WO2014139955A1

WO2014139955A1 - Liquid crosslinkable metal-silicone resin compositions

Info

Publication number: WO2014139955A1
Application number: PCT/EP2014/054592
Authority: WO
Inventors: Frank Sandmeyer
Original assignee: Wacker Chemie Ag
Priority date: 2013-03-12
Filing date: 2014-03-10
Publication date: 2014-09-18
Also published as: DE102013204296A1

Abstract

What are described are liquid crosslinkable metal-silicone resin compositions preparable by hydrolysis and condensation of A) 100 parts by weight of silicone resin formed from 30 to 100 mol% of units of the formulae R'SiO_3/2 (Ia) and/or SiO_4/2 (Ib) and mixtures thereof and 0 to 70 mol% of units of the formulae R'₂SiO_2/2 (Ic) and/or R¹ ₃SiO_1/2 (Id) and mixtures thereof, where R', R and R¹ are each as defined in claim 1, B) 1 to 200 parts by weight of a metal compound of the formula R² _cMX_4-c (II), or partial hydrolysates thereof, where c is 0, 1, 2 or 3, M is Ti or Zr, X is a halogen atom or a -OR³ radical, and R² and R³ are each as defined in claim 1, optionally C) 0 to 100 parts by weight of a silane of the formula R⁴ _dSi(OR⁵)_4-d (III) or partial hydrolysates thereof and optionally D) 0 to 100 parts by weight of a silane of the formula R⁶ _eSiZ_4-e (IV) or partial hydrolysates thereof, where d is 0, 1, 2 or 3, e is 0, 1, 2 or 3, Z is a halogen atom, R⁴, R⁵ and R⁶ are each as defined in claim 1, with E) water, optionally in the presence of F) catalysts that promote hydrolysis and condensation, and optionally in the presence of G) organic solvents, with the proviso that i) the amount of water is always chosen such that it is substoichiometric based on the amount of all the hydrolysable metal- and silicon-bonded hydrolysable groups, ii) that at least one ≡Μ-Ο-Si≡ bond is present, iii) that at least 1% by weight of metal-free silicone resin is present, and iv) that the compositions have a viscosity of 5 to 5 000 000 mPa.s at 25°C, and v) and the hydrolysis and condensation are optionally followed by an addition of (A2) silicone resins.

Description

Liquid crosslinkable metal-silicone resin compositions

The invention relates to metal-silicone resin compositions, to processes for their preparation and to compositions produced therefrom

Shaped bodies and films.

Metal-silicone resin compositions, hereinafter also

Metallo-siloxane Composite called materials that contain both metal-O-Si bonds as well as those that

physical blends of polymetalloxanes and

Polysiloxanes are known. See, for example, Walter Noll, Chemistry and Technology of Silicones, 1968, Chapter 7.1 Heterosiloxanes, pp. 332-347. Physical blends of, in particular organo-organic compounds with polyorganosiloxanes, in which silicone resins are mitgemeint, are for example in the context of

catalyzed chemical crosslinking of polyorganosiloxanes known. An example is made here to the technical data sheet to SILRES ^® MSE 100 (Wacker Chemie AG) in 2001

directed. In addition, be on the product brochure

DuPont ™ Tyzor ^® from 2008, which mentions the addition of organic titanates to silicone elastomers curable titano-siloxane composite systems RTV-1.

To improve in particular the optical as well as the mechanical properties of polyorganosiloxanes, the combination of polyorganosiloxanes with titanate compounds, in particular with titanium esters under hydrolytic conditions has been proposed on numerous occasions. However, because of the high reactivity of titanates to water and their tendency to form insoluble gels, co-hydrolysis processes to obtain soluble, transparent products are problematic. DE 34 07 087 discloses a process for the production of hard, scratch-resistant coatings by coating and curing a lacquer on a substrate, wherein the lacquer by a hydrolytic precondensation of a titanium or zirconium compound of the type MR4 (R = halogen atom, hydroxy group,

Alkoxy group, acyloxy group or a chelate ligand), a hydrolytically vulnerable group-carrying silane,

Has alkyl groups or olefinically unsaturated alkenyl groups, which may optionally be functionalized, and optionally a soluble in the reaction medium non-volatile oxide of a

Element of the main groups Ia to Va or the subgroups IVb or Vb, with the exception of titanium and zirconium, or optionally in the reaction medium, a soluble non-volatile oxide-forming compound of an element of main groups Ia to Va or subgroups IVb or Vb, with the exception of Titanium and zirconium is prepared using an amount of water which is smaller than the amount of water required for complete hydrolysis of all hydrolyzable groups. In a second step, a complementary condensation with

at least that amount of water used to

complete hydrolysis of all remaining hydrolyzable groups is necessary.

This process consists of two discrete steps leading to individually identifiable products and requires the use of a stoichiometric amount of water for

complete hydrolysis of all styrenizable groups. The result is a completely hydrolyzed product, which in the course of the preparation of the coating composition

Precipitation occurs, so that transparent masses can only be obtained by filtration. The exact composition of the coating compositions is difficult to control due to the losses in the filtration step material losses, so that the

Properties of the coatings obtained in the context of

Scatter the variation bandwidth of the compositions. Aromatic groups are excluded as substituents on the silane. DE 34 40 652 AI claims a process for the preparation of optical moldings, which is characterized in that for polytitanosiloxanes, as described in DE 34 07 087 for

Production of scratch-resistant coatings have been used, being used in DE 34 40 652 AI the extent of allowed for the production of hydrolytic precondensates

Silane was extended to DE 34 07 087, so that here are also aromatic substituted silanes for the preparation of the hydrolytic precondensates are permitted. The method suffers from the same weaknesses as described in DE 34 07 087 for the production of scratch-resistant coatings. In particular, again, this is a stepwise process of the two steps of pre- and post-condensation with isolable defined intermediates, again using the stoichiometric amount of water required for complete hydrolysis of all hydrolyzable groups present. The target products are solids which, in a suitable process, become optical shaped articles

are processed.

EP 669 362 B1 teaches a process for the preparation of polytitanosiloxanes which are soluble in organic solvents. By hydrolysis and condensation of a mixture of tetraalkytitanate and tetraalkyl silicate using less than 80% of the hydrolysis and condensation of all in the mixture

existing water at low temperatures of up to minus 100 ° C and subsequent reaction with at least one triorganosilane carrying a hydroxy group or an acyloxy having at most 8 carbon atoms. The organic groups on the silane are methyl, phenyl or vinyl groups. In this process, in addition to cooling the reaction mixture, appropriate measures must be taken to prevent it from being gelled. Such measures are either a gradual addition of water, a dilution of the Water with a water-soluble solvent or the addition of water in the form of an adsorbate to a solid. By adding the triorganosilane are not consumed

Alkoxy groups reacted and the product to stabilize against progressive condensation and associated gelling. In this case, up to five times more triorganosilane is added than to alkoxy groups after hydrolysis and

Condensation of Tetraalkoxytitanats remained with the Tetraalkoxysilikat.

The polytitanosiloxanes thus obtained are not self-crosslinking. The process is due to the low temperatures required for a large scale application

Scale not suitable and therefore uneconomical. No. 5,596,060 claims curable compositions comprising the vinyl-functional polytitanosiloxanes described in EP 669 362 Bl, as well as Si-H-functional polyorganosiloxanes, a platinum catalyst for hydrosilylation and an organic peroxide as further crosslinking catalyst.

No. 5,596,060 teaches that the curing of the polytitanosiloxanes described in EP 669 362 B1 achieves better application properties with regard to mechanical strength, solvents and temperature resistance. US 5,357,024 (corresponding EP 429 325 B1) teaches

Process for the preparation of a polyorganosiloxane resin

Composition obtained in a two-stage process. The composition serves as abrasion resistant

Cover material for organic glasses. In the first step, optionally organically substituted alkoxysilanes or

Silane with a relative to the hydrolyzable

Hydrolyzed groups of stoichiometric amount of water until the water used for it is almost completely consumed. By silane mixtures is meant, in particular, those comprising an epoxy silane. This one obtained from the first step practically anhydrous silane hydrolyzate, the formation of which takes several hours, typically between 10 and 20 hours, is combined in a second step with an acyl titanate obtained from a tetraalkoxy titanate under the action of an organic acid and reacted with further water so that forms a titanium-siloxane copolymer without causing precipitate formation.

The resulting coating compositions are thermally cured using two catalysts, one of which causes cure by opening the epoxide ring of the preferred epoxysilane used and the second catalyzes the thermal cure.

Through the use of acyl titanates is during the

Synthesis formed organic acid, which is difficult to separate. As the obtained alkoxy and acylfunktionellen

titanium-modified silicone resins can condense acid catalyzed, this leads to a destabilization of the products formed. Free acid is also formed during the curing of the acyl-containing copolymers produced here, which can lead to corrosion on metal substrates in particular. These disadvantages considerably limit the applicability of the copolymers described herein.

The fact that this process does not precipitate during the synthesis is explained by the fact that the reactivity of the acyl titanates over the alkoxy titanates, which are predominantly used in the prior art, is so markedly reduced that they can be converted into the alkoxysilane hydrolysates

to react, without precipitation from Titangelen from the

Homocondensation of the titanium compounds to form. This is bought by the disadvantage of the extremely limited

Raw material selection. In avoiding eventual precipitation from titanic rocks, the acidic environment is likely to play a role, leading to a charge - induced stabilization of

Titanium oxide particles, an effect that is used in the production of titanium dioxide nanoparticles. EP 023 096 B1 claims organometallic copolymers of polycarbosilanes and etallosiloxanes. The described

Copolymers serve as raw materials for the production of

Molded bodies of inorganic carbide. They are from one

Polycarbosilanteil constructed, which has a Si-CH ₂ skeleton, and a Metallosiloxananteil having an MO skeleton, where M = Ti, Zr or Si. The titanium or optionally zirconium ^¬ atoms are alkoxy, phenoxy or acetyloxy-substituted, the silicon atoms of the siloxane units are alkyl, phenyl or hydrogen-substituted. There are bonding interactions in the form of MO-Si or Si-O-Si bonds between the carbosilane portion of the composition and the metallosiloxane portion. The ratio of metal to silicon atoms in the metallosiloxanes is 30: 1 to 1:30.

US-A-3,846,359 teaches coating compositions containing an alkyl silicate and / or an alkyl polysilicate, an alkyl titanate and / or an alkyl polytitanate, a film-forming resin such as a silicone resin and conventional solvents which cure after air-drying.

WO 2007/077130 A1 describes coating compositions comprising a silicone resin, alkyl titanates, aluminum pigments, further pigments and fillers, and optionally

Alkyl silicates described.

WO 2012/078617 A1 teaches preparations of low molecular weight alkenyl-functional siloxane components with organohydrogensiloxanes which contain Si-H functions, a hydrosilylation catalyst and nanoparticulate titanium dioxd. The titanium dioxide nanoparticles preferably have a particle size below 25 nm and are used as solvent dispersion. These preparations serve as encapsulating material for

Semiconductor devices with a high refractive index. US 8,258,636 Bl (corresponding DE 10 2012 010 203 A1) teaches high refractive index curable liquid light-emitting diode encapsulating materials consisting of phenoxyphenol substituted

Polyorganosiloxanes and titanium dioxide domains, wherein the preparations according to the invention are obtained by a process in which an organotitanate in the presence of a generated in a first stage from the respective alkoxysilane precursors in an aprotic solvent in situ

Phenoxyphenolsubstituierten polyorganosiloxane is condensed to domains. The phenoxyphenylgruppentragenden

Siloxane units are always D units and make up the largest proportion of polyorganosiloxanes according to the invention, which thus have mainly silicone oil character. The synthesis of the phenoxyphenyl-substituted starting silanes is complicated by Grignard reactions.

Object of the present invention is to provide liquid crosslinkable metal-silicone resin compositions, such as titanium-silicone resin composite materials, with good storage stability and broad applicability in different applications, these being obtained by a simple, industrially feasible and economical single-stage synthesis, so that the disadvantages of the prior art

be overcome and this is significantly further developed. The object is achieved by the invention.

The invention relates to liquid crosslinkable metal silicone resin compositions produced by hydrolysis and condensation of

(A) 100 parts by weight of a silicone resin of 30 to 100 mol%, preferably 50 to 100 mol%, preferably 80 to 100 mol%, of units selected from the group of units of

Formulas R'Si0 _3/2 (Ia) and Si0 _4/2 (Ib) and mixtures thereof and 0 to 70 mol%, preferably 0 to 50 mol%, preferably 0 to 20 mol% of units selected from the group consisting of units of the formulas R _'2 Si0 _2/2 (Ic) and R' ₃ Si0 _1/2 (Id) and mixtures thereof, wherein

R 'may be the same or different and is a radical R or a radical of the formula -OR ¹ ,

with the proviso that at least 3 mol%, preferably at least 5 mol%, preferably at least 7 mol%, of all radicals R 'are radicals of the formula -OR ¹ ,

R may be the same or different and is a monovalent optionally substituted hydrocarbon radical having 1 to 18 carbon atoms or a hydrogen atom, and

R ^{1 may be the} same or different and a

Represents hydrogen atom or a monovalent optionally substituted hydrocarbon radical having 1 to 18 carbon atoms,

(B) 1 to 200 parts by weight, based on 100 parts by weight

Silicone resin (A), a metal compound of the formula

R ² _c MX ₄ -c (II), or their partial hydrolysates, wherein

c is 0, 1, 2 or 3, preferably 0 or 1, preferably 0,

M is titanium or zirconium, preferably titanium in the

Oxidation state + IV, is

X is a halogen atom, preferably a chlorine atom, or a

Rest is -OR ³ ,

R ^{2 has} the same meaning as R independently of R and

R ^{3 has} the same meaning as R ¹ independently of R ¹ , if necessary

(C) 0 to 100 parts by weight, based on 100 parts by weight

Silicone resin (A), a silane of the formula R ⁴ _d Si (OR ⁵ ) ₄ -d (HD or its partial hydrolysates, with the proviso that the partial hydrolysates are different from silicone resin (A) and at least 3 mol%, preferably at least 5 mol%, preferably at least 10 mol% %, and preferably at most 85 mol%, based on all Si-bonded radicals, C1-C12 alkoxy radicals or hydroxy radicals, wherein

R ^{4 may be the} same or different and is a monovalent optionally substituted hydrocarbon radical having 1 to 18 carbon atoms or a hydrogen atom,

R ^{5 has} the same meaning as R ¹ independently of R ¹ , d is 0, 1, 2 or 3, preferably 0, 1 or 2, preferably 1,

and possibly

(D) 0 to 100 parts by weight, based on 100 parts by weight

Silicone resin (A), a silane of the formula

or their partial hydrolysates, wherein

Z is a halogen atom, preferably a chlorine atom,

R ^{6 may be the} same or different and is a monovalent optionally substituted hydrocarbon radical having 1 to 18 carbon atoms or a hydrogen atom,

e is 0, 1, 2 or 3, preferably 0, 1 or 2, preferably 0 or 1, particularly preferably 1,

With

(E) water,

if necessary in the presence of

(F) the hydrolysis and condensation promoting catalysts, preferably acids,

and possibly in the presence of (G) organic solvents

with the proviso that

(I) the amount of water is always chosen so that, based on the amount of all metal and silicon-bonded hydrolyzable groups, is substoichiometric, and preferably not more than 80 mol%, preferably not more than 75 mol%, of the complete Hydrolysis of all hydrolyzable groups required amount of water,

(ii) that the metal-silicone resin compositions have at least one s -O-Sis bond (M is Ti or Zr),

preferably ^ i-O-Si ^ bond,

(iii) that the compositions

(AI) at least 1 wt .-%, preferably at least

5 wt .-%, preferably at least 10 wt .-%, and preferably at most 90 wt .-%, based on the compositions, metal-free silicone resin (A) or metal-free condensates selected from the group of component (A),

(C) and (D) or mixtures thereof, and

(iv) that the compositions have a viscosity of 5 to

5,000,000 mPa.s, preferably 10 to 1,000,000 mPa.s, each at 25 ° C and atmospheric pressure of 1013 hPa,

(v) and optionally subsequent to the hydrolysis and condensation, an addition of

(A2) Silicone resins other than silicone resin (A) and having a viscosity of 5 to 5,000,000 mPa.s, preferably 10 to 1,000,000 mPa.s, each at 25 ° C and normal pressure of 1013 hPa ,

The invention relates to a process for the preparation of the liquid crosslinkable metal-silicone resin compositions by hydrolysis and condensation of

(A) 100 parts by weight of a silicone resin of 30 to 100 mol%, preferably 50 to 100 mol%, preferably 80 to 100 mol%, of units selected from the group of units of Formulas R'Si0 _{_3/2} (Ia) and S1O _{_4/2} (Ib) and mixtures thereof and

0 to 70 mol%, preferably 0 to 50 mol%, preferably

0 to 20 mole% units selected from the group consisting of units of the formulas R _'2 Si02 _/ 2 (Ic) and R' ₃ SIOI _{/ 2} (Id), and mixtures thereof, wherein

R ^{1 may be the} same or different and is a radical R or a radical of the formula -OR ¹ ,

R ^{1 may be the} same or different and a

Hydrogen atom or a monovalent optionally substituted hydrocarbon radical having 1 to 18

Carbon atoms means

1 to 200 parts by weight, based on 100 parts by weight

Silicone resin (Ά), a metal compound of the formula

R ² _c MX ₄ -c (II), or their partial hydrolysates, wherein

c is 0, 1, 2 or 3, preferably 0 or 1, preferably 0, M is titanium or zirconium, preferably titanium in the

Oxidation state + IV, is

X is a halogen atom, preferably a chlorine atom, or a

Rest is -OR ³ ,

R ^{2 has} the same meaning as R independently of R and

R ^{3 has} the same meaning as R ¹ independently of R ¹ , 0 to 100 parts by weight, based on 100 parts by weight of silicone resin (A), of a silane of the formula

or their partial hydrolysates, with the proviso that the partial hydrolysates are different from silicone resin (A) and at least 3 mol%, preferably at least 5 mol%, preferably at least 10 mol%, and preferably at most 85 mol%, based on all Si-bonded radicals, C ₁ -C ₁₂ -

Alkoxy or hydroxy are, wherein

and possibly

(D) 0 to 100 parts by weight, based on 100 parts by weight

Silicone resin (A), a silane of the formula

R ⁶ eSiZ ₄ - _e (IV) or their partial hydrolysates, wherein

Z is a halogen atom, preferably a chlorine atom,

With

(E) water,

if necessary in the presence of (F) the hydrolysis and condensation promoting catalysts, preferably acids,

and possibly in the presence of

(G) organic solvents

with the proviso that

(I) the amount of water is always chosen so that, based on the amount of all metal and silicon ^¬ bound hydrolyzable groups, is substoichiometric, and preferably not more than 80 mol%, preferably not more than 75 mol% of is the amount of water required for complete hydrolysis of all hydrolyzable groups present,

(ii) that the metal-silicone resin compositions have at least one ^ M-0-Si = bond (M is Ti or Zr),

preferably Ξ Ι-Ο-ΞΙΞ bond,

(iii) that the compositions

(Äl) at least 1 wt .-%, preferably at least

5 wt .-%, preferably at least 10 wt .-%, and preferably at most 90 wt .-%, based on the composition sets, metal-free silicone resin (Ä) or metal-free

Condensates selected from the group of component (A), (C) and (D) or mixtures thereof, and

(iv) that the compositions have a viscosity of 5 to

(A2) silicone resins other than silicone resin (A) and having a viscosity of 5 to 5,000,000 mPa.s, preferably 10 to 1,000,000 mPa.s, each at 25 ° C and

Normal pressure of 1013 hPa, have occurred.

The crosslinkable metal-silicone resin compositions of the invention are at atmospheric pressure of 1013 hPa and

Room temperature of 25 ° C liquid. It has surprisingly been found that, for the preparation of the metal-silicone resin compositions according to the invention, a significantly substoichiometric amount of water is required on the total amount of hydrolyzable groups in the starting mixture used for the synthesis.

Preferably, the water in small amounts is constant, ie at a fixed metering rate, over a period of at least 1 minute, preferably over a period of 5 to 900 minutes, preferably from 10 to 660 minutes, in particular without added intermediates to the mixture of (A) and (B) and optionally (C) and / or (D) are added constantly. For the constant metering any conventionally known method is suitable which ensures that a defined volume flow is metered over a predetermined time, such as dropping,

Pumping or letting. The metered addition of water preferably takes place at temperatures of the reaction mixture between 0.degree. C. and 90.degree. C., preferably between 10.degree. C. and 80.degree. During the synthesis reaction are preferably no

Temperatures below 0 ° C, preferably set below 5 ° C, so there are no cryogenic steps are used.

Liquid crosslinkable metal-silicone resin compositions according to the invention are preferably those which can be prepared by hydrolysis and condensation containing at least the

following steps that are performed in this order:

(1) Presentation of silicone resin (A)

(2) Addition of metal compound (B)

optionally (3) adding the silanes (C) or (D) or the silanes (C) and (D) or the partial hydrolysates of silane (C) or (D) or the partial hydrolysates of silane (C) and (D), wherein the addition according to step (3) can also take place after step (4), (4) adding water (E) or an aqueous solution of a catalyst (F) or a mixture of water (E) and organic solvents (G) to the reaction mixture, the reaction mixture during the addition of water (E) or an aqueous solution a catalyst (F) or a mixture of water (E) and organic

Solvents (G) has a temperature of 0 ° C to 90 ° C, preferably 10 ° C to 80 ° C,

optionally (5) filtration of the reaction mixture and

(6) volatilizing the reaction mixture.

The process of the invention for preparing the liquid crosslinkable metal-silicone resin compositions is

preferably such by hydrolysis and condensation

containing at least the following steps, which are performed in this order:

(1) Presentation of silicone resin (A)

(2) Addition of metal compound (B)

optionally (3) adding the silanes (C) or (D) or the silanes (C) and (D) or the partial hydrolysates of silane (C) or (D) or the partial hydrolysates of silane (C) and (D), wherein the addition according to step (3) can also take place after step (4),

(4) adding water (E) or an aqueous solution of a catalyst (F) or a mixture of water (E) and organic solvents (G) to the reaction mixture, the reaction mixture during the addition of water (E) or an aqueous solution a catalyst (F) or a mixture of water (E) and organic

optionally (5) filtration of the reaction mixture and

(6) volatilizing the reaction mixture. Further steps can be added. The possibly

Filtration of the reaction mixture before the

Degassing serves to remove slight turbidity. The addition of further reaction components, such as the possibly

carried out addition of silanes (C) or (D) or their

Partial hydrolysates, always carried out subsequently to the addition of the metal compound B, i. not that she is imminent

Connection must be made, but not before the addition of the metal compound B to the silicone resin component A is done and completed.

Selected examples of radicals R and R ¹ are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert. Butyl, n-pentyl, iso-pentyl, neo-pentyl, tert. -Pentyl radical, hexyl radicals such as the n-hexyl radical, heptyl radicals such as the n-heptyl radical, octyl radicals such as the n-octyl radical and iso-octyl radicals such as the 2, 2, 4-trimethylpentyl radical, nonyl radicals such as the n-nonyl radical, decyl radicals such as the n-decyl radical, dodecyl radicals, such as the n-dodecyl radical, and octadecyl radicals, such as the n-octadecyl radical, cycloalkyl radicals, such as cyclopentyl, cyclohexyl,

Cycloheptyl and methylcyclohexyl radicals, alkenyl radicals such as the vinyl radical, aryl radicals such as the phenyl, naphthyl, anthryl and phenanthryl radical, alkaryl radicals such as tolyl radicals, xylyl radicals and ethylphenyl radicals, and aralkyl radicals such as the benzyl radical and the β-phenylethyl radical and the hydrogen radical,

silicon-bonded hydridic and to an oxygen atom

possesses a protic character.

Substituted radicals R are, for example, organofunctional radicals AB, where A is a bivalent hydrocarbon radical comprising 1 to 6 carbon atoms which is bound by a carbon atom to its binding partner in the formula (Ia-Id) ie the silicon atom and at its second valency functional group is bound (spacer between the silicon atom and the functional group) and B is a linear, branched or cyclic hydrocarbon group which may optionally be hydroxy-, alkyloxy- or trimethylsilyl-terminated and in whose main chain non-adjacent carbon atoms may be replaced by oxygen atoms and the olefinically unsaturated groups or ethylene oxide units (oxirane or epoxide structures) may comprise, wherein the

An optionally substituted carboxylic acid or an optionally substituted carboxylic acid ester function, an optionally substituted carboxylic acid anhydride function, an optionally substituted acrylate or methacrylate group, wherein it may be present in a chain as well as terminal or attached to a cycloaliphatic structure optionally present substituents on the acrylate or methacrylate group is a linear, branched or cyclic hydrocarbon radical which may be hydroxy- or alkoxy terminated and in whose main chain non-adjacent carbon atoms may be replaced by oxygen atoms and the olefinically unsaturated groups or ethylene oxide units (oxirane , or epoxy structures), wherein the ethylene oxide units both in a chain and terminal or to a

may have an cycloaliphatic structure annelated, an alkyne radical, a phosphoric acid ester radical, a phosphonic ester residue may mean, where the radicals R are independent

can be different from each other.

Radicals R are preferably unsubstituted hydrocarbon radicals having 1 to 18 carbon atoms. Preferred radicals R are the methyl, ethyl, n-propyl, n-octyl, iso-ooctyl,

Tetradecyl, hexadecyl, octadecyl and the phenyl, wherein the methyl and phenyl are particularly preferred.

Radicals R ¹ are preferably unsubstituted hydrocarbon radicals having 1 to 18 carbon atoms. Preferred radicals R ¹ are the methyl, ethyl and the hydrogen radical. If the radical R is an organofunctional radical, it is bound directly to the silicon atom in the case of the vinyl radical. In all other cases, the organofunctional radical is bonded to the silicon atom via a C 1 -C 6 spacer, the C 1 and C 3 spacers being preferred. The spacer is a divalent linear rather than heteroatoms

interrupted hydrocarbon radical.

Examples of radicals R apply in their entirety to radicals R ² .

R ² radicals are preferably unsubstituted

Hydrocarbon radicals having 1 to 18 carbon atoms.

Preferred radicals R ² are the methyl, ethyl, n-propyl, n-octyl, iso-octyl, tetradecyl, hexadecyl, octadecyl radical and the phenyl radical, with the methyl and phenyl radicals being particularly preferred.

Examples of radicals R ¹ apply in their entirety to radicals R ³ .

R ³ radicals are preferably unsubstituted

Hydrocarbon radicals having 1 to 18 carbon atoms.

Preferred radicals R ³ are the methyl, ethyl, n-propyl, iso-propyl, n-butyl, n-octyl, iso-ooctyl, tetradecyl,

Hexadecyl, octadecyl and the phenyl radical, wherein the

Methyl, ethyl, iso-propyl and n-butyl are particularly preferred.

Selected examples of radicals R ⁴ and R ⁵ are alkyl radicals such as the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert. Butyl, n-pentyl, iso-pentyl, neo-pentyl, tert. -Pentyl radical, hexyl radicals such as the n-hexyl radical, heptyl radicals such as the n-heptyl radical, octyl radicals such as the n-octyl radical and iso-octyl radicals such as the 2, 2, 4-trimethylpentyl radical, nonyl radicals such as the n-nonyl radical, decyl radicals such as the n-decyl radical, dodecyl radicals such as the n-dodecyl radical, tetradecyl radicals, hexadecyl radicals and octadecyl radicals such as the n-octadecyl radical, cycloalkyl radicals such as Cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl radicals, alkenyl radicals such as the vinyl radical, aryl radicals such as

Phenyl, naphthyl, anthryl and phenanthryl radicals, alkaryl radicals such as tolyl radicals, xylyl radicals and ethylphenyl radicals, and

Aralkyl radicals, such as the benzyl radical and the ß-phenylethyl radical and the hydrogen radical, which has silicon-bonded hydridischen and an oxygenatora protic character.

Radicals R ⁴ are preferably unsubstituted hydrocarbon radicals having 1 to 18 carbon atoms. Preferred radicals R ⁴ are the methyl, ethyl, n-propyl, n-octyl, iso-octyl, and the phenyl radical, the methyl and phenyl radical being particularly

is preferred. Radicals R ⁵ are preferably unsubstituted hydrocarbon radicals having 1 to 18 carbon atoms. Preferred radicals R ⁵ are the methyl, the ethyl and the hydrogen radical.

Selected examples of radicals R ⁶ are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert. Butyl, n-pentyl, iso-pentyl, neo-pentyl, tert-pentyl, hexyl, such as the n-hexyl, heptyl, such as the n-heptyl, octyl, such as the n-octyl radical and iso- Octyl radicals, such as the 2, 2, 4-trimethylpentyl radical, nonyl radicals, such as the n-nonyl radical, decyl radicals, such as the n-decyl radical, dodecyl radicals, such as the n-dodecyl radical, tetradecyl radicals, hexadecyl radicals and octadecyl radicals, such as the n-octadecyl radical, cycloalkyl radicals, such as cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl radicals, alkenyl radicals such as the vinyl radical, aryl radicals such as

Aralkyl radicals, such as the benzyl radical and the ß-phenylethyl radical and the hydrogen radical. Radicals R are preferably unsubstituted hydrocarbon radicals having 1 to 18 carbon atoms. Preferred radicals R ⁶ are the methyl, ethyl, n-propyl, n-octyl, iso-octyl, and the phenyl radical, the methyl and phenyl radical being particularly

is preferred.

As catalysts (F) for promoting hydrolysis and

Condensation, an acid or an acidic solid, such as an acid filter aid, can be used, wherein organic acids, such as formic acid and acetic acid, or inorganic acids, such as nitric acid, hydrochloric acid and

Phosphoric acid are preferred, wherein also several different acids can be used, which are used either as a mixture or successively added to the reaction mixture, wherein aqueous hydrochloric acid solutions are particularly preferred and wherein the acid when using halosilanes (D), in particular when using chlorosilanes According to (D) can be formed together with water by the hydrolysis of the halosilanes during the reaction and thus their addition as a separate component in these cases may no longer be necessary, so that if an acid is required to start the reaction, this if is added only in small amount at the beginning of the reaction to initiate the hydrolysis and condensation.

The hydrolysis and condensation promoting catalysts (F), preferably acids, are preferably used in amounts of 400 ppm by weight (parts by weight per million parts by weight) to 5 wt .-%, based on the total weight of the employed

Component (A) used.

In the solvent (G), which can be used for carrying out the reaction, are low molecular weight aromatic

Solvents, such as toluene and xylene, which may be

may be substituted, optionally in admixture with ethylbenzene, and non-aromatic solvents, such as organic esters of Acetic acid such as ethyl acetate, butyl acetate or methyl propyl acetate or low molecular weight, non-aromatic, aliphatic, cycloaliphatic or unsaturated aliphatic or

cycloaliphatic alcohols and glycols are preferred.

The metal-silicone resin compositions according to the invention contain at least one structural unit according to formula (V),

R ⁷ ₃ M-O-SiR ⁸ ₃ (V), where M = Ti or Zr, preferably M = Ti and the

embedded in the surrounding molecular structure at least via the Si atom,

where the radicals R ^{7 can} independently of one another have the meaning of R and where R ^{7 can} also denote a radical of the type -O-Si =, via which the structural element of the formula (V) is incorporated in the surrounding molecular structure,

the radicals R ⁸ independently of one another may denote radicals according to R or OR ¹ or a radical -O-TiR ⁷ ₃ , and at least one radical R ^{8 has} the meaning of -O-Sis, via which the structural unit of the formula (V) in the surrounding molecular structure is involved.

In the metal-silicone resin compositions of the invention are included

(AI) at least 1 wt .-% of a metal-free silicone resin from

Type of component (A) or condensates from the condensation of component (A) with itself, or with (C) and / or with (D) or from the condensation of (C) with itself and / or with (D) or from the condensation of (D) with itself and optionally additionally silicone resins (A2) selected from the group of

(A2.1) at least 1 wt .-%, based on the total weight of the metal-silicone resin compositions, another metal-free organopolysiloxane, which is characterized in that the siloxane units of the type R ⁹ Si0 _{_3/2} and S1O _{_4/2,} preferably of the species R ⁹ SiC> _3/2, which contains, where the radicals R ⁹

independently of one another may have the meaning of R 'and 60 mol% to 99 mol% of the radicals R ^{9 is} an SiC-bonded monovalent hydrocarbon group R, preferably phenyl or methyl radicals, and 1 mol% to 40 mol% of Radicals R ^{9 are} silicon-bonded alkoxy or hydroxy groups -OR ¹ . (A2.2) at least 1 wt .-%, based on the total weight of the metal-silicone resin compositions, another

contains metal-free polyorganosiloxane, which thereby

characterized that there are _{_3/2} or S1O a _{_4/2} siloxane units contains the type R ¹⁰ SiO, of which those of the type R ¹⁰ SiO _3/2 being preferred, and additionally comprises those of the type R2 ^{13 "Si02} / 2, where the units of the type R ₂ ^{i: L} Si0 _{_2/2} can have the molar A2.2 largest proportion of the component with a molar proportion of up to 95%, preferably up to 90%, in particular up to 80%, where the radicals R ¹⁰ and R ^{11 have} the meaning of R 'and this independently, which applies in particular to the radicals R ¹¹ , which are bonded to the same Si atom, and 60 mol% to 99 mol% of the silicon-bonded radicals R ¹⁰ and R ^{11 is} an Si-C-bonded monovalent hydrocarbon group R, preferably phenyl or methyl radicals, and 1 mol% to 40 mol% of R ¹⁰ and R ^{11 are} silicon-bonded alkoxy or hydroxy groups -OR ¹ .

(A2.3) at least 1 wt .-%, based on the total weight of the metal-silicone resin compositions, another

metal-free organopolysiloxane, which is characterized in that it contains siloxane units of the type Si0 _{_4/2.}

Preference is given either polyorganosiloxanes of the type (A2.1) or (A2.2) as a component in the inventive

Compositions, more preferably those of the type (A2.1), and the sum of the components (A2.1), (A2.2) and (A2.3) or mixtures thereof, preferably at most 99 wt .-%, preferably at most 95 wt .-%, based on the total weight of the compositions of the invention.

At least 1.5% by weight, more preferably at least 2% by weight, in particular at least 5% by weight, of the components (A2.1), (A2.2) or (A2.3) or mixtures thereof are preferred , based on the total weight of the compositions, in the compositions according to the invention.

Examples of radicals R '(= R and -OR ¹ ), ie examples of radicals R and R ¹ , apply in their entirety to radicals R ⁹ , R ¹⁰ and R ¹¹ , wherein the radicals R ⁹ , R ¹⁰ and R ^{11 are} independent from each other.

The liquid crosslinkable metal-silicone resin compositions according to the invention give both after

Allow crosslinking by drying as after curing, if necessary

using higher temperatures (heat curing),

Shaped bodies, such as transparent moldings or films.

The crosslinking and curing of the liquid crosslinkable metal-silicone resin compositions according to the invention is preferably carried out at a temperature of 15 ° C to 250 ° C, preferably 20 ° C to 200 ° C.

Non-crosslinked films of the preparations according to the invention preferably have a refractive index greater than or equal to 1.4 at 25 ° C. in the wavelength range of visible light,

preferably at 589 nm.

The films according to the invention preferably have a UV-VIS spectrometric specific transmittance of at least 80% at 25 ° C. With homogeneously miscible preparations of components (A) and (B), the hydrolysis and condensation without solvent (G) can be carried out and the solvent is optionally added to the reaction mixture only at a later time. In terms of better stirrability and to avoid local over ^¬ concentrations in the addition of water, it may be advantageous to already use a solvent for the hydrolysis.

If the silicone resin (A) used is a silicone-resistant resin or a preparation of several silicone resins (A) which are not homogeneously miscible, where appropriate a solid phase which can not be converted into a liquid phase even by the addition of the component B, because the solid phase is not or only partially soluble in the selected as component B titanium or zirconium raw material, so that the or

Silicone solid resins (A) for conversion into a liquid phase inevitably requires the addition of a suitable solvent, the solvent is used from the beginning. Furthermore, a solvent must be used from the beginning if the titanium or Zirkonrohstoff B is not liquid and is not sufficiently soluble in the rest of the reaction mixture. In these cases, the solvent required to dissolve the solid raw materials A and / or B is present in the appropriate amount from the beginning of the process. In this case, aromatic solvents, acetic acid esters and aliphatic alcohols are preferable as the solvent, especially aliphatic alcohols.

The silicone resins (A) may contain both T units (Ia) and Q units (Ib) as crosslinking units. The T units are preferred over the Q units.

In particular, no Q units are present, but only T units in a mixture with D units (Ic) and / or M units (Id). It is in the sense of a good film-forming property and curing to a hard solid on it Note that not less than 30 mole percent of such T and / or Q moieties, of which the T moieties are preferred, are present because the solids or films resulting from the inventive compositions otherwise have too pronounced elastomeric properties upon cure , which leads to an undesirable surface stickiness and thus susceptibility to contamination, in addition to insufficient hardness.

If elastomeric properties are desired, these can be achieved by suitable mixing of the metal-silicone resin compositions according to the invention with a suitable component (A2), in particular with a component (A2.2). In this way a more universal applicability of the fiction, modern metal ^¬ silicone resin compositions is achieved.

It has been found that Q units in the silicone resins (A) easily lead to brittle products, their usefulness in some applications by the addition of a suitable

Admixture component (A2.1) or (A2.2), in particular of (A2.2), is improved, because this better mechanical properties, in particular flexibility can be adjusted. In principle, Q units can also be used. In particular, a proportion of 10 to 50% by weight of Q units, preferably of 10 to 40% by weight, particularly preferably of 10 to 30% by weight, of Q units is possible, although these are fundamentally different from T units are preferred.

The M moieties (Id) can also contain R ¹ 0-units, which can react to form silanol groups in the course of manufacture of the inventive compositions to be used by the hydrolysis and may cause condensation to a D-, a T or a Q unit depending on how many radicals of type R and -OR ¹ were attached to it and how many of the radicals -OR ¹ were reacted by hydrolysis and condensation. Corresponding considerations apply to the D and the T units in the silicone resins (A), from which depending on the substitution pattern according to hydrolysis and

Condensation depending on the degree of implementation T or Q units may arise. Based on 100 mol% of all

Silicon-bonded radicals are at least 3 mol% of the type -OR ¹ , preferably at least 5 mol%, particularly preferably at least 7 mol%. At most 45 mol% of all Si-bonded radicals R 'are preferably a radical of the formula -OR ¹ . When the silicone resin (A) is an alkoxysilicate, which is not preferable, however, 100 mol% of the silicon-bonded radicals are of the -OR ¹ type.

In the silicone resins (A) is at the silicon atoms in the

Units of the formulas (Ic) and (Id) preferably at most one aromatic hydrocarbon radical R bonded. All other SiC-bonded radicals R in these units contain no aromatic groups. Preferably, the radicals R in the

Units of the formulas (Id) no aromatic hydrocarbon radicals. The silicone resins (A) have molecular weights in the range of 600 to 500,000 g / mol (weight average M _w ) with a

Polydispersity of at most 15, preferably 600 to 300,000 g / mol in the weight average with a polydispersity of at most 12, particularly preferably 600 to 80,000 g / mol in the weight average with a polydispersity of at most 10.

The silicone resins (A) can be low-viscosity and liquid or viscous to highly viscous at 25 ° C. and normal pressure (1013 hPa) or else solids with softening points of more than 25 ° C., preferably of more than 30 ° C., more preferably of more than 35 ° C, in particular more than 40 ° C. The liquid ones

Silicone resins (A) have viscosities of from 5 mPas to 5,000,000 mPas at 25 ° C., preferably from 10 mPas to 1,000,000 mPas at 25 ° C., more preferably from 20 mPas to 100,000 mPas at 25 ° C., in particular from 20 mPas up to 75,000 mPas at 25 ° C, with alkoxy-rich low-viscosity methyl-phenyl-silicone resin oligomeric, pure Methylsiliconharzoligomere or pure Phenylsiliconharzoligomere with a viscosity between 100 and 10,000 mPas at 25 ° C have been found to be particularly suitable, and all information on viscosity at 25 ° C and 1013 hPa apply.

The solid silicone resins (A) at 25 ° C and 1013 hPa ambient pressure have glass transition temperatures of 30 ° C to 200 ° C, preferably from 30 ° C to 150 ° C, more preferably from 40 ° C to 100 ° C. In particular, methylphenyl solid resins having an alkoxy content between 1 and 10% by weight, preferably on average 2 to 6% by weight, and in addition have one

Silanol content between 1 and 10 wt .-%, preferably

an average of 2 to 6 wt .-%, and a glass transition temperature of 40 ° C to 80 ° C proven.

Examples of silicone resins (A) are alkoxy- and silanol-functional silicone resins, as known to the person skilled in the art, these examples being not restrictive. Alkoxy- and / or hydroxy-functional silicone resins as suitable herein are commercially available from several companies, such as Bluestar Silicones, Dow Corning, Momentive Performance Materials or Wacker Chemie AG.

Suitable silicone resins from Wacker Chemie AG include SILRES® SY-231, SILRES®IC-232, SILRES®IC-368, SILRES®IC-678, SILRES®IC-836, SILRES®SY 300, SILRES®REN 168, SILRES®SY -409, SILRES®SY-430, SILRES®SY-530, SILRES®KX, SILRES®HK46, SILRES®MK,

SILRES®610, SILRES®MSE 100, without being limited to these. Preferred silicone resins (A) or preparations thereof in

Sense of the present invention are alkoxy-functional and / or hydroxy-functional silicone resins, in particular

alkoxy functional. Particularly preferably these contain

preferred alkoxy- and / or hydroxy-functional

Silicone resins, of which the alkoxy-functional in particular preferred are silicon-bonded methyl and / or

Phenyl groups. The amount of phenyl and / or methyl groups depends on the particular application. For

Applications which require a high refractive index, phenyl substituents are particularly preferred and may optionally in addition to alkoxy and / or hydroxy functions, of which the

Alkoxy functions are preferred as silicon-bonded radicals are also present exclusively phenyl.

To better compatibility with a possibly surrounding

To achieve matrix, for example, an organic polymer, proves to be a mixture of both methyl and

silicon-bonded phenyl groups as advantageous. Conversely, it may be advantageous to targeted intolerance

adjust that only methyl or phenyl groups are used as silicon-bonded radicals. If it is at the

surrounding matrix is not an organic polymer but another silicone species, for example another

Silicone resin or a silicone elastomer, so by the exclusive choice of methyl or phenyl substituents depending on the substitution pattern of the matrix but compatibility can be adjusted just by the restriction only to methyl or only to phenyl. Based on these explanations, it follows that the exact molecular design is determined by the requirements of the particular application. Nevertheless, methyl- and / or phenyl-substituted alkoxy- and / or hydroxy-functional silicone resins are preferred. The silicone resins (A) contain at least 4, preferably

at least 5, in particular at least 7 repeat units as specified above.

The silicone resin component (A) may optionally be a mixture of

be several silicone resins (A). It can both

Preparations of several liquid silicone resins (A) and of liquid and solid silicone resins (A) can be used. The information on the state of aggregation refers to each case 25 ° C and 1013 hPa. In formulations of silicone resins (A), the preparation components may not necessarily be miscible with each other. This means that it is also possible to use biphasic mixtures, in which case both phases have to be liquid or have to form a liquid phase in the course of the production process. This can be achieved, for example, by dissolving an initially solid phase in a cleavage product from the hydrolysis and condensation, generally an alcohol, to a liquid phase. In a biphasic mixture of immiscible or homogeneously soluble

Silicone resins containing units of the formulas (Ia) to (Id)

contain, the solid phase may consist of one or more

Silicone resins containing units of the formulas (Ia) to (Id)

included, even by the use of a suitable

Solvent or by melting at temperatures below 90 ° C, preferably below 80 ° C, optionally in the presence of liquid silicone resins (A) or by dissolving in the zirconium or

Titanium component (B) are converted into a liquid phase. Examples of inventively usable titanium and

Zirconium compounds (B) are monomeric, oligomeric or polymeric tetraalkylorthometallates and tetraarylorthometallates, such as tetramethylorthometalate, tetraethylorthometalate,

Tetrapropylorthometallat, tetraisopropylorthometallate, tetra-n-butylorthometallate, and mixtures thereof, or the mixed optionally obtainable from the mixing process by alkoxy exchange reactions Tetraalkylorthometallate, and the oligomers and polymers obtainable therefrom by hydrolysis and condensation.

The titanium compounds are preferred. Examples of through

Hydrolysis and condensation available oligomers and polymers are titanium tetrabutylate tetramer or titanium tetrabutylate polymer, which are commercially available from various suppliers, for example from DuPont in their product range DuPontTMTyzor®. Preference is given to phenyl (trialkoxy) titanates, titanium tetrahalide, phenyltitanium trichloride, titanium tetraalky- and

Titantetraarylorthotitanate and titanium tetrachloride, more preferably Titantetraalkylorthotitanate and titanium tetrachloride, wherein in the Titantetraalkyorthotitanaten

Titanium tetramethyl orthotitanate, titanium tetraethyl orthotitanate, titanium tetraisopropyl orthotitanate and titanium tetra-n-butyl orthotitanate are particularly preferred.

The list gives only examples and is for the

Not to be understood as limiting the invention.

The silanes (C) of the formula (III) are preferably used as

Silanes, in particular as alkoxysilanes used.

Preferred examples of silanes (C) are phenyltrimethoxysilane, phenyltriethyoxysilane, methyltrimethoxysilane, methyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane,

Octadecylmethyldimethoxysilane, octadecylmethyldiethoxysilane, isooctyltriethoxysilane, isooctyltrimethoxysilane,

Dimethyldiethoxysilane, dimethyldimethoxysilane,

Trimethylmethoxysilane, trimethylethoxysilane, trimethylsilanol, methylphenyldiethoxysilane, methyphenyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, n-octyltriethoxysilane, n-octyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrisopropoxysilane, tetra-n-propoxysilane.

In principle, however, it is also possible to hydrolyze silanes and / or by hydrolysis and partial condensation

resulting oligomers of silanes of the formula (III)

use. However, it is necessary that reactive groups are still present on these partial condensates, which are capable of carrying out condensation reactions. Also, a silicon-bonded hydridic hydrogen under suitable conditions can be eliminated and thus creates a free valence on the silicon for subsequent reactions is suitable. It is known that silicon-bonded hydridic hydrogen in particular in the presence of

Titanates can be easily split off. Examples of partial oligomeric condensates are readily deduced from the above examples. In addition, examples are oligomeric tetraethyl silicates, low molecular weight alpha, omega silanol-functional polydimethylsiloxanes having up to 10 Siloxanwiederholunsgeinheiten, wherein instead of the dimethyl units also Diphenyleinheiten or Phenylmethylsiloxan- units are possible, such as in 1, 1, 5, 5-tetramethyl-3 , 3-diphenyl-trisiloxane-1, 5-diol or in 1, 1, 3, 5, 5-pentamethyl-3-phenyl-trisiloxane-1, 5-diol, not as pure compounds but in admixture with higher and lower Oligomers are present. Examples of hydride-containing representatives are tetramethyldisiloxane, 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane, 1,1,3,5,5-pentamethyl-3-phenyltrisiloxane and higher condensation products thereof. These

Examples are only illustrative. The invention is not limited to these examples.

The silanes (D) of the formula (IV) are preferably used as silanes, in particular as chlorosilanes.

Preferred examples of silanes (D) are phenyltrichlorosilane, methyltrichloro-, n-propyltrichloro-, n-hexyltrichlorosilane, octadecylmethyldichlorosilane, isooctyltrichlorosilane,

Dimethyldichlorosilane, trimethylchlorosilane, methylphenyl-dichlorosilane, diphenyldichlorosilane, n-octyltrichlorosilane, tetrachlorosilane.

resulting oligomers of silanes according to formula (IV)

use. However, it is necessary that always reactive groups are still present on these partial condensates capable of carrying out condensation reactions. A silicon-bonded hydridic hydrogen, which can be split off under suitable conditions and thus creates a free valence on the silicon for subsequent reactions, is suitable for this purpose. These examples are only illustrative. The invention is not limited to these examples.

Examples of a structural unit according to formula (V) with M = Ti

R ⁷ ₃ Ti-0-SiR ⁸ ₃ where R ⁷ and R ^{8 are} those given above

Have meaning

(R "0) ₃ Ti-0-Si (R ⁱ⁴ ) ₂

{R ^1Z 0) ₂ (R ^iJ 0) Ti-O-Si (R) ₂

(R 1 O) (R 0) Ti-O-Si (R) ₂

(R ^1J 0) Ti-O-Si (R ⁱ⁴ ) 2

(R 1 O) (R 1 O) ₂ Ti-O-Si (R ⁱ⁴ ) ₂

(R 1 O) ₃ Ti-O-SiR 14 {R ^1Z 0) 2 (R 0 ^iJ) Ti-O-SiR

(R ^± O) (R ^iJ 0) Ti-O-SiR ¹

(R 1 O) (R ^1J 0) ₂ Ti-0-SiR

(R ^1J 0) Ti-O-SiR

(R ^ O) ₃ Ti-O-Si

(R 1 O) ₂ (R 0) Ti-O-Si (R ⁱ 0) (R ^iJ 0) Ti-O-Si

(R ^ O) (R ^iJ 0) ₂ Ti-0-Si

(R ^iJ 0) Ti-O-Si wherein, in particular, a plurality of titanium atoms can also be connected to one another via oxygen atoms to give titanium oxide cyclic groups having, for example, 4, 8, 16 or more titanium atoms. These

Titanoxycluster can either be interrupted by Si-O groups or they are surrounded by a shell of organopolysiloxane.

For M = Zr, these examples would apply mutatis mutandis in the same way. The radicals R ¹² and R ^{13 are} monovalent hydrocarbon groups, preferably monovalent alkyl group or a

monovalent aryl group wherein the alkyl groups are preferred over the aryl groups and the monovalent alkyl groups are preferably linear or branched monovalent alkyl groups. The radicals R ¹² and R ^{13 are} in

same molecule always different from each other.

Examples of radicals R ¹² and R ¹³ are methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert. Butyl, n-pentyl, iso-pentyl, neo-pentyl, tert. -Pentyl radical, hexyl radicals such as the n-hexyl radical, heptyl radicals such as the n-heptyl radical, octyl radicals such as the n-octyl radical and iso-octyl radicals such as the 2, 2, 4-trimethyl-pentyl radical, nonyl radicals such as the n-nonyl radical , Decyl radicals such as the n-decyl radical, dodecyl radicals such as the n-dodecyl radical, tetradecyl radicals, hexadecyl radicals and octadecyl radicals such as the n-octadecyl radical, cycloalkyl radicals such as cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl radicals, alkenyl radicals such as Vinyl radical, aryl radicals, such as the phenyl, naphthyl, anthryl and phenanthryl radical, alkaryl radicals, such as tolyl radicals, xylyl radicals and ethylphenyl radicals, and aralkyl radicals, such as the benzyl radical and the β-phenylethyl radical.

The radicals R ¹² and R ¹³ are preferably unsubstituted

Hydrocarbon radicals having 1 to 18 carbon atoms, wherein the methyl, ethyl, iso-propyl, and the n-butyl radical are preferred.

In the examples of formula (V), in each case a chemical bond in the surrounding molecular structure, by means of which units of the formula (V) are incorporated in the metallo-siloxane molecule, in each case an oxygen atom, the then further connected to a Si atom or a metal atom, ie a Ti or Zr atom, Ti being preferred as the metal.

An example taken from the above for such a structural fragment, including the oxygen atoms as the next binding partner, is as follows:

(R ¹² 0) (R ¹³ 0) Ti-O-Si- 0 - (Formula VI)

I i

0 0

1 I

However, in the metallo-siloxane composite preparation according to the invention, which also comprises metal-free constituents, at least one such unit according to formula (V) must be present, ie at least one molecule containing such a structural fragment. Radicals R ¹⁴ may be identical or different and denote a monovalent optionally substituted hydrocarbon radical having 1 to 18 C atoms or a hydrogen atom or a radical of the formula -OR ¹ , where R ^{1 has} the meaning given above. Selected examples of radicals R ¹⁴ are alkyl radicals such as

Methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert. Butyl, n-pentyl, iso-pentyl, neo-pentyl, tert. Pentyl radical, hexyl radicals, such as the n-hexyl radical, heptyl radicals, such as the n-heptyl radical, octyl radicals, such as the n-octyl radical and iso-octyl radicals, such as the 2, 2, 4-trimethylpentyl radical, nonyl radicals, such as the n-nonyl radical, decyl radicals, such as the n-decyl, dodecyl, such as the n-dodecyl, tetradecyl, hexadecyl and

Octadecyl radicals, such as the n-octadecyl radical, cycloalkyl radicals, such as cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl radicals, alkenyl radicals, such as the vinyl radical, aryl radicals, such as

Aralkyl radicals, such as the benzyl radical and the .beta.-phenylethyl radical and the hydrogen radical, which may each be bonded directly to the silicon atom via an Si carbon bond or which may be bound to the Si atom via an oxygen atom. If the hydrogen radical is silicon-bonded, it has a hydridic character and is bound to an oxygen atom of a protic character.

In the case of the radicals R ¹⁴ , which may be different independently of one another, which means in particular that several radicals R ^{17 may be} partially bonded via an oxygen atom while others are bonded directly to the Si atom via a carbon-silicon bond, this is preferably unsubstituted hydrocarbon radicals having 1 to 18 carbon atoms, more preferably the methyl, ethyl, iso-octyl, n-octyl, n-propyl and the phenyl radical. The radicals R ¹⁴ are, in particular, the methyl, the ethyl and the phenyl radicals, the phenyl radical preferably being bonded directly to the silicon atom via an Si-C bond to form the methyl radical, which is both directly Si-C- may be bonded as well as Si-OC may be linked, and to the ethyl radical, which is preferably present via an oxygen atom, ie Si-OC-linked, these lists are not limiting to

understand. As concrete preferred examples of structural elements according to formula (V), the following are mentioned above

Structures, wherein the oxygen atoms, over which the

Structural elements incorporated into the surrounding molecular structure are omitted here and should be added according to the representation in formula (VI):

((CH ₃ ) ₂ CHO) ₃ Ti-O-Si (OCH ₃ ) (C ₆ H ₅ )

((CH ₃ ) ₂ CHO) ₂ (CH ₃ O) Ti-O-Si (CH ₃ ) (OCH ₃ )

(CH ₃ CH ₂ O) ((CH ₃ ) ₂ CHO) Ti-O-Si (C ₆ H ₅ )

(CH ₃ CH ₂ O) ((CH ₃ ) ₂ CHO) ₂ Ti-O-Si (CH ₃ )

(CH ₃ CH ₂ O) ((CH ₃ ) ₂ CHO) ₂ Ti-O-Si

(CH ₃ ) ₂ CHO-Ti-O-Si

These examples of groups according to formula (V) serve to illustrate and are not limiting. The components A2.1, A2.2 and A2.3 serve to improve the mechanical properties of the metalloid according to the invention. Siloxane composite materials. The pure metallosiloxane components tend to due to their brittleness in

Applications to train mechanical defects such as cracks. This deficiency can be counteracted by adding flexibilizing components to the metallo-siloxane composites, which advantageously takes place by means of silicone building blocks, because they do not reduce the high temperature stability of the metallo-siloxane composite materials. To obtain the binding power of the metallo-siloxane composites, the

Components A2.1, A2.2 and A2.3 always to those with at least a proportion of resinous structures. The adjustment of the compatibility of the admixing components A2.1, A2.2 and A2.3 and the targeted support of application properties, for example of an optical nature, such as the refractive index and the transmission, is set by the variation of the substitution patterns on the admixing components.

Resinous structures which are contained in component A2.1 are those of the type R ⁹ Si0 _3/2 and Si0 _4/2 , where the radicals R ⁹ independently of one another have the meaning of R '(= R or -OR ¹ ) can. Precursors of such structures from which the resinous structures are found by hydrolysis and condensation those which contain, in addition to the radical R ⁹ having the meaning of R also silicon-bonded radicals of the type R ¹ 0- including HO-. The detailed meaning of the radicals R 'or R and R ¹ is given above.

The component A2.2 contains units of the formula R ¹⁰ SiO _3/2 (where R ^{10 have} the meaning given above) in addition to those of the type R ₂ Si0 _2/2 , which exert a softening or flexibilizing effect, wherein the radicals R ¹¹

independently of one another may have the meaning of R '. Depending on how much flexibility and softness required by the particular application, up to 95 mol% of the Component A2.2 forming units of such

Structure elements of the formula R2 ¹¹ Si0 _2/2 exist.

Component A2.3 contains siloxane units of the type Si0 _4/2 . In addition, A2.3 is only subject to the restrictions imposed by the target application. A high or exclusive amount of Si0 _4/2 units results in a highly crosslinked particulate product which acts as a filler in its surrounding matrix. Possibly. For example, the surface of these fillers can be functionalized to allow directional interaction with the surrounding matrix.

SiC> a _4/2 units in conjunction with other silicone components, such as the M-units of R ^ SIOI ^, where the radicals R ¹¹ independently of one another the meaning of R '(= R or -0R ¹⁾ may have, are the so-called MQ Resins which, depending on the importance of the radicals R ^11, may also be functional and serve as network points in a suitably functionalized matrix. The detailed meaning of R ¹¹ is given above. Can be flexible, the A2.3 component in case of need by inserting R ^{1: L} ₂ Si0 _2/2 units ^_ (D-

Units) . With a very high proportion of such D units of more than 50 mol% of the total molecule, it is also possible for products which have elastomeric properties to be formed. With regard to the substituents and substitution patterns of the silicone building blocks, which make up A2.3 beyond the Si0 _4/2 units, the statements already made for A2.1 and A2.2 apply

The polyorganosiloxane components A2.1, A2.2 and A2.3 are chosen so that the entire preparation is always liquid and homogeneous. Preferably, the components A2.1, A2.2 and A2.3 are themselves liquid with a viscosity of 5 mPas to 5,000,000 mPas, preferably 10 mPas to 1,000,000 mPas, in particular 25 mPas to 500,000 mPas, in each case at 25 ° C and 1013 hPa. If a fixed component A2.1, A2.2 or A2.3 is selected, this must be be clearly and homogeneously soluble in the composite preparation and give a liquid preparation.

All the above symbols of the above formulas each have their meanings independently of each other. In all

Formulas, the silicon atom is tetravalent. Titanium and zirconium are always in the oxidation state +4 in the composite compositions according to the invention. The metallo-siloxane composite preparations according to the invention are transparent to

translucent and colorless to yellowish. Turbidity in the

Composite compositions according to the invention can by

Incompatibilities of individual components arise. Metallo-siloxane composite preparations in which predominantly or exclusively by excessive condensation of individual

Components to insoluble particulate solids having a length extension in at least one direction of more than 400 nm, preferably more than 300 nm, more preferably more than 250 nm, are not inventive. Such would be accessible by modifying the process of the present invention to increase the amount of water or to choose a different mode of adding water to the reaction mixture than what is described herein.

Since the metal-silicone resin compositions according to the invention are always preparations which must have a proportion of polyorganosiloxane, the

Has silicone resin properties, that contains crosslinking building blocks, they also have the typical

Silicon properties. However, these properties are enhanced by the proportion of titanium or zirconium elements and so for many applications that have these properties

need, even better brought to bear. Such

Properties are, for example, and in particular a high long-term resistance to weathering in the open air, against UV radiation, against numerous chemicals and against high heat. Typical applications in which such properties are needed are, for example, exterior coatings,

corrosion-resistant and highly heat-resistant corrosion protection coatings. Silicone resins also act as film-forming components in the coating applications mentioned, but also in

Personal care products and cosmetic preparations (see, for example, EP 1 057 476 B1), where, for example, improved skin feel and more permanence are achieved by these properties. In this example, MQ resins are used.

By promoting film formation in the formulations, the titanium and zirconium elements enhance these properties and increase the efficiency of the silicone component.

Since hydrophobicizing silicone resins usually have an increasingly pronounced hydrophobic effect with increasing crosslinking, the formation of this property is also promoted by an improvement in the crosslinking properties. This is for the hydrophobing and also for the

Early water resistance of coatings and impregnations of mineral or wooden building materials of importance.

Corresponding hydrophobicizing preparations, be they paints, glazes, impregnating agents or others, can thereby achieve their final properties more quickly and may be less sensitive to weathering effects during their application, ie they may still be applied at lower temperatures or at higher atmospheric humidity than at

Comparable preparations would be the case that contain no titanium or zirconium-silicone composite preparation. Due to the film-forming properties of

Polyorganosiloxanes, by their use, the crosslinking temperatures of, for example, alkoxy- and / or hydroxy-functional silicone resins of typically above 150 ° C to significantly lower temperatures in some cases, in particular lower to room temperature. This will be the Use of silicone resins as a binder, for example, for coating applications significantly more economical, since the cost of the baking process can be saved.

In particular, titanium alkoxylates are further known to possess adhesion-improving properties.

Since the metallo-siloxane composite materials may have refractive indexes that exceed those of the pure silicone resins

and go beyond 1.5 and, moreover, are transparent, they are also particularly suitable for optical or electro-optical applications, such as

Production of LEDs suitable. The higher refractive index contributes to an increase in the luminous efficacy of the LED and thereby increases their efficiency and cost-effectiveness. In this application are preferably addition-curing

Silicone systems comprising a Si-H-containing and a vinyl-functional silicone component, which then react by hydrosilylation. Condensation-crosslinking systems are also known. In principle, both mechanisms are possible with the titanium-siloxane-composite preparations according to the invention, the titanium component likewise being opposite

silicon-bonded hydridic hydrogen is reactive, which must be considered in the formulation of appropriate systems, if the way hydrosilylation, ie

addition-crosslinking systems should be used.

In addition to the properties already outlined, the metallo-siloxane composite preparations according to the invention can also be used for the manipulation of further properties of preparations containing them or of solids or films obtained from preparations containing the compounds according to the invention

Metallo-siloxane composites are used, such as:

Control of electrical conductivity and electrical

resistance

- Control of the flow properties of a preparation Control of the gloss of a wet or cured film or object

Increase the weathering resistance

Increase in chemical resistance

Increase in color stability

Reduction of the tendency to chalk

Reduction or increase in static friction and sliding friction on solids or films obtained from preparations comprising a composite preparation according to the invention

Stabilization or destabilization of foam in the

Formulation containing a preparation according to the invention Improvement of the adhesion of the preparation

The composite composition according to the invention contains the substrate to or on top of the substrate

Contains composite composite preparation, is applied,

Control of filler dispersion behavior and pigment wetting and dispersing behavior,

Controlling the rheological properties of the preparation containing a composite composition according to the invention, controlling the mechanical properties, e.g.

Flexibility, scratch resistance, elasticity, ductility, flexing ability, tear behavior, rebound behavior, hardness, density, tear propagation resistance, compression set, behavior at different temperatures, coefficient of expansion, abrasion resistance and other properties such as

Thermal conductivity, flammability, gas permeability,

Resistance to water vapor, hot air, chemicals, weathering and radiation, sterilizability, of

Solids or films obtainable from preparations containing a composite composition according to the invention,

Control of electrical properties, e.g.

Dielectric strength, creep resistance,

Arc resistance, surface resistance, specific breakdown resistance, Flexibility, scratch resistance, elasticity, extensibility, bendability, tear behavior, rebound behavior, hardness, density, tear propagation resistance, compression set, behavior at different temperatures of solids or films obtainable from the preparation according to the invention

Composite preparations included.

Examples of applications in which the inventive

Composite preparation can be used to manipulate the above-described properties are the production of coating materials and impregnations and coatings and coatings to be obtained therefrom on substrates such as metal, glass, wood, mineral substrate, synthetic and natural fibers for the production of textiles, carpets , Floor coverings, or other fiber-produced goods, leather, plastics such as films, moldings. The composite preparations according to the invention can be used in preparations with appropriate

Selection of the preparation components also as an additive for the purpose of defoaming, flow promotion, hydrophobization, hydrophilization, filler and pigment dispersion, filler and pigment wetting, substrate wetting, promotion of surface smoothness, reduction of adhesion and sliding resistance on the surface of the additive from the preparation available hardened mass. The composite preparations according to the invention can be incorporated in liquid or in hardened solid form in elastomer compositions. Here, they may be used for the purpose of enhancing or improving other performance characteristics such as control of transparency, heat resistance, yellowing tendency, weathering resistance. Description of the measuring methods:

In the present text, substances are characterized by specification of data obtained by instrumental analysis. The underlying measurements are either

following publicly available standards or identified according to specially developed procedures. To ensure the clarity of the teaching provided, the ones used are

Methods given here: Viscosity:

Unless stated otherwise, the viscosities are measured by rotational viscometry according to DIN EN ISO 3219

certainly. Unless otherwise stated, all apply

Viscosity data at 25 ° C and atmospheric pressure of 1013 mbar.

Refractive index:

The refractive indices are in the wavelength range of

visible light, unless otherwise indicated at 589 nm at 25 ° C and normal pressure of 1013 mbar according to DIN 51423.

Transmission:

The transmission is determined by UV VIS spectroscopy. A suitable device is, for example, the Analytik Jena Specord 200. The measuring parameters used are: 190 - 1100 nm increment: 0.2 nm, integration time: 0.04 s, measuring mode:

Step operation. First, the reference measurement

(Background). A quartz plate attached to a sample holder (dimension of the quartz plates: HxB approx. 6 x 7 cm, thickness approx. 2.3 mm) is placed in the sample beam path and measured against air. Thereafter, the sample measurement takes place. One on the sample holder

attached quartz plate with applied sample - layer thickness applied sample approx. 1 mm - is placed in the sample beam path and measured against air. Internal offsetting against background spectrum provides the transmission spectrum of the sample. Molecular compositions:

Molecular compositions are determined by nuclear magnetic resonance spectroscopy (for terms, see ASTM E 386: High Resolution Magnetic Resonance Spectroscopy (NMR): Terms and Symbols), which measures the 1H nucleus and the 29Si nucleus.

Description ¹ H-MR measurement

Solvent: CDC13, 99.8% d

Sample concentration: approx. 50 mg / 1 ml CDC13 in 5 mm NMR

Tube Measurement without addition of TMS, spectral referencing of residual CHC13 in CDC13 to 7.24 ppm

Spectrometer: Bruker Avance I 500 or Bruker Avance HD 500 Probe Head: 5 mm BBO Probe Head or SMART Probe Head (Fa.

Bruker)

Measuring parameters:

Pulprog = zg30

TD = 64k

NS = 64 or 128 (depending on the sensitivity of the

Probe head)

SW = 20.6 ppm

AQ = 3, 17 s

Dl = 5 s

SF01 = 500.13 MHz

Oil = 6.175 ppm

Processing parameters:

SI = 32k

WDW = EM

LB = 0, 3 Hz

Depending on the spectrometer type used, individual adjustments of the measuring parameters may be necessary.

Description ²⁹ Si MR measurement

Solvent: C6D6 99.8% d / CC14 1: 1 v / v with lGew%

Cr (acac) 3 as a relaxation reagent

Sample concentration: approx. 2 g / 1.5 ml solvent in 10 mm NMR

tube

Spectrometer: Bruker Avance 300 Probe head: 10 mm 1H / 13C / 15N / 29Si glass-free QNP probe head (Bruker)

Measurement parameters:

Pulprog = zgigöO

TD = 64k

NS = 1024 (depending on the sensitivity of the probe head) SW = 200 ppm

AQ = 2.75 s

Dl = 4 s

SFOl = 300.13 MHz

Oil = -50 ppm

Processing parameters:

SI = 64k

WDW = EM

LB = 0.3 Hz

Molecular weight distributions:

Molecular weight distributions are determined as weight average M _w and as number average M _n , the method of

Gel permeation chromatography (GPC or Size Exclusion

Chromatography (SEC) application is with polystyrene standard and refractive index detector (RI detector). Unless otherwise stated, THF is used as the eluent and DIN 55672-1 is used. The polydispersity is the quotient M _w / M _n . Glass transition emperatures:

The glass transition temperature is determined by differential scanning calorimetry (DSC) according to DIN 53765, perforated Tigel, heating rate 10 K / min. Examples:

Examples of the metal-silicone resin compositions according to the invention, also called metallo-siloxane composite preparation, and their preparation are given below.

All percentages are by weight. Unless otherwise stated, all manipulations are carried out at room temperature of about 25 ° C and under normal pressure (1013 hPa). The devices are commercially available laboratory equipment as they are commercially available from numerous equipment manufacturers.

Ph is a phenyl radical = CeH ₅ - Me is a methyl radical = CH ₃ -.

Me ₂ correspondingly means two methyl radicals.

As component A the following are used in the examples:

1. a Methylphenylsiliconharz MPSH with a

Molecular weight average Mw of 1800 g / mol (number average Mn = 900, polydispersity 2.0) and a viscosity of 440 mm ² / s, the 14.2 wt .-% (corresponding to 43 mol%)

carrying silicon-bonded methoxy groups on the surface, and the average of 60 mol% PhSi0 _3/2 units,

36 mol .-% MeSi0 _3/2 units and 4 mol .-% Me ₂ Si0 _2/2 units, wherein the methoxy groups are distributed over the specified structural units.

2. a phenyl silicone resin PSH having a molecular weight average Mw of 900 g / mol (number average Mn = 500, polydispersity 1.8) and a viscosity of 400 mm ² / s, which is 14.8% by weight (equivalent to 45 mol%) carrying silicon-bonded methoxy groups on the surface and consisting of 100 mol% PhSi0 _3/2 - units, wherein the methoxy groups are distributed over the specified structural units.

3. a methylsilicone resin SH having a weight average molecular weight Mw of 2100 g / mol (number average Mn = 1500, polydispersity 1.5) and a viscosity of 250 mm ² / s containing 31% by weight (corresponding to 86 mol%) of silicon-bonded methoxy groups carries on the surface and which consists of 100 mol% MeSi0 _3/2 - units, wherein the methoxy groups are distributed over the specified structural units. Example 1 :

Preparation of a Metallo-Siloxane Composite Preparation According to the Invention

50.33 g FSH are weighed into a 4 l three-necked glass flask. 59.33 g of titanium tetraisopropoxide are allowed to run in at 15 ° C. from a dropping funnel at 21 ° C. for this initial charge. The temperature in the glass bulb increases from 21 ° C to 33 ° C. The mixture is stirred for 60 minutes while cooling to 24 ° C. 6.25 g of 20% strength aqueous hydrochloric acid solution are weighed into a dropping funnel and then added to the initial charge of titanium tetraisopropylate and PSH within 30 minutes

dropwise. The temperature of the mixture increases to 36 ° C. It is clear and slightly yellow in color. Subsequently, 3.7 g of methydichlorosilane are added dropwise within 10 min, whereupon a whitish cloudy preparation is obtained. The mixture heats up to 37 ° C during the addition of the dichlorosilane.

It is then evacuated to 20 mbar and heated to 160 ° C to escape the mixture. From 60 ° C it is clear again.

This gives 102 g of a clear yellowish liquid. The viscosity is 2000 mPas. The weight average becomes too

Mw = 1110 g / mol, the number average Mn = 870 g / mol

(Polydispersity PD = 1.3). The product contains no Si-H bonds.

The product provides on a sheet of aluminum with a 100 meter doctor blade a clear transparent film, which feels dry after 6 hours drying time (touch dry). The starting silicone resin does not exhibit this behavior, it does not form at room temperature even after several days

drying film. This arises only after you at

Cures temperatures of 230 ° C for at least 30 minutes. This one produced product according to the invention was exposed to a temperature of 150 ° C for 30 min and then provided already a solvent-solid cured coating and thus requires significantly less curing energy than the silicone resin PSH itself.

The detection of Ti-O-Si bonds is clearly accomplished by MALDI-TOF MS (matrix-assisted laser desorption / ionization - time-of-flight mass spectrometry / matrix-assisted

Laser desorption / ionization time-of-flight mass spectrometry) analysis. This method is chosen because no other analytical method gives clear results here. The IR spectroscopy, which has been widely used in the literature, is unsuitable as a detection method since the characteristic bands of the Ti-O-Si structural unit overlap with other Si alkoxy bands, which results in the assignment of Ti-O-Si bands

is arbitrary.

As cationization agent is used for the MALDI-TOF analysis

Silver trifluoroacetate used. The organic matrix used is trans-2- [3- (4-tert-butylphenyl) -2-methyl-2-propenylidenes] malononitrile (DCTB).

Sample, matrix and cationizing reagent are dissolved in toluene, mixed in a suitable ratio and after

Dry the mixture on a stainless steel target in reflectron mode.

The mass spectrum obtained is isotope-resolved with a mean mass resolution of 6000.

The allocation of the molecular peaks is done by matching the measured with simulated peaks. In this way, a number of Ti-O-Si-containing molecular peaks can be assigned to a match of more than 90% (in the table Convention Stim ^¬ tion factor score> 0.9), some of which are exemplified here to the existence of the for prove the metallo-siloxane composites of the invention required Ti-O-Si bridges. The organic radicals are methyl, phenyl, Methoxy and isopropoxy. The molecular peaks are given as silver ion:

Actual

Theoretical Mass Mass

Chemical Formula (Tm) (Am) Tm - At Score

C20 H54O14AgSi5Ti 813,089 813,0988 -0,0098 0,9168

C20 H54014 Ag Si5 Ti 813,089 813,0988 -0,0098 0,9168

C21 H56O14Ag Si5 Ti 827.1047 827.1168 -0.0121 0.9079

C21 H56014 Ag Si5 Ti 827.1047 827.1168 -0.0121 0.9079

C21 H56O14Ag Si5 Ti 827.1047 827.1168 -0.0121 0.9079

C22 H58O16Ag Si5 Ti 873.1102 873.153 -0.0428 0.9003

C22 H58O16AgSi5 Ti 873.1102 873.153 -0.0428 0.9003

C22 H58O16Ag Si5 Ti 873.1102 873.153 -0.0428 0.9003

C23 H60016 Ag Si5 Ti 887.1258 887.161 -0.0352 0.9302

C23 H60O16AgSi5 Ti 887.1258 887.161 -0.0352 0.9302

C26 H64O14AgSi3Ti2 887.1614 887.161 0.0003 0.9097

C26 H66017 Ag Si4 Ti2 965.1387 965.1416 -0.003 0.9382

C27 H68O17AgSi4 Ti2 979.1543 979, 549 -0.0005 0.9555

C27 H68017 Ag Si4 Ti2 979.1543 979.1549 -0.0005 0.9555

C28 H70O17Ag Si4 Ti2 993.17 993.1431 0.0269 0.9223

C29 H74O18Ag Si5 Ti2 1053.1731 1053.1954 -0.0223 0.9171

C33 H82O19Ag Si4 Ti3 1145.2017 1145.1832 0.0184 0.9391

C34 H84O19Ag Si4 Ti3 1159.2173 1159.2127 0.0046 0.9363

C35 H86O9 Ag Si4 Ti3 1173.233 1173.2302 0.0028 0.9571

C36 H90021 Ag Si5 Ti3 1249.231 1249.3076 -0.0766 0.9082

C36 H90021 AgSi5Ti3 1249,231 1249,3076 -0,0766 0,9082

C36 H90021 Ag Si5 Ti3 1249.231 1249.3076 -0.0766 0.9082

C37 H92021 Ag Si5 Ti3 1263.2467 1263.2977 -0.051 0.924

C38 H94021 Ag Si5 Ti3 1277.2623 1277.3094 -0.0471 0.9291

C36 H92023 Ag Si6 Ti3 1311.2134 1311.2581 -0.0447 0.9227

C41 H92021 Ag Si5 Ti3 1311.2467 1311.2581 -0.0114 0.947 C38 H88023 Ag Si7 Ti2 1311, 2111 1311, 2581 -0.047 0.9302

C36 H92023 Ag Si6 Ti3 1311, 2134 1311.2581 -0.0447 0.9227

C41 H92021 Ag Si5 Ti3 1311, 2467 1311, 2581 -0.0114 0.947

C39 H96021 Ag Si4 Ti4 131 1.249 1311.2581 -0.0091 0.9313

C36 H92023 Ag Si6 Ti3 1311, 2134 1311.2581 -0.0447 0.9227

C41 H92021 Ag Si5 Ti3 1311, 2467 1311, 2581 -0.0114 0.947

C36 H92023 Ag Si6 Ti3 1311, 2134 1311.2581 -0.0447 0.9227

C37 H94023 Ag Si6 Ti3 1325, 2291 1325.2817 -0.0526 0.9356

C40 H98021 Ag Si47Ί4 1325, 2646 1325.2817 -0.017 0.9414

C41 H100022 Ag Si4 Ti4 1355, 2752 1355.2954 -0.0202 0.9044

C45 H 100022 Ag Si4 Ti4 1403, 2752 1403.3387 -0.0635 0.9095

C41 H102024 Ag Si5 Ti4 1417, 2576 1417.3024 -0.0448 0.941

C41 H102O24Ag Si5Ti4 1417, 2576 1417.3024 -0.0448 0.941

C41 H102024 Ag Si5 Ti4 1417, 2576 1417.3024 -0.0448 0.941

C46 H102022 Ag Si4Ti4 1417, 2909 1417.3024 -0.0116 0.9306

C42H104O24AgSi5Ti4 1431, 2733 1431.3271 -0.0539 0.9398

C42 H104024 Ag Si5 Ti4 1431, 2733 1431, 3271 -0.0539 0.9398

C44 H100024 Ag Si6 Ti3 1431, 2709 1431, 3271 -0.0562 0.9304

C44H100O24AgSi6Ti3 1431, 2709 1431, 3271 -0.0562 0.9304

C42 H104024 Ag Si5 ΊΊ4 1431, 2733 1431.3271 -0.0539 0.9398

C42 H 104024 Ag Si5 Ti4 1431, 2733 1431.3271 -0.0539 0.9398

C43 H 106024 Ag Si5 Ti4 1445, 2889 1445.3246 -0.0357 0.9385

C43 H 106024 Ag Si5 ΤΊ4 1445, 2889 1445.3246 -0.0357 0.9385

C49 H110O24Ag Si5 Ti4 1521, 3202 1521.3709 -0.0507 0.9069

C49 H112026 Ag Si6 Ti4 1583, 3026 1583, 3943 -0.0917 0.9056

C49 H 112026 Ag Si6 Ti4 1583, 3026 1583.3943 -0.0917 0.9056

C49 H112026 Ag Si6 Ti4 1583, 3026 1583, 3943 -0.0917 0.9056

C54 H112O24Ag Si5 Ti4 1583, 3359 1583.3943 -0.0584 0.936

C49 H112O26Ag Si6 Ti4 1583, 3026 1583, 3943 -0.0917 0.9056

C49H112O26AgSi6Ti4 1583, 3026 1583.3943 -0.0917 0.9056

C49 H 112026 Ag Si6 Ti4 1583, 3026 1583.3943 -0.0917 0.9056

C50H114O26AgSi6Ti4 1597, 3183 1597,4144 -0,0962 0,9075

C50 H114026 Ag Si6Ti4 1597, 3183 1597,4144 -0,0962 0,9075

C50 H 114026 Ag Si6 Ti4 1597, 3183 1597.4144 -0.0962 0.9075

C50 H 14026 Ag Si6 Ti4 1597, 3183 1597.4144 -0.0962 0.9075

C51H16O26AgSi6Ti4 1611, 3339 1611,3983 -0.0644 0.9058

C51 H116026 Ag Si6 Ti4 1611, 3339 1611,3983 -0,0644 0,9058

C57 H 120 O26 Ag Si6 Ti4 1687, 3652 1687, 4583 -0.0931 0.9129 A selection of mass peaks from the same analysis demonstrating the presence of the required titanium-free polyorganosiloxanes as a formulation component is given below:

C19 H50 014 Ag Si5 749.1098 749.1437 -0.0339 0.9007

C21 H48 014 Ag Si6 799.071 1 799.0917 -0.0206 0.9007

C21 H48 014 Ag Si6 799.0711 799.0917 -0.0206 0.9007

C22 H50 O14 Ag Si6 813.0867 813.0988 -0.0121 0.9183

C18 H50 O17 Ag Si6 813.0715 813.0988 -0.0273 0.9075

C22 H50 014 Ag Si6 813.0868 813.0988 -0.0121 0.9183

C22 H50 O14 Ag Si6 813.0867 813.0988 -0.0121 0.9183

C18 H50 017 Ag Si6 813.0715 813.0988 -0.0273 0.9075

C22 H50 014 Ag Si6 813.0868 813.0988 -0.0121 0.9183

C18 H50 017 Ag Si6 813.0715 813.0988 -0.0273 0.9075

C28 H54 013 Ag Si6 873.1231 873.153 -0.0299 0.9553

C24 H54 016 Ag Si6 873.1078 873.153 -0.0451 0.9017

C28 H54 013 Ag Si6 873.1231 873.153 -0.0299 0.9553

C24 H54 016 Ag Si6 873.1078 873.153 -0.0451 0.9017

C28 H54 O13 Ag Si6 873.1231 873.153 -0.0299 0.9553

C24 H54 O16 Ag Si6 873.1078 873.153 -0.0451 0.9017

C25 H56 O16 Ag Si6 887.1235 887.161 -0.0375 0.9301

C24 H56 O15 Ag Si7 887.1055 887.161 -0.0555 0.902

C24 H56 015 Ag Si7 887.1055 887.161 -0.0555 0.902

C29 H56 O13 Ag Si6 887.1387 887.161 -0.0223 0.9369

C25 H56 016 Ag Si6 887.1235 887.161 -0.0375 0.9301

C24 H56 O15 Ag Si7 887.1055 887.161 -0.0555 0.902

C24 H56 015 Ag Si7 887.1055 887.161 -0.0555 0.902

C29 H56 013 Ag Si6 887.1387 887.161 -0.0223 0.9369

C25 H56 016 Ag Si6 887.1235 887.161 -0.0375 0.9301

C24 H56 015 Ag Si7 887.1055 887.161 -0.0555 0.902

C24 H56 015 Ag Si7 887.1055 887.161 -0.0555 0.902 C29 H56013 Ag Si6 887.1387 887.161 -0.0223 0.9369 C29 H56013 Ag Si6 887.1387 887.161 -0.0223 0.9369 C29 H56013 Ag Si6 887.1387 887.161 -0.0223 0.9369 C25 H58015 Ag Si7 901 , 1212 901.165 -0.0438 0.9255 C26 H60O15Ag Si7 915.1368 915.1812 -0.0444 0.9328 C22 H60018 Ag Si7 915.1215 915.1812 -0.0597 0.901 C22 H60O18Ag Si7 915.1215 915.1812 -0.0597 0.901 C27 H60016 Ag Si6 915.1548 915.1812 -0.0264 0.9469 C26 H60015 Ag Si7 915.1368 915.1812 -0.0444 0.9328 C26 H60O15AgSi7 915.1368 915.1812 -0, 0444 0.9328 C22 H60O18Ag Si7 915.1215 915.1812 -0.0597 0.901 C27 H60O16AgSi6 915.1548 915.1812 -0.0264 0.9469 C26 H60O15AgSi7 915.1368 915.1812 -0.0444 0.9328 C26 H60O15Ag Si7 915.1368 915.1812 -0.0444 0.9328 C22 H60O18Ag Si7 915.1215 915.1812 -0.0597 0.901 C27 H60016 Ag Si6 915.1548 915.1812 -0.0264 0.9469 C31 H60 O13Ag Si6 915 , 17 915.1812 -0.0112 0.9433 C31 H60013 Ag Si6 915.17 915.1812 -0.0112 0.9433 C26 H60015 Ag Si7 915.1368 915.1812 -0.0444 0.9328 C26 H60015 Ag Si7 915.1368 915.1812 -0.0444 0.9328 C22 H60018 Ag Si7 915.1215 915.1812 -0.0597 0.901 C22 H60O18Ag Si7 915.1215 915.1812 -0.0597 0.901 C28 H62016 Ag Si6 929.1704 929.2035 -0.033 0.907 C28 H62016 Ag Si6 929.1704 929 2035 -0.033 0.907 C28 H62016 Ag Si6 929.1704 929.2035 -0.033 0.907 C32 H62013 Ag Si6 929.1857 929.2035 -0.0178 0.9043 C24 H56019 Ag Si7 951.0852 951.139 -0.0538 0.9239 C28 H56016 Ag Si7 951.1004 951.139 -0.0386 0.9232 C28 H56O16Ag Si7 951.1004 951.139 -0.0386 0.9232 C28 H56O16Ag Si7 951.1004 951.139 -0.0386 0.9232 C28 H56O16Ag Si7 951.1004 951.139 - 0.0386 0.9232 C23H56O18Ag Si8 951.0672 951.139 -0.0718 0.9025 C24H56O19Ag Si7 951.0852 951.139 -0.0538 0.9239 C28H56O16Ag Si7 951.1004 951.139 -0.0386 0.9232 C28H56O16AgSi7 951.1004 951.139 -0.0386 0.9232 C24 H56019 Ag Si7 951.0852 951.139 -0.0538 0.9239 C28 H56O16AgSi7 951.1004 951.139 -0.0386 0.9232 C24 H56O19Ag Si7 951.0852 951.139 -0.0538 0.9239 C26 H62 O18AgSi8 993.1141 993.1431 -0.029 0.9475 C26 H62 O18AgSi8 993.1141 993.1431 -0.029 0.9475 C26 H62 O18AgSi8 993.1 41 993.1431 -0.029 0.9475 C22 H62021 Ag Si8 993.0989 993.1431 -0.0443 0.9159 C32 H64016 Ag Si7 1007.163 1007.1763 -0.0132 0.9628 C32 H64016 Ag Si7 1007.163 1007.1763 -0.0132 0.9628 C32 H64016 Ag Si7 1007.163 1007.1763 -0.0132 0.9628 C32 H64016 Ag Si7 1007.163 1007.1763 -0.0132 0.9628 C28 H64O19Ag Si7 1007.1478 1007.1763 -0.0285 0.9616 C36 H64015 Ag Si7 1039.1681 1039.2107 -0.0426 0.9122 C36 H64015 Ag Si7 1039.1681 1039.2107 -0.0468 0.9122 C36 H64015AgSi7 1039, 1681 1039.2107 -0.0426 0.9122

C36 H64015Ag Si7 1039, 1681 1039.2107 -0.0426 0.9122

C36 H64015AgSi7 1039, 1681 1039.2107 -0.0426 0.9122

C36H64015AgSi7 1039, 1681 1039.2107 -0.0426 0.9122

C33H66018AgSi7 1053, 1685 1053.1954 -0.0269 0.9289

C37H68018AgSi8 1131, 1611 1131.1778 -0.0167 0.9614

C37 H68018 Ag Si8 1131, 1611 1131.1778 -0.0167 0.9614

C37H68O18AgSi8 1131, 1611 1131.1778 -0.0167 0.9614

C33 H70 O20 Ag Si9 1145, 1435 1145, 1832 -0.0397 0.9371

C29 H70023 Ag Si9 1145, 1282 1145.1832 -0.055 0.9004

C30 H72023 Ag Si9 1159, 1439 1159.2127 -0.0689 0.9025

C39 H72 O18 Ag Si8 1159, 1924 1159.2127 -0.0204 0.9779

C39 H72018 Ag Si8 1159, 1924 1159.2127 -0.0204 0.9779

C42 H80 O20 Ag Si9 1263, 2217 1263, 2977 -0.0759 0.92

C49 H86 O20 Ag Si9 1353, 2687 1353, 3195 -0.0508 0.9561

C45 H86023 Ag Si9 1353, 2534 1353.3195 -0.0661 0.9236

C49 H86 O20 Ag Si9 1353, 2687 1353, 3195 -0.0508 0.9561

C49 H86 O20 Ag Si9 1353, 2687 1353, 3195 -0.0508 0.9561 Example 2:

Preparation of a metallo-siloxane composite composition according to the invention 402.44 g of MSH are weighed into a 4 l three-necked glass flask. To this template 474.64 g at 23 ° C 474.64 g

Titantetraisopropylat within 15 min from a

Allow the dropping funnel to run. The temperature in the glass bulb increases from 23 ° C to 49 ° C. The mixture is stirred for 60 minutes while cooling to 23 ° C. In a

15.22 g of 20% aqueous hydrochloric acid solution are weighed into the dropping funnel. The aqueous solution of hydrochloric acid is slowly added dropwise to the titanium tetraisopropoxide and MSH template while the temperature of the mixture is raised to 85 ° C. The dropwise rate is 0.5 ml / min. At the drop in place

Occurring turbidities are rapidly distributed by the stirrer action and dissolve again and again. Volatile constituents are removed by distillation at 85 ° C. without vacuum. The reaction mixture is filtered with Decalite 478 through a Seitz K 100 filter plate through a pressure filter and the filtrate is then volatilized on a rotary evaporator at 160 ° C and 20 mbar suppression.

This gives 682.9 g of a clear yellowish liquid. The viscosity is 800 mPas. The weight average becomes too

Mw = 1000 g / mol, the number average Mn = 700 g / mol

(Polydispersity PD = 1.4).

The detection of Ti-O-Si bonds is clearly achieved by MALDI-TOF MS (same measurement conditions) as already indicated for Example 1.

If the product prepared here is doctored onto an aluminum panel with a 100 μm doctor blade, it forms a limited solvent-stable dry film after 3 hours. Although the film cures under ambient conditions, the product itself is in the sealed container stable for months. It hardens autocatalytically with atmospheric moisture.

If the product according to this example is mixed with 10% by weight of a 50% xylene solution of a methyl silicone resin having a molecular weight average Mw of 76,000 g / mol (number average Mn = 2700, polydispersity 28) and a solution viscosity of 50 mm ² / s, wherein the silicone resin carries 3.9% by weight of silicon-bonded ethoxy groups on the surface and 0.4% by weight

silicon-bonded hydroxyl groups and 85 mol% of MeSi0 _3/2 - units to 13 mole% of Me ₂ Si0 _2/2 ^_ units and 2 mole% of Me ₃ SIOI / 2 units, wherein the ethoxy - And distribute the hydroxy groups on the specified structural units, and pulls this preparation, which itself

According to the invention, with a 100 pm squeegee on a

Aluminum sheet, it is observed a rapid curing of the preparation to a solvent-resistant film. The preparation itself is storage-stable over a period of several weeks. Although the admixed methyl resin forms a dry film on an aluminum panel by itself after the solvent has evaporated, it is not solvent-stable. He lets himself be soaked in methyl ethyl ketone

Rub the cotton ball completely again.

Example 3:

In a 4 1 three-necked glass flask, 50.33 g

Tetraethyl silicate oligomer (average 7

Repeating units, 40% Si02 content after complete theoretical condensation). 59.33 g of titanium tetraisopropylate are allowed to run in at 23 ° C. from a dropping funnel over a period of 15 minutes. The temperature in the glass bulb increases from 22.1 ° C to 28.9 ° C. The

Mixture is stirred for 30 minutes while cooling to 26 ° C. Thereafter, a mixture of 4,4g phenyltrichlorosilane and 4,4g phenyltriethoxysilane within 10 min from a

Added dropping funnel and then heated to 50 ° C. At this temperature, after 60 minutes, a mixture of 2.47 g of demineralized water and 24.7 g of ethanol from a

Dropping funnel added within 30 min stirred at 50 ° C for 30 min. The mixture is volatilized at 150 ° C and 20 mbar suppression. This gives 89 g of a clear, colorless

Liquid with a viscosity of 432 mPas. The

Weight average is determined to Mw = 700 g / mol, the number average to Mn = 400 g / mol (polydispersity PD = 1.9).

The detection of Ti-O-Si bonds is clearly achieved by MALDI-TOF MS analysis as described in Example 1. Example 4:

50.33 g MPSH are weighed into a 4 l three-neck glass flask. 59.33 g of titanium tetraisopropylate are allowed to run in at 23 ° C. from a dropping funnel over a period of 15 minutes. The temperature in the glass bulb increases from 21.5 ° C to 27.6 ° C. The mixture is stirred for 30 minutes while cooling to 24.3 ° C. After that, a mixture of 10.29g

Phenyltrichlorosilane and 10.29g phenyltriethoxysilane added within 10 min from a dropping funnel and then heated to 75 ° C. At this temperature, after 60 minutes, a mixture of 2.47 g of demineralized water and 24.7 g of ethanol from a dropping funnel is added over 30 minutes and stirred at 80 ° C. for 30 minutes.

The reaction mixture is filtered with Decalite 478 through a Seitz K 100 filter plate through a pressure filter and the filtrate is then volatilized on a rotary evaporator at 150 ° C and 20 mbar vacuum. This gives 86 g of a clear, colorless liquid having a viscosity of 328 mPas. The Weight average is determined to be Mw = 1400 g / mol, the number average to Mn = 800 g / mol (polydispersity PD = 1.8).

The detection of Ti-O-Si bonds is clearly achieved by MALDI-TOF MS analysis as described in Example 1.

The refractive index is 1.521.

If the product prepared here is doctored onto an aluminum panel with a 100 μm doctor blade, it forms after 3 hours a limited solvent-stable transparent dry film.

Although the film cures under ambient conditions, the product itself is in sealed container for months

storage stable. It hardens autocatalytically with atmospheric moisture.

Example 5:

201.32 g PSH are weighed into a 4 l three-neck glass flask. To this template at 22 ° C 237.32 g

Titantetraisopropylat within 15 min from a

Allow the dropping funnel to run. The temperature in the glass bulb increases from 22 ° C to 41 ° C. The mixture is stirred for 60 minutes while cooling to 29 ° C. Subsequently, 7.4 g of methydichlorosilane and 1, 1, 3, 3-tetramethyl-l, 3-divinyldisiloxan mixed together, placed in a dropping funnel and added dropwise within 30 min, whereupon the mixture is heated to 45 ° C. It is clear and slightly yellowish. Subsequently, 25 g of 20% aqueous hydrochloric acid solution are weighed into the dropping funnel and added evenly over 30 minutes to the reaction mixture. The mixture becomes cloudy and highly viscous, but clears when heated above 60 ° C and becomes transparent. At 20 mbar is heated to 160 ° C to escape the mixture. This gives 328 g of a

yellowish, clear, colorless product. It is viscous with a viscosity of 6100 mPas. The weight average becomes too Mw = 1300 g / mol, the number average to Mn = 1000 g / mol (polydispersity PD = 1.3).

The refractive index is 1.55, which is higher than that of any silicone component used.

The product prepared here was added again with 12.5 g of 20% aqueous hydrochloric acid solution and up to 160 ° C.

heated. Immediately after addition of the hydrochloric acid, turbidity was observed as before, which dissolves on heating from 70 ° C. 39.5 g of aqueous alcohol mixture are distilled off at 160 ° C. and 20 mbar, giving 300 g of a clear, yellowish, barely flowable product which contains a

Refractive index of 1.60 has. It is in solvents such as e.g. Toluene soluble. The refractive index increases with increasing degree of condensation of metallo-siloxane composite according to the invention and allows values above that of

To achieve output silicone materials. This will be the

Suitability for, for example, optical applications requiring a high refractive index.

Comparative Example 1 Non-inventive Procedure with Too High Water Quantity:

The same experiment as in Example 2 is repeated except that, unlike Example 2, 18.75 g of 20% aqueous

Hydrochloric acid mixed with 216 g of water are added dropwise. This gives a whitish turbid highly viscous mixture with a voluminous precipitate, which does not dissolve.

Comparative Example 2 Non-inventive procedure in which it is attempted to prepare the silicone resin (A) in situ and to react same with a titanium tetraalkoxylate. Instead of using the FSH from Example 5, this is tried in situ to produce from phenyltriethoxysilane and this in situ mixture immediately further implement with a Tetraalkytitanat.

In a 4 1 three-necked glass flask 50,33g Phenyltriethoxy ^¬ silane are weighed and 18.75 g of 20% aqueous hydrochloric acid was added to this template from a dropping funnel over a period of 3 minutes. The temperature in the reaction flask increases from 22.5 to 27.2 ° C due to the heat of reaction. The mixture is then heated for 30 minutes at 80 ° C, no distillate is removed to prevent too much condensation of the silane and allowed to cool the aqueous alcoholic mixture to 30 ° C. Then add 59.33 g of titanium tetra isopropylate from a dropping funnel within 30 minutes. The further procedure corresponds to that in Example 4. In contrast to the procedure according to the invention, no clear preparation is obtained, but an inhomogeneous mass which contains a voluminous white precipitate.

In a repeat experiment, after the addition of the titanium tetraisopropylate, another 5 g of water are added at room temperature within 10 minutes. Otherwise one proceeds in the same way and receives here also a white preparation, in which the precipitate formed no longer dissolves.

Comparative Example 3: Procedure does not correspond to the preferred procedure in the dosing order.

50.33 g of MPSH are weighed into a 4 l three-necked glass flask and 18.75 g of 20% strength aqueous hydrochloric acid are added to this initial charge, followed by 2.47 g of water from a dropping funnel, each within 10 minutes. Then, 59.33 g of titanium tetraisopropylate are added from a dropping funnel within 10 Minutes too. An exothermic increase in temperature is observed to be 36.4 ° C. The reaction mixture becomes turbid during the addition of the titanium component and becomes viscous. It is heated slowly to reflux temperature of 80 ° C and leaves 6

Stir at this temperature for hours. Subsequently, will

distilled off, whereupon a transparent highly viscous product having a viscosity of 96,000 mPas is obtained, which turns brownish during storage after 4 weeks. An elevator of this product of ethanol on an aluminum panel with a 100 μπι spiral blade gives after curing at 150 ° C for 30 minutes, a likewise brown and brittle, brittle film.

Claims

Patent claims:

1. Liquid crosslinkable metal-silicone resin compositions can be produced by hydrolysis and condensation of

(A) 100 parts by weight of a silicone resin

30 to 100 mol% units selected from the group of units of the formulas R'Si0 _3/2 (Ia) and Si0 _4/2 (Ib) and mixtures thereof and

0 to 70 mol% units selected from the group of units of the formulas R' ₂ SiO ₂ /2 (Ic) and R' ₃ SiOi _/2 (Id) and mixtures thereof, where

R 'can be the same or different and represents a radical R or a radical of the formula -OR ¹ , with the proviso that at least 3 mol% of all radicals R' are radicals of the formula -OR ¹ ,

R can be the same or different and represents a monovalent, optionally substituted hydrocarbon radical with 1 to 18 carbon atoms or a hydrogen atom and

R ¹ can be the same or different and a

Hydrogen atom or a monovalent

means an optionally substituted hydrocarbon radical with 1 to 18 carbon atoms,

(B) 1 to 200 parts by weight based on 100 parts by weight

Silicone resin (A), a metal compound of the formula

R ² _c MX ₄ _c (II), or their partial hydrolysates, where

c is 0, 1, 2 or 3,

M titanium or zirconium, preferably titanium in the

Oxidation state +IV, is, X is a halogen atom, preferably a chlorine atom, or a radical -OR ³ ,

R ² has the same meaning as R regardless of R and R ³ has the same meaning as R ¹ regardless of R ¹ , if necessary.

(C) 0 to 100 parts by weight, based on 100 parts by weight

Silicone resin (A), a silane of the formula

R _d Si(OR ⁵ ) ₄ - _d (III! or their partial hydrolysates, with the proviso that the partial hydrolysates are different from silicone resin (A) and at least 3 mol%, based on all Si-bonded residues, Ci-Ci ₂ -Alkoxy radicals or hydroxy radicals, where R ⁴ can be the same or different and one

monovalent, optionally substituted

means a hydrocarbon radical with 1 to 18 carbon atoms or a hydrogen atom,

R ⁵ independently of R ¹ has the same meaning as R ¹ , d is 0, 1, 2 or 3,

and if necessary

(D) 0 to 100 parts by weight, based on 100 parts by weight

Silicone resin (A), a silane of the formula

or their partial hydrolysates, where

X is a halogen atom, preferably a chlorine atom, R ⁶ can be the same or different and one

monovalent, optionally substituted

means a hydrocarbon radical with 1 to 18 carbon atoms or a hydrogen atom,

e is 0, 1, 2 or 3,

with

(E) water, if necessary in the presence of

(F) promoting hydrolysis and condensation

Catalysts, preferably acids,

and if necessary in the presence of

(G) organic solvents

with the proviso that

(i) the amount of water is always chosen so that, based on the amount of all metal- and silicon-bonded hydrolyzable groups present, it is substoichiometric and preferably not more than 80 mol%. preferably not more than 75 mol% of the amount of water required for complete hydrolysis of all hydrolyzable groups present,

(ii) that the metal-silicone resin compositions

have at least one ^M-O-Si^ bond (M means Ti or Zr), preferably sTi-O-Si^ bond,

(iii) that the compositions

(AI) at least 1% by weight, based on the

Compositions containing metal-free silicone resin (A) or metal-free condensates selected from the group of components (A), (C) and (D) or mixtures thereof, and

(iv) that the compositions have a viscosity of 5 to 5,000,000 mPa.s at 25 ° C and normal pressure of 1013 hP,

(v) and, if necessary, following the hydrolysis and

Condensation an addition of

(A2) Silicone resins derived from silicone resin (A)

are different and have a viscosity of 5 to 5,000,000 mPa.s at 25 ° C and normal pressure of 1013 hP.

Liquid crosslinkable metal-silicone resin compositions according to claim 1 which can be produced by hydrolysis and Condensation containing at least the following

Steps taken in this order:

(1) Presenting the silicone resin (A)

(2) Addition of the metal compound (B)

if necessary (3) addition of the silanes (C) or (D) or the silanes (C) and (D) or the partial hydrolysates of silane (C) or (D) or the partial hydrolysates of silane (C) and (D), whereby the addition according to step (3) can also take place after step (4),

(4) adding water (E) or an aqueous solution of a catalyst (F) or a mixture of water (E) and organic solvents (G) to the reaction mixture, the reaction mixture upon addition of water (E) or an aqueous Solution of a catalyst (F) or a mixture of water (E) and organic solvents (G) has a temperature of 0 ° C to 90 ° C, preferably 10 ° C to 80 ° C, if necessary (5) filtration of the reaction mixture and

(6) Devolatize the reaction mixture.

3. A process for producing the liquid crosslinkable metal-silicone resin compositions according to claim 1

Hydrolysis and condensation of

(A) 100 parts by weight of a silicone resin

R 'can be the same or different and represents a radical R or a radical of the formula -OR ¹ , with the proviso that at least 3 mol% of all radicals R' are radicals of the formula -OR ¹ , R can be the same or different and one

monovalent, optionally substituted

Hydrocarbon radical with 1 to 18 carbon atoms or a hydrogen atom means and

R ¹ can be the same or different and a

Hydrogen atom or a monovalent

optionally substituted hydrocarbon radical with 1 to 18 carbon atoms means, (B) 1 to 200 parts by weight, based on 100 parts by weight

Silicone resin (A), a metal compound of the formula

R ² _c MX ₄ -c (II), or their partial hydrolysates, where

c is 0, 1, 2 or 3,

M titanium or zirconium, preferably titanium in the

Oxidation state +IV, is,

X is a halogen atom, preferably a chlorine atom, or a radical -OR ³ ,

(C) 0 to 100 parts by weight, based on 100 parts by weight

Silicone resin (A), a silane of the formula

or their partial hydrolysates, with the proviso that the partial hydrolysates are different from silicone resin (A) and at least 3 mol%, based on all Si-bonded radicals, are Ci-Ci ₂ alkoxy radicals or hydroxy radicals, where R ⁴ can be the same or different can and one

monovalent, optionally substituted means a hydrocarbon radical with 1 to 18 carbon atoms or a hydrogen atom,

R ⁵ independently of R ¹ has the same meaning as R ¹ , d is 0, 1, 2 or 3,

and if necessary

(D) 0 to 100 parts by weight, based on 100 parts by weight

Silicone resin (A), a silane of the formula

R ⁶ _e SiZ ₄ - _e (IV) or their partial hydrolysates, where

Z is a halogen atom, preferably a chlorine atom, R ⁶ can be the same or different and one

monovalent, optionally substituted

means a hydrocarbon radical with 1 to 18 carbon atoms or a hydrogen atom,

e is 0, 1, 2 or 3,

with

(E) water,

if necessary- in the presence of

(F) promoting hydrolysis and condensation

Catalysts, preferably acids,

and if necessary in the presence of

(G) organic solvents

with the proviso that

(i) the amount of water is always chosen so that,

based on the amount of all metal and silicon-bonded hydrolyzable groups present,

is substoichiometric and preferably not more than 80 mol%, preferably not more than 75 mol%, of the amount of water required for complete hydrolysis of all hydrolyzable groups present, (ii) that the metal-silicone resin compositions

have at least one ^M-O-Si^ bond (M means Ti or Zr), preferably sTi-O-Si bond,

(iii) that the compositions

(AI) at least 1% by weight, based on the

(iv) that the compositions have a viscosity of 5 to

5,000,000 mPa.s at 25 °C and normal pressure of 1013 hPa,

(v) and, if necessary, following the hydrolysis and

Condensation an addition of

(A2) Silicone resins derived from silicone resin (A)

are different and have a viscosity of 5 to

5,000,000 mPa.s at 25 ° C and normal pressure of 1013 hPa.

Process for producing the liquid crosslinkable

Metal-silicone resin compositions according to claim 3 by hydrolysis and condensation containing at least the following steps in this order

be carried out:

(1) Presenting the silicone resin (A)

(2) Addition of the metal compound (B)

(4) adding water (E) or an aqueous solution of a catalyst (F) or a mixture of water (E) and organic solvents (G), whereby the Reaction mixture when adding water (E) or an aqueous solution of a catalyst (F) or a mixture of water (E) and organic

Solvents (G) have a temperature of 0°C to 90°C, preferably 10°C to 80°C,

possibly.

(5) filtration of the reaction mixture and

(6) Devolatize the reaction mixture.

Moldings produced by crosslinking the liquid crosslinkable metal-silicone resin compositions according to claim 1 or 2 or produced according to claim 3 or 4.

Shaped bodies produced by crosslinking

Preparations containing the liquid crosslinkable metal-silicone resin compositions according to claim 1 or 2 or prepared according to claim 3 or 4.

Shaped body according to claim 5 or 6, characterized in that they are films.

Shaped bodies or films according to claims 5 to 7, characterized

characterized in that the shaped bodies or films have one

Have a refractive index of greater than or equal to 1.4 at 25 ° C at at least one wavelength in the visible light range, preferably at 589 nm.

Use of the composition according to claim 1 or 2 or prepared according to claim 3 or 4 as a potting and

Electrical or electronic embedding material

components.

0. Use of the compositions according to claim 1 or 2 or produced according to claim 3 or 4 as potting or embedding compounds for LEDs (light emitting devices).