EP2032613A2 - Alkoxysilyl functional oligomers and particles surface-modified therewith - Google Patents

Abstract

The invention relates to alkoxysilyl functional oligomers (A) and the hydrolysis and condensation products thereof, obtained from polymerisation of 100 parts by weight of ethylenically unsaturated alkoxy functional silane (S) together with 0 to 100 parts by weight of ethylenically unsaturated comonomers (C), core-shell particles (PA), with oligomers (A) on the surface thereof and use of said particles (PA) for producing composite materials (K).

Description

 Alkoxysilyl-functional oligomers and thus surface-modified particles

The invention relates to alkoxysilyl-functional oligomers, core-shell particles (PA), which carry on its surface oligomer (A) and use of the particles (PA) for the production of composite materials (K).

The filler is a finely divided solid, which changes its properties by addition to a matrix. Fillers are used today in the chemical industry for many purposes. They can change the mechanical properties of plastics, e.g. Hardness, tear strength, chemical resistance, electrical or thermal conductivities, adhesion or even shrinkage with temperature changes. Furthermore, they influence u.a. also the rheological behavior of plastic melts and improve the scratch resistance of coatings.

A common problem when using the - usually inorganic - particles and in particular the nanoparticles in organic systems consists in a usually insufficient compatibility of particles and matrix. This can lead to the particles not being able to disperse sufficiently well in the organic matrix. In addition, even well-dispersed particles can settle at longer stand or storage times, possibly forming larger aggregates or agglomerates, which can not or only with difficulty be separated into the original particles during a redispersion. The processing of such inhomogeneous systems is in any case extremely difficult, often even impossible. For example, paints that have smooth surfaces after being applied and cured can be applied this way usually not or only after costly process produce.

It is therefore advantageous to use particles which have organic groups on their surface which lead to better compatibility with the surrounding matrix. In this way, the inorganic particle is masked by an organic shell. In addition, if the particle surface has a suitable reactivity with respect to the matrix, so that it can react with the binder system under the respective curing conditions of the formulation, it is possible to chemically incorporate the particles into the matrix during the curing, which often results in particularly good mechanical properties, but also in improved chemical resistance results. For example, amine or carbinol groups, e.g. can react with polyesters, polyurethanes or polyacrylates. Such systems are described for example in EP 832 947 A.

For surface modification, hydrolyzable silanes, for example γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane and γ-methacrylatopropyltrimethoxysilane, which are reactive with respect to the particle surface and form a siloxane shell masking the particle core when reacted with the particle, are preferably used in the prior art. Such production processes are described, for example, in EP 505 737 A. These particles have a very good compatibility with an organic matrix due to the organofunctional radicals. However, a problem with these systems may be that, when using silanes with low hydrolysis and condensation reactivity, the siloxane shell formed still has a large number of alkoxysilyl and silanol groups. The stability of these particles is under the conditions of manufacture - especially under the conditions of solvent exchange - and therefore limited storage. Despite masking siloxane shell, agglomeration or aggregation of the particles may occur. The reasons mentioned do not usually allow it

To isolate particles as a solid and then to redisperse in a solvent or in the composite matrix. In this case, such a redispersibility of the particles would be particularly desirable since the production of the composite materials would thereby be substantially facilitated.

The production of core-shell particles which are free of alkoxysilyl and silanol groups on their surface and consequently have a lower tendency to agglomerate is taught by the documents EP 0 492 376 A and DE 10 2004 022 406 A. For this purpose, in a first step Cocondensation of various silanes and siloxanes, wherein at least one silane or siloxane carries methacrylic groups, produces a siloxane particle onto which a polymethyl methacrylate shell is grafted in the subsequent step by reaction with methyl methacrylate. The resulting particles show excellent compatibilities in organic polymers, e.g. Polymethyl methacrylate and PVC. These siloxane graft polymers also have the advantage that they are redispersible with a suitable composition and thickness of the grafted shell. However, they have the disadvantage of being relatively expensive to produce, which leads to high production costs.

It is an object of the present invention to provide a surface modifier which enables the production of core-shell particles and, moreover, overcomes the disadvantages of the prior art. The invention relates to alkoxysilyl-functional oligomers (A) and their hydrolysis and condensation products, obtainable by polymerization of 100 parts by weight of ethylenically unsaturated alkoxy-functional silane (S) together with

0 to 100 parts by weight of ethylenically unsaturated comonomer (C).

In this context, an "oligomer" is understood as meaning a relatively high molecular weight molecule composed of at least 2 (degree of polymerization 2) but not more than 100 (degree of polymerization 100) of monomeric units. Preference is given to degrees of polymerization of from 2 to 50, particularly preferably degrees of polymerization of from 2 to 20 The degree of polymerization is calculated, for example, from the number-average molar mass Mn, determined by GPC or NMR, divided by the molar weighted average of all molar masses of the monomers used The sequence of the silane building blocks (S) and optionally of the comonomers (C) in the oligomer (A) can each be According to the type of polymerization, they may be random, block-like, alternating or gradient-shaped, with particular preference being given to statistical and block-like sequences.

As silane (S) come all silanes or their hydrolysis and

Condensation products in question, which carry ethylenically unsaturated bonds, which are a polymerization, especially radical polymerization accessible. Examples of such polymerizable silanes are, for example, vinylsilanes, such as vinyltrimethoxysilane, vinyltriethoxysilane or

Vinyltriacetoxysilane and acrylic and methacrylic silanes, for example, by Wacker Chemie AG, Munich, Germany, marketed silanes GENIOSIL® ^® GF-31, XL-33, XL-32, XL-34 and XL-36. Particular preference is given to silanes (S) of the general formula [1],

R ¹ _H (R ¹¹ O) _{3 n} Si-LO-CO-CR ²¹ = CH ₂ [1]

in which

R ¹ , R ¹¹ , R ²¹ C ^ Cg -Al kylreste s ind, n 0, 1 or 2 and

L is a C _] _ -Cg -Al alkylene radical.

The radicals R ^ -, R ^, R ² ^ may be linear, branched or cyclic. Preferably, R ^U and R ² ^ methyl, ethyl, n-

Propyl or isopropyl radicals. In particular, R ^, R ^ -, R ² ^ are methyl. In particular, n = 0. L is preferably a methylene or propylene radical. Further preferred are as

Silanes (S) the compounds methacryloxypropyltrimethoxysilane, acrylamidopropyltrimethoxysilane,

Methacrylamidopropyltrimethoxysilane, acrylamidomethyltrimethoxysilane, methacrylamidomethyltrimethoxysilane. Likewise, the corresponding di- and monoalkoxysilanes of said ethylenically unsaturated silanes (S) are suitable. Preferably, at least 10 mol%, particularly preferably at least 30 mol%, in particular at least 50 mol%, of the silanes (S) or their hydrolysis and condensation products have alkoxy groups.

Suitable comonomers (C) are compounds from the group consisting of vinyl esters, (meth) acrylic esters, vinylaromatics, olefins, 1,3-dienes, vinyl ethers and vinyl halides. Particularly suitable vinyl esters are those of carboxylic acids having 1 to 15 carbon atoms. Preference is given to vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, 1-methylvinyl acetate, vinyl pivalate and vinyl esters of CC-branched monocarboxylates. acids having 9 to 11 carbon atoms, for example VeoVa9 ^® or VeoValO ^® (trade names of Resolution). Particularly preferred is vinyl acetate.

Suitable monomers from the group of acrylic esters or methacrylic esters are, for example, esters of unbranched or branched alcohols having 1 to 15 C atoms. Preferred methacrylic esters or acrylic esters are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, iso-butyl acrylate, isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl acrylate and norbornyl acrylate , Particularly preferred are methyl acrylate, methyl methacrylate, n-butyl acrylate, iso-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, and norbornyl acrylate. Preferred vinyl aromatic compounds are styrene, alpha-methylstyrene, the isomeric vinyltoluenes and vinylxylenes, and divinylbenzenes. Particularly preferred is styrene. Vinyl halide compounds include vinyl chloride, vinylidene chloride, tetrafluoroethylene, difluoroethylene, hexylperfluoroethylene, 3,3,3-trifluoropropene, perfluoropropyl vinyl ether, hexafluoropropylene, chlorotrifluoroethylene and vinyl fluoride. Particularly preferred is vinyl chloride.

A preferred vinyl ether is, for example, methyl vinyl ether. The preferred olefins are ethene, propene, 1-alkyl ethenes and polyunsaturated alkenes, and the preferred dienes are

1,3-butadiene and isoprene. Particularly preferred are ethene and 1, 3-butadiene. Further comonomers (C) are ethylenically unsaturated mono- and dicarboxylic acids, preferably acrylic acid, methacrylic acid, fumaric acid and maleic acid; ethylenically unsaturated carboxylic acid amides and nitrites, preferably

Acrylamide and acrylonitrile; Mono- and diesters of fumaric acid and maleic acid, such as the diethyl and diisopropyl esters and maleic anhydride, ethylenically unsaturated sulfonic acids or their salts, preferably vinylsulfonic acid, 2-acrylamido-2-methyl-propanesulfonic acid. Further examples are precrosslinking comonomers such as multiply ethylenically unsaturated comonomers, for example divinyl adipate, diallyl maleate, allyl methacrylate or triallyl cyanurate, or postcrosslinking comonomers, for example acrylamidoglycolic acid (AGA), methyl acrylamido glycolic acid methyl ester (MAGME), N-methylolacrylamide (NMA), N-methylol methacrylamide, N- Methylolallyl carbamate, alkyl ethers such as the isobutoxy ether or esters of N-methylolacrylamide, N-methylolmethacrylamide and N-methylolallylcarbamate. Also suitable are epoxide-functional comonomers such as glycidyl methacrylate and glycidyl acrylate. Mention may also be made of monomers having hydroxyl or CO groups, for example methacrylic acid and acrylic acid hydroxyalkyl esters such as hydroxyethyl, hydroxypropyl or hydroxybutyl acrylate or methacrylate, and also compounds such as diacetoneacrylamide and acetylacetoxyethyl acrylate or methacrylate.

Particularly preferred comonomers (C) are one or more monomers from the group of vinyl acetate, vinyl esters of C-C-branched monocarboxylic acids having 9 to 11 C atoms,

Vinyl chloride, ethylene, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, styrene, 1,3-butadiene. Also particularly preferred are comonomers (C) which introduce organofunctionalities into the polymer backbone, for example glycidyl (meth) acrylates, hydroxyalkyl (meth) acrylates, aminoalkyl (meth) acrylates and ZV-methylolacrylamide.

As a polymerization method for the preparation of the oligomers (A) are preferably used radical and ionic methods in their different forms: Thus, the preparation can be carried out in bulk or in a suitable solvent on free, radical polymerization. In this case, the polymerization is initiated by means of the initiators or redox initiator combinations customary in polymer chemistry or mixtures of these. Decisive for the choice of the suitable initiator here is, among other things, the solubility in the solvent / monomer mixture used, which must be different from zero. An overview of suitable initiators can be found in the "Handbook of Free Radical Initiators", ET Denisov, TG Denisova, TS Pokidova, 2003, Wiley Verlag Examples of initiators are the sodium, potassium and ammonium salts of peroxodisulfuric acid, hydrogen peroxide, t-butyl peroxide , t-butyl hydroperoxide, potassium peroxodiphosphate, t-butyl peroxypivalate, cumene hydroperoxide, isopropylbenzene monohydroperoxide,

Dibenzoyl peroxide or azobisisobutyronitrile. The initiators mentioned are preferably used in amounts of from 0.01 to 4.0% by weight, based on the total weight of the monomers. As the redox initiator combinations used above

Initiators in conjunction with a reducing agent. Suitable reducing agents are sulfites and bisulfites of monovalent cations, for example sodium sulfite, the derivatives of sulfoxylic acid, such as zinc or alkali metal formaldehyde sulfoxylates, for example sodium hydroxymethanesulfinate and ascorbic acid. The amount of reducing agent is preferably 0.15 to 3% by weight of the amount of monomer used. In addition, small amounts of a metal compound soluble in the polymerization medium can be introduced, the metal component of which is redox-active under the polymerization conditions, for example based on iron or vanadium.

Alternatively, the radical polymerization also on controlled manner, for example by the methods of ATRP (atom transfer radical polymerization), the NMP (Nitroxide mediated polymerization) or the RAFT polymerization (rapid addition fragmentation transfer). In the case of ATRP polymerization, it is expedient to work in the presence of a Cu (I) nitrogen complex which is known to serve as a catalyst. However, other transition metal complexes can serve as catalysts. An overview of possible transition metal complexes can be found in K. Matyjaszewski, J. Xia, Chem. Rev. 2001, 101, 2921-2990.

Preference is given to a complex consisting of a Cu (I) center and 2,2'-bipyridine. This may have been previously formed or first formed in-situ, including from Cu (O) - or Cu (II) -Vorlauferverbindungen which form the catalytically active species by oxidation and reduction processes. Suitable initiators are CC halocarboxylic acid derivatives such as esters, amides or thioesters. Also suitable are compounds with CC halogenated fluorene units. Also polyhalogenated compounds such as chloroform HCCI3 or carbon tetrachloride CCI4 are conceivable. Also, sulfonyl halides and

Halogenimides conceivable initiators. Most preferred, however, are CC halocarboxylic acid derivatives, e.g. 2-chloro / bromopropionic acid ethyl ester or 2-chloro / isobutyric acid ethyl ester. Preferred solvent is toluene.

In the case of the NMP reaction, TEMPO (2,2,6,6-tetramethylpiperidine 1-oxyl) and its derivatives are particularly preferred as the reversible terminating reagent. Particularly preferred is 4-hydroxy-TEMPO, 4-acetamido-TEMPO and polymer-bound TEMPO, such as bound on silica or polystyrene. Preference is in this case, a polymerization in the presence of <1 wt .-% acetic anhydride or acetic acid. All come as initiators discussed radical starter in question. The reaction proceeds preferably in organic solution and at temperatures> 100 ⁰ C. The preferred solvent is the solvent in which the oligomer is used later.

In the case of RAFT polymerization, preference is given in particular to xanthates and dithiocarbamides as reversible terminating reagent, particular preference being given to O-alkylxanthan acids and their salts. Very particular preference is given to the sodium salt of O-ethylxanthanoic acid. Initiators are all radical starters already discussed. The reaction preferably proceeds in organic solution and at temperatures <100 ^° C. The preferred solvent is the solvent in which the oligomer is used later.

The polymerization is preferably carried out as a free or controlled radical or ionic polymerization. Preference is given to polymerization via ATRP methods and by free radical polymerization. The polymerization is preferably carried out in a solvent. The preferred solvent is the solvent in which the oligomer is used later.

Alternatively, the polymerization may be by ionic methods such as cationic or anionic polymerization.

The polymerization can be carried out batchwise, semicontinuously or continuously, with presentation of all or individual constituents of the reaction mixture, with partial introduction and subsequent addition of individual constituents of the reaction mixture or after the metering process without presentation. All dosages are preferably carried out to the extent of consumption the respective component. In the case of a controlled polymerization, the polymerization preferably proceeds in batch mode, unless block structures are realized where a semi-continuous procedure is preferred. In the case of free radical polymerization, a semi-continuous procedure is preferred.

Another object of the invention are core-shell particles (PA), which carry on its surface, the oligomer (A) or its hydrolysis and condensation products.

The particles (PA) of the invention preferably have a specific surface area of from 0.1 to 1000 m 2 / g, more preferably from 10 to 500 m 2 / g (measured by the BET method according to DIN EN ISO 9277 / DIN 66132). The average size of the primary particles is preferably less than 10 .mu.m, more preferably less than 1000 nm, wherein the primary particles can be present as aggregates (definition according to DIN 53206) and agglomerates (definition according to DIN 53206), which in

Depending on the external shear stress (for example, due to the measurement conditions) sizes may have from 1 to 1000 microns.

In the core-shell particle (PA), the oligomers (A) may be covalently attached to the particle surface via ionic or van der Waals interactions. Preferably, the oligomers (A) are covalently attached.

The oligomers (A) are outstandingly suitable for the functionalization of particles (P). The resulting particles (PA) are redispersible in common organic solvents and have excellent compatibility with various matrix systems. The oligomers (A) can be produced relatively inexpensively from the corresponding unsaturated silanes (S). In addition, production of the redispersible and compatible particles (PA) from particles (P) and the oligomers (A), which can usually already be carried out simply by mixing both components, is very simple. Thus, the oligomers (A) according to the invention and the particles (PA) accessible therefrom represent a great advantage over the prior art.

Another object of the invention is a process for the preparation of the particles (PA), in which particles (P) are reacted with the oligomers (A).

In a preferred process for producing the particles (PA), particles (P) having functions selected from metal-OH, metal-O-metal, Si-OH, Si-O-

Si, Si-O metal, Si-X, metal-X, metal-OR ² , Si-OR ² reacted with oligomers (A) or their hydrolysis, alcoholysis and condensation products, wherein

R.2 represents a substituted or unsubstituted alkyl radical and X represents a halogen atom.

R.2 is preferably an alkyl radical having 1 to 10, in particular 1 to 6 carbon atoms. The radicals methyl, ethyl, n-propyl, i-propyl are particularly preferred. X is preferably chlorine.

Are used for the preparation of the particles (PA) particles (P), which have functions that are selected from metal-OH, Si-OH, Si-X, metal-X, metal-OR ² , Si-OR ² , so takes place the attachment of the oligomers (A) preferably by Hydrolysis and / or condensation. If there are exclusively metal-O-metal, metal-O-Si or Si-O-Si functions in the particle (P), the covalent attachment of the oligomers (A) can be effected by an equilibration reaction. The procedure and the needed for the Aquilibrierungsreaktion

Catalysts are familiar to the person skilled in the art and have been described many times in the literature.

As particles (P) are suitable for reasons of technical handling oxides with covalent bond fraction in the metal-oxygen bond, preferably oxides of the 3rd main group, such as boron, aluminum, gallium or indium, the 4th main group, such as silica Germanium dioxide, tin oxide, tin dioxide, lead oxide, lead dioxide, or oxides of the 4th subgroup, such as titanium oxide, zirconium oxide and hafnium oxide. Further examples are nickel, cobalt, iron, manganese, chromium and vanadium oxides.

In addition, metals with oxidized surface, zeolites (a list of suitable zeolites can be found in: Atlas of Zeolite Framework Types, 5th edition, Ch. Baerlocher, W.M. Meier D.H. Olson, Amsterdam: Elsevier 2001), silicates, aluminates, aluminophosphates, titanates and

Aluminum phyllosilicates (eg bentonites, montmorillonites, smectites, hectorites), the particles (P) preferably having a specific surface area of from 0.1 to 1000 m 2 / g, particularly preferably from 10 to 500 m 2 / g (measured by the BET standard). Method according to DIN 66131 and 66132). The particles (P), which preferably have an average diameter of less than 10 .mu.m, particularly preferably less than 1000 nm, can be used as aggregates (definition according to DIN 53206) and agglomerates

(Definition according to DIN 53206) are present, which depending on the external shear stress (eg due to the measurement conditions) may have large from 1 to 1000 microns. Particularly preferred as particles (P) is fumed silica, which is prepared in a flame reaction of organosilicon compounds, for example of silicon tetrachloride or methyldichlorosilane, or hydrogentrichlorosilane or

Hydrogenmethyldichlorosilane, or other methylchlorosilanes or alkylchlorosilanes, also in admixture with hydrocarbons, or any volatilizable or sprayable mixtures of organosilicon compounds, as mentioned, and hydrocarbons, e.g. in a hydrogen-oxygen flame, or even a carbon monoxide oxygen flame is produced. The preparation of the silica can be carried out optionally with and without the addition of water, for example in the step of purification; preferred is no addition of water.

Pyrogenic silica or silica is known for example from Ullmann's Encyclopedia of Industrial Chemistry 4th Edition, Volume 21, page 464. The unmodified fumed silica has a BET specific surface area, measured according to DIN EN ISO 9277 / DIN 66132 of

10 m ^ / g to 600 m ^ / g, preferably from 50 m ^ / g to 400 m ^ / g. Preferably, the unmodified fumed silica has a tamped density measured in accordance with DIN EN ISO 787-11 of 10 g / l to 500 g / l, preferably from 20 g / l to 200 g / l and particularly preferably from 30 g / l to 100 g / l on.

Preferably, the fumed silica has a fractal surface dimension of preferably less than or equal to 2.3, more preferably less than or equal to 2.1, most preferably from 1.95 to 2.05, the fractal dimension of surface D ₃ here defined as:

Particle surface A is proportional to the particle radius R high D ₃ . In a further preferred embodiment of the invention, the particles (P) used are colloidal silicon or metal oxides, which are generally present as a dispersion of the corresponding submicron-sized oxide particles in an aqueous or organic solvent. Among other things, the oxides of the metals aluminum, titanium, zirconium, tantalum, tungsten, hafnium and tin or the corresponding mixed oxides can be used. Particularly preferred are silica sols. Suitable examples of commercially available silica sols which are suitable for producing the particles (PA), silica sols of product lines LUDOX ^® are (Grace Davison), Snowtex ^® (Nissan Chemical), Klebosol ^® (Clariant) and Levasil ^® (HC Starck), silica sols in organic solvents such as IPA-ST (Nissan Chemical) or those silica sols which can be prepared by the Stöber process.

In a further preferred embodiment of the invention are as particles (P) organopolysiloxanes of the general formula [2],

[R ³ ₃ SiO _1/2] i [R ³ 2Siθ2 / 2] j [R ³ Si0 _3/2] k ^[SiO 4/2] 1 ^[2 I

used, where

R.3 is an OH function, an optionally halogen, hydroxyl, amino, epoxy, phosphonato, thiol, (meth) acrylic, carbamate or NCO-substituted

Hydrocarbon radical having 1-18 carbon atoms, wherein the carbon chain may be interrupted by non-adjacent oxygen, sulfur or amine groups and i, j, k, 1 denote a value of greater than or equal to 0, with the proviso that i + j + k + 1 are greater than or equal to 3, in particular at least 10. For the preparation of the particles (PA) according to the invention, the particles (P) with the oligomers (A) are preferably reacted at 0 ^° C. to 150 ^° C., more preferably at 20 ^° C. to 80 ^° C. The process can be carried out both with the inclusion of solvents or solvent-free. When using solvents, protic and aprotic solvents and mixtures of various protic and aprotic solvents are suitable. Preferred are protic solvents, such as water, methanol, ethanol, isopropanol, or polar aprotic solvents, such as

THF, DMF, NMP, diethyl ether or methyl ethyl ketone used. Also preferred are solvents or

Solvent mixtures having a boiling point or boiling range of up to 120 ⁰ C at 0.1 MPa. Very particularly preferred is the use of an isopropanol / toluene mixture.

The oligomers (A) used to modify the particles (P) are preferably present in an amount of greater than 1% by weight (based on the particles (P)), preferably greater than 5% by weight, more preferably greater than 8% by weight. % used.

In the reaction of the particles (P) with the oligomers (A) is optionally carried out under vacuum, under pressure or at normal pressure (0.1 MPa). The cleavage products, if any, formed in the reaction, e.g.

Alcohols can either remain in the product and / or be removed by applying a vacuum or increasing the temperature of the reaction mixture.

In the reaction of the particles (P) with the oligomers (A) catalysts can be added.

In this case, all the catalysts commonly used for this purpose, such as organic tin compounds, eg Dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetylacetonate, dibutyltin diacetate or dibutyltin dioctoate etc., organic titanates, eg titanium (IV) isopropylate, iron (III) compounds, eg iron (III) acetylacetonate, or also amines, eg triethylamine, tributylamine, 1, 4- Diazabicyclo [2, 2, 2] octane, 1,8-

Diazabicyclo [5.4.0] undec-7-ene, l, 5-diazabicyclo [4.3.0] non-5-ene, N, N-bis- (N, N-dimethyl-2-aminoethyl) -methylamine, N, N-dimethylcyclohexylamine, N, N-dimethylphenlyamine, N-ethyl-morpholine, etc. are used. Also organic or inorganic Bronsted acids such as acetic acid,

Trifluoroacetic acid, hydrochloric acid, phosphoric acid and their mono- and / or diesters, e.g. Butyl phosphate, isopropyl phosphate, dibutyl phosphate, etc. and acid chlorides such as benzoyl chloride are suitable as catalysts. The catalysts are preferably used in concentrations of 0.01-10 wt .-%. The various catalysts can be used both in pure form and as mixtures of different catalysts.

The catalysts used are deactivated after the reaction of the particles (P) with the oligomers (A), preferably by addition of so-called anti-catalysts or catalyst poisons, before they can lead to a cleavage of the Si-O-Si groups. This side reaction is dependent on the catalyst used and does not necessarily occur, so that it may optionally be possible to dispense with a deactivation. Examples of catalyst poisons are, for example, acids when using bases and, for example, when using acid, bases which neutralize the bases or acids used. Optionally, the products formed by the neutralization reaction may be separated or extracted by filtration. Preferably, the reaction products remain in the product.

Optionally, the addition of water is preferred for the reaction of the particles (P) with the oligomers (A).

In the preparation of the particles (PA) from particles (P), in addition to the oligomers (A), it is additionally possible to use silanes (S1), silazanes (S2), siloxanes (S3) or other compounds (L). The silanes (S1), silazanes (S2), siloxanes (S3) or other compounds (L) are preferably reactive toward the functions of the surface of the particle (P). The silanes (S1) and siloxanes (S3) have either silanol groups or hydrolyzable silyl functions, the latter being preferred. The silanes (S1), silazanes (S2) and siloxanes (S3) can have organic functions, but it is also possible to use silanes (S1), silazanes (S2) and siloxanes (S3) without organo functions. The oligomers (A) can be used as a mixture with the silanes (S1), silazanes (S2) or siloxanes (S3). In addition, the particles can also be successively functionalized with the oligomers (A) and the different silane types. Suitable compounds (L) are, for example, metal alcoholates, e.g. Titanium (IV) isopropoxide or aluminum (III) butanolate, protective colloids such as e.g. Polyvinyl alcohols, cellulose derivatives or vinylpyrrolidone-containing polymers and emulsifiers such. ethoxylated alcohols and phenols (alkyl radical CzpCig,

EO grade 3-100), alkali metal and ammonium salts of alkyl sulfates (C3 ~ C] _g), sulfuric acid and phosphoric acid esters and

Alkyl sulfonates. Particularly preferred are succinic acid esters and alkali alkyl sulfates and polyvinyl alcohols. It is also possible to use a plurality of protective colloids and / or emulsifiers as a mixture. Particular preference is given to mixtures of oligomers (A) with silanes (SI) of the general formula [3],

(R ⁴ O) ₄ _ _a _ _b (Z) _a Si (R ¹⁴ ) _b [3]

in which

Z is halogen atom, pseudohalogen radical, Si-N-bonded amine radical,

Amide radical, oxime radical, aminoxy radical or acyloxy radical, a denotes 0, 1, 2 or 3, b denotes 0, 1, 2 or 3,

R.4 has the meanings of R ^^ R ^ and di _e meanings of R ^, and a + b is less than or equal to the fourth

In this case, a is preferably 0, 1 or 2, while b is preferably 0 or 1. R ^ preferably has the meanings of ^RU .

As silazanes (S2) or siloxanes (S3), particular preference is given to using hexamethyldisilazane or hexamethyldisiloxane or linear siloxanes having organofunctional chain ends.

The silanes used to modify the particles (P)

(Sl), silazanes (S2), siloxanes (S3) or other compounds (L) are preferably used in an amount of> 1 wt .-% (based on the particles (P)).

The modified particles (PA) obtained from the particles (P) can be isolated by conventional methods such as evaporation of the solvents used or by spray drying as a powder. Alternatively, it is possible to dispense with isolation of the particles (PA).

In addition, in a preferred procedure in the Subsequent to the production of the particles (PA) Methods for deagglomerating the particles are used, such as pin mills or devices for grinding screening, such as pin mills, hammer mills, countercurrent mills, bead mills, ball mills, impact mills or devices for grinding sifting.

Another object of the invention is a process for the preparation of the particles (PA), in which the attachment of the oligomers (A) takes place during the synthesis of the particles (P). According to this process, the particles (P) can preferably be prepared by cohydrolysis of oligomers (A) with alkoxysilanes (S1) of the general formula [3], silazanes (S2) or siloxanes (S3).

Another object of the invention is the use of the particles (PA) according to the invention for the production of composite materials (K).

Both inorganic and organic polymers are used as matrix materials (M) for the production of the composite materials (K). Examples of such polymer matrices (M) are polyethylenes, polypropylenes, polyamides, polyimides, polycarbonates, polyesters, polyetherimides, polyethersulfones, polyphenylene oxides, polyphenylene sulfides, polysulfones (PSU), polyphenylsulfones (PPSU), polyurethanes, polyvinyl chlorides, polytetrafluoroethylenes (PTFE), polystyrenes (PS ), Polyvinyl alcohols (PVA), polyether glycols (PEG), polyphenylene oxides (PPO), polyaryl ether ketones, epoxy resins, polyacrylates, polymethacrylates and silicone resins.

Polymers which are likewise suitable as matrix (M) are oxidic materials which are accessible by customary sol-gel processes known to the person skilled in the art. According to the sol-gel process, hydrolyzable and condensable silanes are used and / or organometallic reagents are hydrolyzed by means of water and optionally in the presence of a catalyst and cured by suitable methods to the silicate or oxidic materials. If the silanes or organometallic reagents carry organofunctional groups (such as, for example, epoxy, methacrylic, amine groups) which can be used for crosslinking, then these modified sol-gel materials can additionally be cured via their organic fraction. The hardening of the organic fraction can take place, optionally after addition of further reactive organic components, inter alia thermally or by UV irradiation. For example, sol-gel materials are thus suitable as matrix (M), which are accessible by reaction of an epoxy-functional alkoxysilane with an epoxy resin and optionally in the presence of an amine curing agent. Another example of such inorganic-organic polymers are sol-gel materials (M) which can be prepared from amino-functional alkoxysilanes and epoxy resins. By introducing the organic fraction, for example, the elasticity of a sol-gel film can be improved. Such inorganic-organic polymers are described, for example, in Thin Solid Films 1999, 351, 198-203.

Other suitable matrix materials (M) are mixtures of different matrix polymers or the corresponding copolymers.

It is also possible to use reactive resins as matrix material (M). Reactive resins are compounds which have one or more reactive groups. Examples of reactive groups here are hydroxyl, amino, isocyanate, epoxide Groups, ethylenically unsaturated groups and moisture-curing alkoxysilyl groups called. In the presence of a suitable hardener or an initiator, the reactive resins can be polymerized by thermal treatment or actinic radiation.

The reactive resins may be present in monomeric, oligomeric and polymeric form. Examples of common reactive resins are: hydroxy-functional resins, e.g. hydroxyl-containing polyacrylates or polyesters which are crosslinked with isocyanate-functional curing agents; acrylic and methacrylic functional resins which are cured thermally or by actinic radiation upon addition of an initiator; Epoxy resins crosslinked with amine curing agents; vinyl-functional siloxanes which can be crosslinked by reaction with a SiH-functional hardener; SiOH-functional siloxanes which can be cured by a polycondensation.

The particles (PS) according to the invention may have a distribution gradient or be homogeneously distributed in the composite material (K). Depending on the matrix system chosen, both a homogeneous distribution and an uneven distribution of the particles can have an advantageous effect, for example, with respect to mechanical stability or chemical resistance.

If the particles (PA) according to the invention carry organofunctional groups which are reactive with respect to the matrix (M), the particles (PA) can be covalently bonded to the matrix (M) after the particles have been dispersed.

The amount of the particles (PA) contained in the composite material (K) is preferably at least, based on the total weight 1 wt .-%, preferably at least 5 wt .-%, particularly preferably at least 10% and preferably at most 90 wt .-%. The composite materials (K) may contain one or more different particle types (PA). Thus, for example, composites (K) are the subject of the invention containing modified silica and modified alumina.

The preparation of the composite materials (K) is preferably carried out in a two-stage process. In a first stage dispersions (D) are prepared by incorporation of the particles (PA) into the matrix material (M). In a second step, the dispersions (D) are converted into the composite materials (K).

To prepare the dispersions (D), the matrix material (M) and the particles (PA) according to the invention are dissolved or dispersed in a solvent, preferably a polar aprotic or protic solvent, or a solvent mixture. Suitable solvents are

Dimethylformamide, dimethylacetamide, dimethylsulfoxide, ZV-methyl-2-pyrrolidone, water, ethanol, methanol, propanol. In this case, the matrix (M) can be added to the particles (PA) or the particles (PA) to the matrix (M). To disperse the particles (PA) in the matrix material (M) it is possible to use further additives and additives usually used for dispersion. These include Brönsted acids, such as hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid, trifluoroacetic acid, acetic acid, methylsulfonic acid, Bronsted bases, such as triethylamine and ethyldiisopropylamine. In addition, all commonly used emulsifiers and / or protective colloids can be used as further additives. Examples of protective colloids are polyvinyl alcohols, Cellulose derivatives or vinylpyrrolidone-containing polymers. Common emulsifiers are, for example, ethoxylated alcohols and phenols (alkyl radical C4-C18 / EO grade 3-100), alkali metal and ammonium salts of alkyl sulfates (C3-C17_g), sulfuric acid and phosphoric acid esters and alkyl sulfonates.

Particularly preferred are succinic acid esters as well as alkali alkyl sulfates and polyvinyl alcohols. It is also possible to use a plurality of protective colloids and / or emulsifiers as a mixture.

If particles (PA) and matrix (M) are present as solids, the dispersions (D) can also be prepared by a melt or extrusion process.

Alternatively, the dispersion (D) can be prepared by modifying particles (P) in the matrix material (M). For this purpose, the particles (P) in the matrix material (M) are dispersed and then reacted with the oligomers (A) to the particles (PA).

If the dispersions (D) contain aqueous or organic solvents, the corresponding solvents are removed after preparation of the dispersion (D). The removal of the solvent is preferably carried out by distillation. Alternatively, the solvent may remain in the dispersion (D) and be removed by drying in the course of the preparation of the composite material (K).

The dispersions (D) can also contain common solvents and the additives and additives customary in formulations. Amongst others, leveling agents, surface-active substances, adhesion promoters, light stabilizers such as UV absorbers and / or free-radical scavengers, thixotropic agents should be mentioned here as well as other solids and fillers. To produce the respective desired property profiles of both the dispersions (D) and the composites (K), such additives are preferred.

For the preparation of the composite materials (K) are the

Dispersions (D) containing particles (PA) and matrix (M) on a substrate geräkelelt. Further processes are immersion, spraying, casting and extrusion processes. Suitable substrates include i.a. Glass, metal, wood, silicon wafers and plastics such as e.g. Polycarbonate, polyethylene, polypropylene, polystyrene and PTFE.

If the dispersions (D) are mixtures of particles (PA) and reactive resins (M), the curing of the dispersions preferably takes place after addition of a hardener or

Initiator by actinic radiation or thermal energy.

Alternatively, the composite materials (K) can be produced by forming the particles (PA) according to the invention in the matrix (M). One common method of making these composite materials (K) is sol-gel synthesis which involves the use of particle precursors, e.g. hydrolyzable organometallic or organosilicon compounds and the oligomers (A) are dissolved in the matrix (M) and then the particle formation, for example by adding a

Catalyst is initiated. Suitable particle precursors are tetraethoxysilane, tetramethoxysilane,

Methyltrimethoxysilane, phenyltrimethoxysilane, etc. The sol-gel mixtures are applied to a substrate for the preparation of the composite (K) and dried by evaporation of the solvent. In a likewise preferred method, a cured polymer is swollen by a suitable solvent and immersed in a solution containing as particle precursors, for example, hydrolyzable organometallic or organosilicon compounds and the oligomers (A). The particle formation of the particle precursors enriched in the polymer matrix is then initiated by the methods mentioned above.

Due to their excellent chemical, thermal and mechanical properties, the composite materials (K) can be used in particular as adhesives and sealants, coatings and as sealants and potting compounds.

In a further embodiment of the invention, the particles (PA) according to the invention are characterized in that they are used in polar systems, such as solvent-free polymers and resins, or solutions, suspensions, emulsions and dispersions of organic resins, in aqueous systems or in organic solvents (eg: Polyester, vinyl esters, epoxies, polyurethanes, alkyd resins, etc.) have a high thickening effect, and are therefore suitable as rheological additives in these systems. As a rheological additive in these systems, the particles (PA) provide the necessary viscosity required,

Intrinsic viscosity, thixotropy and yield strength sufficient for standing on vertical surfaces.

In a further embodiment of the invention, the surface-modified particles (PA) are characterized in that they prevent caking or clumping, eg under the influence of moisture, in pulverulent systems, but also do not tend to Reagglomeration, and thus get the undesirable separation, but powders flowable and thus allow load-stable and storage-stable mixtures. In general, particle amounts of from 0.1 to 3% by weight, based on the powdery system, are used.

This is especially true for use in nonmagnetic and magnetic toners and developers and charge control aids, e.g. in contactless or electrophotographic printing / reproduction processes, the 1- and 2-component systems can be. This also applies in powdered resins used as paint systems.

Another object of the invention is the use of the particles (PA) in toners, developers and

Charge control aids. Such developers and toners are, for example, magnetic 1-component and 2-component toner, but also non-magnetic toner. These toners may contain, as a principal ingredient, resins such as styrene and acrylic resins, preferably milled to particle distributions of 1-100 microns, or may be resins used in dispersion or emulsion or solution polymerization processes or in bulk to particle distributions of preferably 1-100 μm were produced. Silicon and metal oxide is preferably used to improve and control the powder flow behavior, and / or to regulate and control the triboelectric charging properties of the toner or developer. Such toners and developers can be used in electrophotographic printing and printing processes, and are useful in direct image transfer processes. All the above symbols of the above formulas each have their meanings independently of each other. In all formulas, the silicon atom is tetravalent.

Unless otherwise indicated, all quantities and

Percentages based on weight, all pressures 0.10 MPa (abs.) And all temperatures 20 ⁰ C.

Example 1 (Synthesis of an oligomer A, according to the invention): To a mixture of 48 mmol of methacryloxymethyltriethoxysilane (GENIOSIL® XL-36, Wacker Chemie AG, Munich, Germany), 0.6 mmol of Cu (I) Cl and 1.32 mmol 2,2'-bipyridine in 10 ml of toluene are added under a nitrogen atmosphere 1.8 mmol of ethoxybromo-isobutyrate. The mixture is heated over a period of 12 h at 70 ⁰ C. The mixture is filtered through a coarse sieve (100 mesh) to give a 56% solution of Oligomethacrylsilan in toluene with a particular by GPC number average molecular weight of 4280 g / mol and a weight average molecular weight of 6670 g / mol at a polydispersity of 1.55. The determined by ^ H-NMR conversion is 85%.

Example 2 (Synthesis of an oligomer A, according to the invention): To a mixture of 48 mmol of methacryloxymethyl (diethoxy) methylsilane (GENIOSIL® XL-34, Wacker Chemie AG, Munich, Germany), 0.6 mmol of Cu (I) Cl and 1 , 32 mmol 2,2'-

Bipyridine in 10 ml of toluene are added under nitrogen atmosphere 1.8 mmol Ethoxybromoisobutyrat. The mixture is heated over a period of 12 h at 70 ⁰ C. The mixture is filtered through a coarse sieve (100 mesh) to give a 52% solution of Oligomethacrylsilan in toluene with a particular by GPC number average molecular weight of 3860 g / mol and a weight average molecular weight of 6030 g / mol at a polydispersity of 1.57. The determined by IH-NMR conversion is 75%. Example 3 (Synthesis of an oligomer A, according to the invention):

To a mixture of 48 mmol methacryloxypropyl-trimethoxysilane

(GENIOSIL® GF-31, Wacker Chemie AG, Munich, Germany), 0.6 mmol of Cu (I) Cl and 1.32 mmol of 2,2'-bipyridine in 10 ml of toluene are added under a nitrogen atmosphere 1.8 mmol Ethoxybromoisobutyrat. The mixture is heated to 70 ^° C. over a period of 12 hours. The mixture is filtered through a coarse sieve

(100 mesh) and obtains a 45% solution of oligomethacrylsilane in toluene with a GPC number average molecular weight of 5672 g / mol and a weight-average molecular weight of 10200 g / mol at a polydispersity of 1.81. The determined by IH-NMR conversion is 70%. The molecular weight distribution suggests a low degree of condensation between individual oligomer molecules.

Example 4 (Synthesis of an oligomer A according to the invention): To a mixture of 48 mmol methacryloxymethyl- (dimethoxy) methylsilane (GENIOSIL® XL-32, Wacker Chemie AG, Munich, Germany), 0.6 mmol Cu (I) Cl and 1 , 32 mmol 2,2'-

Bipyridine in 10 ml of toluene are added under nitrogen atmosphere 1.8 mmol Ethoxybromoisobutyrat. The mixture is heated over a period of 12 h at 70 ⁰ C. The mixture is filtered through a coarse sieve (100 mesh) to give a 53% solution of Oligomethacrylsilan in toluene with a particular by GPC number average molecular weight of 3730 g / mol and a weight average molecular weight of 6100 g / mol at a polydispersity of 1.81. The determined by ^ H-NMR conversion is 65%.

Example 5 (Synthesis of an oligomer A, according to the invention):

To a mixture of 48 mmol methacryloxymethyltrimethoxysilane (GENIOSIL® XL-33, Wacker Chemie AG, Munich, Germany), 0.6 mmol of Cu (I) Cl and 1.32 mmol of 2,2'-bipyridine in 10 ml of toluene 1.8 mmol Ethoxybromoisobutyrat be added under nitrogen atmosphere. The mixture is heated over a period of 15 h at 70 ⁰ C. The mixture is filtered through a coarse sieve (100 mesh) to give a 56% solution of Oligomethacrylsilan in toluene with a particular by GPC number average molecular weight of 4730 g / mol and a weight average molecular weight of 8160 g / mol at a polydispersity of 1.72. The determined by ^ H-NMR conversion is> 95%.

Example 6 (Synthesis of an oligomer A, according to the invention):

To a mixture of 96 mmol methacryloxypropyl-trimethoxysilane (GENIOSIL® GF-31, Wacker Chemie AG, Munich, Germany), 1.2 mmol of Cu (I) Cl and 2.62 mmol of 2,2'-bipyridine in 20 ml of toluene 7.2 mmol Ethoxybromoisobutyrat added under nitrogen atmosphere. One heats over one

Period of 15 hours at 70 ⁰ C. The mixture is filtered through a coarse sieve (100 mesh) to give a 51% solution of Oligomethacrylsilan in toluene with a particular by GPC number average molecular weight of 5000 g / mol and a weight average molecular weight of 7610 g / mol at a polydispersity of 1.52. The determined by IH-NMR conversion is> 95%.

Example 7 (Synthesis of an oligomer A, according to the invention):

To a mixture of 10 mmol hydroxypropyl methacrylate, 96 mmol methacryloxypropyl-trimethoxysilane (GENIOSIL® GF-31, Wacker Chemie AG, Munich, Germany), 1.2 mmol of Cu (I) Cl and 2.62 mmol of 2,2'-bipyridine in To 20 ml of toluene are added 7.2 mmol of ethoxybromo-isobutyrate under a nitrogen atmosphere. The mixture is heated to 70 ^° C. over a period of 15 hours. The product is filtered through a coarse sieve (100 mesh) to obtain a 58% solution of hydroxypropyl-modified oligomethacrylosilane in toluene with a GPC-determined number average molecular weight of 4636 g / mol and a weight average Molecular weight of 7600 g / mol at a polydispersity of 1.64. The determined by IH-NMR conversion is> 80%.

Example 8 (Synthesis of an oligomer A, according to the invention): To a mixture of 10 mmol butyl methacrylate, 96 mmol

Methacryloxymethyltrimethoxysilane (GENIOSIL® XL-33, Wacker Chemie AG, Munich, Germany), 1.2 mmol of Cu (I) Cl and 2.62 mmol of 2,2'-bipyridine in 20 ml of toluene under a nitrogen atmosphere, 7.2 mmol Ethoxybromoisobutyrate added. The mixture is heated to 70 ^° C. over a period of 15 hours. The product is filtered through a coarse sieve (100 mesh) to obtain a 53% solution of butyl-modified oligomethacrylosilane in toluene with a GPC-determined number average molecular weight of 4820 g / mol and a weight average Molar mass of 7220 g / mol at a polydispersity of 1.50. The determined by ^ H-NMR conversion is> 95%.

Example 9 (Synthesis of an oligomer A, according to the invention): To a mixture of 10 g mmol of methacryloxymethyltrimethoxysilane (GENIOSIL® XL-33, Wacker Chemie AG, Munich, Germany), 0.3 g of laurylmercaptan and 0.3 g of tert-butyltrimethoxysilane. Butyl peroxybenzoate in 20 ml of toluene are heated to 110 ⁰ C under a nitrogen atmosphere over a period of 7 h. A 33% solution of oligomethacrylsilane in toluene is obtained.

Example 10 (Synthesis of an oligomer A, according to the invention): To a mixture of 10 grams of methacryloxypropyltrimethoxysilane (GENIOSIL® GF-31, Wacker Chemie AG, Munich, Germany), 0.3 grams of laurylmercaptan and 0.3 grams of tert-butyl peroxybenzoate in 20 ml of toluene are heated to 110 ^° C. under a nitrogen atmosphere over a period of 7 hours. This gives a 33% solution of oligomethacrylsilane in Toluene with a number average molecular weight of about 7000 g / mol determined by GPC.

Example 11. Modification of a particle with subsequent solvent exchange

To 5.00 g of a silica sol in isopropanol (IPA- ^ST® from Nissan Chemical, 30.5% by weight of SiC> 2, average particle size 12 nm), a solution of 150 μl of the 51% solution of that described in Example 6 is obtained Dropped oligomers and the reaction mixture stirred for 12 h at room temperature. After addition of 15 g of methoxypropyl acetate, the reaction mixture is concentrated under reduced pressure to a solids content of 10 wt .-%. A modified silica sol is obtained which shows a slight Tyndall effect and contains only traces of isopropanol.

Example 12. Modification of a particle with subsequent solvent exchange

To 5.00 g of a silica sol in isopropanol (IPA- ^ST® from Nissan Chemical, 30.5% by weight of SiC> 2, mean particle size 12 nm) is added a solution of 75 μl of the 56% solution described in Example 5 Dropped oligomers and the reaction mixture stirred for 12 h at room temperature. After addition of 15 g of methoxypropyl acetate, the reaction mixture is concentrated under reduced pressure to a solids content of 10 wt .-%. A modified silica sol is obtained which shows a slight Tyndall effect and contains only traces of isopropanol.

Example 13. Modification of a particle with subsequent isolation and redispersion

To 5.00 g of a silica sol in isopropanol (IPA- ^ST® from Nissan Chemical, 30.5% by weight of SiC> 2, average particle size 12 nm), a solution of 150 .mu.l of the 51% solution of the oligomer described in Example 6 is added dropwise and the reaction mixture is stirred for 12 h at room temperature. The solvent is then evaporated off and the precipitate obtained is redispersed in isopropanol. This gives a transparent

Dispersion which, like the unmodified silica sol, has a slight Tyndall effect.

Example 14. Preparation of coating formulations, the paints obtainable therefrom and characterization of the coatings

For the preparation of a coating formulation, an acrylate-based paint polyol having a solids content of 52.4% by weight (solvent: solvent naphtha, methoxypropyl acetate (10: 1)), a hydroxyl group content of 1.46 mmol / g resin solution and an acid number of 10-15 mg KOH / g with Desmodur® BL 3175 SN from Bayer (butanoxime-blocked polyisocyanate, blocked NCO content of 2.64 mmol / g). The amounts of the respective components used can be found in Table 1. Subsequently, the amounts indicated in Table 1 are added to the dispersions prepared according to Synthesis Examples 10 and 11, respectively. In each case, molar ratios of protected isocyanate functions to hydroxyl groups of about 1.1: 1 are achieved. Furthermore, in each case 0.01 g of a dibutyltin dilaurate and 0.03 g of a 10% strength solution ADDID® 100 from TEGO AG (flow control agent based on polydimethylsiloxane) in isopropanol are admixed, as a result of which coating formulations having a solids content of about 50% are obtained. These initially slightly cloudy mixtures are stirred for 48 h at room temperature to give clear coating formulations.

Table 1: Formulations of the paints

* Proportion of particles in the total solids content of the respective coating formulation

The coating compositions of the compositions shown in Table 1 are each wound on a glass plate by means of a film applicator Coatmaster® 509 MC from Erichsen using a squeegee with a gap height of 120 μm. Subsequently, the resulting coating films are dried in a circulating air dryer for 30 minutes at 70 ⁰ C and then at 150 ⁰ C for 30 min. From all paint formulations optically flawless, smooth coatings are obtained.

The gloss of the coatings is determined with a gloss meter Micro gloss 20 ° from Byk and is in all paint formulation between 159 and 164 gloss units. The scratch resistance of the cured coating films produced in this way is determined using a scouring tester according to Peter-Dahn. For this, a scouring fleece Scotch Brite® 2297 with an area of 45 x 45 mm and a weight of 500 g is weighted. With this, the paint samples are scratched with a total of 50 strokes. Both before and after the end of the scratching tests, the Gloss of the respective coating with a gloss meter Micro gloss 20 ° from the Byk company.

As a measure of the scratch resistance of the respective coating, the loss of gloss is determined in comparison with the starting value:

Table 2: Loss loss in the scratch test according to Peter-Dahn

The results show the significant improvement of the composites by addition of suitably modified particles.

Claims

claims

1. Alkoxysilyl-functional oligomers (A) and their hydrolysis and condensation products, obtainable by polymerization of

100 parts by weight of ethylenically unsaturated alkoxy-functional silane (S) together with

0 to 100 parts by weight of ethylenically unsaturated comonomer (C).

2. Alkoxysilyl-functional oligomers (A) according to claim 1, in which the silanes (S) are compounds of the general formula [1],

Ri _n (R ¹¹ O) _3-n Si-LO-CO-CR ²¹ = CH ₂ [1]

wherein R ¹ , R ¹¹ , R ^{21 are} C 1 -C 8 -alkyl radicals and n is 0, 1 or 2 and

L is a C] _Cg alkylene radical.

3. core-shell particles (PA), which are oligomeric on their surface

(A) according to claim 1 or 2 or carry its hydrolysis and condensation products.

4. A process for producing the particles (PA) according to claim 3, wherein the particles (P) are reacted with the oligomers (A) according to claim 1 or 2.

5. The method of claim 4, wherein particles (P) having functions selected from metal-OH, Metal-O-metal, Si-OH, Si-O-Si, Si-O metal, Si-X, metal

X, metal OR ² , Si-OR ² are reacted with oligomers (A) or their hydrolysis, alcoholysis and condensation products, wherein

R.2 represents a substituted or unsubstituted alkyl radical and X represents a halogen atom.

6. A process for the preparation of the particles (PA) according to claim 3, wherein the attachment of the oligomers (A) during the

Synthesis of the particles (P) takes place.

7. Use of the particles (PA) according to claim 3 for the production of composite materials (K) with inorganic or organic polymers as matrix materials (M).