DE102013204296A1 - Liquid crosslinkable metal-silicone resin compositions - Google Patents

Abstract

Liquid crosslinkable metal-silicone resin compositions are described which can be prepared by hydrolysis and condensation of (A) 100 parts by weight of silicone resin from 30 to 100 mol% of units of the formulas R'SiO3 / 2 (Ia) and / or SiO4 / 2 ( Ib) and their mixtures and 0 to 70 mol% of units of the formulas R'2SiO2 / 2 (Ic) and / or R'3SiO1 / 2 (Id) and their mixtures, (B) 1 to 200 parts by weight of one Metal compound of the formula R2 cMX4-c (II) or its partial hydrolyzates, optionally (C) 0 to 100 parts by weight of a silane of the formula R4 dSi (OR5) 4-d (III) and optionally (D) 0 to 100 Parts by weight of a silane of the formula R6 eSiZ4-e (IV) or their partial hydrolyzates of (C) and (D), where R ', R, R1, R2, R3, R4, R5 and R6 have the properties specified for this in claim 1 M is Ti or Zr, X is a halogen atom or -OR3 and c, d and e are each 0, 1, 2 or 3, with (E) water, optionally in the presence of (F) the hydrolysis and condensation promoting catalysts and / or (G) organic solvents with the proviso that (i) the amount of water is always chosen so that it is substoichiometric, based on the amount of all hydrolyzable metal and Si-bonded hydrolyzable groups present, (ii) at least one ≡MO-Si≡ bond is present, (iii) at least 1% by weight of metal-free silicone resin is contained, and (iv) the compositions have a viscosity of 5 to 5000000 mPa · s at 25 ° C and (v) and, if appropriate, an addition of (A2) after the hydrolysis and condensation Silicone resins are made.

Description

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

Metal-silicone resin compositions, also referred to below as metallo-siloxane composite materials, which contain both metal-O-Si bonds and those which are physical blends of polymetalloxanes and polysiloxanes are known. For this example, on Walter Noll, Chemistry and Technology of Silicones, 1968, Chapter 7.1 Heterosiloxanes, pp. 332-347 , referenced.

Physical blends of, in particular, organo-organic compounds with polyorganosiloxanes which include silicone resins are known, for example, in the context of the catalyzed chemical crosslinking of polyorganosiloxanes. Exemplarily 100 (Wacker Chemie AG) in 2001, reference is made here to the technical data sheet to SILRES ^® MSE. In addition, please refer to the product brochure DuPont ^TM Tyzor ^® from 2008, where systems are mentioned type RTV-1 by the addition of organic titanates to silicone elastomers curable Titano-siloxane composite.

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 method for producing hard, scratch-resistant coatings by coating and curing a lacquer on a substrate, wherein the lacquer is obtained 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 having alkyl groups or olefinically unsaturated alkenyl groups, which may be functionalized if necessary, and optionally a soluble in the reaction medium non-volatile oxide of an element of main groups Ia to Va or subgroups IVb or Vb, with the exception of titanium and zirconium, or optionally, a soluble non-volatile oxide-forming compound in the reaction medium of an element of main groups Ia to Va or subgroups IVb or Vb, except for titanium and zirconium, using a quantity of water smaller than that is as the complete one Hydrolysis of all hydrolyzable groups required amount of water. In a second step, a complementary condensation is carried out with at least that amount of water which is necessary for complete hydrolysis of all remaining hydrolyzable groups. 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 the styrenizable groups. The result is a completely hydrolyzed product which precipitates in the course of the preparation of the coating composition so that transparent masses can only be obtained by filtration. The exact composition of the coating compositions is difficult to control due to the material losses due to the filtration step, so that the properties of the coatings obtained are scattered within the range of variation of the compositions. Aromatic groups are excluded as substituents on the silane.

DE 34 40 652 A1 claims a process for the preparation of optical molded articles, which is characterized in that polytitanosiloxanes, as described in DE 34 07 087 have been used for the production of scratch-resistant coatings are used, wherein in DE 34 40 652 A1 the scope of approved for the preparation of hydrolytic precondensates silanes was extended to DE 34 07 087, so that here also allowed aromatic substituted silanes for the preparation of the hydrolytic precondensates are. 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 are processed into optical shaped articles in a suitable process.

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 amount of water necessary for the hydrolysis and condensation of all present in the mixture alkoxy groups at low temperatures of down to -100 ° C and subsequent reaction with at least one triorganosilane carrying a hydroxy group or an acyloxy group 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. The addition of the triorganosilane causes unused alkoxy groups to react and stabilize the product against continued condensation and associated gelling. In this case, up to five times more triorganosilane is added than are left over to alkoxy groups after the hydrolysis and condensation of the tetraalkoxytitanate with the tetraalkoxysilicate. The polytitanosiloxanes thus obtained are not self-crosslinking. Due to the low temperatures required, the process is not suitable for use on an industrial scale and is therefore uneconomical.

U.S. 5,596,060 claims curable preparations which comply with the in EP 669 362 B1 described vinyl functional polytitanosiloxanes, as well as Si-H-functional polyorganosiloxanes, a platinum catalyst for the hydrosilylation and an organic peroxide as a 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 a process for producing a polyorganosiloxane resin composition obtained in a two-step process. The composition serves as an abrasion-resistant coating material for organic glasses. In the first step, if appropriate, organically substituted alkoxysilanes or silane mixtures are hydrolyzed with a stoichiometric amount of water, based on the hydrolyzable groups, until the water used for this is almost completely consumed. By silane mixtures is meant, in particular, those comprising an epoxy silane. This practically anhydrous silane hydrolyzate obtained from the first step, which takes several hours to form, 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 with further water Reaction so that forms a titanium-siloxane copolymer without causing precipitation. 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, organic acid is formed during the synthesis, which is difficult to separate. Since the resulting alkoxy- and acyl-functional titanium-modified silicone resins can condense in an acid-catalyzed manner, this leads to 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 significantly reduced that they react with the alkoxysilane hydrolyzates without precipitation from titanions from the homocondensation of titanium compounds. This is bought by the disadvantage of the extremely limited selection of raw materials. In avoiding possible precipitation from titanic ions, the acidic environment, which leads to a charge-induced stabilization of titanium oxide particles, an effect that is used in the production of titanium dioxide nanoparticles, is also likely to play a role.

EP 023 096 B1 claims organometallic copolymers of polycarbosilanes and metallosiloxanes. The copolymers described serve as raw materials for the production of shaped bodies of inorganic carbide. They are composed of a polycarbosilane moiety having a Si-CH ₂ skeleton and a metallosiloxane moiety 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.

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

WO 2012/078617 A1 teaches preparations of low molecular weight alkenyl-functional siloxane components with organohydrogensiloxanes containing 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 formulations serve as encapsulant material for high refractive index semiconductor devices.

US 8,258,636 B1 (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, the compositions of this invention being obtained by a process comprising reacting an organotitanate in the presence of a first stage alkoxysilane precursor in an aprotic solvent In situ generated phenoxyphenolsubstituierten polyorganosiloxane is condensed to domains. The phenoxyphenylgruppenden bearing siloxane units are always D units and make up the largest proportion of polyorganosiloxanes according to the invention, which thereby 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 are overcome and this is significantly further developed. The object is achieved by the invention.

• (A) 100 Gew.-teilen eines Siliconharzes aus 30 bis 100 Mol.-%, vorzugsweise 50 bis 100 Mol.-%, bevorzugt 80 bis 100 Mol.-%, Einheiten ausgewählt aus der Gruppe von Einheiten der Formeln R'SiO_3/2 (Ia) und SiO_4/2 (Ib) und deren Mischungen und 0 bis 70 Mol.-%, vorzugsweise 0 bis 50 Mol.-%, bevorzugt 0 bis 20 Mol.-%, Einheiten ausgewählt aus der Gruppe von Einheiten der Formeln R'₂SiO_2/2 (Ic) und R'₃SiO_1/2 (Id) und deren Mischungen, wobei R' gleich oder verschieden sein kann und einen Rest R oder einen Rest der Formel -OR¹ bedeutet, mit der Maßgabe, dass mindestens 3 Mol.-%, vorzugsweise mindestens 5 Mol.-%, bevorzugt mindestens 7 Mol.-%, von allen Resten R' Reste der Formel -OR¹ sind, R gleich oder verschieden sein kann und einen einwertigen gegebenenfalls substituierten Kohlenwasserstoffrest mit 1 bis 18 Kohlenstoffatomen oder ein Wasserstoffatom bedeutet und R¹ gleich oder verschieden sein kann und ein Wasserstoffatom oder einen einwertigen gegebenenfalls substituierten Kohlenwasserstoffrest mit 1 bis 18 Kohlenstoffatomen bedeutet,
• (B) 1 bis 200 Gew.-teile, bezogen auf 100 Gew.-teile Siliconharz (A), einer Metallverbindung der Formel R² _cMX_4-c (II), oder deren Teilhydrolysate, wobei c 0, 1, 2 oder 3, vorzugsweise 0 oder 1, bevorzugt 0, ist, M Titan oder Zirkonium, vorzugsweise Titan in der Oxidationsstufe +IV, ist, X ein Halogenatom, vorzugsweise ein Chloratom, oder ein Rest -OR³ ist, R² unabhängig von R die gleiche Bedeutung wie R hat und R³ unabhängig von R¹ die gleiche Bedeutung wie R¹ hat, ggf.
• (C) 0 bis 100 Gew.-teile, bezogen auf 100 Gew.-teile Siliconharz (A), eines Silans der Formel R⁴ _dSi(OR⁵)_4-d (III) oder deren Teilhydrolysate, mit der Maßgabe, dass die Teilhydrolysate verschieden von Siliconharz (A) sind und mindestens 3 Mol.-%, vorzugsweise mindestens 5 Mol.-%, bevorzugt mindestens 10 Mol.-%, und vorzugsweise höchstens 85 Mol.-%, bezogen auf alle Si-gebundenen Reste, C₁-C₁₂-Alkoxyreste oder Hydroxyreste sind, wobei R⁴ gleich oder verschieden sein kann und einen einwertigen gegebenenfalls substituierten Kohlenwasserstoffrest mit 1 bis 18 Kohlenstoffatomen oder ein Wasserstoffatom bedeutet, R⁵ unabhängig von R¹ die gleiche Bedeutung wie R¹ hat, d 0, 1, 2 oder 3, vorzugsweise 0, 1 oder 2, bevorzugt 1 ist, und ggf.
• (D) 0 bis 100 Gew.-teile, bezogen auf 100 Gew.-teile Siliconharz (A), eines Silans der Formel R⁶ _eSiZ_4-e (IV) oder deren Teilhydrolysate, wobei Z ein Halogenatom, vorzugsweise ein Chloratom, ist, R⁶ gleich oder verschieden sein kann und einen einwertigen gegebenenfalls substituierten Kohlenwasserstoffrest mit 1 bis 18 Kohlenstoffatomen oder ein Wasserstoffatom bedeutet, e 0, 1, 2 oder 3, vorzugsweise 0, 1 oder 2, bevorzugt 0 oder 1, besonders bevorzugt 1, ist, mit
• (E) Wasser, ggf. in Gegenwart von
• (F) die Hydrolyse und Kondensation fördernden Katalysatoren, vorzugsweise Säuren, und ggf. in Gegenwart von
• (G) organischen Lösungsmitteln mit der Maßgabe, dass (i) die Wassermenge stets so gewählt wird, dass sie, bezogen auf die Menge aller vorhandenen metall- und siliziumgebundenen hydrolysierbaren Gruppen, unterstöchiometrisch ist und vorzugsweise nicht mehr als 80 Mol.-%, bevorzugt nicht mehr als 75 Mol.-%, der zur vollständigen Hydrolyse aller vorhandenen hydrolysierbaren Gruppen benötigten Wassermenge beträgt, (ii) dass die Metall-Siliconharz-Zusammensetzungen mindestens eine ≡M-O-Si≡ Bindung (M bedeutet Ti oder Zr), vorzugsweise ≡Ti-O-Si≡ Bindung, aufweisen, (iii) dass die Zusammensetzungen (A1) mindestens 1 Gew.-%, vorzugsweise mindestens 5 Gew.-%, bevorzugt mindestens 10 Gew.-%, und vorzugsweise höchstens 90 Gew.-%, bezogen auf die Zusammensetzungen, metallfreies Siliconharz (A) oder metallfreie Kondensate ausgewählt aus der Gruppe der Komponente (A), (C) und (D) oder deren Mischungen enthalten, und (iv) dass die Zusammensetzungen eine Viskosität von 5 bis 5000000 mPa·s, bevorzugt 10 bis 1000000 mPa·s, jeweils bei 25°C und Normaldruck von 1013 hPa, aufweisen, (v) und ggf. anschließend an die Hydrolyse und Kondensation eine Zugabe von (A2) Siliconharzen, die von Siliconharz (A) verschieden sind und eine Viskosität von 5 bis 5000000 mPa·s, bevorzugt 10 bis 1000000 mPa·s, jeweils bei 25°C und Normaldruck von 1013 hPa, aufweisen, erfolgt.

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 the formulas R'SiO _{3 / 2} (Ia) and SiO _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 of units of the formulas R ' ₂ SiO _2/2 (Ic) and R' ₃ SiO _1/2 (Id) and mixtures thereof, where R 'may be identical or different and is a radical R or a radical of the formula -OR ¹ , with 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 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 hydrogen atom or a monovalent optionally substituted Ko hydrocarbon radical having 1 to 18 carbon atoms,
• (B) 1 to 200 parts by weight based on 100 parts by weight of 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, preferably 0 or 1, preferably 0, M is titanium or zirconium, preferably titanium in the oxidation state + IV, X is a halogen atom, preferably a chlorine atom, or a radical -OR ³ , R ^{2 has} the same meaning as R irrespective 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 of silicone resin (A), of a silane of the formula R ⁴ _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%, 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 radicals or hydroxy radicals, where R ^{4 may be} identical or different and is a monovalent optionally substituted hydrocarbon radical having 1 to 18 carbon atoms or a hydrogen atom, R ^{5 is} independent of R ¹ has the same meaning as R ¹ , d is 0, 1, 2 or 3, preferably 0, 1 or 2, preferably 1, and optionally
• (D) 0 to 100 parts by weight, based on 100 parts by weight of silicone resin (A), of a silane of the formula R ⁶ _e SiZ _4-e (IV) or their partial hydrolysates, wherein Z is a halogen atom, preferably a chlorine atom, R ^{6 may be} identical or different and represents 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, is, with
• (E) water, if necessary in the presence of
• (F) the hydrolysis and condensation promoting catalysts, preferably acids, and optionally 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%, which is the amount of water required for the complete hydrolysis of all hydrolyzable groups present, (ii) the metal-silicone resin compositions have at least one ≡MO-Si≡ bond (M is Ti or Zr), preferably ≡Ti (Iii) that the compositions (A1) have at least 1% by weight, preferably at least 5% by weight, preferably at least 10% by weight, and preferably at most 90% by weight, 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) the compositions have a viscosity of 5 to 5,000,000 m Pa · 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, the silicone resin (A ) are different and have a viscosity of 5 to 5,000,000 mPa · s, preferably 10 to 1,000,000 mPa · s, in each case at 25 ° C and atmospheric pressure of 1013 hPa, takes place.

• (A) 100 Gew.-teile eines Siliconharzes aus 30 bis 100 Mol.-%, vorzugsweise 50 bis 100 Mol.-%, bevorzugt 80 bis 100 Mol.-%, Einheiten ausgewählt aus der Gruppe von Einheiten der Formeln R'SiO_3/2 (Ia) und SiO_4/2 (Ib) und deren Mischungen und 0 bis 70 Mol.-%, vorzugsweise 0 bis 50 Mol.-%, bevorzugt 0 bis 20 Mol.-%, Einheiten ausgewählt aus der Gruppe von Einheiten der Formeln R'₂SiO_2/2 (Ic) und R'₃SiO_1/2 (Id) und deren Mischungen, wobei R' gleich oder verschieden sein kann und einen Rest R oder einen Rest der Formel -OR¹ bedeutet, mit der Maßgabe, dass mindestens 3 Mol.-%, vorzugsweise mindestens 5 Mol.-%, bevorzugt mindestens 7 Mol.-%, von allen Resten R' Reste der Formel -OR¹ sind, R gleich oder verschieden sein kann und einen einwertigen gegebenenfalls substituierten Kohlenwasserstoffrest mit 1 bis 18 Kohlenstoffatomen oder ein Wasserstoffatom bedeutet und R¹ gleich oder verschieden sein kann und ein Wasserstoffatom oder einen einwertigen gegebenenfalls substituierten Kohlenwasserstoffrest mit 1 bis 18 Kohlenstoffatomen bedeutet,
• (B) 1 bis 200 Gew.-teile, bezogen auf 100 Gew.-teile Siliconharz (A), einer Metallverbindung der Formel R² _cMX_4-c (II), oder deren Teilhydrolysate, wobei c 0, 1, 2 oder 3, vorzugsweise 0 oder 1, bevorzugt 0, ist, M Titan oder Zirkonium, vorzugsweise Titan in der Oxidationsstufe +IV, ist, X ein Halogenatom, vorzugsweise ein Chloratom, oder ein Rest -OR³ ist, R² unabhängig von R die gleiche Bedeutung wie R hat und R³ unabhängig von R¹ die gleiche Bedeutung wie R¹ hat, ggf.
• (C) 0 bis 100 Gew.-teile, bezogen auf 100 Gew.-teile Siliconharz (A), eines Silans der Formel R⁴ _dSi(OR⁵)_4-d (III) oder deren Teilhydrolysate, mit der Maßgabe, dass die Teilhydrolysate verschieden von Siliconharz (A) sind und mindestens 3 Mol.-%, vorzugsweise mindestens 5 Mol.-%, bevorzugt mindestens 10 Mol.-%, und vorzugsweise höchstens 85 Mol.-%, bezogen auf alle Si-gebundenen Reste, C₁-C₁₂-Alkoxyreste oder Hydroxyreste sind, wobei R⁴ gleich oder verschieden sein kann und einen einwertigen gegebenenfalls substituierten Kohlenwasserstoffrest mit 1 bis 18 Kohlenstoffatomen oder ein Wasserstoffatom bedeutet, R⁵ unabhängig von R¹ die gleiche Bedeutung wie R¹ hat, d 0, 1, 2 oder 3, vorzugsweise 0, 1 oder 2, bevorzugt 1 ist, und ggf.
• (D) 0 bis 100 Gew.-teile, bezogen auf 100 Gew.-teile Siliconharz (A), eines Silans der Formel R⁶ _eSiZ_4-e (IV) oder deren Teilhydrolysate, wobei Z ein Halogenatom, vorzugsweise ein Chloratom, ist, R⁶ gleich oder verschieden sein kann und einen einwertigen gegebenenfalls substituierten Kohlenwasserstoffrest mit 1 bis 18 Kohlenstoffatomen oder ein Wasserstoffatom bedeutet, e 0, 1, 2 oder 3, vorzugsweise 0, 1 oder 2, bevorzugt 0 oder 1, besonders bevorzugt 1, ist, mit
• (E) Wasser, ggf. in Gegenwart von
• (F) die Hydrolyse und Kondensation fördernden Katalysatoren, vorzugsweise Säuren, und ggf. in Gegenwart von
• (G) organischen Lösungsmitteln mit der Maßgabe, dass (i) die Wassermenge stets so gewählt wird, dass sie, bezogen auf die Menge aller vorhandenen metall- und siliziumgebundenen hydrolysierbaren Gruppen, unterstöchiometrisch ist und vorzugsweise nicht mehr als 80 Mol.-%, bevorzugt nicht mehr als 75 Mol.-%, der zur vollständigen Hydrolyse aller vorhandenen hydrolysierbaren Gruppen benötigten Wassermenge beträgt, (ii) dass die Metall-Siliconharz-Zusammensetzungen mindestens eine ≡M-O-Si≡ Bindung (M bedeutet Ti oder Zr), vorzugsweise ≡Ti-O-Si≡ Bindung, aufweisen, (iii) dass die Zusammensetzungen (A1) mindestens 1 Gew.-%, vorzugsweise mindestens 5 Gew.-%, bevorzugt mindestens 10 Gew.-%, und vorzugsweise höchstens 90 Gew.-%, bezogen auf die Zusammensetzungen, metallfreies Siliconharz (A) oder metallfreie Kondensate ausgewählt aus der Gruppe der Komponente (A), (C) und (D) oder deren Mischungen enthalten, und (iv) dass die Zusammensetzungen eine Viskosität von 5 bis 5000000 mPa·s, bevorzugt 10 bis 1000000 mPa·s, jeweils bei 25°C und Normaldruck von 1013 hPa, aufweisen, (v) und ggf. anschließend an die Hydrolyse und Kondensation eine Zugabe von (A2) Siliconharzen, die von Siliconharz (A) verschieden sind und eine Viskosität von 5 bis 5000000 mPa·s, bevorzugt 10 bis 1000000 mPa·s, jeweils bei 25°C und Normaldruck von 1013 hPa, aufweisen, erfolgt.

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 the formulas R'SiO _{3 / 2} (Ia) and SiO _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 of units of the formulas R ' ₂ SiO _2/2 (Ic) and R' ₃ SiO _1/2 (Id) and mixtures thereof, where R 'may be identical or different and is a radical R or a radical of the formula -OR ¹ , with 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 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 hydrogen atom or a monovalent optionally substituted Koh means hydrogen radical having 1 to 18 carbon atoms,
• (B) 1 to 200 parts by weight based on 100 parts by weight of 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, preferably 0 or 1, preferably 0, M is titanium or zirconium, preferably titanium in the oxidation state + IV, X is a halogen atom, preferably a chlorine atom, or a radical -OR ³ , R ^{2 has} the same meaning as R irrespective 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 of silicone resin (A), of a silane of the formula R ⁴ _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%, 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 radicals or hydroxy radicals, where R ^{4 may be} identical or different and is a monovalent optionally substituted hydrocarbon radical having 1 to 18 carbon atoms or a hydrogen atom, R ^{5 is} independent of R ¹ has the same meaning as R ¹ , d is 0, 1, 2 or 3, preferably 0, 1 or 2, preferably 1, and optionally
• (D) 0 to 100 parts by weight, based on 100 parts by weight of silicone resin (A), of a silane of the formula R ⁶ _e SiZ _4-e (IV) or their partial hydrolysates, wherein Z is a halogen atom, preferably a chlorine atom, R ^{6 may be} identical or different and represents 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, is, with
• (E) water, if necessary in the presence of
• (F) the hydrolysis and condensation promoting catalysts, preferably acids, and optionally 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%, which is the amount of water required for the complete hydrolysis of all hydrolyzable groups present, (ii) the metal-silicone resin compositions have at least one ≡MO-Si≡ bond (M is Ti or Zr), preferably ≡Ti (Iii) that the compositions (A1) have at least 1% by weight, preferably at least 5% by weight, preferably at least 10% by weight, and preferably at most 90% by weight, 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) the compositions have a viscosity of 5 to 5,000,000 m Pa · 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, the silicone resin (A ) are different and have a viscosity of 5 to 5,000,000 mPa · s, preferably 10 to 1,000,000 mPa · s, in each case at 25 ° C and atmospheric pressure of 1013 hPa, takes place.

The crosslinkable metal-silicone resin compositions of the invention are liquid at atmospheric pressure of 1013 hPa and room temperature of 25 ° C.

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 constant dosing, 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 preferably no temperatures below 0 ° C, preferably below 5 ° C are set, so there are no low-temperature steps are used.

• (1) Vorlegen des Siliconharzes (A)
• (2) Zugabe der Metallverbindung (B) ggf. (3) Zugabe der Silane (C) oder (D) oder der Silane (C) und (D) oder der Teilhydrolysate von Silan (C) oder (D) oder der Teilhydrolysate von Silan (C) und (D), wobei die Zugabe gemäß Schritt (3) auch nach Schritt (4) erfolgen kann,
• (4) Zugabe von Wasser (E) oder einer wässrigen Lösung eines Katalysators (F) oder einer Mischung von Wasser (E) und organischen Lösungsmitteln (G) zur Reaktionsmischung, wobei die Reaktionsmischung während der Zugabe von Wasser (E) oder einer wässrigen Lösung eines Katalysators (F) oder einer Mischung von Wasser (E) und organischen Lösungsmitteln (G) eine Temperatur von 0°C bis 90°C, bevorzugt 10°C bis 80°C, aufweist, ggf. (5) Filtration der Reaktionsmischung und
• (6) Entflüchtigen der Reaktionsmischung.

Liquid crosslinkable metal-silicone resin compositions according to the invention are preferably those which can be prepared by hydrolysis and condensation, comprising at least the following steps, which are carried out in this order:

• (1) Presentation of silicone resin (A)
• (2) adding the 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.

• (1) Vorlegen des Siliconharzes (A)
• (2) Zugabe der Metallverbindung (B) ggf. (3) Zugabe der Silane (C) oder (D) oder der Silane (C) und (D) oder der Teilhydrolysate von Silan (C) oder (D) oder der Teilhydrolysate von Silan (C) und (D), wobei die Zugabe gemäß Schritt (3) auch nach Schritt (4) erfolgen kann,
• (4) Zugabe von Wasser (E) oder einer wässrigen Lösung eines Katalysators (F) oder einer Mischung von Wasser (E) und organischen Lösungsmitteln (G) zur Reaktionsmischung, wobei die Reaktionsmischung während der Zugabe von Wasser (E) oder einer wässrigen Lösung eines Katalysators (F) oder einer Mischung von Wasser (E) und organischen Lösungsmitteln (G) eine Temperatur von 0°C bis 90°C, bevorzugt 10°C bis 80°C, aufweist, ggf. (5) Filtration der Reaktionsmischung und
• (6) Entflüchtigen der Reaktionsmischung.

The process of the present invention for preparing the liquid crosslinkable metal-silicone resin compositions is preferably that by hydrolysis and condensation containing at least the following steps, which are carried out in this order:

• (1) Presentation of silicone resin (A)
• (2) adding the 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.

Further steps can be added. If necessary, filtration of the reaction mixture prior to escape serves to remove slight turbidity. The addition of further reaction components, such as the optionally performed addition of the silanes (C) or (D) or their partial hydrolysates, is always carried out subsequently to the addition of the metal compound B, d. H. not that they must be made immediately thereafter, but not before the addition of the metal compound B to the silicone resin component A occurs and is 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, hexyl, such as n-hexyl, heptyl, such as n-heptyl, octyl, such as n-octyl and iso-octyl, such as 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 radicals, 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, the silicon-bonded hydridischen and to a Oxygen atom possesses 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 attached (spacer between the silicon atom and the functional group) and B is a linear, branched or cyclic hydrocarbon group, which may 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 ethylene oxide units may be present in a chain as well as terminal or attached to a cycloaliphatic structure, an optionally substituted Carboxylic acid or an optionally substituted carboxylic acid ester function, an optionally substituted carboxylic anhydride, an optionally substituted acrylate or methacrylate group, wherein the optionally present substituent on the acrylate or methacrylate group is a linear, branched or cyclic hydrocarbon radical, the optionally hydroxyl- or alkyloxy-terminated and in whose main chain non-adjacent carbon atoms can be replaced by oxygen atoms and the olefinically unsaturated groups or ethylene oxide units (oxirane, or epoxide) may comprise, 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 acid ester radical, wherein the radicals R may be independently different.

Radicals R are preferably unsubstituted hydrocarbon radicals having 1 to 18 carbon atoms. Preferred radicals R are the methyl, ethyl, n-propyl, n-octyl, isooctanoyl, tetradecyl, hexadecyl, octadecyl radical and the phenyl radical, the methyl and phenyl radical being 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 to C ₆ spacer, the C ₁ and C ₃ spacers being preferred. The spacer is a divalent linear hydrocarbon radical which is not interrupted by heteroatoms.

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

Radicals R ³ 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, isobutyl, 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 and iso-octyl, such as 2,2, 4-trimethylpentyl, nonyl, such as n-nonyl, decyl, such as n-decyl, dodecyl, such as n-dodecyl, tetradecyl, hexadecyl and octadecyl, such as n-octadecyl, cycloalkyl, 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 which is silicon-bonded has hydridic and protonic character to an oxygen atom.

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 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 and iso-octyl, such as the 2,2,4-trimethylpentyl 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 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.

Radicals R ⁶ 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 preferred.

As the catalysts (F) for promoting the hydrolysis and condensation, an acid or an acidic solid such as an acid filter aid may be used, with organic acids such as formic acid and acetic acid or inorganic acids such as nitric acid, hydrochloric acid and phosphoric acid being preferred , wherein also several different acids can be used, which are used either as a mixture or which are added successively 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) may be formed together with water by the hydrolysis of the halosilanes during the reaction and so 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 at all, in less Quantity at the beginning of the reac tion is added 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 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 optionally 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.

The metal-silicone resin compositions according to the invention contain at least one structural unit according to formula (V), R ⁷ ₃ MO-SiR ⁸ ₃ (V), where M = Ti or Zr, preferably M = Ti and which is incorporated into 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 be a radical of the type -O-Si≡, via which the structural element of the formula (V) is incorporated into 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-Si≡, via which the structural unit of the formula (V) in involved in the surrounding molecular structure.

• (A1) mindestens 1 Gew.-% eines metallfreien Siliconharzes vom Typ der Komponente (A) oder Kondensate aus der Kondensation der Komponente (A) mit sich selbst, oder mit (C) und/oder mit (D) oder aus der Kondensation von (C) mit sich selbst und/oder mit (D) oder aus der Kondensation von (D) mit sich selbst vorhanden und ggf. zusätzlich Siliconharze (A2) ausgewählt aus der Gruppe von
• (A2.1) mindestens 1 Gew.-%, bezogen auf das Gesamtgewicht der Metall-Siliconharz-Zusammensetzungen, eines weiteren metallfreien Polyorganosiloxans, das dadurch gekennzeichnet ist, dass es Siloxaneinheiten der Art R⁹SiO_3/2 und SiO_4/2, bevorzugt der Art R⁹SiO_3/2, enthält, wobei die Reste R⁹ unabhängig voneinander die Bedeutung von R' haben können und 60 mol-% bis 99 Mol.-% der Reste R⁹ eine SiC-gebundene monovalente Kohlenwasserstoffgruppe R bedeuten, vorzugsweise Phenyl- oder Methylreste bedeuten, und 1 mol-% bis 40 Mol.-% der Reste R⁹ siliziumgebundene Alkoxy- oder Hydroxygruppen -OR¹ bedeuten.
• (A2.2) mindestens 1 Gew.-%, bezogen auf das Gesamtgewicht der Metall-Siliconharz-Zusammensetzungen, eines weiteren metallfreien Polyorganosiloxans enthält, das dadurch gekennzeichnet ist, dass es Siloxaneinheiten der Art R¹⁰SiO_3/2 oder SiO_4/2 enthält, von denen diejenigen der Art R¹⁰SiO_3/2 bevorzugt sind, und zusätzlich solche der Art R₂ ¹¹SiO_2/2 enthält, wobei die Einheiten der Art R₂ ¹¹SiO_2/2 den molar größten Anteil an der Komponente A2.2 haben können, mit einem molaren Anteil von bis 95%, vorzugsweise bis zu 90%, insbesondere bis zu 80%, wobei die Reste R¹⁰ und R¹¹ die Bedeutung von R' haben und dies unabhängig voneinander, was insbesondere auch auf die Reste R¹¹ zutrifft, die am gleichen Si-Atom gebunden vorliegen, und 60 mol-% bis 99 Mol.-% der siliziumgebundenen Reste R¹⁰ und R¹¹ eine Si-C-gebundene monovalente Kohlenwasserstoffgruppe R bedeuten, vorzugsweise Phenyl- oder Methylreste bedeuten, und 1 mol-% bis 40 Mol.-% der Reste R¹⁰ und R¹¹ siliziumgebundene Alkoxy- oder Hydroxygruppen -OR¹ bedeuten.
• (A2.3) mindestens 1 Gew.-%, bezogen auf das Gesamtgewicht der Metall-Siliconharz-Zusammensetzungen, eines weiteren metallfreien Polyorganosiloxans, das dadurch gekennzeichnet ist, dass es Siloxaneinheiten der Art SiO_4/2 enthält.

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

• (A1) at least 1 wt .-% of a metal-free silicone resin of the 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 present and optionally additionally silicone resins (A2) selected from the group of
• (A2.1) at least 1% by weight, based on the total weight of the metal-silicone resin compositions, of a further metal-free polyorganosiloxane, which is characterized in that it comprises siloxane units of the type R ⁹ SiO _3/2 and SiO _4/2 , preferably of the type R ⁹ SiO _3/2 , wherein 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 denote an SiC-bonded monovalent hydrocarbon radical R, preferably phenyl or methyl radicals, and 1 mol% to 40 mol% of R ^{9 are} silicon-bonded alkoxy or hydroxy groups -OR ¹ .
• (A2.2) contains at least 1 wt .-%, based on the total weight of the metal-silicone resin compositions, of a further metal-free polyorganosiloxane, which is characterized in that it siloxane units of the type R ¹⁰ SiO _3/2 or SiO _4/2 of which those of the type R ¹⁰ SiO _{3/2 are} preferred, and in addition those of the type R ₂ ¹¹ SiO _2/2 contains, wherein the units of the type R ₂ ¹¹ SiO _2/2 the molar largest proportion of the component A2 .2, with a molar fraction of up to 95%, preferably up to 90%, in particular up to 80%, wherein the radicals R ¹⁰ and R ^{11 have} the meaning of R 'and this independently of one another, which is particularly the case R ¹¹ radicals which are bonded to the same Si atom and 60 mol% to 99 mol% of the silicon-bonded radicals R ¹⁰ and R ^{11 denote} 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 mean alkoxy or hydroxy groups -OR ¹ .
• (A2.3) at least 1 wt .-%, based on the total weight of the metal-silicone resin compositions, of a further metal-free polyorganosiloxane, which is characterized in that it contains siloxane units of the type SiO _4/2 .

Preferably, either polyorganosiloxanes of the type (A2.1) or (A2.2) are present as a component in the compositions according to the invention, particularly preferably those of the type (A2.1), and the sum of the components (A2.1), (A2. 2) and (A2.3) or mixtures thereof preferably make up at most 99% by weight, preferably at most 95% by weight, based on the total weight of the compositions according to 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 moldings, such as transparent moldings or films, both after crosslinking by drying and after curing, if appropriate using higher temperatures (heat curing). 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 the interests of better stirrability and to avoid local excess concentrations in the addition of water, it may be advantageous to use a solvent already 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 titanium or zirconium raw material selected as component B, so that the silicone solid resin (s) inevitably requires the addition of a suitable solvent for conversion into a liquid phase, the solvent is from the beginning used on. 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) can contain both T units (Ia) and Q units (Ib) as crosslinking components. 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). Care must be taken in the sense of a good film-forming property and curing to a hard solid that not less than 30 mol% of such T and / or Q units, of which the T units are preferred, are present since the Otherwise, solid or film-forming solids or films resulting from the curing of the compositions according to the invention have too pronounced elastomeric properties, which, in addition to insufficient hardness, leads to undesirable surface tackiness and thus to susceptibility to soiling.

If elastomeric properties are desired, they can be achieved by suitably mixing 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 metal-silicone resin compositions of the invention 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 (A2.2 ), because in this way better mechanical properties, in particular flexibility, can be set. 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 units (Id) can also contain R ¹ O units which can react by hydrolysis to form silanol functions in the course of the preparation of the compositions to be used according to the invention and can lead to a D, a T or a Q unit by condensation 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 T units in the silicone resins (A), from which, depending on the substitution pattern, T or Q units can be formed, depending on the degree of reaction, by hydrolysis and condensation. Based on 100 mol .-% of all silicon-bonded radicals are at least 3 mol% of the type -OR ¹ , preferably at least 5 mol%, more 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), at most one aromatic hydrocarbon radical R is bonded to the silicon atoms in the units of the formulas (Ic) and (Id). All other SiC-bonded radicals R in these units contain no aromatic groups. The radicals R in the units of the formulas (Id) are preferably not aromatic hydrocarbon radicals.

The silicone resins (A) have molecular weights in the range of 600 to 500,000 g / mol (weight average M _w ) having a polydispersity of at most 15, preferably 600 to 300,000 g / mol in weight average with a polydispersity of at most 12, particularly preferably 600 to 80,000 g / moles by weight with a maximum polydispersity of 10. The silicone resins (A) may be low viscosity and liquid or viscous to highly viscous at 25 ° C and atmospheric pressure (1013 hPa) or solids with softening points of more than 25 ° C, preferably from greater than 30 ° C, more preferably greater than 35 ° C, in particular greater than 40 ° C. The liquid silicone resins (A) have viscosities of from 5 mPas to 5000000 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 to 75,000 mPas at 25 ° C, with alkoxy-rich low-viscosity methyl phenyl silicone resin oligomers, pure Methylsiliconharzoligomere or pure Phenylsiliconharzoligomere having a viscosity between 100 and 10,000 mPas at 25 ° C have been found to be particularly suitable, and all information on the 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, Methylphenylfestharze having an alkoxy content between 1 and 10 wt .-%, preferably on average 2-6 wt .-%, and in addition a silanol content between 1 and 10 wt .-%, preferably on average 2-6 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 of Wacker Chemie AG comprise 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 ^®, but are not limited to these.

Preferred silicone resins (A) or formulations thereof in the context of the present invention are alkoxy-functional and / or hydroxy-functional silicone resins, in particular alkoxy-functional. These preferred alkoxy- and / or hydroxy-functional silicone resins, of which the alkoxy functional groups are particularly preferred, particularly preferably contain 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, in addition to alkoxy and / or hydroxyl functions, of which the alkoxy functions are preferred, as silicon-bonded radicals, it is also possible for exclusively phenyl radicals to be present. In order to achieve better compatibility with an optionally surrounding matrix, for example an organic polymer, a mixture of both methyl- and silicon-bonded phenyl groups proves to be advantageous. Conversely, it may be advantageous to set targeted incompatibility that only methyl or phenyl groups are used as silicon-bonded radicals. However, if the surrounding matrix is not an organic polymer but another silicone species, for example another silicone resin or a silicone elastomer, then the choice of methyl or phenyl substituents, depending on the substitution pattern of the matrix, can only be tolerated only be adjusted to methyl or only to phenyl radicals. 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 repeating units as specified above.

The silicone resin component (A) may optionally be a mixture of several silicone resins (A). Both preparations of several liquid silicone resins (A) and of liquid and solid silicone resins (A) can be used. The details of the state of aggregation relate in each case to 25 ° C. and 1013 hPa. In formulations of silicone resins (A), the preparation components do not necessarily have to be miscible with one another. 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), the solid phase may also be composed of one or more silicone resins containing units of the formulas (Ia) to (Id) be converted 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) in a liquid phase.

Examples of titanium and zirconium compounds (B) which can be used according to the invention are monomeric, oligomeric or polymeric tetraalkylorthometallates and tetraarylorthometallates, such as tetramethylorthometallate, tetraethylorthometallate, tetrapropylorthometallate, tetraisopropylorthometalate, tetra-n-butylorthometallate, and mixtures thereof, or the mixture from the mixing process, if necessary Alkoxy exchange reactions available mixed substituted tetraalkylorthometallates, as well as the oligomers and polymers obtainable therefrom by hydrolysis and condensation.

The titanium compounds are preferred. Examples of oligomers and polymers obtainable by hydrolysis and condensation are titanium tetrabutylate tetramer or titanium tetrabutylate polymer, which are commercially available from various suppliers, e.g. From DuPont in their DuPontTMTyzor ^{® range} .

Preferred are phenyl (trialkoxy) titanates, titanium tetrahalide, phenyltitanium trichloride, Titantetraalky- and Titantetraarylorthotitanate and titanium tetrachloride, more preferably Titantetraalkylorthotitanate and titanium tetrachloride, wherein in the titanium tetraalkyorthotitanates titanium tetramethylorthotitanate, Titantetraethylorthotitanat, Titantetraisopropylorthotitanat and titanium tetra-n-butylorthotitanat are particularly preferred. The list gives only examples and is not to be construed as limiting the invention.

The silanes (C) of the formula (III) are preferably used as silanes, in particular as alkoxysilanes.

Preferred examples of silanes (C) are phenyltrimethoxysilane, Phenyltriethyoxsilan, methyltrimethoxysilane, methyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, octadecylmethyldimethoxysilane, Octadecylmethyldiethoxysilan, iso-octyltriethoxysilane, 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 use anhydrolyzed silanes and / or oligomers of silanes according to formula (III) formed by hydrolysis and partial condensation. However, it is necessary that reactive groups are still present on these partial condensates, which are 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. It is known that silicon-bonded hydridic hydrogen can be easily split off, especially in the presence of titanates. Examples of partial oligomeric condensates are readily deduced from the above examples. In addition, oligomeric tetraethyl silicates may also be mentioned by way of example, low molecular weight alpha, omega silanol-functional polydimethylsiloxanes having up to 10 siloxane repeating units, it also being possible to use diphenyl units or phenylmethylsiloxane units instead of the dimethyl units, for example 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, which are not present as pure compounds but in admixture with higher and lower oligomers. Examples of hydride-containing representatives are tetramethyldisiloxane, 1,1,5,5-tetramethyl-3,3-diphenyl-trisiloxane, 1,1,3,5,5-pentamethyl-3-phenyl-trisiloxane 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, iso-octyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, methylphenyldichlorosilane, diphenyldichlorosilane, n-octyltrichlorosilane, tetrachlorosilane. In principle, however, it is also possible to use anhydrolyzed silanes and / or oligomers of silanes according to formula (IV) formed by hydrolysis and partial condensation. However, it is necessary that reactive groups are still present on these partial condensates, which are 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.

wobei insbesondere auch mehrere Titanatome über Sauerstoffatome zu Titanoxyclustern mit beispielsweise 4, 8, 16 oder mehr Titanatomen miteinander verbunden sein können. Diese Titanoxycluster können entweder durch Si-O-Gruppen unterbrochen sein oder sie sind von einer Hülle aus Organopolysiloxan umgeben. Für M = Zr würden diese Beispiele sinngemäß in gleicher Weise gelten.Examples of a structural unit according to formula (V) with M = Ti

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 denote monovalent hydrocarbon groups, preferably monovalent alkyl group or a monovalent aryl group, the alkyl groups being preferred over the aryl groups and the monovalent alkyl groups preferably being linear or branched monovalent alkyl groups. The radicals R ¹² and R ¹³ in the same molecule are always different from each other.

Examples of radicals R ¹² and R ¹³ are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 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 and iso-octyl, such as the 2,2,4-trimethylpentyl, nonyl 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 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.

"|" And "-" in the examples of formula (V) each represent a chemical bond in the surrounding molecular structure by which units of formula (V) are incorporated in the metallo-siloxane molecule. The next binding partner is in each case an oxygen atom, which is then further connected to an Si atom or a metal atom, that is to say 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:

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 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 and iso-octyl, such as the 2,2,4-trimethylpentyl 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 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, each directly, the is linked to the silicon atom via an Si-carbon bond or via a pig can be bound to the Si atom 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 phenyl. The radicals R ¹⁴ are in particular the methyl, the ethyl and the phenyl radical, the phenyl radical preferably being direct bonded via a Si-C bond to the silicon atom to the methyl radical, which may be both directly Si-C bonded and Si-OC may be linked, and the ethyl radical, preferably via an oxygen atom, ie Si -OC-linked, these lists are not to be understood as limiting.

As concrete preferred examples of structural elements according to formula (V), the following structures are described above, wherein the oxygen atoms via which the structural elements are incorporated into the surrounding molecular structure are omitted here and supplemented as shown in formula (V.1) would be:

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 metallo-siloxane composite materials according to the invention. The pure metallosiloxane components tend to form mechanical defects such as cracks due to their brittleness in applications. 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 these do not reduce the high temperature stability of the metallo-siloxane composite materials. In order to obtain the binding power of the metallo-siloxane composites, the components A2.1, A2.2 and A2.3 are always 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 SiO _3/2 and SiO _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 result by hydrolysis and condensation are those which, in addition to the radical R ⁹ with the meaning of R, also contain silicon-bonded radicals of the type R ¹ O-including HO-. The detailed meaning of the radicals R 'or R and R ¹ is given above.

Component A2.2 contains units of the formula R ¹⁰ SiO _3/2 (where R ^{10 has} the meaning given above), as well as those of the type R ₂ ¹¹ SiO _2/2 , which exert a softening or flexibilizing effect, the Radicals R ¹¹ independently of one another may have the meaning of R '. Depending on how much flexibility and softness required by the respective application, up to 95 mol% of the units forming the component A2.2 can consist of such structural elements of the formula R ₂ ¹¹ SiO _2/2 .

Component A2.3 contains siloxane units of the type SiO _4/2 . In addition, A2.3 is only subject to the restrictions imposed by the target application. A high or exclusive proportion of SiO _4/2 units results in a highly cross-linked 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. SiO _4/2 units together with other silicone building blocks, for example the M units according to R ¹¹ ₃ SiO _1/2 , where the radicals R ¹¹ independently of one another may have the meaning of R '(= R or -OR ¹ ) form 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. If desired, component A2.3 can be made more flexible by incorporating R ¹¹ ₂ SiO _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 SiO _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 solid component A2.1, A2.2 or A2.3 is chosen, it must 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 preparations according to the invention can be caused by incompatibilities of individual components. Metallo-siloxane composite preparations in which predominantly or exclusively by excessive condensation of individual components to insoluble particulate solids with 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 according to the invention. 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 have to have a proportion of polyorganosiloxane which possesses silicone resin properties, ie contains crosslinking components, they also have the typical silicone properties. However, these properties are enhanced by the proportion of titanium or zirconium elements, which makes them even more effective for many applications that require these properties. Such properties include, for example, and in particular a high long-term resistance to weathering in the open air, to UV radiation, to numerous chemicals and to high heat.

Typical applications in which such properties are required are, for example, exterior coatings, corrosion resistant and high heat resistant corrosion protection coatings. Silicone resins also act as film-forming constituents in the coating applications mentioned, but also in personal care products and cosmetic preparations (see, for example, US Pat. EP 1 057 476 B1 ), where by these properties, for example an improved skin feel and more permanence is achieved. 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 important for the hydrophobization and also for the early water resistance of coatings and impregnations of mineral or wooden building materials. 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 do not contain titanium or zirconium silicone composite preparation.

Due to the film-forming properties of polyorganosiloxanes, the crosslinking temperatures of, for example, alkoxy- and / or hydroxy-functional silicone resins of typically above 150 ° C. can be lowered to significantly lower temperatures in some cases, in particular down to room temperature. This makes the use of silicone resins as binders, 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.

Because the metallo-siloxane composite materials can have refractive indexes beyond those of the pure silicone resins and can reach values above 1.5, and are also transparent, they are also particularly useful for optical or electro-optical applications such as the manufacture 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, it is preferable to use addition-crosslinking silicone systems comprising an 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, wherein the titanium component is likewise reactive toward silicon-bonded hydridic hydrogen, which must be taken into account in the formulation of appropriate systems if the route via hydrosilylation, ie addition-crosslinking systems, is to be followed.

• – Steuerung des elektrischen Leitfähigkeit und des elektrischen Widerstandes
• – Steuerung der Verlaufseigenschaften einer Zubereitung
• – Steuerung des Glanzes eines feuchten oder gehärteten Filmes oder eines Objektes
• – Erhöhung der Bewitterungsbeständigkeit
• – Erhöhung der Chemikalienresistenz
• – Erhöhung der Farbtonstabilität
• – Reduzierung der Kreidungsneigung
• – Reduzierung oder Erhöhung der Haft- und Gleitreibung auf Festkörpern oder Filmen erhalten aus Zubereitungen, eine erfindungsgemäße Composite Zubereitung enthaltend
• – Stabilisierung oder Destabilisierung von Schaum in der Zubereitung, die eine erfindungsgemäße Zubereitung enthält
• – Verbesserung der Haftung der Zubereitung die eine erfindungsgemäße Composite Zubereitung enthält zu Substraten auf oder zwischen die die Zubereitung die eine erfindungsgemäße Composite Zubereitung enthält, aufgetragen wird,
• – Steuerung des Füllstoffdispergierverhaltens und Pigmentnetz- und -dispergierverhaltens,
• – Steuerung der rheologischen Eigenschaften der Zubereitung, die eine erfindungsgemäße Composite Zubereitung enthält,
• – Steuerung der mechanischen Eigenschaften, wie z. B. Flexibilität, Kratzfestigkeit, Elastizität, Dehnbarkeit, Biegefähigkeit, Reißverhalten, Rückprallverhalten, Härte, Dichte, Weiterreißfestigkeit, Druckverformungsrest, Verhalten bei verschiedenen Temperaturen, Ausdehnungskoeffizient, Abriebfestigkeit sowie weiterer Eigenschaften wie der Wärmeleitfähigkeit, Brennbarkeit, Gasdurchlässigkeit, Beständigkeit gegen Wasserdampf, Heißluft, Chemikalien, Bewitterung und Strahlung, der Sterilisierbarkeit, von Festkörpern oder Filmen erhältlich aus Zubereitungen, eine erfindungsgemäße Composite Zubereitungen enthaltend,
• – Steuerung der elektrischen Eigenschaften, wie z. B. Durchschlagfestigkeit, Kriechstromfestigkeit, Lichtbogenbeständigkeit, Oberflächenwiderstand, spezifischer Durchschlagswiderstand,
• – Flexibilität, Kratzfestigkeit, Elastizität, Dehnbarkeit, Biegefähigkeit, Reißverhalten, Rückprallverhalten, Härte, Dichte, Weiterreißfestigkeit, Druckverformungsrest, Verhalten bei verschiedenen Temperaturen von Festkörpern oder Filmen erhältlich aus der Zubereitung die die erfindungsgemäßen Composite Zubereitungen enthalten.

In addition to the properties already outlined, the metallo-siloxane composite preparations according to the invention can also be used to manipulate further properties of preparations containing them or of solids or films obtained from preparations containing the metallo-siloxane composites according to the invention such as B .:

• - Control of electrical conductivity and electrical resistance
• - Control of the flow properties of a preparation
• Control the gloss of a wet or cured film or object
• - Increasing the weathering resistance
• - increase of chemical resistance
• - Increase of color stability
• - Reduction of the tendency to chalk
• Reduction or increase of static friction and sliding friction on solids or films obtained from preparations containing a composite preparation according to the invention
• Stabilization or destabilization of foam in the preparation containing a preparation according to the invention
• Improving the adhesion of the preparation containing a composite preparation according to the invention to substrates on or between which the preparation containing a composite preparation according to the invention is applied,
• Control of filler dispersion behavior and pigment wetting and dispersing behavior,
• Control of the rheological properties of the preparation containing a composite preparation according to the invention,
• - Control of mechanical properties, such. B. Flexibility, scratch resistance, elasticity, ductility, bending, tear, rebound, hardness, density, tear strength, compression set, behavior at different temperatures, expansion coefficient, abrasion resistance and other properties such as thermal conductivity, flammability, gas permeability, resistance to Water vapor, hot air, chemicals, weathering and radiation, the sterilizability, of solids or films obtainable from preparations containing a composite compositions according to the invention,
• - Control of electrical properties, such. B. 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 containing the composite preparations according to the invention.

Examples of applications in which the composite compositions according to the invention can be used to manipulate the abovementioned properties are the preparation of coating materials and impregnations and coatings and coatings to be obtained therefrom on substrates, such as metal, glass, wood, mineral substrate, plastic and natural fibers for the production of textiles, carpets, floor coverings, or other fiber-produced goods, leather, plastics such as films, moldings. The composite compositions according to the invention can also be used in formulations with appropriate selection of the preparation components as an additive for the purpose of defoaming, flow control, hydrophobing, hydrophilization, filler and pigment dispersion, filler and pigment wetting, substrate wetting, promotion of surface smoothness, reduction of adhesion and sliding resistance the surface of the hardened mass obtainable from the additized preparation can be used. 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 carried out according to publicly available standards or determined using specially developed methods. To ensure the clarity of the teaching taught, the methods used are given here:

Viscosity:

The viscosities are, unless otherwise indicated, by rotational viscometric measurement according to DIN EN ISO 3219 certainly. Unless otherwise stated, all viscosity data apply at 25 ° C and atmospheric pressure of 1013 mbar.

Refractive index:

The indices of refraction are determined in the wavelength range of visible light, unless otherwise stated at 589 nm at 25 ° C and normal pressure of 1013 mbar according to the Standard DIN 51423 ,

Transmission:

The transmission is determined by UV VIS spectroscopy. A suitable device is, for example, the Analytik Jena Specord 200. The measurement parameters used are Range: 190-1100 nm Increment: 0.2 nm, Integration time: 0.04 s, Measurement mode: Stepping. The first step is the reference measurement (background). A quartz plate attached to a sample holder (dimension of the quartz plates: H × W about 6 × 7 cm, thickness about 2.3 mm) is placed in the sample beam path and measured against air. Thereafter, the sample measurement takes place. A quartz plate attached to the sample holder with a sample applied - layer thickness applied to the 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.

Molecule compositions:

The molecular compositions are determined by nuclear magnetic resonance spectroscopy (for concepts, see ASTM E 386 : High resolution nuclear magnetic resonance (NMR): terms and symbols), measuring the 1H nucleus and the 29Si nucleus. Description ¹ H-NMR measurement Solvent: CDCl3, 99.8% d Sample concentration: about 50 mg / 1 ml CDCl3 in 5 mm NMR tubes Measurement without addition of TMS, spectral referencing of residual CHCl3 in CDCl3 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
• D1 = 5 s
• SFO1 = 500.13 MHz
• O1 = 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 NMR measurement Solvent: C6D6 99.8% d / CCl4 1: 1 v / v with 1 wt% Cr (acac) 3 as a relaxation reagent Sample concentration: about 2 g / 1.5 ml of solvent in 10 mm NMR tubes Spectrometer: Bruker Avance 300 Probe head: 10 mm 1H / 13C / 15N / 29Si glass-free QNP probe head (Bruker)

Measurement parameters:

• Pulprog = zgig60
• TD = 64k
• NS = 1024 (depending on the sensitivity of the probe head)
• SW = 200 ppm
• AQ = 2.75 s
• D1 = 4 s
• SFO1 = 300.13 MHz
• O1 = -50 ppm

Processing parameters:

• SI = 64k
• WDW = EM
• LB = 0.3 Hz

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

Molecular weight distributions:

Molecular weight distributions are determined as weight average M _w and as number average M _n , using the method of gel permeation chromatography (GPC or Size Exclusion Chromatography (SEC)) with polystyrene standard and refractive index detector (RI detector). Unless otherwise stated, THF is used as the eluent and DIN 55672-1 applied. The polydispersity is the quotient M _w / M _n .

Glass transition temperature:

The glass transition temperature is determined by Differential Scanning Calorimetry (DSC) 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 = C ₆ H ₅ -
Me means a methyl radical = CH ₃ -.
Me ₂ correspondingly means two methyl radicals.

• 1. ein Methylphenylsiliconharz MPSH mit einem Molekulargewichtsmittel Mw von 1800 g/mol (Zahlenmittel Mn = 900; Polydispersität 2,0) und einer Viskosität von 440 mm²/s, das 14,2 Gew.-% (entsprechend 43 mol-%) siliziumgebundene Methoxygruppen auf der Oberfläche trägt und das durchschnittlich aus 60 mol-% PhSiO_3/2-Einheiten, 36 Mol.-% MeSiO_3/2-Einheiten und 4 Mol.-% Me₂SiO_2/2-Einheiten besteht, wobei sich die Methoxygruppen auf die angegebenen Struktureinheiten verteilen.
• 2. ein Phenylsiliconharz PSH mit einem Molekulargewichtsmittel Mw von 900 g/mol (Zahlenmittel Mn = 500; Polydispersität 1,8) und einer Viskosität von 400 mm²/s, das 14,8 Gew.-% (entspricht 45 mol-%) siliziumgebundene Methoxygruppen auf der Oberfläche trägt und das aus 100 mol-% PhSiO_3/2-Einheiten besteht, wobei sich die Methoxygruppen auf die angegebenen Struktureinheiten verteilen.
• 3. ein Methylsiliconharz MSH mit einem Molekulargewichtsmittel Mw von 2100 g/mol (Zahlenmittel Mn = 1500; Polydispersität 1,5) und einer Viskosität von 250 mm²/s, das 31 Gew.-% (entspricht 86 mol-%) siliziumgebundene Methoxygruppen auf der Oberfläche trägt und das aus 100 mol-% MeSiO_3/2-Einheiten besteht, wobei sich die Methoxygruppen auf die angegebenen Struktureinheiten verteilen eingesetzt.

As component A the following are used in the examples:

• 1. a methyl phenyl silicone resin MPSH having a weight average molecular weight Mw of 1800 g / mol (number average Mn = 900, polydispersity 2.0) and a viscosity of 440 mm ² / s, which is 14.2% by weight (corresponding to 43 mol%) carrying silicon-bonded methoxy groups on the surface and consisting on average of 60 mol% PhSiO _3/2 units, 36 mol .-% MeSiO _3/2 units and 4 mol .-% Me ₂ SiO _2/2 units, wherein distribute the methoxy groups to 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% PhSiO _3/2 units, wherein the methoxy groups are distributed over the specified structural units.
• 3. a methyl silicone resin MSH having a molecular weight Mw of 2100 g / mol (number average Mn = 1500, polydispersity 1.5) and a viscosity of 250 mm ² / s containing 31 wt% (corresponding to 86 mol%) of silicon-bonded methoxy groups carries on the surface and which consists of 100 mol% MeSiO _3/2 units, wherein the methoxy groups used to distribute the structural units indicated.

Example 1:

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

50.33 g PSH are weighed into a 4 l three-neck 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 dropwise to the initial charge of titanium tetraisopropylate and PSH within 30 minutes. 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 is determined to be Mw = 1110 g / mol, the number average to Mn = 870 g / mol (polydispersity PD = 1.3). The product contains no Si-H bonds.

The product provides a clear transparent film on an aluminum sheet with a 100 μm doctor blade, which feels dry to the touch after a drying time of 6 hours (touch dry). The starting silicone resin does not show this behavior, it does not form a room temperature drying film even after several days. This is formed only after curing at temperatures of 230 ° C for at least 30 min. The product according to the invention prepared here was exposed to a temperature of 150 ° C. for 30 minutes and then already provided a solvent-solid cured coating and thus required significantly less curing energy than the silicone resin PSH itself.

The detection of Ti-O-Si bonds is clearly achieved using 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 widely used in the literature is unsuitable as a detection method because the characteristic bands of the Ti-O-Si structural unit overlap with other Si alkoxy bands, whereby the assignment of Ti-O-Si bands is arbitrary. The cationization agent used for the MALDI-TOF analysis is silver trifluoroacetate. 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 an appropriate ratio and measured after drying the mixture on a stainless steel target in reflectron mode. The mass spectrum obtained is isotope-resolved with an average mass resolution of 6000. The assignment of the molecular peaks is carried out by comparison of the measured with simulated peaks. In this way, it is possible to assign numerous Ti-O-Si-containing molecular peaks with a correspondence of more than 90% (in the table score score> 0.9), some of which are given here by way of example, in order to verify the existence of the compounds according to the invention Metallo-siloxane composite required to prove Ti-O-Si bridges. The organic radicals are methyl, phenyl, methoxy and isopropoxy. The molecular peaks are indicated as silver ion:

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:

Example 2:

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

402.64 g of MSH are weighed into a 4 L three-neck glass flask. 474.64 g of titanium tetraisopropoxide are allowed to run in at 23 ° C. from this dropping funnel over a period of 15 minutes. This increases the temperature in the glass flask from 23 ° C to 49 ° C. The mixture is stirred for 60 minutes while cooling to 23 ° C. In a dropping funnel 15.22 g of 20% aqueous hydrochloric acid solution are weighed. 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. Occurring at the dropping point occasionally 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 vacuum. This gives 682.9 g of a clear yellowish liquid. The viscosity is 800 mPas. The weight average is determined to be Mw = 1000 g / mol, the number average to 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 is stable even for months in a sealed container. 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 of silicon-bonded hydroxy groups and 85% by mole of MeSiO _3/2 units and 13 mol% of Me ₂ SiO _{2 / 2} units and to 2 mol% consists of Me ₃ SiO _1/2 units, wherein the ethoxy and the hydroxy groups are distributed over the specified structural units, and this preparation, which itself is also according to the invention, with a 100 microns Squeegee on an 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. It can be completely rubbed off with a cotton ball soaked in methyl ethyl ketone.

Example 3:

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

50.33 g of tetraethyl silicate oligomer (average of 7 repeat units, 40% SiO ₂ content after theoretical complete condensation) are weighed into a 4 l three-necked 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 22.1 ° C to 28.9 ° C. The mixture is stirred for 30 minutes while cooling to 26 ° C.

Thereafter, a mixture of 4.4 g of phenyltrichlorosilane and 4.4 g of phenyltriethoxysilane is added within 10 minutes from a 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 is added over 30 minutes and stirred at 50 ° C. for 30 minutes. The mixture is volatilized at 150 ° C and 20 mbar vacuum. This gives 89 g of a clear, colorless liquid with a viscosity of 432 mPas. The weight average is determined to be 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:

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

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. Thereafter, a mixture of 10.29 g phenyltrichlorosilane and 10.29 g of phenyltriethoxysilane is added within 10 minutes 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 a limited solvent-stable transparent dry film after 3 hours. Although the film cures under ambient conditions, the product is stable even for months in a sealed container. It hardens autocatalytically with atmospheric moisture.

Example 5:

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

201.32 g PSH are weighed into a 4 l three-neck glass flask. 237.32 g of titanium tetraisopropylate are allowed to run in from this dropping funnel over a period of 15 minutes at 22 ° C. to this initial charge. 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-1,3-divinyldisiloxane 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. 328 g of a yellowish, clear, colorless product are obtained. It is viscous with a viscosity of 6100 mPas. The weight average is determined to be 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 detection of Ti-O-Si bonds is clearly achieved by MALDI-TOF MS analysis as described in Example 1.

The product prepared here was added again with 12.5 g of 20% aqueous hydrochloric acid solution and heated to 160 ° C. 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, hardly flowable product which has a refractive index of 1.60. It is in solvents such. As toluene soluble. The index of refraction increases with increasing degree of condensation of the metallo-siloxane composites of the invention and allows values to be achieved over those of the starting silicone materials. This improves 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 now deviating from Example 2, 18.75 g of 20% strength 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 PSH from Example 5, it is attempted to prepare this in situ from phenyltriethoxysilane and to further react this in situ mixture with a tetraalkytitanate.

In a 4 l three-neck glass flask 50.33 g phenyltriethoxysilane are weighed and added to this template 18.75 g of 20% aqueous hydrochloric acid from a dropping funnel within 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 tetraisopropylate 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.

In a 4 l three-necked glass flask 50.33 g MPSH are weighed and added to this template 18.75 g of 20% aqueous hydrochloric acid and then 2.47 g of water from a dropping funnel in each case within 10 minutes. Then add 59.33 g of titanium tetraisopropylate from a dropping funnel within 10 minutes. 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. The mixture is heated slowly to reflux temperature of 80 ° C and stirred for 6 hours at this temperature. It is then distilled off, whereupon a transparent highly viscous product having a viscosity of 96,000 mPas is obtained, which discolors during storage after 4 weeks brownish. An elevator of this product of ethanol on an aluminum panel with a 100 micron spiral blade gives after curing at 150 ° C for 30 minutes, a likewise brown and brittle, brittle film.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• DE 3407087 [0005, 0006]
• DE 3440652 A1 [0006]
• EP 669362 B1 [0007, 0008]
• US 5596060 [0008]
• US 5357024 [0009]
• EP 429325 B1 [0009]
• EP 023096 B1 [0010]
• US 3846359A [0011]
• WO 2007/077130 A1 [0012]
• WO 2012/078617 A1 [0013]
• US 8258636 B1 [0014]
• DE 102012010203 A1 [0014]
• EP 1057476 B1 [0087]

Cited non-patent literature

• Walter Noll, Chemistry and Technology of Silicones, 1968, Chapter 7.1 Heterosiloxanes, pp. 332-347 [0002]
• DIN EN ISO 3219 [0094]
• Standard DIN 51423 [0095]
• ASTM E 386 [0097]
• DIN 55672-1 [0100]
• DIN 53765 [0101]

Claims (10)

Liquid crosslinkable metal-silicone resin compositions preparable by hydrolysis and condensation of (A) 100 parts by weight of a silicone resin of 30 to 100 mol .-% units selected from the group of units of the formulas R'SiO _3/2 (Ia) and SiO _4/2 (Ib) and mixtures thereof and 0 to 70 mol% of units selected from the group of units of the formulas R ' ₂ SiO _2/2 (Ic) and R' ₃ SiO _1/2 (Id) and their Mixtures, 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 .-% of all radicals R' are radicals of the formula -OR ¹ , R is the same or may be different and represents a monovalent optionally substituted hydrocarbon group having 1 to 18 carbon atoms or a hydrogen atom and R ^{1 may be the} same or different and represents a hydrogen atom or a monovalent optionally substituted hydrocarbon group having 1 to 18 carbon atoms, (B) 1 to 200 wt , parts, based on 100 parts by weight of 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 is titanium or zirconium, preferably titanium in the oxidation state + IV, X is a halogen atom, preferably a chlorine atom, or a radical -OR ³ , R ^{2 is} independent of R has the same meaning as R and R ^{3 has} the same meaning as R ¹ independently of R ¹ , optionally (C) 0 to 100 parts by weight, based on 100 parts by weight of silicone resin (A), of a silane of formula R ⁴ _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 radicals, C ₁ -C ₁₂ alkoxy radicals or hydroxy radicals, wherein R ^{4 is the} same or may be different and is a monovalent optionally substituted hydrocarbon radical having 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 optionally (D) 0 to 100 parts by weight, based on 100 parts by weight of silicone resin (A), of a silane of the formula R ⁶ _e SiX _4-e (IV) or their partial hydrolysates, wherein X is a halogen atom, preferably a chlorine atom, R ^{6 may be} identical 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, with E) water, optionally in the presence of (F) the hydrolysis and condensation promoting catalysts, preferably acids, and optionally in the presence of (G) organic solvents with the proviso that (i) the amount of water is always chosen so that they , 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 amount of water required for complete hydrolysis of all hydrolyzable groups present, ii) that the metal-silicone resin compositions at least one ≡MO-Si≡ bond (M is Ti or Zr), preferably ≡Ti-O-Si≡ Bindun g, have, (iii) that the compositions (A1) contain at least 1% by weight, based on the compositions, of the 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 from 5 to 5,000,000 mPa.s at 25 ° C and normal pressure of 1013 hPa, (v) and optionally subsequent to hydrolysis and condensation, addition of (A2) silicone resins derived from Silicone resin (A) are different and have a viscosity of 5 to 5000000 mPa · s at 25 ° C and atmospheric pressure of 1013 hPa, takes place. Liquid crosslinkable metal-silicone resin compositions according to claim 1 preparable by hydrolysis and condensation containing at least the following steps, which are carried out 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 being acidified upon addition of water (E) or an aqueous solution 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, optionally (5) filtration of the reaction mixture and (6) volatilizing the reaction mixture. A process for producing the liquid crosslinkable metal-silicone resin compositions of claim 1 by hydrolysis and condensation of (A) 100 parts by weight of a silicone resin of 30 to 100 mole% units selected from the group of units of the formulas R'SiO _{3 / 2} (Ia) and SiO _4/2 (Ib) and mixtures thereof and 0 to 70 mol% of units selected from the group of units of the formulas R ' ₂ SiO _2/2 (Ic) and R' ₃ SiO _{1 / 2} (Id) and mixtures thereof, where R 'may be identical or different and is 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 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 hydrogen atom or a monovalent optionally substituted hydrocarbon radical having 1 to 18 carbon (B) 1 to 200 parts by weight, based on 100 parts by weight of 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 is titanium or zirconium, preferably titanium in the oxidation state + IV, X is a halogen atom, preferably a chlorine atom, or a radical -OR ³ , R ^{2 is} independent of R has the same meaning as R and R ^{3 has} the same meaning as R ¹ independently of R ¹ , optionally (C) 0 to 100 parts by weight, based on 100 parts by weight of silicone resin (A), of a silane of formula R ⁴ _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 radicals, C ₁ -C ₁₂ alkoxy radicals or hydroxy radicals, wherein R ^{4 is the} same or may be 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, and optionally (D) 0 to 100 parts by weight, based on 100 parts by weight of silicone resin (A), of a silane of the formula R ⁶ _e SiZ _4-e (IV) or their partial hydrolysates, wherein Z is a halogen atom, preferably a chlorine atom, R ^{6 may be} identical 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, with E) water, optionally in the presence of (F) the hydrolysis and condensation promoting catalysts, preferably acids, and optionally in the presence of (G) organic solvents with the proviso that (i) the amount of water is always chosen so that they , 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 amount of water required for complete hydrolysis of all hydrolyzable groups present, ii) that the metal-silicone resin compositions at least one ≡MO-Si≡ bond (M is Ti or Zr), preferably ≡Ti-O-Si≡ Bindun g), (iii) the compositions (A1) comprise at least 1% by weight, based on the compositions, of the metal-free silicone resin (A) or of the metal-free condensates selected from the group consisting of components (A), (C) and (D) or mixtures thereof, and (iv) the compositions have a viscosity of from 5 to 5,000,000 mPa.s at 25 ° C. and normal pressure of 1013 hPa, (v) and optionally after the hydrolysis and condensation, an addition of (A2) Silicone resins, which are different from silicone resin (A) and have a viscosity of 5 to 5,000,000 mPa · s at 25 ° C and atmospheric pressure of 1013 hPa, takes place. Process for the preparation of the liquid crosslinkable metal-silicone resin compositions according to claim 3 by hydrolysis and condensation comprising at least the following steps, which are carried out 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), wherein the reaction mixture upon the 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, optionally (5) filtration of the reaction mixture and (6) volatilizing the reaction mixture. Moldings made by crosslinking the liquid crosslinkable metal-silicone resin compositions according to claim 1 or 2 or prepared according to claim 3 or 4. Shaped body prepared by allowing compositions 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 claim 5 to 7, characterized in that the shaped bodies or films have a refractive index of greater than or equal to 1.4 at 25 ° C at least one wavelength in the range of visible light, preferably at 589 nm. Use of the composition according to claim 1 or 2 or produced according to claim 3 or 4 as encapsulant and embedding compound of electrical or electronic components. Use of the compositions according to claim 1 or 2 or prepared according to claim 3 or 4 as potting or embedding masses of LEDs (light emitting devices).