EP2376564A2

EP2376564A2 - Dispersions comprising functionalized oxidic nanoparticles

Info

Publication number: EP2376564A2
Application number: EP09771342A
Authority: EP
Inventors: Andrey Karpov; Hartmut Hibst; Berend Eling; Jörn DUWENHORST; Richard Riggs; Alexander Traut; Christof Kujat; Cornelia Roeger; Christian Krausche
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2008-12-12
Filing date: 2009-12-09
Publication date: 2011-10-19
Also published as: WO2010066768A2; US8940814B2; US20110245391A1; WO2010066768A3

Abstract

Dispersions comprising functionalized metal oxide particles, polymerizable compounds and optionally a solvent, and the use thereof for stabilizing polymers.

Description

DESCRIPTION The present invention relates to dispersions with functionalized metal oxide particles, their use and a process for their preparation.

It is known to incorporate inorganic compounds, in particular inorganic oxides, into organic polymers in order to improve their properties, for example their UV stability.

From US 2004/0099975 A1 it is known to modify the surface of such inorganic oxides present as nanoparticles with an alkoxysilane.

It is known from US 2006/0134339 A1 to functionalize colloidal metal oxides with a silane, for example an aminosilane, and to add a water-dispersible polymer to the resulting aqueous dispersion. Such compositions should be used as a corrosion inhibitor.

WO 2006/083817 A1 discloses light-stable copolyether esters with nanoparticulate titanium dioxide, cerium oxide or zinc oxide, it being possible for the titanium oxide to be treated with a silane.

WO 2006/099918 A2 discloses aqueous preparations for coating substrate surfaces which contain polyurethane compounds present in dispersed form and dispersed mineral particles, where the mineral particles may consist of zinc oxide and the zinc oxide may be hydrophobicized.

WO 2006/102669 A1 discloses a method for dispersing particles in polymers, where the particles may be, for example, titanium dioxide and zinc oxide, and wherein the particles may be functionalized.

WO 2006/124670 A2 discloses coated metal oxide nanoparticles with phosphonic acid ligands on the metal oxide surface.

From WO 2007/075654 A2 it is known to improve the stability of polymers by using zinc oxide nanoparticles, wherein the zinc oxide nanoparticles may be modified on their surface in order to reduce their aggregation.

A disadvantage of the known measures for improving the light and UV stability of polymers by the use of inorganic oxides, such as zinc oxides, is that the inorganic oxides used by the photocatalytic Effect can affect the surrounding polymer matrix and thus adversely affect the color, transparency and mechanical properties of the polymer matrix.

It is generally known that amorphous coatings such. For example, a coating containing SiC> ₂ can suppress the photocatalytic effect on the UV-absorbing particles [Journal of the American Ceramic Society, 2002, 85 [8], pages 1937-1940].

Methods for depositing an amorphous cladding, for example a SiO ₂ cladding on UV-absorbing particles, are also known. According to WO 03/104319 A1, ZnO is coated with an SiO ₂ layer by depositing products of the hydrolysis of tetraethoxysilane. The SiO ₂ -coated ZnO has a lower photocatalytic activity.

WO 2007/059841 discloses zinc oxide nanoparticles having an average particle size in the range from 3 to 50 nm, whose particle surface is modified with silica dispersed in an organic solvent. These are obtainable by a process in which in one step a) one or more precursors for the nanoparticles in an alcohol are converted to the nanoparticles, in a step b) the growth of the nanoparticles by adding at least one modifier, the precursor for silica is terminated when in the UV / VIS spectrum of the reaction solution, the absorption edge has reached the desired value and optionally in step c) the alcohol from step a) is removed and replaced by another organic solvent. The term "silica" refers to materials consisting essentially of silicon dioxide or silicon hydroxide In one variant, in a further step, a surface modifier may be added, which may be an organofunctional silane.

A disadvantage of this method is that very small ZnO particles with a preferably average particle size of 7 to 15 nm are formed and thereby very large amounts of silanes are consumed. These large amounts of silanes are introduced into the polymer matrix and can thereby lead to deterioration of, for example, mechanical properties. A further disadvantage of the very small ZnO particles produced according to WO 2007/059841 lies in a reduced UV-protecting area.

WO 2007/134712 discloses a preparation process for producing nanoparticles (inter alia of Zn oxide, Ti oxide or Ce oxide) having an average particle size in the range from 3 to 50 nm. In this process, precursors to nanoparticles with a silane

Precursor reacted to the nanoparticles. The disadvantage of this method is that while very large amounts of silanes are consumed. Another disadvantage of the method is that it produces very small particles of ZnO. This is a disadvantage in terms of UV-protecting properties.

There is a need for improved inorganic UV-absorbing particles which can be distributed agglomerate-free in polymers without having such polymer properties such. B. Transparency are affected. It is important to minimize the proportion of functionalizing groups so that they have the least possible influence on the polymer properties.

The object of the present invention was therefore to provide improved dispersions for stabilizing polymers.

The invention relates to a dispersion containing

1) functionalized UV-absorbing inorganic particles FM, which has a medium

Particle size, measured according to the dynamic light scattering (DLS) method, in the nano range, preferably in the range of 10 nm to 80 nm, in particular 10 nm to 50 nm, and 2) polymerizable compounds PP, in particular monomers, oligomers or prepolymers, by preferably non-radical polymerization into polymers and optionally a solvent S, and / or 3) a solvent soluble in the solvent S,

characterized in that the particles FM have an amorphous cladding.

The particles FM are nanoparticles of metal oxides, other metal compounds, metals or nonmetals. In a preferred embodiment, the functionalized UV-absorbing particle FM is a metal oxide particle, in particular a zinc, titanium or cerium oxide or a mixture thereof, in particular a zinc oxide.

The term "metal oxide particles" refers to particles consisting essentially of metal oxide, which particles, depending on the particular environmental conditions, may also have a certain hydroxide concentration on their surface, as is known to the person skilled in the art Therefore, in one embodiment, for example, the ZnO particles are ZnO / zinc hydroxide / zinc oxide hydrate particles, TiO ₂ -Tii I chenum TiO ₂ / titanium hydroxide / titanium oxide hydrate particles, in the CeO ₂ - _x particles (0 <x <0.5) to CeO ^ _x / cerium hydroxide / hydrated cerium oxide particles. in addition may beispiels- example depending on the nature of the used metal precursor fragments or products of the metal precursor on the Metal oxide surface, for example ace- tat groups in the case of the use of Zn (OAc) ₂ or Zn (OAc) ₂ dihydrate for the production of zinc oxide.

In addition, the metal oxide particles FM can be doped with foreign atoms, for example with metal atoms, in particular Fe ²⁺ , Fe ³⁺ , Co ²⁺ , Co ³⁺ , Cu ²⁺ , Al ³⁺ , In ³⁺ , Ga ³⁺ , Ni ²⁺ , Mg ²⁺ , V ⁵⁺ , Cr ³⁺ , Mn ²⁺ , Mn ⁴⁺ , Nb ⁵⁺ , Mo ⁵⁺ , Ta ⁵⁺ , La ³⁺ , Y ³⁺ , preferably in an amount of 10 to 20000 ppm, more preferably from 100 to 10000 ppm, based on the main metals (Zn, Ti, Ce or their both mechanical mixtures and chemical mixed oxides). The doping can be done in a conventional manner, for. Example, according to the known from DE 10 2006 035 136 A1 method of atomization of corresponding metal compounds to form an aerosol, reaction at appropriate temperatures with oxygen and workup or according to [Optical Materials, 2007, 30, pp 314-317] by a Co Precipitation and subsequent thermal treatment of solutions containing metal oxide precursors and doping metal precursors.

Functionalization is preferably understood to mean that the surface of the particles FM is modified by addition of or by reaction with compounds which have an affinity for the respective surface, the particles FM, in particular the metal oxide particles, having a functionalizing compound F in Interacting. This may be in the form of an adsorption, a coordinate bond or a chemical bond, depending on the nature of the functionalizing compound and the other conditions, such as the chemical nature and the surface structure of the particles FM.

In a preferred embodiment, the metal oxide particles FM are functionalized with a compound F of the formula I.

R ¹ LF ¹ wherein

R ¹ oxygen-containing radical, in particular alkoxy; aryloxy; ether group-containing ON gomer or polymer L divalent linking group, in particular alkylene having preferably 1 to 10 C

Atoms, in particular methylene, ethylene or propylene

F ¹ metal oxide affine group, preferably silanes, amines, carboxylic acids, carboxylates, phosphonic acid, phosphonate, phosphoric acid, phosphates, sulfonic acid or sulfonates, in particular, NH _2, NH, COOH, [COO] ^", PO ₃ H _2, [PO ₃ H] ^" , [PO ₃ ] ^2" , [PO ₄ H] ^{2 "} , [PO ₄ H ₂ ] ^" , [SO ₃ ] ^" , CO-CH ₂ -CO, especially a Trialkoxisilanrest the formula

-Si (OR) ₃ , wherein R represents an alkyl radical. In a particularly preferred embodiment, the functionalizing compound F corresponds to the following formula II:

R ²³ O (CH ₂ CR ²¹ R ²² O) _p (CH ₂ ) - F ¹

in which mean

R ²¹ , R ^{22 are} identical or different, are hydrogen or an alkyl radical, in particular having 1 to 4 C atoms, preferably hydrogen, methyl or ethyl, where R ²¹ and R ²² may have different meanings when occurring repeatedly and the group indicated by p is blockwise or statistically distributed

R ^{23 is} hydrogen, an alkyl radical, in particular having 1 to 4 C atoms, in particular methyl or ethyl, an alkaryl radical, in particular benzyl, an aryl radical, in particular phenyl, an alkoyl radical, in particular acetyl, or an aroyl radical, in particular benzoyl

p is 0 or an integer from 1 to 100, in particular 0 or 1 to 50, preferably 0 or 1 to 30

q is 0 or an integer from 1 to 10, in particular 0 or an integer from 1 to 3,

and wherein F ^{1 has} the meaning given in formula I.

In a very preferred embodiment, the metal oxide is a zinc, titanium or cerium oxide or a mixture thereof and F corresponds to the following formula III:

R ³¹

R- (CH ₂ ) _q Si R ³²

R ³³ in which mean

RR ¹⁰ O (CH ₂ CHR ¹¹ O) _P p 0 or an integer, in particular 1 to 100, preferably 1 to

30, wherein the group indicated by p may be composed of radicals having different meanings for R ¹¹ R ^{10 is} H or C _r C ₄ -alkyl, in particular methyl or ethyl

R ¹¹ H, alkyl having 1 to 4 carbon atoms, in particular hydrogen, methyl or

ethyl R ³¹ , R ³² , R ^{33 are} identical or different, hydrogen or alkoxy, in particular C 1 -C ₄ -alkyloxy, in particular methoxy or ethyloxy; Acyloxy, especially acetoxy; amino; Halogen, in particular Cl, where at least one of the groups R ¹ , R ² , R ^{3 is} hydrolyzable and in particular methoxy or ethoxy, q is an integer, in particular 1-10, preferably 1-3.

In a preferred embodiment, q 3 and / or

R ³¹ , R ³² and R ^{33 are} each alkoxy, in particular methoxy or ethoxy and / or

R is CH ₃ O (CH ₂ CHR ¹ V, where R ^{11 is} H, CH ₃ or C ₂ H ₅ and p is an integer from 1 to 15,

wherein combinations of the preferred embodiments are possible.

Very particularly preferred compounds F are CH ₃ O (CH ₂ CH ₂ O) _6-9 (CH ₂₎ ₃ Si (OR) _3, CH ₃ O [CH ₂ CH (CH ₃₎ O] i ₀ (CH ₂ CH ₂ O) ₅ (CH ₂ ) ₃ Si (OR) ₃ , CH ₃ O [CH ₂ CH (CH ₂ CH ₃ ) O] ₂ [CH ₂ CH (CH ₃ ) O] ₅ (CH ₂ ) ₃ Si (O) ₃ , wherein R is methyl or ethyl.

The functionalization of the particles FM is preferably carried out by contacting non-functionalized particles or a dispersion containing nichtfunktionalisie- rende particles in a solvent with a functionalizing compound F or with mixtures of functionalizing compounds optionally in the presence of one or more catalysts. This can be done, for example, by introducing a suspension of metal oxide in a solvent and subsequent dropwise addition of the functionalizing compound F preferably with stirring at temperatures from crystallization points to boiling points of the solvents used, preferably from 5 to 100 ⁰ C, in particular from room temperature to 80 ⁰ C. In addition to or instead of heating and / or stirring, further energy sources, such as, for example, can be used to accelerate the functionalization process. As microwaves, ultrasound or grinding can be used. The functionalizing compound F can be added in pure form or as a solution or suspension. Usually, from 1 to 100% by weight, in particular from 5 to 50% by weight, of the functionalizing compound F is added with respect to metal oxide particles. If a catalyst is required for the functionalization, this may already be, for example, in addition to the metal oxide particles in the template or added after the dropwise addition of the functionalizing compound. For the functionalization of metal oxide particles with silanes, water, acids or bases are preferably added as catalysts. These may be added to the reaction mixture prior to the addition of the functionalizing compound F or after the addition of the functionalizing compound F.

According to the present invention, it has surprisingly been found that the functionalized particles FM can be further enveloped with an amorphous layer. In a preferred embodiment, the functionalized particles FM are completely enveloped by an amorphous layer, so that on the surface of the coated and functionalized particles FM the surface present before functionalization and cladding, e.g. B. of ZnO, with the usual methods for surface analysis se, especially by transmission electron microscopy (TEM) is no longer seen. This also means that the functional groups bound to the particle surface do not prevent the coating process. In the context of the present invention, amorphous is understood to mean that the molecules in the enveloping layer are arranged irregularly and not in a crystal lattice.

The coating of functionalized metal oxide particles can be carried out, for example, by contacting with one or more precursors of the amorphous layer, if appropriate in the presence of one or more catalysts. This can be done, for example, by introducing a suspension of functionalized metal oxide particles in a solvent and then dropwise addition of the precursor of the amorphous layer, preferably with stirring at temperatures from crystallization points to boiling points of the solvents used, preferably from 5 to 100 ⁰ C, in particular from room temperature to 80 ⁰ C. respectively. In addition to or instead of heating and / or stirring can be used to accelerate the functionalization process other energy sources such. As microwaves, ultrasound or grinding can be used. The cladding can be detected in particular by electron microscopic methods, in particular by transmission electron microscopy (TEM).

In a preferred embodiment, the amorphous cladding contains aluminum oxide, zirconium oxygen or silicon oxygen compounds or a mixture thereof. The coating with an amorphous layer is preferably the coating with oxides, oxide hydroxides or hydrated oxides of silicon, aluminum or zirconium. Such coatings are known per se z. From US Pat. No. 2,885,366, DE-A-159 29 51, US Pat. No. 4,447,270 and EP-A-449 888, and are, for example, by depositing hydrolyzable Si, Al or Zr -containing precursors available. For example, silicates, aluminates or zirconates (eg sodium silicate, sodium aluminate or sodium zirconate) or mixtures thereof are used. Furthermore, acids can be used, for. For example, for the SiO ₂ -containing coating, silicic acids (for example the orthosilicic acid H ₄ SiO ₄ , or their condensation products, for example silica H ₆ Si ₂ O ₇ or polysilicic acids); for ZrO ₂ -containing coating z. For example, tazirconic acid H ₂ ZrO ₃ or orthozirconic acid H ₄ ZrO ₄ or hydroxides (eg Al (OH) ₃ ). In addition, organometallic precursors of Si, Al or Zr or their mixtures are used, which produce in the hydrolysis SiC> ₂ -, Al ₂ O 3 or ZrC> ₂ or their hydrates or oxyhydroxides. Such precursors are known to the person skilled in the art. For producing a SiO ₂ -containing layer, for example tetraalkoxysilanes (Si (OR) ₄ , eg tetramethoxysilane, tetraethoxysilane) are used. Al-alcoholates (for example aluminum isopropylate, aluminum isobutylate) are used, for example, to prepare an Al ₂ C ₃ -containing layer. Zr-alcoholates (for example zirconium isopropylate, zirconium n-butoxide, zirconium isobutylate) are used, for example, to prepare a ZrO ₂ -containing layer.

Particularly preferred is an amorphous SiO ₂ -containing layer. Particularly preferred precursors for coating with an amorphous SiO ₂ -containing layer are tetraethoxysilane, tetramethoxysilane or water glass.

The precursors can be added in pure form or as a solution or suspension. Usually, the precursor is used in the amount corresponding to 2 to 25 wt .-%, preferably 4 to 15 wt .-% of the amorphous layer, based on the particles FM. If a catalyst is required for the functionalization, this may for example already be in the template next to the optionally functionalizing metal oxide particles or may be added after the dropwise addition of the amorphous layer precursor. For example, to coat metal oxide particles with an SiO ₂ -containing layer, it is preferable to add water, acids or bases as catalysts. These may be added to the reaction mixture prior to the addition of the precursor or after the addition of the precursor.

The particles FM can either be first functionalized and then coated or first encased and then functionalized. Simultaneous functionalization and wrapping is also possible. Preferably, the particles FM are first functionalized and then coated. In this process, agglomerates of the particles FM are broken up and the average particle size, measured by means of DLS, is lowered to a value of less than 80 nm (% by volume). Such agglomerate-free particles FM are particularly well suited for further cladding with an amorphous layer. Even after the enveloping of the particles FM with an amorphous layer, the mean particle size measured by means of DLS should remain less than 80 nm (% by volume). Before the enclosure of the functionalized particles FM by-products z. By distillation, filtration (eg by nano-, ultra- or micro-cross-filtration), centrifugation or decanting. It is also possible, the solvent used for functionalization or coating against other solvents z. B. by nano-, ultra- or micro-cross-filtration, extraction, distillation and redispersion exchange. If water was used during the functionalization or coating, it may be necessary to remove these water residues before use. The removal of residual water can be done in any known manner, for. Example by distillation (at normal or reduced pressure), drying by molecular sieves or by a chemical drying by adding chemical compounds that react with water.

Preferred polymerizable compounds PP are polyesterols, polyetherols, polyetheramines and epoxide compounds. In a particularly preferred embodiment, the polymerisable compound PP is an isocyanate-reactive compound, in particular a polyol customary in polyurethane chemistry, polyetherpolyol, an oligo- or polyetheramine, or a polyesterpolyol. In a preferred embodiment, these polyols are diols. Particularly preferred examples of polymerizable compounds PP are:

I) polyether polyols

Polyether polyols based on ethylene oxide and / or propylene oxide and / or butylene oxide having a functionality of 2 to 8, preferably 2 to 3, and molecular weights of 100 to 10,000, preferably from 300 to 6000, further polyether polyols based on tetrahydrofuran having molecular weights of 250 - 5000. Furthermore, polyether polyol based on fatty acid esters such as castor oil or soybean oil.

The polyether polyols may be used singly or in the form of mixtures.

II) polyester polyols

Polyester polyols having a functionality of 2 to 3 and molecular weights of 500 to 5000

For example, polyester polyols based on dicarboxylic acid compounds and diol compounds are suitable for this purpose.

As dicarboxylic acid compounds, in principle all C ₂ -C ₄ o-aliphatic, C ₃ - C ₂ o-cycloaliphatic, aromatic or heteroaromatic compounds can be used which have two carboxylic acid groups or derivatives thereof. Particularly suitable derivatives are C 1 -C 10 -alkyl, preferably methyl, ethyl, n-propyl or isopropyl mono- or diesters of the abovementioned dicarboxylic acids, the corresponding dicarboxylic acid halides, in particular the dicarboxylic acid dichlorides and the corresponding dicarboxylic acid anhydrides. Examples of such compounds are ethanedioic acid (oxalic acid), propanedioic acid (malonic acid), butanedioic acid (succinic acid), pentanedioic acid (glutaric acid), hexanedioic acid (adipic acid), heptanedioic acid (pi melanic acid), octanedioic acid (suberic acid), nonanedioic acid (azelaic acid), decanedioic acid (sebacic acid), undecanedioic acid, dodecanedioic acid, tridecanedioic acid (brassylic acid), C ₃₂ -dimer fatty acid (commercial product from Cognis Corp., USA), benzene-1,2-dicarboxylic acid (Phthalic acid), benzene-1,3-dicarboxylic acid (isophthalic acid) or benzene-1,4-dicarboxylic acid (terephthalic acid), the methyl esters thereof, for example dimethyl ethanedioate, dimethyl propane, dimethyl butanedioate, dimethyl pentanedioate, dimethyl hexanedioate, heptanedioic dimethyl ester, octanedioic dimethyl ester, Nonandisäuredimethylester, Decandisäuredimethylester, Undecandi- acid dimethyl ester, dodecanedioic acid, dimethyl tridecanedioate, C ₃₂ - Dimerfettsäuredimethylester, dimethyl phthalate, dimethyl isophthalate or dimethyl terephthalate, the dichlorides, for example Ethansäuredich- dichloride, Propandisäuredichlorid, Butandisäuredichlorid , Heptandisäuredichlorid, Octandisäuredichlorid, Nonandisäuredichlorid, Decandisäuredichlorid, Undecandisäuredichlorid, Dodecandisäuredichlorid, tridecanoic diacid dichloride Pentandisäuredichlorid, hexanediamine dichloride, C3 ₂ -Dimerfettsäuredichlorid, phthaloyl chloride, terephthaloyl chloride, and Isophthalsäuredich- dichloride or their anhydrides, for example Butandicar- bonsäure-, pentanedicarboxylic acid or phthalic anhydride. Of course, mixtures of the aforementioned dicarboxylic acid compounds can be used.

As diol compounds all C aromatic or heteroaromatic compounds can in this case in principle -Ci8 _2-aliphatic, C5-C ₂ 0- cycloaliphatic, are used, which of them have two alcohol groups or derivatives (for example, diol ether or diol esters). Examples of suitable alkanediols are ethylene glycol, 1,2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 1, 1-undecanediol, 1, 12-dodecanediol, 1, 13-tridecanediol, 2,4-dimethyl-2-ethyl-1,3-hexanediol , 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol or 2,2,4 Trimethyl-1,6-hexanediol. Particularly suitable are ethylene glycol, 1, 3-propanediol, 1, 4-butanediol and 2,2-dimethyl-1, 3-propanediol, 1, 6-exhaled or 1, 1 2-dodecanediol. Examples of cycloalkanediols are 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol (1,2-dimethylolcyclohexane), 1,3 - Cyclohexanedimethanol (1, 3-dimethylolcyclohexane), 1, 4-cyclohexanedimethanol (1, 4-dimethylolcyclohexane) or 2,2,4,4-tetramethyl-1, 3-cyclobutandiol. Examples of suitable aromatic diols are 1,4-dihydroxybenzene, 1,3-dihydroxybenzene, 1,2-dihydroxybenzene, bisphenol A (2,2-bis (4-hydroxyphenyl) -propane), 1,3-dihydroxynaphthalene, 1, 5-dihydroxynaphthalene or 1, 7-dihydroxynaphthalene.

In addition, polyester polyols can also be made from alpha, omega hydroxycarboxylic acids or their cyclic esters such as. For example, Lactides or lactones are produced.

The hydroxycarboxylic acids mentioned preferably include aromatic, aliphatic see and heterocyclic compounds, including the corresponding lactones. Preference is given, for example, to 2,2-dimethyl-3-hydroxypropionic acid and also to its cyclic lactone (pivalolactone), omega-hydroxycaproic acid, omega-hydroxypalmitic acid, bicyclic acid, 4-hydroxybutyric acid, 4- (β-hydroxyethyl) benzoic acid, (β-hydroxyethoxy) benzoic acid, 4-hydroxymethylbenzoic acid, 4-hydroxymethylcyclohexanecarboxylic acid, 4- (β-hydroxyethoxy) -cyclohexanecarboxylic acid.

Other preferred hydroxycarboxylic acids include lactic acid, glycolic acid and cyclic esters such as lactides and caprolactone.

The polyester polyols can be used singly or in the form of mixtures.

III) polyetheramines

Polyetheramines having a functionality of 2 to 3 and molecular weights of 500 to 10,000

Suitable polyetheramines include, for example, di- or triaminopolyalkylene oxide compounds. By this is meant that these compounds on the one hand contain two or three amino functions (NH or NH ₂ functions), on the other hand alkylene oxide units. The last-mentioned building blocks are, in particular, ethylene oxide and / or propylene oxide and / or butylene oxide.

The polyetheramines may be used singly or in the form of mixtures.

IV) epoxide compounds

Aliphatic, alicyclic, aromatic or heterocyclic monomeric or oligomeric epoxide compounds. Preference is given to using epoxide compounds having at least 2 polymerizable epoxide groups per molecule.

Particularly preferred epoxy compounds are polyphenol glycidyl ethers, eg. Glycidyl ethers of resorcinol, hydroquinone, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3-methylphenyl) methane, bis (4-hydroxy-3,5-dibromophenyl) methane, bis (4-hydroxy-3,5-difluorophenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis ( 4-hydroxy-3-methylphenyl) -propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) -propane, 2 , 2-bis- (4-hydroxy-3,5-dichlorophenyl) -propane, bis- (4-hydroxyphenyl) -phenylmethane, bis- (4-hydroxyphenyl) -diphenylmethane, bis- (4-hydroxyphenyl) -4'- methylphenylmethane, 1, 1-bis (4-hydroxyphenyl) -2,2,2-trichloroethane, bis (4-hydroxyphenyl) - (4-chlorophenyl) -methane, 1, 1-bis- (4-hydroxyphenyl) - cyclohexane, bis (4-hydroxyphenyl) -cyclohexylmethane, 4,4'- Dihydroxydiphenyl, 2,2'-dihydroxydiphenyl, 4,4'-dihydroxydiphenylsulfone. Particularly preferred are glycidyl ethers of bisphenol A (2,2-bis (4-hydroxyphenyl) propane) or bisphenol F (bis (4-hydroxyphenyl) methane). Such epoxy resins have a preferred epoxide equivalent of 160-500.

The epoxy compounds may be used singly or in the form of mixtures.

V) polyols

Diols and / or triols with molecular weights less than 600, preferably less than 400. In

Consider, for example, aliphatic, cycloaliphatic, and / or araliphatic diols having 2 to 20, preferably 4 to 14 carbon atoms, such as. B. ethylene glycol, propanediol-1, 3, butanediol-1, 4, hexanediol-1, 6, dodecane-1, 10, o-, m-, p-dihydroxycyclohexane, diethylene glycol, dipropylene glycol, bis (2-hydroxyethyl ) - hydroquinone. Examples of triols are 1, 2,4- and 1, 3,5-trihydroxycyclohexane, triethanolamine, diethanolamine, glycerol. In a further embodiment, reaction products of these polyols with propylene oxide and / or ethylene oxide are used, preferably 1 to 5 mol of propylene and / or ethylene oxide being used per mole of polyol.

VI) diamines

Suitable diamine compounds are all organic diamine compounds which have two primary or secondary amino groups, preference being given to primary amino groups. The organic backbone having the two amino groups may have a C ₂ -C ₂ o-aliphatic, C ₃ -C ₂ o-cycloaliphatic, aromatic or heteroaromatic structure. Examples of two primary amino groups containing e Verbi nd un gen si nd 1, 2-diaminoethane, 1, 3-diaminopropane, 1, 2-diaminopropane, 2-methyl-1, 3-diaminopropan, 2,2-dimethyl-1, 3 diaminopropane (neopentyldiamine), 1,4-diaminobutane, 1,2-diaminobutane, 1,3-diaminobutane, 1-methyl-1,4-diaminobutane, 2-methyl-1,4-diaminobutane, 2,2- Dimethyl-1,4-diaminobutane, 2,3-dimethyl-1,4-diaminobutane, 1,5-diaminopentane, 1,2-diaminopentane, 1,3-diamino-pentane, 1,4-diaminopentane, 2-methyl- 1, 5-diaminopentane, 3-methyl-1,5-diaminopentane, 2,2-dimethyl-1,5-diaminopentane, 2,3-dimethyl-1,5-diaminopentane, 2,4-dimethyl-1,5 diaminopentane, 1,6-diaminohexane, 1,2-diaminohexane, 1,3-diaminohexane, 1,4-diaminohexane, 1,5-diaminohexane, 2-methyl-1,5-diaminohexane, 3-methyl-1,5 diaminohexane, 2,2-dimethyl-1, 5-diaminohexane, 2,3-dimethyl-1,5-diaminohexane, 3,3-dimethyl-1,5-diaminohexane, N, N'-dimethyl-1,6-diaminohexane , 1, 7-diaminoheptane, 1, 8-diaminooctane, 1, 9-diaminononane, 1, 10-diaminodecane, 1, 1 1-diaminoundecane, 1, 12-diaminododecane, 1, 2-diaminocyclohexane, 1, 3-diaminocyclohexane, 1, 4-diamino-cyclohexane, 3,3'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexylmethane (dicy- (on), 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane (Laromin ^®), isophorone diamine 3-aminomethyl-3,5,5,5-trimethylcyclohexylamine), 1, 4-diazine (piperazine), 1, 2 -Diaminobenzene, 1, 3-diaminobenzene, 1, 4-diaminobenzene, m-xylylenediamine [1, 3- (diamino- methyl) benzene] and p-xylylenediamine [1, 4- (diaminomethyl) benzene], Diethyltoluenedia- mine , Isophorone diamines. Of course, mixtures of the aforementioned compounds can be used.

Preference is given to 1,6-diaminohexane, 1,1,2-diaminododecane, 2,2-dimethyl-1,3-diaminopropane, 1,4-diaminocyclohexane, isophoronediamine, 3,3'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexyl methane, m-xylylenediamine or p-xylylenediamine used as optional diamine compounds.

VII) Amino alcohol compounds

As amino-alcohol compounds in principle all, but preferably C ₂ -C ₁₂ - aliphatic, cycloaliphatic C ₅ -C ₀ or aromatic organic compounds are used which have a secondary or primary, but preferably a primary amino group only one hydroxy group and , Examples which may be mentioned are 2-aminoalkanol, 3-aminopropanol, 4-aminobutanol, 5-aminopentanol, 6-aminohexanol, 2-aminocyclopentanol, 3-aminocyclopentanol, 2-aminocyclohexanol, 3-aminocyclohexanol, 4-aminocyclohexanol and 4-aminomethylcyclohexanemethanol (1-methylol-4-aminomethyl cyclohexane). Of course, mixtures of the aforementioned amino-alcohol compounds can be used.

VIII) aminocarboxylic acid compounds

Suitable aminocarboxylic acid compounds are all organic compounds which have an amino and a carboxy group in free or derivatized form, but in particular the C ₂ -C ₃ o-aminocarboxylic acids, the C ₁ -C ₅ -alkyl esters of the abovementioned aminocarboxylic acids, the corresponding C _β- bis-lactam compounds, the C ₂ -C ₃ o-aminocarboxamides or the C ₂ -C ₃₀ -aminocarbonitriles. Exemplary of the free C ₂ -C ₃ o-aminocarboxylic acids are the naturally occurring aminocarboxylic acids, such as VaNn, leucine, isoleucine, threonine, methionine, phenylalanine, tryptophan, lysine, alanine, arginine, aspartic acid, cysteine, glutamic acid, glycine, Histidine, proline, serine, tyrosine, asparagine or glutamine; and 3-aminopropionic acid, 4-aminobutyric acid, 5-aminovaleric acid, 6-aminocaproic acid, 7-aminoanthic acid, 8-aminocaprylic acid, 9-aminopelargonic acid, 10-aminocapric acid, 1-aminoundecanoic acid , 12-aminolauric acid, 13-aminotridecanoic acid, 14-aminotetradecanoic acid or 15-aminopentadecanoic acid. Exemplary of the -C ₅ - alkyl esters of the aforementioned amino carboxylic acids are the 3-aminopropionamide, 4- aminobutyric acid, 5-Aminovaleriansäure-, 6-aminocaproic acid, 7-Aminoönanth- acid, 8-aminocaprylic, 9-aminopelargonic, 10-aminocapric, 1,1-aminoundecanoic, 12-aminolauric, 13-aminotridecanoic, 14-aminotetradecanoic or 15-aminopentadecanoic acid methyl and ethyl ester. Examples of the Cs-cis-lactam compounds are β-propiolactam, γ-butyrolactam, δ-valerolactam, ε-caprolactam, 7-enantholactam, 8-caprylolactam, 9-pelargolactam, 10-caprinlactam, 1 l-undecanoic acid lactam, ω Laurolactam, 13-tridecanoic acid lactam, 14-tetradecanoic acid lactam or 15-pentadecanoic acid lactam. Examples of the aminocarboxamides are 3-aminopropionic acid, 4-aminobutyric acid, 5-aminovaleric acid, 6-aminocaproic acid, 7-amino-nicantric acid, 8-aminocaprylic acid, 9-aminopelargonic acid, 10-aminocapric acid, 11 Aminoundecanoic acid, 12-aminolauric acid, 13-aminotridecanoic acid, 14-aminotetracenecanoic acid or 15-aminopentadecanoic acid amide and as examples of the aminocarboxylic acid nitriles are 3-aminopropionic, 4-aminobutyric, 5-aminovaleric, Aminocapron, 7-aminoanthant, 8-aminocapryl, 9-aminopelargon, 10-aminocaprine, 1 1-aminoundecane, 12-aminolaurin, 13-aminotridecane, 14-aminotetradecane or 15-aminopentadecanenitrile. Preference is given to the Cs-cis-lactam compounds and, in particular, ε-caprolactam and ω-laurolactam. Particularly preferred is ε-caprolactam. Of course, it is also possible to use mixtures of the abovementioned aminocarboxylic acid compounds.

In a further preferred form, the polymerizable compounds PP have a melting point at temperatures below 100 ^° C., particularly preferred polymerizable compounds PP are liquid at room temperature.

The solvent S is water in a preferred embodiment; an alcohol, especially 2-propanol, ethanol, methanol, benzyl alcohol; an amide, especially dimethylformamide, Λ / -methyl-2-pyrrolidone; a ketone, z. Cyclohexanone, acetone, methyl ethyl ketone, an ether, e.g. B. Tetra hydrofu ran, dioxane; an ester z. Ethyl acetate, butyl acetate, propylene glycol methyl ether acetate, an alkane halide, e.g. For example, dichloromethane, chloroform.

The solvent S can also be a mixture of solvents and is characterized in that the component PP therein is either soluble or miscible with it without phase separation and the particles FM with an amorphous coating therein stable dispersions with a mean particle size in the nano range, preferably in the range from 10 nm to 80 nm, in particular from 10 nm to 50 nm, determined by means of DLS.

In a preferred embodiment, the solvent S has a lower boiling point than the polymerizable compounds PP. In a preferred embodiment, in the dispersion, based on the sum of FM, PP and S, contain:

0.1 to 80, in particular parts by weight of functionalized particles FM with an amorphous cladding

40 parts by weight PP and

0 to 1000, in particular 0 to 99 parts by weight S

In a preferred embodiment, the particles FM with an amorphous coating after the partial or complete removal of the solvency S form a stable dispersion having an average particle size in the nanoscale, preferably in the range from 10 nm to 80 nm, in particular 10 nm to 50 nm. determined by DLS.

In a preferred embodiment, the dispersion according to the invention additionally contains further effect substances, in particular additives conventional in polymers per se, eg. In the form of further particles (eg SiC> ₂ , ZrC> ₂ ) and / or soluble molecules (eg UV absorbers, stabilizers, flame retardants, antioxidants, anti-fogging agents, lubricants, anti-blocking agents, organic dyes, IR Dyes, fluorescent dyes, brighteners, antistatic agents, biocides, nucleating agents, herbicides, fungicides or pesticides, radical scavengers).

The invention further relates to functionalized UV-absorbing inorganic particles FM, preferably of a zinc, titanium or cerium oxide or a mixture thereof, having an average particle size, measured by the dynamic light scattering (DLS) method, in the nanoscale, preferably in the range of 10 nm to 80 nm, in particular 10 nm to 50 nm, characterized in that the particles are functionalized with a compound F of the formula

R ¹ LF ¹ wherein

Atoms, in particular methylene, ethylene or propylene

F ¹ metal-oxide-affine group, in particular silanes, amines, carboxylic acids, carboxy late, phosphonic acid, phosphonates, phosphates or sulfonates, in particular

NH ₂ , NH, COOH, [COO] -, PO ₃ H ₂ , [PO ₃ H] -, [PO ₃ ] ^{2 "} , [PO ₄ H] ^2" , [PO ₄ H ₂ ] ^" , [SO ₃ group] ^", CO- CH ₂ -CO, especially a Trialkoxisilanrest of the formula -Si (OR) _3, wherein R kylrest an Al and wherein the particles FM have an amorphous cladding, preferably of oxides and / or oxide hydroxides and / or hydrated oxides of silicon, aluminum or zirconium, in particular an SiO ₂ -containing layer.

The invention further relates to a process for the preparation of amorphously coated, functionalized particles, characterized in that

i) inorganic particles are brought into contact in a solvent with a functionalizing compound, preferably compounds F of the formula R ¹ LF ¹ , where R ¹ , L and F ^{1 have} the abovementioned meaning.

ii) coating of the obtained functionalized particles by precursors of an amorphous coating, in particular of a tetraalkoxysilane, polysiloxane, silica or alkali metal silicate, forming a closed amorphous coating and

iii) optionally removing solvents and other auxiliaries.

The invention furthermore relates to functionalized UV-absorbing inorganic substances FM obtainable by the process according to the invention.

The invention further relates to a process for the preparation of a dispersion according to the invention, characterized in that

a) a dispersion comprising functionalized UV-absorbing inorganic particles FM, preferably UV-absorbing metal oxide particles, in particular zinc oxide particles with an amorphous coating, preferably with a coating based on oxides, oxide hydroxides or hydrated oxides of silicon, aluminum or zirconium, especially with one SiO ₂ -containing cladding with a mean particle size in the nanoscale, preferably in the range of 10 nm to 80 nm, in particular 10 nm to 50 nm, determined by means of DLS, in a solvent S, preferably by dispersing the functionalized metal oxide particles in a continuous phase , preferably THF, benzyl alcohol, dimethylformamide, methyl ethyl ketone, cyclohexanone, Λ / -methyl-2-pyrrolidone, and preferably using conventional dispersing agents such as. B. magnetic or mechanical stirrer, b) addition of the component PP or a solution of the component PP in the solvent S c) optionally complete or partial removal of the solvent S. The dispersions of the invention are suitable for the preparation of a filled polymeric material. The material may be, for example, a polyurethane, polyurea, epoxy, polyester, polyester resin or a blend thereof.

The novel dispersions and functionalized particles are outstandingly suitable for stabilizing polymers, in particular against UV radiation. For the purposes of this invention, polymers are understood as meaning high-molecular compounds, including, for example, polyaddition compounds, in particular polyurethanes. The polyurethanes may be both solid, non-foamed polyurethanes, for example, thermoplastic polyurethanes, e.g. Transparent TPU types for film applications, as well as PU elastomers act. Further, they may also be polyurethane foams, e.g. for shoe systems. In the case of foams, additional water or physical foaming agents are used, for example pentane. A particular embodiment is polyurea, which is e.g. used in coating applications.

The invention also relates to a process for the preparation of a stabilized polymer, characterized in that a dispersion according to the invention is introduced into a polymer, a prepolymer or into the starting components for the preparation of a polymer. In this case, the dispersion according to the invention can be used, for example, together with a polyol to form a polyurethane.

Examples: Dynamic light scattering (DLS)

The measurements are carried out with a Zetasizer Nano S device from Malvern Instruments at room temperature. The average particle size is determined by the volume fraction.

Transmission Electron Microscopy (TEM)

The TEM investigations were carried out on a device Tecnai G2 from Fa. FEI with an integrated Energy Dispersive X-ray Spectroscopy (EDXS) system. The samples were prepared on a C-hole film (Lacey Carbon Film). Element analysis by EXDS was done at those spots where the film had a hole.

UV-VIS transmission spectroscopy The determination of the total diffuse transmission of the product was carried out in a 0.1 mm quartz glass cuvette using a Perkin Elmer Lambda 900 spectrophotometer a 150 mm integration sphere (integrating sphere). The reference was spectral white standards from Labsphere.

example 1

Production of ZnO

73.6 g of zinc acetate dihydrate were suspended in a 42 liter flask in 2236 ml of 2-propanol and heated to 75 ° C. In parallel, 32.8 g of potassium hydroxide in 1 168 mL of 2-propanol were dissolved at 75 ° C. Subsequently, the KOH solution was added to the zinc acetate suspension with vigorous stirring, the resulting mixture was heated for 1 hour at 75 ° C with stirring and cooled to room temperature. The resulting white precipitate was deposited, the supernatant was filtered off with suction, the white residue was washed with 1000 ml of 2-propanol and deposited. The supernatant was again filtered off, the white residue was washed again with 2-propanol and deposited. After re-aspirating the liquid supernatant, the white residue was made up with 2-propanol.

Example 2

Functionalization of ZnO according to the invention with 2- [methoxy (polyethyleneoxy) propyl] trimethoxysilane and subsequent coating with a SiO ₂ -containing layer by hydrolysis of tetramethoxysilane

1348 g of a 4.45 wt .-% dispersion of an unfunctionalized ZnO in 2-propanol were prepared analogously to Example 1. To this solution was then added dropwise a solution of 15 g of 2- [methoxy (polyethyleneoxy) propyl] trimethoxysilane in 631 g of 2-propanol over 190 minutes with vigorous stirring. The suspension was heated to 60 ^° C. and the mixture was refluxed for 30 minutes. Subsequently, 81 g of a 25 wt .-% aqueous NH ₃ solution were added and the resulting suspension for 12 hours at 60 ⁰ C heated with stirring. The suspension became transparent. Furthermore, to the resulting suspension, a solution of 7.5 g of tetramethoxysilane (TMOS) in 1 18 g of 2-propanol was added within 40 minutes with stirring. The resulting suspension was stirred demand for 16 hours at 60 ⁰ C. 2-Propanol and NH ₃ were then removed at 50 ^° C. in a rotary evaporator until the pressure had a constant value <10 mbar. The white residue of coated and functionalized particles FM was then dried under vacuum <110 mbar for a further 60 minutes (resulting N / Zn ratio <0.2% by weight).

Example 3 Dispersion containing 2- [methoxy (polyethyleneoxy) propyl] trimethoxysilane then functionalized SiO ₂ -coated ZnO in a polyester polyol

The white residue obtained from functionalized and coated particles FM obtained according to Example 2 was re-dispersed in THF to form a 5% strength by weight ZnO dispersion. The average particle size determined by DLS was 25 nm (% by volume). A TEM study confirmed the amorphous Si-containing cladding with ZnO particles. A total of about 1150 g of a 5% by weight ZnO dispersion in THF was prepared.

Further, a solution containing 1000 g of a difunctional polyester polyol and 1000 g of THF was prepared. The polyester polyol had a molecular weight of 2,000 and was prepared from adipic acid and equimolar amounts of 1,4-butanediol and ethylene glycol. To this solution was added, with stirring, 1 150 g of the above redispersed ZnO dispersion in THF. The resulting mixture remained transparent.

The composition obtained corresponds to about 2.3 parts by weight ZnO (or about 3 parts by weight of functionalized and SiO ₂ -coated ZnO), 40 parts by weight of polyester polyol and 83 parts by weight of THF.

Subsequently, THF was removed on a rotary evaporator under vacuum at 50 ⁰ C, so that a constant pressure of less than 10 mbar was reached. This gave rise to an approximately 5.35% by weight ZnO dispersion in the polyester polyol. After stripping off THF, no phase separation or clouding was observed. The DLS-determined average particle size (% by volume) was 28 nm. Using UV-Vis spectroscopy, an absorption edge was detected at about 370 nm.

Example 4

Reacting a 5.35 wt .-% with 2- [methoxy (polvethyleneoxy) propyltrimethoxysilane-functionalized and SiO? -Coated ZnO dispersion in Polvesterpolvol to a ZnO-filled polyurethane

In a reaction vessel, 700 g of the ZnO-filled polyesterol from Example 3 and 157.21 g of 1, 4-butanediol were weighed and heated to 80 ⁰ C. Subsequently, known per se antioxidants were added (0.1 wt .-% Irganox ^® 1098, 0.1 wt .-% Irganox ^® 1010 and 0.15 wt .-% Chisorb 622). After subsequent warming the solution to 80 ⁰ C 527.51 g of 4,4'-MDI (methylene diphenyl diisocyanate) was added and stirred until the solution was homogeneous. Subsequently, the reaction mass was poured into a shallow dish and annealed at 125 ° C on a hot plate for 10 min. Thereafter, the resulting rind was in a heating cabinet 15th h annealed at 80 ⁰ C. After granulating the casting plates, they were processed on an injection molding machine into 2 mm spray plates. The product had a Shore hardness of Shore 57D and abrasion of 1 10 mm ³ . The spray plate was translucent and showed almost no shrinkage. As compared to the sample of Example 4, the sample of Example 7 containing ZnO particles with an amorphous cladding had improved UV stability

Example 5

Dispersion containing 2- [methoxy (polyethyleneoxy) propyl] trimethoxysilane, then functionalized with SiO ₂ -coated ZnO in diglycidyl ether of bisphenol A (DGEBA A)

The particles FM obtained according to Example 2 were redispersed in methyl ethyl ketone (MEK) to form a 12% by weight ZnO dispersion. This resulted in a transparent suspension. In total, about 1100 g of a 12% by weight ZnO dispersion were prepared in MEK. The MEK consumption was about 930 g.

A solution containing 500 g of the diglycidyl ether of bisphenol A (DGEBA) and 1000 g of MEK was prepared. Subsequently, to this solution with stirring 1 100 g of the ZnO dispersion in MEK was added. Subsequently, to this solution with stirring were added 1100 g of a 2-methoxy (polyethyleneoxy) propyl-trimethoxysilane-functionalized and SiO ₂ -coated 12% by weight ZnO dispersion in MEK. The resulting mixture remained transparent.

The composition corresponds to about 10.6 parts by weight ZnO (or about 13.8 parts by weight of functionalized and SiO ₂ -coated ZnO), 40 parts by weight DGEBA A and 154 parts by weight of THF.

Subsequently, THF was removed on a rotary evaporator under vacuum at 50 ^° C., so that the vacuum pressure reached a constant value of less than 10 mbar. An approximately 19.7% by weight ZnO dispersion in DGEBA A was obtained. No phase separation or clouding was observed after or during the removal of MEK. The mean particle size determined by DLS (% by volume) was about 15 nm.

Example 6

Preparation of Oliqoethersilane CH ₃ OrCH _? CH (CH ₃ ) O1in (CH _? CH _? O) _s (CH _? ) ₃ Si (OEt) 3 a) Preparation of the allyl alkoxylate HO [CH ₂ CH (CH ₃ ) O] _I O (CH ₂ CH ₂ O) ₅ CH ₂ CHCH ₂ A mixture of allyl alcohol (133.6 g, 2.3 mol) and potassium te / f-butylate (7.90 g) was placed in a 5 l pressure autoclave and heated to 25 ⁰ C.

The mixture was then made inert three times with nitrogen to 5 bar and the temperature increased to 130 ⁰ C. Then ethylene oxide (506 g, 11.5 mol) was metered in and, after the end of the addition, stirring was continued for 2 h. Subsequently, propylene oxide (1334 g, 23 mol) was likewise metered in at 130 ^° C. and stirring was continued overnight. This gave 1954 g of allyl alcohol - 5 EO - 10 PO (OH number 63.6 mg KOH / g, theory 65.4 mg KOH / g).

b) Preparation of allyl alkoxylate methyl ether

CH ₃ O [CH ₂ CH (CH ₃ ) O] _IO (CH ₂ CH ₂ O) ₅ CH ₂ CHCH ₂

In a stirring apparatus, allyl alcohol - 5 EO - PO 10 (459 g, 0.520 mol) were charged and added dropwise aqueous NaOH solution at 50% (238 g, 2.98 mol) was added at 34-36 ⁰ C. Then dimethyl sulfate (87.1 ml, 0.920 mol) within 1 h at 36 ⁰ C added. The reaction mixture was stirred at 40 ^° C. overnight and then after addition of water (520 g) at 95 ^° C. for 1 h. The two phases were separated in a separating funnel and the organic phase was freed of residual water on a rotary evaporator. Thereafter, the compound was added with Ambosol (3% by weight), filtered and stabilized with 0.025% by weight aqueous 33% sodium benzoate solution. This gave 426 g of product.

c) hydrosilylation

The allyl alkoxylate methyl ether (201 g, 0.230 mol) was initially charged and the stirring apparatus was flooded with argon. Subsequently, triethoxysilane (43.2 ml, 0.230 mol) was injected via a septum and the reaction mixture was heated to 80-90 ⁰ C. Hexachloroplatinic acid (0.175 ml, 7.5% solution in isopropanol) was carefully added via a syringe and, after the addition had ended, stirring was continued for a further 15 min. One ER gave 225 g of CH ₃ O [CH ₂ CH (CH ₃₎ O] i ₀ (CH ₂ CH ₂ O) ₅ (CH ₂₎ approximately grade ₃ Si (OEt) ₃ with a Silanie- of 80% ⁽¹ H NMR).

Example 7 Functionalization of ZnO According to the Invention and Subsequent Coating

1200 g of a 2% by weight dispersion of an unfunctionalized ZnO in 2-propanol were prepared analogously to Example 1. To this solution was added a solution of 13 g of ammonia solution (25% in water) at room temperature. Thereafter, a solution of 16 g of CH ₃ O [CH ₂ CH (CH ₃ ) O] i ₀ (CH ₂ CH ₂ O) ₅ (CH ₂ ) ₃ Si (OEt) ₃ from Example 6 in 63 g of 2-propanol within added dropwise over 30 minutes with vigorous stirring. The Suspension was heated to 60 ⁰ C and stirred at 60 ⁰ C for 24 hours. The suspension became translucent. The experiment was repeated five times.

A part of the suspension (ca. 5700 g containing 107 g ZnO) was placed in a Rührappara- structure and heated to 60 ⁰ C. To the suspension was added a solution of 13.6 g of tetramethoxysilane (TMOS) in 209 g of 2-propanol within 60 minutes with stirring at 60 ^° C. The suspension obtained was stirred at 60 ^° C. for 16 hours. 2-Propanol was then removed at 50 ^° C. in a rotary evaporator until the pressure had a constant value <10 mbar. The white residue from coated and functionalized ZnO particles was then dried under vacuum <10 mbar for a further 60 minutes (resulting N / Zn ratio <0.2% by weight).

Example 8 Dispersion in a polyetheramine

The residue of functionalized and coated ZnO particles obtained according to Example 7 was redispersed in THF to give an approximately 6% strength by weight ZnO dispersion. The average particle size determined by DLS was 25 nm (% by volume). A TEM study confirmed an amorphous Si-containing cladding around the ZnO particles.

Further, a solution containing 3165 g of a difunctional polyetheramine having a molecular weight of 2,000 (D-2000, BASF) and 1,000 g of THF was prepared. Subsequently, about 1630 g of the 6% strength by weight ZnO dispersion in THF were added to this solution while stirring. The resulting mixture remained translucent.

The composition obtained corresponds to about 1.25 parts by weight ZnO (or about 1.6 parts by weight of functionalized and SiO ₂ -coated ZnO), 40 parts by weight polyetheramine D-2000 and 31.5 parts by weight THF.

Subsequently, THF was removed on a rotary evaporator under vacuum at 50 ° C, so that the vacuum pressure reached a constant value less than 10 mbar. An approximately 3% strength by weight ZnO dispersion in polyetheramine D-2000 was formed. After removal of THF, no phase separation or turbidity was observed. The average particle size determined by DLS (% by volume) was about 24 nm. An absorption edge was detected at about 370 nm by means of UV-Vis spectroscopy.

Example 9

It was a prepolymer of diphenylmethane diisocyanate (MDI) with a weight fraction of about 50% 2,4 'isomer and about 50% 4,4' isomer (51 parts by weight) and a Polyoxypropylene polyether polyol having a nominal functionality of two and an OH number of 56 mg KOH / g (49 parts by weight). The prepolymer was obtained by a standard method at a mixture temperature of 80 ^° C. and a reaction time of two hours.

The following formulation was used for the modified ZnO-added isocyanate-reactive component:

where:

Polyetheramine D 2000: A commercially available polyoxypropylenediamine from BASF SE with molecular weight 2000.

Polyetheramine D 400: A commercially available aliphatic primary amine-terminated polyoxypropylenediamine from BASF SE.

Ethacure ^® 100: a 80/20 mixture of 3,5-diethyl-2,4-toluenediamine and 3,5-diethyl-2,6-toluenediamine.

The isocyanate-reactive formulation was reacted with the isocyanate-containing prepolymer in sprayed polyurea elastomer. In this case, a mixing ratio of isocyanate-reactive component to isocyanate component of about 100 to 109 was used, which corresponded to an isocyanate index of about 104. A Graco sprayer was used at a component temperature of 65 ° C and a processing pressure of 110 to 120 bar.

The coatings were sprayed onto a steel plate previously provided with a release agent. The coatings were peeled off by gently peeling, starting in one corner of the plate. The resulting coating was exposed to UV light and showed improved UV stability over a coating prepared in an analogous manner but without ZnO particles of the invention.

Claims

claims

1. Dispersion containing

1) functionalized UV-absorbing inorganic particles FM having an average particle size, measured by the dynamic light scattering (DLS) method, in the nanoscale, preferably in the range of 10 to 80 nm, in particular 10 nm to 50 nm, and 2) polymerizable Compounds PP, in particular monomers, oligomers or prepolymers, which are convertible into polymers by preferably non-radical polymerization and optionally a solvent S, and / or 3) a solvent soluble in the solvent S, characterized in that the functionalized particles FM an amorphous

Have wrapping.

Dispersion according to at least one of the preceding claims, characterized in that the UV absorbing particle FM is a metal oxide particle.

3. Dispersion according to at least one of the preceding claims, characterized in that the metal oxide is a zinc, titanium or cerium oxide.

4. Dispersion according to at least one of the preceding claims, characterized in that the amorphous coating consists of oxides and / or oxide hydroxides and / or hydrated oxides of silicon, aluminum or zirconium.

5. Dispersion according to at least one of the preceding claims, characterized in that the metal oxide particles FM are functionalized with a

Compound F of the formula

R ¹ LF ¹ wherein

R ¹ oxygen-containing radical, in particular alkoxy; aryloxy; ether group-containing oligomer or polymer

L is a divalent linking group, in particular alkylene having preferably 1 to 10 C atoms, in particular methylene, ethylene or propylene

F ¹ metal oxide-affine group, in particular a Trialkoxysilanrest.

6. Dispersion according to at least one of the preceding claims, characterized in that the functionalizing compound F corresponds to the formula:

R ²³ O (CH ₂ CR ²¹ R ²² O) _p (CH ₂ ) _q -F ¹ wherein

R ²¹ , R ^{22 are} identical or different, are hydrogen or an alkyl radical, in particular having 1 to 4 C atoms, preferably hydrogen, methyl or ethyl, where R ²¹ and R ²² may have different meanings when used repeatedly and those indicated by p Group in blocks or statistically distributed

R ^{23 is} hydrogen or an alkyl radical, in particular having 1 to 4 C atoms, in particular methyl or ethyl

p is 0 or an integer from 1 to 50, in particular 0 or 1 to 35, preferably 0 or 1 to 20 q 0 or an integer from 1 to 10, in particular 0 or an integer from 1 to 3, and wherein F ¹ has the meaning given in claim 5.

Dispersion according to at least one of the preceding claims, characterized in that the functionalized metal oxide particle FM is essentially a zinc, titanium or cerium oxide or a mixture thereof and F corresponds to the formula:

R ³¹

R- (CH ₂ ) _q Si R ³²

R ³³

in which mean

RR ¹⁰ O (CH ₂ CHR ¹¹ O) _P p 0 or an integer, in particular 1 to 100, preferably

1 to 30, where the group indicated by p can be composed of radicals with different meanings for R ¹¹ R ^{10 is} H or C _r C ₄ -alkyl, in particular methyl or ethyl R ¹¹ H, alkyl having 1 to 4 C atoms, in particular hydrogen, methyl or ethyl

R ³¹ , R ³² , R ^{33 are} identical or different, hydrogen or alkoxy, in particular C 1 -C ₄ -alkyloxy, in particular methoxy or ethyloxy; Acyloxy, in particular acetoxy; amino; Halogen, especially Cl, wherein at least one of the groups R ¹ , R ² , R ^{3 is} hydrolyzable and in particular methoxy or ethoxy and wherein q has the meaning given in claim 6.

8. Dispersion according to at least one of the preceding claims, characterized in that the polymerisable compound PP is an isocyanate-reactive compound, in particular a polyurethane customary in polyurethane, end-extenders or crosslinkers.

9. Functionalized UV-absorbing inorganic particles FM, preferably of a zinc, titanium or cerium oxide or a mixture thereof, having an average particle size, measured according to the dynamic light scattering (DLS) method in the nanoscale, preferably in the range of 1 to 80 nm, in particular 10 nm to 50 nm, characterized in that the particles are functionalized with a compound F of the formula

R ¹ LF ¹

in which mean

F ¹ metal oxide-affine group, in particular silanes, amines, carboxylic acids,

Carboxylates, phosphonic acid, phosphonates, phosphates or sulfonates, in particular, NH _2, NH, COOH, [COO] ^", PO ₃ H _2, [PO ₃ H] ^', [PO _3] ^2," [PO ₄ H] ^{2 "}

, [PO ₄ H ₂ ] ^" , [SO ₃ ] ^" , CO-CH ₂ -CO, especially a Trialkoxisilanrest the formula -Si (OR) ₃ , wherein R is an alkyl radical

and wherein the particles FM have an amorphous cladding, preferably of oxides and / or oxide hydroxides and / or hydrated oxides of silicon, aluminum or zirconium, in particular an SiO ₂ -containing layer.

10. A process for the preparation of functionalized particles according to claim 9, characterized in that i) inorganic particles in a solvent are associated with a functionalizing compound F of the formula given in claim 17

ii) coating the resulting functionalized particles by precursors of an amorphous coating, in particular a tetraalkoxysilane, polysiloxanes, silicic acid or alkali metal silicate to form a closed amorphous coating and iii) optionally removing solvents and further auxiliaries.

1 1. A process for the preparation of a dispersion according to at least one of the preceding claims, characterized in that

a) a dispersion containing functionalized metal oxide, preferably zinc oxide particles having an average particle size, measured by the dynamic light scattering (DLS) method, in the nano range, preferably in the range of 10 to 80 nm, in particular 10 nm to 50 nm, in a solvent S is provided b) addition of the component PP or a solution of the component PP in the solvent S c) optionally complete or partial removal of the solvent S

12. Use of a dispersion according to at least one of the preceding claims for the preparation of a filled polymeric material, in particular of a polyurethane, polyurethane, polyurea, epoxy, polyester resin or a blend thereof.

13. Use of a dispersion according to at least one of the preceding claims for the stabilization of polymers, in particular of polyurethanes.

14. Use according to claim 13, characterized in that the dispersion is used together with a polyol to form a polyurethane.

15. A process for producing a UV-stabilized polymer, characterized in that a particle or a dispersion according to at least one of the preceding claims in a polymer, a prepolymer or in the starting components for the preparation of a polymer are introduced and mixed therewith.