EP2125937A1

EP2125937A1 - Binding agent

Info

Publication number: EP2125937A1
Application number: EP08707243A
Authority: EP
Inventors: Gerhard Jonschker; Joerg Pahnke; Johanna Schuetz-Widoniak; Matthias Koch
Original assignee: Merck Patent GmbH
Current assignee: Merck Patent GmbH
Priority date: 2007-02-20
Filing date: 2008-01-24
Publication date: 2009-12-02
Also published as: US20100120935A1; DE102007008663A1; US8188180B2; JP2010519355A; WO2008101581A1; TW200848455A

Abstract

The present invention relates to a binding agent, a method for the production thereof, and the use thereof in formulations, paints, dyes and plastics.

Description

binder

The present invention relates to binders, processes for their preparation and their use in formulations, paints, inks and plastics or their precursors.

In principle, coating properties can be improved by addition of nanoparticles, but the processing of the nanoparticles poses a challenge since agglomeration and incompatibilities with common coating components can easily occur. Furthermore, the additional introduction of another paint raw material is an undesirable logistical effort, which is associated with costs.

Upon curing of the nanoparticle-containing paints, the polymers are desirably required to react with the nanoparticles to form covalent bonds. For this, the nanoparticles must be provided with groups which are reactive with respect to the polymers used. The curing of the polymers involving the nanoparticles usually occurs under conditions of rapidly increasing viscosity and thus decreasing mobility of the reactants. Due to this circumstance and the steric shielding of the nanoparticles by the first reacting polymer chains, the incorporation of the nanoparticles into the polymers is usually incomplete and the desired property improvements do not or do not occur to the desired and theoretically achievable extent. The incomplete incorporation also reduces the possible structural influence of the nanoparticles on the polymer chains. Due to their high interfacial energy, nanoparticles have the property of forcing polymer chains in their immediate environment into an ordered structure. With incomplete incorporation of the nanoparticles into the polymer structure, this desired effect can not be fully developed. The solutions mentioned in the prior art are not able to overcome all of the above-mentioned disadvantages and to provide a system which combines the stated properties in one component of the later application system. For example, it is known from unpublished application DE 102006012467.7 that redispersible nanoparticles with polymers bound via a sulfur bridge can be prepared and used in paints and coatings as an additive in the quantitative range from 1 to usually 20% by weight. The main component of these coatings and paints are still conventional binders that can crosslink with the nanoparticles during curing and bring all the disadvantages of traditional binders with them.

The object of the present invention was accordingly to provide nanoparticle-containing systems which overcome the aforementioned disadvantages.

Surprisingly, it has been found that binders of the present invention fulfill the complex requirement profile. Accordingly, a first object of the present invention is the provision of

Binders comprising central attachment points (hereinafter referred to as cores) with a diameter of> 1 nm with radially bound oligomers and / or polymers. The oligomers and / or polymers are preferably covalently bonded to the surface of the cores. The proportion of oligomers and / or polymers in the binder is 40 to 99 wt .-%, preferably 70 to 90 wt .-% and in particular 80 to 95 wt .-%, based on the binder. The determination of the proportions is carried out by thermogravimetric analysis (TGA). Here, the residue on ignition is (core portion) of the dried binder determined (apparatus: TGA V4.OD Dupont 2000), heating rate: 10 K / min, temperature range 25- 1000 ⁰ C in air, a platinum crucible). In general terms, the term "binder" in the sense of the present invention means compounds which are responsible for film formation in coating materials and inks, for example printing inks. Film formation is the general term for the transition of a applied coating material from liquid or else powdery (with transition via the In the case of paints and varnishes, binders according to DIN EN 971-1: 1996-09 and DIN 55945: 1999-07 are the nonvolatiles or nonvolatiles without pigment and filler but including plasticizers, driers and other nonvolatile excipients some of which are also applied from the melt (for example in the case of powder coating) or reacted by radiation Binder is present in liquid coating materials in solution or as a dispersion, and provides anchoring of pigments and fillers in the film and adhesion of the movie on the Substrate.

The term "radial" in the sense of the present invention means a linear or branched, preferably rectilinear, one-point orientation of the oligomers and / or polymers In the present invention, the core represents the point from which the oligomers and / or polymers are aligned largely uncrosslinked.

In the case of the binders according to the invention, it is advantageous that the nanodimensioned cores are already completely reacted with the polymers to form covalent bonds even before the 3-dimensional crosslinking in the film or film, so that good incorporation and crosslinking and a maximum effect on the polymer structure can be achieved becomes.

This pre-crosslinking is preferably carried out in an upstream step under conditions which guarantee a high reactivity with the particle surface and sufficient mobility of the polymer chains. This can be achieved in different ways. - A -

The polymer / oligomer chains may be e.g. by polymerization away from a core element.

Accordingly, a further subject of the present invention is a process comprising the dispersion of cores with a diameter of> 1 nm in a solvent or

Solvent mixture and polymerization in the presence of organic monomers, wherein the resulting oligomers and / or polymers are attached radially to the cores.

Another way to prepare the binders of the invention is the reaction of correspondingly reactively modified polymer / oligomer chains with a core. These are preferably one-sidedly terminally modified polymer / oligomer chains or polymer / oligomer chains, which have only one with respect to the core material reactive group. Accordingly, a further subject of the present invention is a process for preparing the binders according to the invention comprising a) preparing or providing oligomers and / or polymers having a group reactive with respect to a core material b). b) dispersing cores with a diameter of> 1 nm in a solvent or solvent mixture in which the oligomers / polymers from a) are at least partially soluble c) reaction, preferably chemical reaction of the oligomers and / or polymers from a) with the cores from b), wherein the oligomers and / or polymers are bound radially to the cores d) optionally working up of the inventively prepared

Binder by distillation, precipitation, solvent exchange, extraction or chromatography ..

Furthermore, it is possible the cores of appropriately modified oligomers / polymers by a suitable reaction (e.g.

Hydrolysis / polycondensation). Terminally covalently bonded hydrolyzable silicon compounds are preferred for this purpose. such as: trimethoxy-organosilanes. Accordingly, another object of the present invention is a process comprising a) preparing or providing oligomers and / or polymers having a hydrolyzable and condensable silicon and / or organometallic group b) hydrolysis and condensation of the hydrolyzable and condensable silicon and / or Organometallic group, preferably under suitable conditions (for example, in a suitable solvent / reactant mixture at a suitable temperature and pH value and optionally catalysts which cause the formation of suitable cores), wherein nuclei are formed with attached oligomers and / or polymers, wherein the oligomers and / or polymers are attached radially to the cores formed c) optionally working up of the binder according to the invention by distillation, precipitation, solvent exchange, extraction or chromatography.

The binders produced in this way have a very advantageous, star-like structure, which in the case of 3-dimensional crosslinking can react to form a polymer nanocomposite with optimum incorporation of the nanoparticles.

The star-like structure achieves a very positive viscosity behavior of the nano-hybrid binders. Since the polymer chains are held together by a central point of attachment, the formation of large, freely deployed polymer chains, as is the case in a conventional polymer solution, is prevented. As a result, very high molecular weight polymer coils can be produced which have a lower viscosity in solution than conventional polymers of the same molecular weight. This property is especially in the

Paint industry has become very difficult, as it has become very difficult due to the limitation in the use of solvents, low viscosity, to formulate readily processable paints. Today, therefore, usually short-chain oligomers and reactive diluents are used, but known to lead to paints with lower mechanical and chemical resistance. The nano-hybrid binders described herein provide an advantageous alternative to raw materials, since they are the

Advantages of high molecular weight polymers with low viscosity and low solvent requirement.

The homogeneously incorporated nanoparticles are not only expected to improve the structure and mechanical / chemical properties. By incorporating suitable nanoparticles further property improvements are possible, for example increased UV stability by means of nanoscale UV absorbers or weather-resistant colors by nanoscale pigments. It is also possible, by selecting the size and refractive index of the cores, to achieve targeted scattering of short-wave light (UV) while maintaining transparency in the visible wavelength range.

In particular, a combination of several properties such as scratch resistance and UV protection could be interesting.

At the center of the binders according to the invention are cores with a diameter of> 1 nm, wherein the cores may comprise inorganic or organic or a mixture of inorganic or organic constituents. Preferably, the cores are inorganic.

The cores preferably have diameters determined by means of a Malvern ZETASIZER (particle correlation spectroscopy, PCS) or transmission electron microscope from 1 to 20 nm in at least one dimension, preferably at most 500 nm in a maximum of two dimensions, such as, for example in phyllosilicates. Particularly preferred are substantially round cores of a diameter of 1 to 25 nm, in particular 1 to 10 nm. Largely round in the sense of the present invention includes ellipsoidal and irregularly shaped cores with one. In specific, likewise preferred embodiments of the present invention, the distribution of the particle sizes is narrow, ie the fluctuation range is less than 100% of the mean value, particularly preferably at most 50% of the mean value.

Suitable cores may be nanoparticles prepared separately or in an upstream step, as are well known to those skilled in the art, such as: SiO ₂ , ZrO ₂ , TiO ₂ , CeO ₂ , ZnO, etc. but also 3-dimensionally crosslinked organosilsesquioxane structures and metal oxides A-hydroxides , in particular silsesquioxane structures (known, for example, under the trade name POSS ™ from Hybrid Plastics), or heteropolysiloxanes, in particular cubic or other 3-dimensional representatives of this class of material. Hybrids of nanoparticles and silsesquioxane structures can also be used as nuclei. Furthermore, cores based on phyllosilicates, sulfates, silicates, carbonates, nitrides, phosphates, sulfides of appropriate size can in principle be used. Another suitable core material are cores selected from organic polymers / oligomers, in particular organic nanoparticles, for example consisting of free-radically polymerized monomers. In principle, dendrimers or hyperbranched polymers can also serve as core material. The core can also be built in situ from suitable polymer chains. For this purpose, preferably terminally reactive modified polymers are suitable, which form the core or relevant parts of the core in a linking step. Especially for this offer

_**

Alkoxysilane-modified polymer chains, particularly preferably trialkoxysilane-modified. The nucleation in these polymers is preferably carried out under reaction conditions which are suitable for the formation of spherical structures. In silane modification, these are above all basic reaction conditions, comparable to the Stöber synthesis known to the person skilled in the art. In addition to alkoxysilanes can Of course, other suitable metal compounds, eg. B. of Ti, Zr, AI are used and are reacted under optimum conditions for each species. The reaction can also be carried out in the presence of an already formed template (germ, nanoparticles, etc.) or other reaction partners (silanes, metal alkoxides, salts) in order to achieve the object according to the invention.

Preferred cores are selected from the group consisting of hydrophilic and hydrophobic, in particular hydrophilic, cores based on sulfates or carbonates of alkaline earth compounds or of oxides or hydroxides of silicon, titanium, zinc, aluminum, cerium, cobalt, chromium, nickel, iron , Yttrium or zirconium or mixtures thereof, which may optionally be coated with metal oxides or hydroxides, for example of silicon, zirconium, titanium, aluminum, or with metal oxides or hydroxides, for example of silicon, zirconium, titanium,

Aluminum, coated metals such as Ag, Cu, Fe, Au, Pd, Pt or alloys. The individual oxides can also be present as mixtures. Preferably, the metal of the metal oxide or hydroxide is silicon. The cores are particularly preferably selected from SiO ₂ particles, or they are selected from ZnO or cerium oxide particles or TiO ₂ particles, which may optionally contain metal oxides or hydroxides, for example silicon, zirconium, titanium, aluminum, can be coated.

In the case of ZnO or cerium oxide particles as cores, the binders according to the invention can be used as UV-absorbing binders due to the absorption properties of zinc oxide or cerium oxide. Suitable zinc oxide particles having a particle size of from 3 to 50 nm can be obtained, for example, by a process in which one or more precursors for the ZnO nanoparticles in an organic solvent are converted to the nanoparticles in a step a), and in step b) the growth of nanoparticles by adding at least one modifier, which is precursor for silica, is terminated when, in the UV / VIS spectrum of the reaction solution, the absorption edge has reached the desired value. The method and the suitable modifiers and method parameters are described in DE 10 2005 056622.7.

Alternatively, suitable zinc oxide particles can be produced by a process in which one or more precursors for the ZnO nanoparticles in an organic solvent are converted to the nanoparticles in a step a), and in a step b) the growth of the nanoparticles by addition at least one copolymer of at least one monomer having hydrophobic radicals and at least one monomer having hydrophilic radicals is terminated when, in the UV / VIS spectrum of the reaction solution, the absorption edge has reached the desired value. This process and the suitable copolymers, monomers and process parameters are described in DE 10 2005 056621.9.

It can also nanohectorites which are sold for example by Südchemie branded Optigel® ^® or by Laporte under the brand name Laponite ^®, are used. Or dispersions of deposited from the gas phase particles such as Aerosil ^® from Degussa or Nanopure ^® from: Very particularly preferred also silica sols (SiO ₂ in water) made of ion-exchanged water glass (. Starck example Levasil® ^® from H. C) SDC.

If the core does not already have a high reactivity and the possibility of forming covalent bonds with the oligomers / polymers, it is advantageous to apply a coupling agent or another suitable surface modification. Accordingly, in another embodiment of the present invention, the surface of the cores is modified with at least one surface modifier.

These are e.g. organofunctional silanes, organometallic compounds, e.g. Zirconium tetra-n-propylate, or mixtures or polyfunctional organic molecules which have optimized reactivity with respect to the core material and the oligomers / polymers to be connected therewith.

Preferably, it is a chemical

Surface modification, that is, the connection via hydrogen bonds, electrostatic interactions, chelate bonds or via covalent bonds. Preferably, the surface modifier is covalently bonded to the surface of the core.

Preferably, the at least one surface modifier is selected from the group comprising organofunctional silanes, quaternary ammonium compounds, carboxylic acids, phosphonates, phosphonium and sulfonium compounds, or mixtures thereof. Particularly preferably, at least one surface modifier has at least one functional group selected from the group comprising thiols, sulfides, disulfides or polysulfides.

Common processes for preparing surface-modified nanoparticles are based on aqueous particle dispersions to which the surface modifier is added. The reaction with the surface modifiers can also be carried out in an organic solvent or in solvent mixtures. This applies in particular to ZnO nanoparticles. Preferred solvents are alcohols or ethers, the use of methanol, ethanol, diethyl ether, tetrahydrofuran and / or dioxane or mixtures thereof is particularly preferred. In this case, methanol has proved to be a particularly suitable solvent. If appropriate, assistants may also be present during the reaction, for example surfactants or protective colloids (eg hydroxypropylcellulose).

The surface modifiers may be used alone, as mixtures or in admixture with other, optionally non-functional surface modifiers.

In particular, according to the invention, the described requirements for surface modifiers fulfill an adhesion promoter which carries two or more functional groups. One group of the coupling agent chemically reacts with the oxide surface of the nanoparticle. Particularly suitable here are alkoxysilyl groups (for example methoxy-, ethoxysilanes), halosilanes (for example chlorine) or acidic groups of phosphoric ester or phosphonic acids and phosphonic acid esters or carboxylic acids. Via a more or less long spacer, the groups described are linked to a second, functional group. This spacer is unreactive alkyl chains, siloxanes, polyethers, thioethers or urethanes or combinations of these

Groupings of the general formula (C, Si) _n H _m (N, O, S) χ where n = 1-50, m = 2-100 and x = 0-50. The functional group is preferably thiol, sulfide, polysulfide, in particular tetrasulfide, or disulfide groups.

In addition to the thiol, sulfide, polysulfide or disulfide groups, the adhesion promoter described above may have further functional groups. The additional functional groups are in particular acrylate, methacrylate, vinyl, amino, cyano, isocyanate, epoxy, carboxy or hydroxy groups. Silane-based surface modifiers are described, for example, in DE 40 11 044 C2. Phosphoric acid-based surface modifiers are available, inter alia, as Lubrizol® 2061 and 2063 from LUBRIZOL (Langer & Co.). A suitable silane is, for example, mercaptopropyltrimethoxysilane. This and other silanes are commercially available, for example, from ABCR GmbH & Co., Karlsruhe, or from Degussa, Germany, under the brand name Dynasilan. Mercaptophosphonic acid or diethyl mercaptophosphonate can also be listed here as adhesion promoters.

Alternatively, it may be at the surface modifier amphiphilic silanes of the general formula (R) ₃ Si-Sp-A _hp -BH _b, where the radicals R may be the same or different and are hydrolytically removable radicals, Sp is -O- or straight-chain or branched alkyl having 1-18 C atoms, straight-chain or branched alkenyl having 2-18 C atoms and one or more double bonds, straight-chain or branched alkynyl having 2-18 C atoms and one or more triple bonds, saturated, partially or completely unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by alkyl groups having 1-6 C atoms, A _{hp is} a hydrophilic block, B _{hb is} a hydrophobic block and wherein at least one thiol, sulfide or disulfide to A _hp and / or B _hb is present bound is. When amphiphilic silanes are used, nanoparticles are obtained which are particularly readily redispersible, in both polar and nonpolar solvents.

The amphiphilic silanes contain a head group (R 1 Si, where the radicals R may be identical or different and represent radicals which can be split off hydrolytically The radicals R are preferably the same and suitable hydrolytically removable radicals are, for example

Alkoxy groups having 1 to 10 carbon atoms, preferably having 1 to 6 carbon atoms, halogens, hydrogen, acyloxy groups having 2 to 10 carbon atoms and in particular having 2 to 6 C atoms or NRV groups, where the radicals R ^{'may be} identical or different and are selected from hydrogen or alkyl having 1 to 10 C atoms, in particular having 1 to 6 C atoms. Suitable alkoxy groups are, for example, methoxy, ethoxy, propoxy or butoxy groups. Suitable halogens are in particular Br and Cl. Examples of acyloxy groups are acetoxy or propoxy groups. Oximes are also suitable as hydrolytically removable radicals. The oximes may hereby be substituted by hydrogen or any organic radicals. The radicals R are preferably alkoxy groups and in particular methoxy or ethoxy groups.

Covalently bonded to the above-mentioned head group is a spacer Sp, which acts as a link between the Si head group and the hydrophilic block Ah _P and performs a bridging function in the context of the present invention. The group Sp is either -O- or straight-chain or branched alkyl having 1-18 C atoms, straight-chain or branched alkenyl having 2-18 C atoms and one or more double bonds, straight-chain or branched alkynyl having 2-18 C atoms and one or more triple bonds, saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by alkyl groups having 1-6 C atoms.

The C 1 -C ₈ -alkyl group of Sp is, for example, a methyl, ethyl, isopropyl, propyl, butyl, sec-butyl or tert-butyl, and also pentyl, 1, 2 or 3-methylbutyl, 1, 1, 1, 2 or 2,2-dimethylpropyl, 1 -

Ethylpropyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl or tetradecyl. Optionally it may be perfluorinated, for example as difluoromethyl, tetrafluoroethyl, hexafluoropropyl or octafluorobutyl. A straight-chain or branched alkenyl having 2 to 18 C atoms, wherein several double bonds may also be present, is, for example, vinyl, allyl, 2- or 3-butenyl, isobutenyl, sec-butenyl, furthermore 4-pentenyl, iso-pentenyl, hexenyl, heptenyl, octenyl, -C ₉ Hi ₆ , -Ci ₀ H ₁₈ to -Ci ₈ H ₃₄ , preferably allyl, 2- or 3-butenyl, isobutenyl, sec-butenyl, furthermore preferably 4- Pentenyl, iso-pentenyl or hexenyl.

A straight-chain or branched alkynyl having 2 to 18 C atoms, wherein a plurality of triple bonds may also be present, is, for example, ethynyl, 1- or 2-propynyl, 2- or 3-butynyl, furthermore 4-pentynyl, 3-pentynyl, hexynyl, Heptynyl, octynyl, -CgHi ₄ , -CioH ₁₆ to -Ci _B H ₃₂ , preferably ethynyl, 1- or 2-propynyl, 2- or 3-butynyl, 4-pentynyl, 3-pentynyl or hexynyl.

Unsubstituted saturated or partially or fully unsaturated cycloalkyl groups having 3-7 C atoms may include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl, cyclopenta-1,3-dienyl, cyclohexenyl, cyclohexa-1, 3-dienyl, cyclohexa-1, 4-dienyl,

Phenyl, cycloheptenyl, cyclohepta-1, 3-dienyl, cyclohepta-1, 4-dienyl or cyclohepta-1, 5-dienyl be substituted with Cr to Ce- alkyl groups.

The spacer group Sp is followed by the hydrophilic block A _hP . This may be selected from nonionic, cationic, anionic or zwitterionic hydrophilic polymers, oligomers or groups. In the simplest embodiment, the hydrophilic block is ammonium, sulfonium, phosphonium groups, alkyl chains having carboxyl, sulfate and phosphate side groups, which may also be present as a corresponding salt, partially esterified anhydrides with free acid or Salt group, OH-substituted alkyl or cycloalkyl chains (eg, sugars) having at least one OH group, NH- and SH-substituted alkyl or cycloalkyl chains or mono-, di- tri- or oligo-ethylene glycol groups. The length of the corresponding alkyl chains can be 1 to 20 C atoms, preferably 1 to 6 C atoms. The nonionic, cationic, anionic or zwitterionic hydrophilic polymers, oligomers or groups can be prepared from corresponding monomers by polymerization in accordance with methods generally known to the person skilled in the art. Suitable hydrophilic monomers contain at least one dispersing functional group which consists of the group consisting of

(i) functional groups which can be converted into anions by neutralizing agents and anionic groups, and / or (ii) functional groups which can be covalently converted by neutralizing agents and / or quaternizing agents, and / or cationic groups, and / or (iii ) nonionic hydrophilic groups.

Preferably, the functional groups (i) from the group consisting of carboxylic acid, sulfonic acid and phosphonic acid groups, acidic sulfuric acid and phosphoric acid ester groups and carboxylate, sulfonate, phosphonate, sulfate ester and phosphate ester groups, the functional groups (ii) from A group consisting of primary, secondary and tertiary amino groups, primary, secondary, tertiary and quaternary ammonium groups, quaternary phosphonium groups and tertiary sulfonium groups, and the functional groups (iii) selected from the group consisting of omega-hydroxy and omega-alkoxy-poly ( alkylene oxide) -1-yl groups.

Unless neutralized, the primary and secondary amino groups may also serve as isocyanate-reactive functional groups.

Examples of suitable hydrophilic monomers having functional groups (i) are acrylic acid, methacrylic acid, beta-carboxyethyl acrylate, ethacrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid; olefinically unsaturated sulfonic or phosphonic acids or their partial esters; or maleic acid mono (meth) acryloyloxyethyl ester, succinic acid mono (meth) acryloyloxyethyl ester or phthalic acid mono (meth) acryloyloxyethyl ester, in particular acrylic acid and methacrylic acid.

Examples of suitable hydrophilic monomers with functional groups (ii) are 2-aminoethyl acrylate and methacrylate or allylamine.

Examples of highly suitable hydrophilic monomers having functional groups (iü) are omega-hydroxy or omega-methoxy-polyethylene oxide-1-yl, omega-methoxy-polypropylene oxide-1-yl, or omega-methoxy-poly (ethylene oxide-co-) polypropylene oxide) -1-yl acrylate or methacrylate, as well as hydroxy-subsitituted ethylene, acrylates or methacrylates, such as, for example, hydroxyethyl methacrylate.

Examples of suitable monomers for the formation of zwitterionic hydrophilic polymers are those in which a betaine structure occurs in the side chain. Preferably, the side group is selected from -iCH ₂ ) _m - (N ⁺ (CH ₃ ) ₂ ) - (CH ₂ ) n -SO ₃ -, - (CH ₂ ) _m - (N ⁺ (CH 3) 2HCH ₂ ) _n - PO3 ² -, - (CH2) m- (N ⁺ (CH3) 2HCH2) n-0-PO ₃ ^{2 'or-} (CH ₂₎ m- (P ⁺ _(CH3) 2) - (CH ₂₎ _n - SO3 ^" , where m is an integer from the range of 1 to 30, preferably from the range 1 to 6, particularly preferably 2, and n is an integer from the range of 1 to 30, preferably from the range 1 to 8, particularly preferably 3.

It may be particularly preferred if at least one structural unit of the hydrophilic block has a phosphonium or sulfonium radical.

When selecting the hydrophilic monomers, it should be noted that preferably the hydrophilic monomers with functional groups (i) and the hydrophilic monomers with functional groups (ii) with one another be combined so that no insoluble salts or complexes are formed. On the other hand, the hydrophilic monomers having functional groups (i) or functional groups (ii) can be arbitrarily combined with the hydrophilic monomers having functional groups (iii).

Of the hydrophilic monomers described above, the monomers having the functional groups (i) are particularly preferably used.

Preferably, the neutralizing agents for the anionic functional groups (i) are selected from the group consisting of ammonia, trimethylamine, triethylamine, tributylamine, dimethylaniline, diethylaniline, triphenylamine, dimethylethanolamine, diethylethanolamine, methyldiethanolamine, 2-aminomethylpropanol, dimethylisopropylamine, dimethylisopropanolamine, triethanolamine , Diethylenetriamine and

Triethylenetetramine, and the neutralizing agents for the cation-functional functional groups (ii) selected from the group consisting of sulfuric acid, hydrochloric acid, phosphoric acid, formic acid, acetic acid, lactic acid, dimethylolpropionic acid and citric acid.

Most preferably, the hydrophilic block is selected from mono- and triethylene glycol structural units.

Attached to the hydrophilic block A _hp follows the hydrophobic block B _hb - The block B _hb is based on hydrophobic groups or, like the hydrophilic block, on the polymerization of suitable hydrophobic monomers.

Examples of suitable hydrophobic groups are straight-chain or branched alkyl having 1-18 C atoms, straight-chain or branched alkenyl having 2-18 C atoms and one or more double bonds, straight-chain or branched alkynyl having 2-18 C atoms and one or a plurality of triple bonds, saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by alkyl groups having 1-6 C atoms. Examples of such groups are already mentioned in advance. In addition, aryl, polyaryl, aryl-CrCβ-alkyl or esters with more than 2 C-atoms are suitable. In addition, the groups mentioned may also be substituted, in particular with halogens, with perfluorinated groups being particularly suitable.

ArylCrCβ-alkyl is, for example, benzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl or phenylhexyl, where both the phenyl ring and the alkylene chain, as described above, may be partially or completely substituted by F, more preferably benzyl or phenylpropyl.

Examples of suitable hydrophobic olefinically unsaturated monomers for the hydrophobic block B _hP are

(1) substantially acid-group-free esters of olefinically unsaturated acids, such as (meth) acrylic acid, crotonic acid, ethacrylic acid, vinylphosphonic acid or vinylsulfonic acid alkyl or cycloalkyl esters having up to 20 carbon atoms in the alkyl radical, in particular methyl, ethyl, propyl, n-butyl, sec-butyl, tert-butyl, hexyl, ethylhexyl, stearyl and lauryl acrylate, methacrylate, crotonate, ethacrylate or vinyl phosphonate or vinyl sulfonate; cycloaliphatic (meth) acrylic acid, crotonic acid, ethacrylic acid, vinylphosphonic acid or vinylsulfonic acid esters, in particular cyclohexyl, isobornyl, dicyclopentadienyl, octahydro-4,7-methano-1H-indenemethanol or tert-butylcyclohexyl (meth ) acrylate, crotonate, ethacrylate, vinyiphosphonate or vinyl sulfonate. These may be minor amounts of higher-functional (meth) acrylic acid, crotonic acid or ethacrylic alkyl or cycloalkyl esters such

Ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, pentane-1, 5-diol, hexane-1, 6-diol, octahydro-4,7-methano- 1 H-indenedimethanol or cyclohexane-1, 2-, -1, 3- or -1, 4-diol di (meth) acrylate, trimethylolpropane tri (meth) acrylate or pentaerythritol tetra (meth) acrylate and the analogous ethacrylates or Crotonate included. In the context of the present invention, minor amounts of higher-functional monomers (1) are amounts which do not lead to crosslinking or gelation of the polymers;

(2) monomers which carry at least one hydroxyl group or hydroxymethylamino group per molecule and are substantially free of acid groups, such as

Hydroxyalkyl esters of alpha, beta-olefinically unsaturated carboxylic acids, such as hydroxyalkyl esters of acrylic acid, methacrylic acid and ethacrylic acid, in which the hydroxyalkyl group contains up to 20 carbon atoms, such as 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3

Hydroxybutyl, 4-hydroxybutyl acrylate, methacrylate or ethacrylate; 1,4-bis (hydroxymethyl) cyclohexane, octahydro-4,7-methano-1H-indenedimethanol or methylpropanediol monoacrylate, monomethacrylate, monoethacrylate or monocrotonate; or reaction products of cyclic esters, e.g. epsilon-caprolactone and these hydroxyalkyl esters;

- olefinically unsaturated alcohols such as allyl alcohol

Allyl ethers of polyols, such as trimethylolpropane monoallyl ether or pentaerythritol mono-, di- or triallyl ether. The higher functionality monomers are generally used only in minor amounts. In the context of the present invention, minor amounts of higher-functional monomers are amounts which do not lead to crosslinking or gelation of the polymers, - Reaction products of alpha, beta-olefinic carboxylic acids with glycidyl esters of an alpha-branched monocarboxylic acid having 5 to 18 carbon atoms in the molecule. The reaction of the acrylic or methacrylic acid with the glycidyl ester of a carboxylic acid having a tertiary alpha carbon atom may be carried out before, during or after the

Polymerization reaction take place. The monomer (2) used is preferably the reaction product of acrylic and / or methacrylic acid with the glycidyl ester of Versatic® acid. This glycidyl ester is commercially available under the name Cardura® E10. In addition, reference is made to Römpp Lexikon Lacke and Druckfarben, Georg Thieme Verlag, Stuttgart, New York, .1998, pages 605 and 606;

Formaldehyde adducts of aminoalkyl esters of alpha, beta-olefinically unsaturated carboxylic acids and alpha, beta-unsaturated carboxylic acid amides, such as N-methylol and N, N-dimethylol aminoethyl acrylate, aminoethyl methacrylate, acrylamide and methacrylamide; such as

Acryloxysilane groups and hydroxyl-containing olefinically unsaturated monomers, preparable by reaction of hydroxy-functional silanes with epichlorohydrin 30 and subsequent reaction of the intermediate with an alpha, beta-olefinically unsaturated carboxylic acid, in particular acrylic acid and methacrylic acid, or their hydroxyalkyl esters;

(3) vinyl esters of alpha-branched monocarboxylic acids having 5 to 18 carbon atoms in the molecule, such as the vinyl esters of Versatic® acid sold under the trademark VeoVa®;

(4) cyclic and / or acyclic olefins such as ethylene, propylene, but-1-ene, pent-1-ene, hex-1-ene, cyclohexene, cyclopentene, norbornene, butadiene, isoprene, cyclopentadiene and / or dicyclopentadiene; (5) amides of alpha.beta.-olefinically unsaturated carboxylic acids, such as (meth) acrylamide, N-methyl, N, N-dimethyl, N-ethyl, N, N-diethyl, N-propyl, N, N Dipropyl, N-butyl, N, N-dibutyl and / or N, N-cyclohexylmethyl (meth) acrylamide;

(6) monomers containing epoxide groups, such as the glycidyl esters of acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid and / or itaconic acid;

(7) vinyl aromatic hydrocarbons such as styrene, vinyltoluene or alpha-alkylstyrenes, especially alpha-methylstyrene;

(8) nitriles, such as acrylonitrile or methacrylonitrile;

(9) vinyl compounds selected from the group consisting of vinyl halides such as vinyl chloride, vinyl fluoride, vinylidene dichloride, vinylidene difluoride; Vinylamides, such as N-vinylpyrrolidone; Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether and vinyl cyclohexyl ether; and vinyl esters such as vinyl acetate, vinyl propionate, and vinyl butyrate;

(10) allyl compounds selected from the group consisting of allyl ethers and esters such as propyl allyl ether, butyl allyl ether, ethylene glycol diallyl ether, trimethylolpropane triallyl ether or allyl acetate or allyl propionate; As far as the higher-functional monomers are concerned, what has been said above applies mutatis mutandis;

(11) Siloxane or polysiloxane monomers which may be substituted with saturated, unsaturated, straight-chain or branched alkyl groups or other hydrophobic groups already mentioned above. In addition, polysiloxane macromonomers having a number average molecular weight Mn of 1,000 to 40,000 and on average 0.5 to 2.5 are suitable have ethylenically unsaturated double bonds per molecule, such as polysiloxane macromonomers having a number average molecular weight Mn of from 1,000 to 40,000 and an average of from 0.5 to 2.5 ethylenically unsaturated double bonds per molecule; in particular polysiloxane macromonomers which have a number-average molecular weight Mn of 2,000 to 20,000, more preferably 2,500 to 10,000 and in particular 3,000 to 7,000 and an average of 0.5 to 2.5, preferably 0.5 to 1, 5, ethylenically unsaturated double bonds per molecule, as in DE 38 07 571 A 1 on pages 5 to 7, DE 37 06 095 A 1 in columns 3 to 7, EP 0 358 153 B 1 on pages 3 to 6, in US 4,754,014 A 1 in columns 5 to 9, in DE 44 21 823 A1 or in international patent application WO 92/22615 on page 12, line 18, to page 18, line 10; and

(12) carbamate or allophanate group-containing monomers, such as

Acryloyloxy or methacryloyloxyethyl, propyl or butyl carbamate or allophanate; Further examples of suitable monomers containing carbamate groups are described in patents US 3,479,328 A 1, US 3,674,838 A 1, US 4,126,747 A 1, US 4,279,833 A 1 or US 4,340,497 A 1.

The polymerization of the above-mentioned monomers can be carried out in any manner known to those skilled in the art, e.g. by polyaddition or cationic, anionic or radical polymerizations. Polyadditions are preferred in this context, because they can be combined with each other in a simple manner different types of monomers, such as epoxides with dicarboxylic acids or isocyanates with diols.

The respective hydrophilic and hydrophobic blocks can in principle be combined with one another in any desired manner. Preferably, the amphiphilic silanes according to the present invention have an HLB value in the range of 2-19, preferably in the range of 4-15. The HLB value is defined as

_{T JT} _ mass of polar parts _.

HLB = - • 20

Molar mass and indicates whether the silane behaves rather hydrophilic or hydrophobic, ie which of the two blocks A _hp and Bh _{b dominates} the properties of the silane according to the invention. The HLB value is calculated theoretically and results from the mass fractions of hydrophilic and hydrophobic groups. An HLB value of 0 indicates a lipophilic compound, a chemical compound with an HLB value of 20 has only hydrophilic moieties.

The suitable amphiphilic silanes are furthermore distinguished by the fact that they are advantageously bonded at least one thiol, sulfide or disulfide group to Ah _P and / or B _hb . Preferably, the reactive functional group is at the hydrophobic block B _hb and there particularly preferably bound to the end of the hydrophobic block. In the preferred embodiment, the headgroup (R ^ Si and the thiol, sulfide or disulfide group are spaced as far as possible This allows a particularly flexible design of the chain lengths of the blocks A _hP and B _hb , without the possible reactivity of the thiol, sulfide - Or disulfide, for example, with the surrounding medium, significantly restrict.

In addition, in addition to the thiol, sulfide, polysulfide or disulfide further reactive functional group may be present, in particular selected from silyl groups with hydrolytically removable radicals, OH, carboxy, NH, SH groups, halogens or double bonds containing reactive groups, such as for example, acrylate or vinyl groups. Suitable silyl groups with hydrolytically removable radicals have already been described in advance in the description of the head group (R) ₃ Si. Preferably, the additional reactive group is an OH group. In the binders according to the invention, oligomers and / or polymers are radially bonded to the cores. The polymer or oligomer chains may be reacted with any of the methods known to those skilled in the art to form the core material, preferably to form at least one covalent bond.

Another object of the present invention is thus a process for the preparation of the binders of the invention comprising the dispersion of cores with a diameter of> 1 nm in a solvent or solvent mixture and polymerization in

Presence of organic monomers, wherein the resulting oligomers and / or polymers are preferably attached radially to the cores. It is desirable that the oligomer / polymer react with the core material with only one reaction center per polymer / oligomer chain, and it is particularly preferred that this reaction center be terminally attached to the polymer chain. In this case, polymers or oligomers formed both in an upstream step or in an external reaction can be used, as well as the polymers / oligomers are formed in situ during the covalent bonding with the core material. This may be the case, for example, during free-radical polymerization with unsaturated monomers in the presence of the preferably corresponding (-SH) surface-modified core material. In general, it may be advantageous to one another because of the steric hindrance of the polymers / oligomers when the polymers are formed starting from the core material and are not subsequently connected to the core. By Wegpolymerisieren thus, if appropriate, a substantially complete and dense coverage of the core material can be ensured with polymer. The formation of the polymer chain can take place via various chain growth reactions known to the person skilled in the art. Examples are ionic polymerizations (starting from epoxy functions, or halogenated Aromatics) and radical polymerizations, the latter being preferred since they can also be carried out in aqueous environments.

The synthesis of the polymers and / or oligomers can be carried out via chain growth reactions known to the person skilled in the art, wherein the chains are started or terminated with a reactive group which can react with the particle surface. Exemplary here are the anionic polymerization, and called controlled and free radical polymerization.

In a further preferred case, the core material is formed during the covalent linking of the polymer / oligomer chains. For this purpose, terminally modified with hydrolysable / condensable silane or organometallic compounds modified polymers / oligomers are used, which are reacted in a hydrolysis and polymerization (also in the presence of other silicon and organometallic compounds) to form a core material. Examples of typical oligomers / polymers according to the invention are: trialkoxysilylmercaptopropyl-terminated polyacrylates which are obtainable, for example, by free-radical polymerization of one or more unsaturated compounds with mercaptopropyltrialkoxysilane as chain transfer agent or bis [3-trimethoxysilylpropyl] disulfide as initiator. Furthermore, preference is given to using the reaction products of terminally -OH-modified polyesters or polyethers with isocyanatoalkyltrialkoxysilane. Alternatively, polymers with a hydrolyzable silyl compound in the polymer chain can be used, which then realizes a linkage of 2 oligomer / polymer strands via a link. Such oligomers / polymers are obtainable, for example, by free-radical polymerization of unsaturated compounds in the presence of methacryloxypropyltrimethoxysilane. In addition to silyl and organometallic reaction centers, it is also possible to use suitable organic reaction centers, such as, for example, amine, epoxy, hydroxyl, mercapto, isocyanate, carboxylate, allyl or vinyl groups, with suitable reaction partners on the side of the core material to react. For example, an epoxy-functional

Core material with an amino-functional polymer react or an amine-modified core material with an isocyanate-functional polymer / oligomer. The polymers / oligomers can be composed of all known polymeric substance groups, or mixtures thereof.

In particular, the oligomers and / or polymers are selected from the group comprising poly (meth) acrylates, polyesters, polyurethanes, polyureas, silicones, polyethers, polyamides, polyimides or mixtures thereof and hybrids.

Examples of suitable monomers for forming corresponding oligomers and / or polymers having functional groups are acrylic acid, methacrylic acid, beta-carboxyethyl acrylate, ethacrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid; olefinically unsaturated sulfonic or phosphonic acids or their partial esters; or maleic acid mono (meth) acryloyloxyethyl ester, succinic acid mono (meth) acryloyloxyethyl ester or phthalic acid mono (meth) acryloyloxyethyl ester, in particular acrylic acid and methacrylic acid. Further examples of well-suited monomers having functional groups are 2-aminoethyl acrylate and methacrylate or allylamine.

Further suitable monomers with functional groups are omega-hydroxy or omega-methoxy-polyethylene oxide-1-yl, omega-methoxy-polypropylene oxide-1-yl, or omega-methoxy-poly (ethylene oxide-co-polypropylene oxide) -1- yl acrylate or methacrylate, as well as hydroxy subsitituted ethylenes, acrylates or methacrylates, such as, for example, hydroxyethyl methacrylate or hydroxypropyl methacrylate.

Examples of suitable monomers for the formation of zwitterionic hydrophilic polymers are those in which a betaine structure occurs in the side chain.

Preferably, the side group is selected from - (CH ₂ ) _m - (N ⁺ (CH ₃ ) 2) - (CH ₂ ) n -SO ₃ -, - (CH ₂ ) _m - (N ⁺ (CH ₃ ) ₂ HCH ₂ ) n-Pθ ₃ ² -, - (CH ₂ ) _m - (N ⁺ (CH ₃ ) ₂ ) - (CH ₂ ) _n - O-PO ₃ ^{2 "} or - (CH ₂ ) _m - (P ⁺ (CH ₃ ) 2) - (CH ₂ ) n-SO 3 ^' , where m is an integer from the range of 1 to 30, preferably from the range 1 to 6, particularly preferably 2, and n is an integer from the

Range from 1 to 30, preferably from the range 1 to 8, particularly preferably 3.

At least three and more preferably at least six polymer / oligomer chains are covalently attached per core. The maximum number of bound to a core polymer / oligomer chains is limited only by the technical handling and manufacturability.

The polymers consist of a monomer or (preferably) of monomer mixtures. The monomers may also be reactive

Carry groups in the side chains, e.g. Hydroxy, epoxy, allyl, blocked isocyanate, etc.

Furthermore, the side chains can be additionally functionalized: e.g. Hydroxybenzophenone, benzotriazole as UV absorber or fluorescent dyes that are incorporated into the polymer chain via acrylate function.

Preferably, the polymer / oligomer shell is reactive with others

Components of the paints, e.g. Crosslinker (especially isocyanate or

Melamine crosslinker) or curable by energy irradiation (e.g., UV light, electron beam curing or heat), e.g. by contained blocked

Isocyanates. For this purpose, the polymers bound to the core material desirably have further reactive groups with which they can then react to form a 3-dimensionally crosslinked polymer. These may, for example, unsaturated groups such as acrylic or vinyl, or groups which can react with an external crosslinker, such as epoxy groups, NH, COOH, alkoxysilyl or OH groups, which can be crosslinked with isocyanates. In particular, the functional group is an OH group.

In the preferred embodiment of the present invention, the surface of the cores is coated with at least one surface modifier having at least one functional group selected from the group consisting of thiols, sulfides, disulfides or polysulfides. The cores modified in this way are then reacted in a second step in the presence of organic monomers in the course of a radical polymerization, wherein the surface modifier applied in the first step acts as a radical chain transfer agent. A radically growing polymer chain may e.g. abstracting the hydrogen of an SH group, thus creating a new radical at the sulfur capable of starting a new polymer chain.

Methods of making the preferred binders having surface modifiers bonded to the surface of the cores comprise the steps of a) applying at least one surface modifier, at least one surface modifier having at least one functional group, cores dispersed in a solvent, and b) free radical polymerization in the presence of organic Monomers, wherein the surface modifier applied in step a) functions with at least one functional group as a radical chain transfer agent, c) optionally working up of the inventively prepared Binder by distillation, precipitation, solvent exchange, extraction or chromatography.

With particular preference, the surface modifier used in the process according to the invention has at least one functional group selected from the group comprising thiols, sulfides, disulfides or polysulfides.

In principle, all types known to the person skilled in the art are suitable for starting the free-radical polymerization. The free-radical polymerization is preferably initiated in a manner known to the person skilled in the art with AIBN or AIBN derivatives.

All the process types known to the person skilled in the art are likewise suitable for carrying out the polymerization. For example, the addition of the monomers and the radical initiator can be done in one step, this is the preferred embodiment. Furthermore, it is also possible that the addition of the monomers and the radical initiators occurs stepwise, e.g. with re-initiation and portionwise addition of the monomers. Furthermore, it is also possible to gradually change the monomer composition in the course of the polymerization, e.g. through timed

Add first hydrophilic, then hydrophobic monomers or vice versa. This is possible in particular when using a controlled radical polymerization process known to those skilled in the art.

The above-mentioned solvent or solvent mixture is selected from water, organic solvents or mixtures thereof. If the solvent mixture and monomers chosen so that, although the monomers, the polymers formed therefrom but are no longer soluble from a certain chain length, the binders of the invention are excluded from the reaction mixture. The precipitated binders can be separated from the free polymer or unreacted surface modifier present in the reaction medium. This can be done by conventional methods known in the art. In a preferred embodiment, the polymerization is carried out in a solvent or solvent mixture in which the monomers are soluble, but the polymers formed above a certain chain length not. As a result, the binders fall out of the

Reaction solution. Residual monomers and any reagents or dissolved by-products which may be unreacted in the production of the cores or their functionalization, are still readily separable, for example by filtration. In another method, an external trigger, e.g. Temperature change, salt addition or addition of a non-solvent induces a phase separation at a certain time. The binder synthesis can thus be interrupted at any time, for example to control the surface coverage.

The binders according to the invention can be used alone or as a mixture with free polymers.

The cores with radially bound oligomers and / or polymers obtainable from the abovementioned processes are particularly suitable for use as binders, as described above. The use of the binders according to the invention in formulations, paints (preferably clearcoats), paints, foams, adhesives, potting compounds and plastics or in their precursors is likewise an object of the present invention. Particularly preferred is the use as a coating raw material in solvent and water-based paints, as well as in powder coatings. In the applications mentioned, for example, the improvement in scratch resistance and chemical resistance of clearcoats (eg in commercial powder coatings, UV-curing coatings, dual-cure coatings) and plastics such as polycarbonate or PMMA can be achieved. Other applications relate, for example, to the transparent weathering protection or the transparent coloring of paints and plastics with functional nanoparticles.

In the uses mentioned serve the invention

Binder as a substitute for conventional binders. In the property as a binder this already carries the known advantages of nanoadditives in itself.

The new binders differ in appearance hardly from conventional binders. In the application, they can be dissolved, for example, with common paint solvents and dried again, without using an irreversible crosslinking. Furthermore, the handling and processing of the binders according to the invention correspond to those of conventional binders. Difficulties in the preparation of nanocomposites according to the prior art (dispersion, handling of powders) are eliminated.

The viscosity of the binders according to the invention is significantly reduced compared to the viscosity of conventional binders of the same molar mass, since instead of one long, several shorter chains emanate from a central point. This is particularly advantageous in the formulation of high solids and especially in very high solid paints, which have to do with a very low solvent content. Here, in conventional polymers often short-chain polymers and the mechanical properties worsening Reactiwerdünner be used. Thus, with the new binder class, the use of reactive diluents can be reduced.

The lower viscosity observed with the binders according to the invention can be illustrated by the following model comparison: a) Schematic representation of a conventional binder of a polymer having 30 monomer units

b) schematic representation of a binder according to the invention with 30 monomer units, bound radially to a core

The schematic representation of a direct comparison between a polymer having 30 monomer units (corresponding to approximately 3000-4000 g / mol average molecular weight) with a nuclear-bridged nano-hybrid binder according to the invention also having 30 monomer units shows that the long, linear polymer chain will have a higher viscosity, as the approximately spherical shape of the binder according to the invention, which can also show Newtonian behavior. The binders of the invention are particularly suitable for use in clearcoats or adhesives. Also and especially in the field of powder coatings, the nanoparticle-bound binders can be used. The reduced viscosity allows better flow and thus a better surface quality.

An important side effect of this alternative binder approach is the possible incorporation of additional functions through the nanoparticle core into the paint matrix. Thus, electromagnetic radiation can be influenced (UV absorption, IR absorption), catalytic effects can be exerted, inorganic nanocolour pigments can be used or e.g. Nanophosphors are used as an inorganic core. Thus, the use of the binders of the invention as opacifiers for short-wave radiation in paints, foams, adhesives, potting compounds and plastics or in their precursors, also subject of the present invention.

In the above uses, the binders according to the invention may be present together with surface-modified particles with a diameter <1 μm, which are homogeneously distributed or present in the form of a gradient in a cured coating material.

Formulations, lacquers, paints, foams, adhesives, potting compounds and plastics containing binders according to the present invention are likewise provided by the present invention.

The following examples merely illustrate the invention without limiting the scope of protection. In particular, the features, properties and advantages of the defined compound (s) underlying the example in question are also applicable to other substances and compounds not mentioned in detail but within the scope of the claims, unless otherwise stated elsewhere , Examples:

Example 1 :

a) Preparation of a silyl-terminated polyacrylate

Successively, 130 ml of methyl methacrylate, 170 ml of n-butyl acrylate, 32.5 ml of 2-hydroxyethyl methacrylate and 38 ml of 3-mercaptopropyltrimethoxysilane are dissolved in 1.5L of THF. To the mixture, 5 g of azoisobutyronitrile are added and heated to 60 ⁰ C for 6 hours. The solvent is removed on a rotary evaporator. The polymer having reactive silyl end groups is obtained as a colorless product.

b) Alkaline-catalyzed condensation to the binder

100 g of the polymer prepared in a) are dissolved in 500 ml of toluene. There are also 50 ml of 25% aqueous ammonia solution. With vigorous mixing, heat to 6OC for 4h.

Water and toluene are removed on a rotary evaporator and the residue taken up in 500 ml of butyl acetate. A colorless, transparent solution of the binder in butyl acetate is obtained.

Example 2 Preparation of Terminally Silyl-Modified Polyacrylate Polyols A monomer mixture consisting of n-butyl acrylate, methyl methacrylate and 2-hydroxyethyl methacrylate (HEMA) is admixed with 250 ml of isopropanol. After the addition of the chain transfer agent 3-mercaptopropyltrimethoxysilane (MPTMS) and azobisisobutyronitrile (AIBN), nitrogen is passed through the reaction mixture for 10 minutes. It is then heated at 60 ^° C. for 16 h. After the reaction time, the mixture is allowed to cool to room temperature and the polymerization mixtures are dried on a rotary evaporator and then in a fine vacuum overnight. According to this regulation, the following approaches are carried out: Tab. 1: Polymerisationsansätze at different concentrations of

Chain transfer agent. nBuAc [ml] MMA [ml] HEMA [ml] MPTMS [μl] AIBN [g]

1 13 9.6 2.4 1.0

2 13 9,6 2,4 10 1,0

3 13 9,6 2,4 100 1,0

4 13 9,6 2,4 500 1,0

5 13 9.6 2.4 930 1.0

Example 3: Modification of SiO _Σ nanoparticles with silane-terminated polymers from Example 2 by the grafting-to process

Starting from a 5 wt .-% - dispersion of SiO ₂ nanoparticles in isopropanol (HIGHLINK, Fa. Clariant), the polymers prepared in 1 are used according to Table 2 for surface modification. The reaction mixtures are heated under reflux for 16 h.

Tab. 2: Modification of SiO ₂ nanoparticles terpolymer polymer per gram SiO ₂ [g]

2 2

3 2 4 ₂

5 2

After cooling, the isopropanol is removed on a rotary evaporator and the remaining solid in a paint solvent (eg.

Butyl acetate). Example 4: Binder Synthesis

Silyl-modified polymers are prepared according to the synthesis instructions of Example 2 with the exception that the last step (removal of the solvent in vacuo) is omitted. To the still 60 ° C warm reaction mixtures instead of each 10 g of NH ₃ -

Solution (20% by weight) and stirred for a further 2 h at 60 ° C on. Then 250 g of butyl acetate are added and the solvent on a rotary evaporator removed until a solution of 30% by mass of the binder in butyl acetate.

Example 5: Binder Synthesis

There are 166.66 g of ion-exchanged silica sol (Levasil 300-30%, corresponding to 50.0 g of SiO ₂ ) with 833.34 g of isopropanol diluted to 5 GewSiO ₂ % (total batch = 1000g) and 3.91g 3-

Mercaptopropyltrimethoxysilane added. After stirring for 12 h, the mixture is added to:

HEMA (hydroxyethyl methacrylate): 25 g MMA (methyl methacrylate): 125 g BuMA (butyl acrylate): 150 g AIBN (azoisobutyronitrile). 7 g

At 70 ⁰ C, the reaction mixture is stirred for 12 h. Subsequently, 300 g of butyl acetate are added and distilled off under vacuum isopropanol, water and butyl acetate so that a dispersion of 50% by mass of binder solid in butyl acetate is obtained.

Claims

claims

1. Binder comprising cores with a diameter of> 1 nm with radially bound oligomers and / or polymers.

2. A binder according to claim 1, characterized in that the oligomers and / or polymers are covalently bound to the surface of the cores.

3. A binder according to claim 1 or 2, characterized in that the proportion of oligomers and / or polymers to the binder is 40 to 99 wt .-%, based on the binder.

4. A binder according to one or more of claims 1 to 3, characterized in that the cores are inorganic or organic or comprise a mixture of inorganic or organic constituents.

5. A binder according to one or more of claims 1 to 4, characterized in that the cores on sulfates or carbonates of alkaline earth compounds or oxides or hydroxides of silicon, titanium, zinc, aluminum, cerium, cobalt, chromium, nickel, iron, Yttrium or zirconium or mixtures thereof, which may optionally be coated with metal oxides or hydroxides, or metals coated with metal oxides or hydroxides, such as Ag, Cu, Fe, Au, Pd, Pt or alloys based.

6. Binder according to one or more of claims 1 to 5, characterized in that the cores are selected from SiO ₂ - particles, or are selected from ZnO or cerium oxide particles or

TiO ₂ particles optionally coated with metal oxides or hydroxides.

7. A binder according to one or more of claims 1 to 6, characterized in that the cores are selected from 3-dimensionally crosslinked organosilsesquioxane structures and metal oxides / hydroxides.

8. A binder according to one or more of claims 1 to 4, characterized in that the cores are selected from organic polymers / oligomers.

9. A binder according to one or more of claims 1 to 8, characterized in that the cores diameter, determined by particle correlation spectroscopy or transmission electron microscope, from 1 to 20 nm in at least one dimension, preferably a maximum of 500 nm in a maximum of two dimensions.

10. A binder according to one or more of claims 1 to 9, characterized in that the surface of the cores is modified with at least one surface modifier.

11. A binder according to claim 10, characterized in that at least one surface modifier has at least one functional group selected from the group comprising thiols, sulfides, disulfides or polysulfides.

12. A binder according to claim 10 or 11, characterized in that the surface modifiers are selected from the group of organofunctional silanes, quaternary ammonium compounds, carboxylic acids, phosphonates, phosphonium and

Sulfonium compounds or mixtures thereof.

13. A binder according to one or more of claims 1 to 12, characterized in that the oligomers and / or polymers are selected from the group comprising poly (meth) acrylates, polyesters, polyurethanes, polyureas, silicones, polyethers, polyamides, polyimides, or . their mixtures and hybrids.

14. A process for the preparation of binders according to one or more of claims 1 to 13 comprising the dispersion of cores with a diameter of> 1 nm in a solvent or solvent mixture and polymerization in the presence of organic monomers, wherein the resulting oligomers and / or polymers radially the cores are tied up.

15. The method according to claim 14 comprising the steps of a) applying at least one surface modifier, wherein at least one surface modifier having at least one functional group on cores dispersed in a solvent and b) free radical polymerization in the presence of organic monomers, wherein the surface modifier applied in step a) c) optionally working up of the binder according to the invention by distillation, precipitation, solvent exchange, extraction or chromatography.

16. The method according to claim 15, characterized in that the functional group is selected from the group comprising thiols, sulfides, disulfides or polysulfides.

17. A process for the preparation of binders according to one or more of claims 1 to 13 comprising a) producing or providing oligomers and / or polymers having a relation to a core material b) reactive group. b) dispersing cores with a diameter of> 1 nm in a solvent or solvent mixture in which the oligomers and / or polymers from a) are at least partially soluble c) reaction of the oligomers and / or polymers from a) with the cores from b in which the oligomers and / or polymers are bound radially to the cores; d) if appropriate, workup of the binder prepared according to the invention by distillation, precipitation, solvent exchange, extraction or chromatography.

18. A process for the preparation of binders according to one or more of claims 1 to 13 comprising a) preparing or providing oligomers and / or polymers having a hydrolyzable and condensable silicon and / or organometallic group b) hydrolysis and condensation of the hydrolyzed and condensable silicon and / or organometallic group wherein cores form with attached oligomers and / or polymers, wherein the

Oligomers and / or polymers are attached radially to the nuclei formed, c) optionally working up of the binder according to the invention by distillation, precipitation, solvent exchange, extraction or chromatography.

19. The method according to one or more of claims 14 to 18, characterized in that the solvent or solvent mixture is selected from water, organic solvents or mixtures thereof.

20. Use of binders according to one or more of claims 1 to 13 in formulations, paints, dyes, foams, adhesives, potting compounds and plastics or in their precursors.

21.Use of binders according to one or more of

Claims 1 to 13 as opacifiers for short-wave radiation in paints, foams, adhesives, potting compounds and plastics or in their precursors.

22. Use according to claim 21 or 22, characterized in that the binders are present together with surface-modified particles with a diameter <1 micron, which are homogeneously distributed or in the form of a gradient in a cured coating material.

23. Formulations, lacquers, paints, foams, adhesives, potting compounds and plastics containing binder according to one or more of claims 1 to 13.