-resistant clearcoats in the context of color and / or effect multicoat systems on conventional and known substrates (compare International Patent Application WO 03/016411, page 41, line 6, to page 43, line 6, in conjunction with page 44, line 6, to page 45, line 6).

The preparation of the thermoplastic and thermoset materials according to the invention from the curable materials according to the invention has no methodological

Special features on, but is using standard and known methods and Devices which are typical of the respective thermoplastic or thermosetting material according to the invention carried out.

In particular, the coating materials according to the invention are applied to substrates by means of the customary and known methods and devices described in International Patent Application WO 03/016411, page 37, lines 4 to 24.

The curing of the curable materials according to the invention can be carried out as described in international patent application WO 03/016411, page 38, line 1, to page 41, line 4.

The curable materials according to the invention provide thermoplastic and thermoset, in particular thermoset, materials according to the invention, in particular coatings, especially clearcoats, moldings, especially optical moldings, and self-supporting films which are highly scratch-resistant and chemically stable. In particular, the coatings according to the invention, especially the clearcoats, can also be produced in layer thicknesses> 40 μm without stress cracks occurring.

The thermoplastic and thermoset, in particular thermoset, materials according to the invention are therefore outstandingly suitable as highly scratch-resistant, decorative, protective and / or effect paint finishes of bodies of

Means of locomotion of any kind (in particular with muscle power

Means of transportation, such as bicycles, carriages or trolleys; powered by motors

Means of locomotion, such as aircraft, in particular aircraft, helicopters or zeppelins; Floating bodies, such as ships or buoys; Rail vehicles, such as locomotives, railcars and railway cars; and motor vehicles, such as motorcycles, buses, trucks or cars) or parts thereof; of buildings in the interior and exterior; of furniture, windows and doors; Of plastic moldings, especially of polycarbonate, especially CDs and

Windows, especially windows in the automotive sector; of small industrial parts; of coils, containers and packaging; of white goods; of films; of optical, electrotechnical and mechanical components as well as of glass hollow bodies and

Items of daily use.

In particular, the coatings according to the invention, in particular the clearcoats, can be used in the technologically and aesthetically particularly demanding field of automotive OEM finishing. In doing so, they excel first and foremost by a particularly high wash resistance and scratch resistance, in particular dry scratch resistance.

example

The preparation of a copolymer (A)

In a steel reactor of a volume of five liters, 1716.9 g of deionized water were introduced and heated to 90 ⁰ C. Subsequently, at this temperature, three simultaneously started, separate feeds were added uniformly within four hours (feed 1), 3.75 hours (feed 2) and 4.5 hours (feed 3) with stirring.

Feed 1 consisted of 47.7 g of acrylic acid, 75.3 g of 2- (acetoacetoxy) ethyl methacrylate (Lonzamon® AAEMA from Lonza), 199.5 g of methyl methacrylate, 267.3 g of 2-ethylhexyl methacrylate, 113 g of styrene and 50, 1 g of diphenylethylene.

Feed 2 consisted of 46.4 g of 25 percent ammonia solution and 232.2 g of deionized water.

Feed 3 was a solution of 75.5 g of ammonium peroxodisultate in 176 g of water.

After the end of feed (= end of feed 3) followed by a three-hour postpolymerization at 90 ⁰ C. This gave a yellowish-white dispersion of the copolymer (A) of a pH of 4.7 and a solids content of 27 wt .-% (60 minutes / 130 ⁰ C).

The dispersion of the copolymer (A) was outstandingly suitable as a crystallization inhibitor and dispersant for the preparation of deagglomerated barium sulfate nanoparticles.

Claims

claims

1. Copolymers of (A) olefinically unsaturated monomers (a), preparable by one or more stages of controlled free radical copolymerization in an aqueous medium of

(a21) monomers of the general formula I

R ¹ R ² C = CR ³ R ⁴ (I),

wherein R ¹ , R ² , R ³ and R ^{4 are} each independently hydrogen or substituted or unsubstituted alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl,

Cycloalkylaryl-arylalkyl or arylcycloalkyl radicals, with the proviso that at least two of the variables R ¹ , R ² , R ³ and R ^{4 are} substituted or unsubstituted aryl, arylalkyl or arylcycloalkyl radicals, in particular substituted or unsubstituted aryl radicals;

(a22) olefinically unsaturated terpene hydrocarbons and

(a23) dimeric alpha-alkyl vinylaromatics.

2. Copolymers (A) according to claim 1, characterized in that the at least one chelating group of the monomer (a1) is at least bidentate.

3. Copolymers (A) according to claim 1 or 2, characterized in that the at least one chelating group of the monomer (a1) at least two

Contains atomic groupings that act as electron donors.

4. Copolymers (A) according to claim 3, characterized in that the atomic groupings from the group consisting of carbonyl groups (> C = O), thiocarbonyl groups (> C = S), ether groups (-CH ₂ -O-CH ₂ -) , Thioether groups (-CH ₂ - S-CH ₂ -), primary, secondary and tertiary amino groups (> C-NR ⁵ ₂ ) with R =

Hydrogen atom or alkyl radical having 1 to 6 carbon atoms, primary and secondary imino groups (> C = NR ⁵ ) with R ⁵ = hydrogen atom or alkyl radical having 1 to 6 carbon atoms, oxime groups (> C = NOH), imino ether groups (> C = NO-R ⁶ with R ⁶ = alkyl radical having 1 to 10 carbon atoms or cycloalkyl radical having 4 to 10 carbon atoms, and primary, secondary and tertiary phosphine groups (-

PR ⁷ ₂ ) with R ⁷ = hydrogen atom or alkyl radical having 1 to 6 carbon atoms, cycloalkyl radical having 4 to 10 carbon atoms or aryl radical having 6 to 10 carbon atoms.

5. Copolymers (A) according to claim 4, characterized in that the atomic groups are carbonyl groups (> C = O).

6. Copolymers (A) according to claim 5, characterized in that the chelating groups are 1, 3-dicarbonyl groups.

7. Copolymers (A) according to any one of claims 1 to 6, characterized in that the olefinically unsaturated groups of the monomers (a1) from the group consisting of (meth) acrylate, ethacrylate, crotonate, cinnamate, vinyl ether Vinyl ester, dicyclopentadienyl, norbomenyl, isoprenyl, isopropenyl, allyl or butenyl groups; Dicyclopentadienyl, norbomenyl, isoprenyl, isopropenyl, allyl or butenyl ether groups or dicyclopentadienyl, norbornyl, isoprenyl, isopropenyl, allyl or butenyl ester groups.

8. Copolymers (A) according to claim 7, characterized in that the olefinically unsaturated groups are (meth) acrylate groups.

9. Copolymers (A) according to claim 7 or 8, characterized in that in a monomer (a1) the chelating (n) group (s) with the or the olefinically unsaturated group (s) via at least one covalent bond or via an at least divalent linking group is or are linked.

10. Copolymers (A) according to any one of claims 7 to 9, characterized in that in a monomer (a1) a chelating group is linked to an olefinically unsaturated group via a divalent linking group.

11. Copolymers (A) according to claim 9 or 10, characterized in that the divalent linking group is an alkylene group.

12. Copolymers (A) according to any one of claims 1 to 11, characterized in that it is the aryl radicals R ¹ , R ² , R ³ and / or R ^{4 of} the monomers (a21) are phenyl or naphthyl radicals.

13. Copolymers (A) according to any one of claims 1 to 12, characterized in that it is the aryl radicals R ¹ , R ² , R ³ and / or R ^{4 of} the monomers (a21) are phenyl radicals.

14. Copolymers (A) according to any one of claims 1 to 13, characterized in that the substituents in the radicals R ¹ , R ² , R ³ and / or R ^{4 of} the monomers (a21) from the group consisting of electron withdrawing or electron-donating atoms or organic radicals.

15. Copolymers (A) according to claim 14, characterized in that the substituents from the group consisting of halogen atoms, nitrile, nitro, partially or fully halogenated alkyl, cycloalkyl, alkylcycloalkyl, Cycloalkylalkyl-, aryl, alkylaryl -, Cycloalkylaryl- arylalkyl and Arylcycloalkylreste; Aryloxy, alkyloxy and cycloalkyloxy radicals; Arylthio, alkylthio and cycloalkylthio radicals and primary, secondary and tertiary amino groups.

16. Copolymers (A) according to any one of claims 1 to 15, characterized in that the terpene hydrocarbon (a22) from the group consisting of acyclic diterpenes, monocyclic terpenes, bicyclic terpenes, acyclic

Sesquiterpenes, monocyclic sesquiterpenes, bicyclic sesquiterpenes, tricyclic sesquiterpenes, acyclic diterpenes, monocyclic diterpenes, and tricyclic diterpenes.

17. Copolymers (A) according to any one of claims 1 to 16, characterized in that the terpene hydrocarbon (a22) from the group consisting of acyclic Monoterpenes, monocyclic terpenes and bicyclic terpenes.

18. Copolymers (A) according to any one of claims 1 to 17, characterized in that the terpene hydrocarbon (a22) from the group consisting of Ocimen,

Myrcene, menthenes, menthadienes, alpha-pinene and beta-pinene.

19. Copolymers (A) according to claim 18, characterized in that the menthadienes (a22) from the group consisting of alpha-terpinene, beta-terpinene, gamma-terpinene, terpinolene, alpha-phellandrene, beta-phellandrene, limonene and dipentene , are selected.

20. Copolymers (A) according to claim 19, characterized in that gamma- terpinene (a22) is selected.

21. Copolymers (A) according to any one of claims 1 to 20, characterized in that the dimeric alpha-Alkylvinylaromaten (a23) are dimeric alpha-alkylstyrenes.

22. Copolymers (A) according to claim 21, characterized in that dimeric alpha-methylstyrene (a23) is used as the dimeric alpha-alkylstyrene.

23. Copolymers (A) according to any one of claims 1 to 22, characterized in that the olefinically unsaturated monomers (a1) and (a2) are copolymerized with at least one different olefinically unsaturated monomer (a3).

24. A process for the preparation of copolymers (A) according to any one of claims 1 to 23, characterized in that at least

(a2) at least one olefinically unsaturated monomer other than the olefinically unsaturated monomer (a1) selected from the group consisting of (a21) monomers of the general formula I

R ¹ R ² C = CR ³ R ⁴ (I),

wherein the radicals R ¹ , R ² , R ³ and R ^{4 are} each independently

Are hydrogen atoms or substituted or unsubstituted alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl or arylcycloalkyl radicals, with the proviso that at least two of the variables R ¹ , R ² , R ³ and R ⁴ for substituted or unsubstituted aryl, arylalkyl or

Arylcycloalkylreste, in particular substituted or unsubstituted aryl radicals, are;

(a22) olefinically unsaturated terpene hydrocarbons and

(a23) dimeric alpha-alkyl vinylaromatics;

in a aqueous medium controlled free-radical copolymerization.

25. Use of the copolymers (A) according to any one of claims 1 to 23 and the copolymers prepared by the process according to claim 24 (A) as crystallization inhibitors and / or dispersants for nanoparticles.

26. Use according to claim 25, characterized in that the nanoparticles are barium sulfate nanoparticles.

27. Use according to claim 26, characterized in that the barium sulfate nanoparticles are deagglomerated.

28. Use according to claim 27, characterized in that the deagglomerated barium sulfate nanoparticles have a primary particle size <50 nm.

29. Use according to any one of claims 25 to 29, characterized in that the nanoparticles are used for the production of materials that are physically, thermally curable, with actinic radiation and thermally and with actinic radiation.

30. Use according to claim 29, characterized in that the curable materials are used to produce thermoplastic and thermosetting materials.

31. Use according to claim 29, characterized in that the curable materials are coating materials, adhesives, sealants and precursors for moldings and films.

32. Use according to claim 30, characterized in that the thermoplastic and thermosetting materials coatings, adhesive layers,

Seals, moldings and films are.