DE19603242A1 - Functional carbosilane dendrimers, organic-inorganic carbosilane hybrid materials, in each case a process for their preparation, a process for the preparation of paints from the functional carbosilane dendrimers and their use - Google Patents

Description

The present invention relates to new functional carbosilane dendrimers, organic-inorganic carbosilane hybrid materials, in each case processes for their Manufacture, process for the production of paints from the functional Carbosilane dendrimers and their use.

Dendrimers are highly branched molecules with a highly ordered structure mostly three-dimensional structure, the molecular weight of which is in the range of that of oligo- or polymers.

However, dendrimers have the advantage that they have an exactly uniform molecular weight can be built up specifically, while the usual polymers always one show certain molecular weight distribution. In addition, certain are functional Dendrimers such as e.g. B. those with vinyl end groups, with a defined number such reactive groups can be produced.

The previously known carbosilane dendrimers are based on an initia gate core built up by alternating hydrosilylation and Grignard reaction (US-A-5,276,110, Adv. Mater. 1993, 5, 466-468, Macromolecules 1993, 26, 963- 968, J. Chem. Soc., Chem. Commun. 1994, 2575-2576 and Organometallics 1994, 13, 2682-2690). For example, the initiator molecule is tetravinylsilane in THF brought under reaction with Pt catalysis with HSiCl₂CH₃. By implementing with Vinyl magnesium halide is in turn a vinyl silane, which is again available for hydrosilylation.

However, it has so far been impossible to use a higher molecular weight carbosilane dendrimer to provide a defined number of functional end groups Si-OH.

However, Si-OH-functional carbosilane dendrimers enable a large number of Reactions such as B. the connection to metal connections, according to equation 1

with M = metal and X = alkyl, alkoxy, halogeno or hydrido
and are therefore of great interest. For example, the connection of catalytically active metal compounds, e.g. B. for their immobilization or the production of organic-inorganic hybrid materials, extremely important. It is already known from WO 94/06807 that organic-inorganic hybrid materials can be produced by reacting carbosilanes with trialkoxysilane groups with water and a catalyst or a carboxylic acid in a suitable solvent. By immersing suitable substrates in these solutions (dip coating), very thin, transparent films can be obtained without cracks. These carbosilane dendrimers with Si-O-alkyl end groups are slowly subject to hydrolysis in the presence of moisture. The reactivity of metal alkoxides towards hydrolysis and condensation is very different. Alkoxides of titanium, zirconium or aluminum react with water much faster than the corresponding silicon alkoxides. A co-condensation of the above-mentioned alkoxides is very difficult, since the reactive species react so quickly with water that they are often not embedded in a homogeneous network, but rather form precipitates from the corresponding metal (hydroxy) oxides. To prevent this, the concentration of water in the reaction solution must be as small as possible.

There was therefore a great need for Si-OH-functional carbosilane dendri mers that can be reacted with reactive metal alkoxides without the System must also contain water.

In addition, it is particularly sufficient for use as a paint raw material Storage stability of functional carbosilane dendrimers is desirable.

The object of the present invention was therefore to provide high moles kular functional carbosilane dendrimers that have a defined number of have terminal Si-OH groups, thus without the presence of water with metal alkoxides, such as. B. Ti (OR) ₄, Zr (OR) ₄, Al (OR) ₃ or Si (OR) ₄, too Carbosilane dendrimers with O-metal bonds can be implemented  in the hydrolysis with water the disadvantages described above Precipitation formation by metal (hydroxy) oxides do not have and form homogeneous networks. In addition, the carbosilane dendrimers should have unlimited storage stability. The connections should also be simple be producible.

Surprisingly, it has now been found that carbosilane dendrimers with terminal Si-OH residues which are stabilized with alkyl and / or aryl groups, meet these requirements.

The present invention therefore relates to functional carbosilane den drimere of the formula

R _4-i Si [(CH₂) _n SiX _a R _3-a ] _i (I)

with i = 3.4, preferably i = 4, n = 2-6, preferably n = 2 and R = alkyl and / or Aryl, where n can be the same or different within the molecule and where the other residues have the following meaning:

• a) X = OH with a = 1

or

• b) X = [(CH₂) _n Si (OH) R₂] with a = 1 to 3, preferably a = 3

or

• c) X = [(CH₂) _n SiR _3-a [(CH₂) _n Si (OH) R₂] _a ] with a = 1-3, preferably a = 3

or

• d) X = [(CH₂) _n SiR _3-a [(CH₂) _n SiR _3-a [(CH₂) _n Si (OH) R₂] _a ] _a ] with a = 1-3, preferably a = 3.

The alkyl radicals R in the sense of the invention are preferably linear or ver branched, optionally substituted C₁-C₅ alkyl radicals.

The term substituted in the sense of the invention includes all common Substituents such as B. halogen, alkyl, amine, etc.

The aryl radicals R in the sense of the invention are preferably optionally sub substituted C₆ rings.

Formulated, the carbosilane dendrimers according to the invention correspond to the Formulas (Ia-d)

R _4-i Si [(CH₂) _n Si (OH) R₂] _i or (Ia)

R _4-1 Si [(CH ₂ ) _n SiR _3-a [(CH ₂ ) _n Si (OH) R ₂ ] _a ] _i or (Ib)

R _4-i Si [(CH₂) _n SiR _3-a [(CH₂) _n SiR _3-a [(CH₂) _n Si (OH) R₂] _a ] _a ] _i or (Ic)

R _4-i Si [(CH₂) _n SiR _3-a [(CH₂) _n SiR _3-a [(CH₂) _n SiR _3-a [(CH₂) _n Si (OH) R₂] _a ] _a ] _a ] _i (Id).

In a preferred embodiment of the present invention, the values are of indices n within the molecule.

Carbosilane dendrimers of the formulas are particularly preferred

Si [(CH₂) ₂Si (OH) Me₂] ₄, Si [(CH₂) ₂Si (CH₂) ₂Si (OH) Me₂] ₃] ₄ or

Si [(CH₂) ₃Si (OH) Me₂] ₄.

Also noteworthy is the excellent storage stability of the invention according carbosilane dendrimers. The colorless powders can also be wet Air is kept unchanged for months. In contrast to already known carbosilane dendrimers with functional end groups, such as. B. Si Vinyl, Si-O-alkyl or Si-Cl is only available for the new carbosilane dendrimers effective cleaning step is available, which in contrast to chromatographic methods can also be carried out on an industrial scale.  

Outstandingly fine and therefore uniform carbosilane dendrimers can be found in large quantities are made available. From these Si-OH functional Carbosilane dendrimers are present in the presence of metal alkoxides of a catalyst carbosilane dendrimers with O-metal bonds available. In addition, it was found that after hydrolysis with water and Crosslinking by condensation via a sol-gel process organic-inorganic Hybrid materials with outstanding properties result. Find this Use as a varnish for the transparent coating of surfaces. Especially mention should be made of the high scratch resistance combined with flexibility, Transparency, good thermal stability and chemical resistance.

The present invention also relates to a method for the production the carbosilane dendrimers according to formula (I) according to the invention, after which the den drimere of the formulas (II)

R _4-i [Si (CH₂) _n SiZ _c R _3-c ] _i (II)

with i = 3.4, preferably i = 4, n = 2 to 6, preferably n = 2 and R = alkyl and / or Aryl, wherein n can be the same or different within the molecule and where the other residues have the following meaning:

• a) Z = Cl, Br, I, OR with c = 1,

or

• b) Z = [(CH₂) _n SiWR₂] with c = 1 to 3, preferably c = 3 and
  W in the following has the meaning of Cl, Br, I or OR

or

• c) Z = [(CH₂) _n SiR _3-c [(CH₂) _n SiWR₂] _c ] with c = 1 to 3, preferably c = 3,

or

• d) Z = [(CH₂) _n SiR _3-c [(CH₂) _n SiR _3-c [(CH₂) _n SiWR₂] _c ] _c ] with c = 1 to 3, preferably c = 3,

hydro in the presence of a base with water in a non-polar solvent be lysed.

Bases in the sense of the invention are preferably triorganoamines, the organo residues all common alkyl, aryl and phenyl residues, linear or branched and given optionally substituted, preferably trialkylamines, particularly preferably ent alkyl speaks a C₁-C₃ radical. Water and trialkylamine are preferred used in excess.

The process according to the invention is preferred at room temperature temperatures temperature, particularly preferably at 25 to 50 ° C, very particularly preferably at 30 ° C. carried out. Non-polar solvents in the sense of the invention are aliphatic Ethers, preferably tert-butyl methyl ether.

The starting materials can be mixed in any order. In a preferred embodiment of the present invention becomes a compound of the formulas (IIa-d) dissolved in a non-polar solvent to give a mixture, consisting of base, water and non-polar solvent at temperatures Dripped room temperature dropwise with stirring and then at least 1 hour continued stirring.

The compounds of formula (IIa) can by conventional methods by Reaction of a suitable unsaturated silane with a hydridosilane, such as. B. an alkoxy or halosilane, in the presence of a catalyst, e.g. B. Hexa chloroplatinic acid in isopropanol, made in a non-polar solvent will.

The silanes of the formula (IIa) obtained in this way can be used in a further Step in a Grignard reaction with an alkenyl magnesium halide in ali  phatic ether converted to compounds with alkenylsilane functionality will. The compounds of the formulas (IIb), (IIc) and (IId) can be prepared the above steps are repeated.

General preparation instructions for the compounds IIa to IId are also described in US Pat. 5,276,110, Adv. Mater. 1993, 5, 466-468, Macromolecules 1993, 26, 963-968, J. Chem. Soc., Chem. Commun. 1994, 2575-2576 and Organometallics 1994, 13, 2682-2690.

For the preparation of compounds of formula (III) by hydrosilylation of Alkenylsilanes of the formula (IV) with hydridosilanes of the formula (V) are u. a. in the above-mentioned literature hexachloroplatinic acid and a bis [divinyltetramethyl siloxane] platinum (0) complex (Karstedt catalyst) as homogeneous catalysts described. These are solved, e.g. B. in alcohols or in xylene.

In many hydrosilylations, these catalysts give very good results Regioselectivity and yield, however, has been shown to with them disadvantages are also associated. This becomes particularly clear when Reactions are transferred from the laboratory scale to the technical scale should.

An example is the reaction of tetravinylsilane with chlorodimethylsilane, as described in DE-A-197 17 839 and Organometallics 1995, 28, 6657-6661, called. Catalysis with hexachloroplatinic acid in isopropanol or with the Karstedt catalyst provides the desired Si [(CH₂) ₂SiClMe₂] ₄ in good Yield. The addition takes place regioselectively and the formation of Markoffnikov Products take place, if at all, only in negligible quantities.

The reactions of tetravinylsilane with HSiCl₃, HSiCl₂Me or HSiClMe₂, at which four Si-C bonds are formed are all strongly exo therm. As described in Macromolecules 1993, 26, 963-968, it is often already for batches of a few grams, the reaction vessel with a Cool the cooling bath, because a reflux condenser alone low-boiling chlorosilane can no longer condense back.

In addition to the strong heat development, it is also very difficult to take off estimate exactly when the reaction starts. All of the starting materials were thoroughly  cleaned and the catalyst freshly prepared immediately before the reaction the reaction sometimes gets underway without additional heating. In the in most cases, however, heat is required. When inserting the The preheated mixture is then all the more difficult to react due to cooling, for example to get under control. Both traces of impurities in the educts (Water, HCl), as well as an altered catalyst activity could be used for this Cause.

In Adv. Organometallic Chem. 1979, 17, 407-409 this reaction behavior is considered "Induction Period" is described, and is based on the formation of the actually catalytically active species stirred during this "induction period".

Such a somewhat unpredictable course of the reaction is necessary for a technical through leadership unfavorable. The rapid heat dissipation after the onset of the exothermic Reaction is only with great technical effort, if at all, realizable.

Another disadvantage of homogeneous catalysis is that the catalyst, if only in low concentration, remains in the product. Besides the fact The fact that valuable precious metal is lost usually results from the installation harmful influences on subsequent products.

It has now been found that the regioselective addition of hydridosilanes to Alkenylsilanes to form the desired anti-Markoffnikov products without that disadvantages mentioned above and in high yield (typically around 90% (pure of the alkenylsilane used is not taken into account)) if this reaction is catalyzed heterogeneously.

This heterogeneous catalysis also has the advantage that partial substitution products (remaining alkenyl groups) and Markoffnikov products not at all or if at all, can only be found in very small quantities.

It can be used with the heterogeneous ones used in the process according to the invention Catalysts the course of the hydrosilylation reaction and also the heat Control development reliably via the catalyst content. A diminished one Catalyst concentration leads directly to reduced heat  winding. This is a simple, large-scale implementation of the method possible.

In addition, the use of the catalyst according to the invention often makes it unnecessary the pre-cleaning of the starting materials.

Another advantage of the hetero used in the method according to the invention gene catalysts in an industrial implementation is that the hydrosilylie tion can be carried out in continuous operation if necessary, which the Space-time yield increases significantly.

In continuous and discontinuous operation, the separation of the dr gerten catalyst, for. B. by filtration, easily possible.

One obtains in both continuous and discontinuous operation Products that are free of catalyst residues.

In addition, the supported catalysts, in contrast to the after State of the art homogeneous catalysts, such as. B. Hexachloro platinic acid in isopropanol, without loss of activity and without special measures be stored.

The invention therefore relates to a process for the preparation of carbosilane Dendrimers of the formula (III),

R _4-i Si [(CH₂) _p SiZ _e R _3-e ] _i (III)

with p = 2-10, e = 1-3, i = 3, 4 and R = alkyl and / or aryl, where p within the Molecule may be the same or different, preferably the same, and the other residues have the following meaning:

• a) Z = halogen, OR, preferably Z = Cl

or

• b) Z = [(CH₂) _p SiW _e R _3-e ] with W = halogen, OR, preferably W = Cl,

or

• c) Z = [(CH₂) _p SiR _3-e [(CH₂) _p SiW _e R _3-e ] _e ] with W = halogen, OR, preferably W = Cl,

characterized in that alkenylsilanes of the formula (IV)

R _4-i Si [(CH₂) _p-2 Q] _i

with p = 2-10, i = 3, 4, R = alkyl and / or aryl and

• a) Q = C₂H₃ or
• b) Q = [(CH₂) _p Si (C₂H₃) _e R _3-e ] with e = 1-3 or
• c) Q = [(CH₂) _p SiR _3-e [(CH₂) _p Si (C₂H₃) _e R _3-e ] _e ] with e = 1-3 with hydridosilanes of the formula (V) HSiP _e R _3-e with e = 1-3, P = halogen, OR, preferably P = Cl, and R = alkyl and / or aryl in the presence of heterogeneous catalysts.

Tetravinylsilane is preferred as the alkenylsilane and hydridosilanes as the HSiCl₃, HSiCl₂Me or HSiClMe₂ used.

Tetravinylsilane and HSiClMe₂ are particularly preferably used.

The heterogeneous catalyst preferably consists of platinum or a platinum ver bond, which are applied to a wide variety of substrates can. Substances based on coal or metal oxides are considered as carrier materials or metal oxide mixtures mentioned as examples. The day materials can syn be of theoretical or natural origin, d. H. e.g. B. from clay minerals, pumice stone, kaolin, bleaching earth, bauxite, bentonite, diatomaceous earth, asbestos or zeolite consist. In a preferred embodiment of the invention, the  catalytically active ingredient on a carbonaceous support, such as. B. activated carbon, Carbon black, graphite or coke applied, with activated carbon being preferred.

The supported catalyst can be both in powder form and in pieces, e.g. B. as Balls, cylinders, rods, hollow cylinders or rings can be used.

The catalyst used in the process according to the invention is preferred applied to a suitable carrier. Its reactive component exists preferably in the reactive state from a platinum halide or one Platinum halide-containing complex compound, which also, for example Can contain olefins, amines, phosphines, nitriles, carbon monoxide or water, like A₂PtCl₆, where A is, for example, for H, Li, Na, K, NH₄, Rb, Cs, NR₄ with R: organic radical C₆ to C₁₀ aryl, C₇ to C₁₂ aralkyl and / or C₁ to C₂₀- Alkyl radical, and Hal is a halogen, such as F, Cl, Br, I. Such Halogen-containing platinum complex compounds are generally known.

In a preferred embodiment of the invention, the invention in the used catalyst generated in situ. For that the platinum Halide or the complex compound containing the platinum halide during the preparation from a suitable halogen-free platinum metal compound and a halide-containing compound prepared on the support in situ. As Halogen-free platinum metal compounds come e.g. B. platinum nitrate, oxide, hy hydroxide, acetylacetonate and other compounds familiar to the expert in Question. Halogen-containing compounds are halogen-containing salts and Complex compounds of the elements of the first to third main group and the first to eighth subgroup of the Periodic Table of the Elements (Mendeleev) and the rare earth metals (atomic numbers 58-71) in question. Examples are NaBr, NaCl, MgBr₂, AlCl₃, NaPF₆, MnCl₂, CoBr₂, CeCl₃, SmI₂, CuCl₂, Na₂ZnCl₄, TiCl₄.

The amount of the platinum halide or that containing the platinum halide Complex compound in the reactive state is preferably 0.01 to 15% by weight, particularly preferably 0.05 to 10% by weight, calculated as platinum metal and based on the total weight of the catalyst.  

Preferred solvents for the preparation of carriers according to the invention Catalysts are e.g. B. water, aliphatic hydrocarbons, such as pentane, n-hexane, cyclohexane, etc., aliphatic halogenated hydrocarbons, such as Dichloromethane, trichloromethane, etc., aromatic hydrocarbons, such as Benzene, toluene, xylene, etc., halogenated aromatic hydrocarbons such as Chlorobenzene, dichlorobenzene, etc., primary, secondary or tertiary alcohols, such as Methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, t-butanol, Cumyl alcohol, iso-amyl alcohol, diethylene glycol, etc., ketones, such as acetone, 2-butanone, methyl isobutyl ketone, acetylacetone etc., ethers such as diethyl ether, Diisopropyl ether, methyl t-butyl ether, dioxane, tetrahydrofuran, etc., esters such as Methyl acetate, ethyl acetate, etc., nitriles such as acetonitrile, benzonitrile, etc., Carbonates such as dimethyl carbonate, diethyl carbonate, diphenyl carbonate, etc., Dimethylacetamide, N-methylpyrrolidinone and tetramethyl urea called. Mixtures of such solvents can of course also be used will.

A catalyst to be used according to the invention is produced after Methods that are generally known to the person skilled in the art. So can platinum containing solutions and the halide-containing compounds mentioned Soaking, adsorption, dipping, spraying, impregnation and ion exchange on the Be brought according to the invention catalyst support. It is still possible to use platinum and the halide-containing compounds mentioned to fix a base on the carrier. As a base come e.g. B. NaOH, Li₂CO₃ and Potassium phenolate in question. Platinum and the halide compound can both in succession in any order and simultaneously on the Carrier brought.

In the case of application of the platinum by impregnation with a platinum-containing one Solution, the duration of the impregnation depends slightly on the platinum level used Binding, the shape and porosity of the carrier used and of the solvent from. It is preferably a few minutes to a few hours, for example 0.01 to 30 h, particularly preferably 0.05 to 20 h, very particularly preferably 0.1 until 15 h.

The mixture can be stirred during the impregnation. But it can also be advantageous to allow the mixture to stand or to shake with it if the molded body used is not damaged by a stirrer.  

After the impregnation, the supported catalyst should, for. B. by filtration, sedimentation ren or centrifugation are separated. Excess solvent can be separated off by distillation.

After the impregnation, the supported catalysts thus obtained are dried. This can be done in air, in a vacuum or in a gas stream. Suitable gases for drying the supported catalyst in the gas stream z. B. nitrogen, Oxygen, carbon dioxide or noble gases as well as any mixtures of mentioned gases, preferably z. B. air. Drying is preferably at 20 to 200 ° C, particularly preferably at 40 to 180 ° C, very particularly preferably at 60 to 150 ° C.

The drying time depends e.g. B. from the porosity of the carrier used and from used solvents. It is preferably a few hours, for example 0.5 to 50 h, particularly preferably 1 to 40 h, very particularly preferably 1 up to 30 h.

After drying, the dried supported catalysts can be calcined will. This can be done in air, in a vacuum or in a gas stream. Suitable gases for the calcination of the supported catalyst in the gas stream are e.g. B. nitrogen, oxygen, carbon dioxide or noble gases and any Mixtures of the gases mentioned, preferably z. B. air. The calcination takes place preferably at 100 to 800 ° C, particularly preferably at 100 to 700 ° C, entirely particularly preferably at 100 to 600 ° C.

The calcination time is preferably a few hours, for example 0.5 to 50 h, preferably 1 to 40 h, particularly preferably 1 to 30 h.

The supported catalysts can be used as powders or moldings and from the reaction mixture z. B. by filtration, sedimentation or centri fugieren be separated.

The present invention also relates to organic-inorganic Hybrid materials obtainable by the implementation of the carbo according to the invention silane dendrimers according to formula I.

R _4-i Si [(CH₂) _n SiX _a R _3-a ] _i (I)

with i = 3, 4, preferably i = 4, n = 2-6, preferably n = 2 and R = alkyl and / or Aryl, where n can be the same or different within the molecule and where the other residues have the following meaning:

• a) X = OH with a = 1

or

• b) X = [(CH₂) _n Si (OH) R₂] with a = 1 to 3, preferably a = 3

or

• c) X = [(CH₂) _n SiR _3-a [(CH₂) _n Si (OH) R₂] _a ] with a = 1-3, preferably a = 3,

or

• d) X = [(CH₂) _n SiR _3-a [(CH₂) _n SiR _3-a [(CH₂) _n Si (OH) R₂] _a ] _a ] with a = 1-3, preferably a = 3,

with metal alkoxides of the formula

M (OR ′) _x

with M = Si, Ge, Sn, B, Al, Ga, In, Ti, Zr, Hf, V, Nb or Ta, R ′ = an un branched or branched C₁-C₅ alkyl radical and x, corresponding to the oxidation state of M, 3 or 4 means with water and in the presence of a catalyst.

The alkyl radicals R in the sense of the invention are preferably linear or branched, optionally substituted C₁-C₅ alkyl radicals.  

The aryl radicals for the purposes of the invention are preferably, if appropriate substituted C₆ rings.

In a preferred embodiment of the present invention, the values are equal to the indicis n within the molecule. N = 2 and is particularly preferred i = 4.

In a preferred embodiment of the present invention, M = Si, Al, Ti or Zr, R 'is an unbranched or branched alkyl radical and x, accordingly the oxidation state of M, 3 or 4.

The metal alkoxide particularly preferably corresponds to the formula Si (OEt) ₄.

Catalysts in the sense of the invention are inorganic or organic acids, preferably organic acids or organometallic compounds, such as. B. Zinc octate.

The concentration of the catalyst in the total mixture is preferably 0.1 to 5 mol / l, particularly preferably 0.1 to 1.0 mol / l.

In a preferred embodiment of the present invention, the Um setting of the functional carbosilane dendrimers of the formulas Ia to Id with the Metal alkoxide in the presence of a catalyst in a solvent.

The ratio of carbosilane dendrimer to metal alkoxide is by number of the silanol groups. 1 to 4 moles per mole of silanol group are preferred one mole of the metal alkoxide can be used.

The present invention also relates to a method for the production of paints, characterized in that carbosilane dendrimers of the formula (I)

R _4-i Si [(CH₂) _n SiX _a R _3-a ] _i (I)

with i = 3, 4, preferably i = 4, n = 2-6, preferably n = 2 and R = alkyl and / or Aryl, where n can be the same or different within the molecule and where the other residues have the following meaning:

• a) X = OH with a = 1

or

• b) X = [(CH₂) _n Si (OH) R₂] with a = i to 3, preferably a = 3

or

• c) X = [(CH₂) _n SiR _3-a [(CH₂) _n Si (OH) R₂] _a ] with a = 1-3, preferably a = 3

or

• d) X = [(CH₂) _n SiR _3-a [(CH₂) _n SiR _3-a [(CH₂) _n Si (OH) R₂] _a ] _a ] with a = 1-3, preferably a = 3,

with metal alkoxides of the formula

M (OR ′) _x

with M = Si, Ge, Sn, B, Al, Ga, In, Ti, Zr, Hf, V, Nb or Ta, particularly preferred Si, Al, Ti, R '= an unbranched or branched C₁-C₅ alkyl radical and x, ent speaking of the oxidation state of M, 3 or 4 means with water and in The presence of a catalyst can be reacted in a solvent.

The alkyl radicals R in the sense of the invention are preferably linear or ver branched, optionally substituted C₁-C₅ alkyl radicals.

The aryl radicals in the sense of the invention are preferably optionally substi tuated C₆ rings.  

In a further preferred embodiment of the present invention the values on the indicator n are the same within the molecule. Is particularly preferred n = 2 and i = 4.

In a preferred embodiment of the present invention, M = Si, Al, Ti or Zr, R ′; an unbranched or branched alkyl radical and x, accordingly the oxidation state of M, 3 or 4.

The metal alkoxide particularly preferably corresponds to the formula Si (OEt) ₄.

Catalysts in the sense of the invention are preferably inorganic or organic acids, preferably organic acids or organometallic compounds applications such as B. zinc octate.

The concentration of the catalyst in the total mixture is preferably 0.1 to 5 mol / l, particularly preferably 0.1 to 1.0 mol / l.

In a preferred embodiment of the present invention, the Um setting of the functional carbosilane dendrimers of the formulas Ia to Id with the Metal alkoxide in the presence of a catalyst in a solvent.

The solvent not only ensures a homogeneous solution, but can also also have a significant influence on the reaction rate. The Gelation should be slow enough to take the varnish solution a few hours to be able to process. Solvents in the sense of the invention are e.g. B. alcohols. Aqueous alcohols are preferred. Ethanol or Isopropanol with a water content of 5 to 25%, preferably 20%.

The ratio of carbosilane dendrimer to metal alkoxide is by number of the silanol groups. 1 to 4 moles per mole of silanol group are preferred one mole of the metal alkoxide can be used.

The inventive method is preferably carried out so that the Carbosilane dendrimer according to one of the formulas Ia to Id in the appropriate amount aqueous alcohol dissolved or suspended and mixed with the metal alkoxide becomes. Then the catalyst is added, whereupon a given if the present suspension becomes homogeneous in a few minutes. By distributing  a drop of the lacquer solution on a slide can now be determined when the viscosity is high enough for good processing.

The present invention also relates to the use of the invention Si-OH-functional carbosilane dendrimers according to the invention as a carrier for tannins formation of catalytically active metal compounds.

The present invention also relates to the use of the invention functional carbosilane dendrimers with O-metal bond as paints.

The varnish can be applied to a wide variety of surfaces using standard methods be applied. For example, it can be applied using a squeegee or by immersion (dip coating) in the paint solution, resulting in very thin layers (a few µm) result.

The paint solution applied to the surface is preferred if it is suitable Air cured temperature.

Before forced drying at higher temperatures is preferred the majority of the volatile components evaporated at room temperature.

Suitable temperatures for curing the paint films are in the temperature range from 15 ° C to 250 ° C. With wet film thicknesses of 120 µm and more one Complete curing at room temperature takes days. Prefers Here is a temperature range from 50 ° C to 120 ° C, which is a hardening in guaranteed within a few hours.

The property profile is based on a paint Si [(CH₂) ₂Si (OH) Me₂] ₄ and Si (OEt) ₄ (1: 4) described in more detail.

The paint films produced in this way are absolutely transparent and have a high level Shine. The extinction is in the range from 360 to 560 nm less than 0.002 and in Range from 560 to 810 nm about 0.03.

The determination of the scratch resistance via pencil hardness according to ASTM 3363 shows that a 27 µm film on a glass surface which has been cured for 24 hours at 20 ° C,  cannot be scratched with a pencil of hardness 5H. At the same The result is obtained with an appropriately coated steel plate.

The adhesion of the coatings was checked according to ISO 2409. Both on Glass as well as steel, iron, aluminum or silicon became the best possible classification "0" reached.

Solvent resistance was achieved by vigorously rubbing the Coating tested with a cotton swab soaked in solvent. By none the solvents used ethanol, acetone, dimethylformamide, toluene, The paint was chloroform or n-butyl acetate in some way changed.

The thermogravimetric analysis (TGA) under air shows no mass loss up to 210 ° C, i.e. H. the film is at this temperature at least for a short time thermally stable. Above 210 ° C a mass loss of approx. 10%, mainly from solvent leakage or post-crosslinking tongue comes from. Decomposition takes place between 230 ° C and 450 ° C (oxidation) of the organic part.

As the TGA shows under nitrogen, there is a loss of mass of approx. 235 ° C 4%, between 235 ° C and 490 ° C only about 3%. This loss of mass can can only be traced back to components that are included in the paint (e.g. Solvent) or by post-crosslinking at this temperature. It is outstanding that the film itself, at least briefly, does not decompose up to 490 ° C can be thermally stressed. Above 490 ° C the organic content in the Coating removed.

The surface determined from wetting angle measurements is also surprising tension of 28.5 mN / m, the non-polar portion 25.0 mN / m and the polar Share is 3.4 mN / m. The non-polar portion predominates strongly, what with one System with many siloxane and silanol groups is unusual. The carbosilane Accordingly, scaffold has a great influence on these parameters.

The thermal expansion coefficient is also surprisingly high at 63 × 10 ^-6 / K. Conventional gels result even when using silanes with a high organic content, such as. B. N-octyl groups, only expansion coefficients in the range Be from 1 to 22 × 10 ^-6 / K, as in Mat. Res. Symp. Proc. 1988, 121, 811-816.

The coefficient of expansion determined in the paint film according to the invention agrees with that of z. B. polycarbonate (approx. 60 × 10 ^-6 / K) match very well. It follows from the surface tension that the wetting of plastics should also be satisfactory.

The mechanical test of a paint film applied to an iron sheet reveals a value of 11 mm for a slow deformation (depth test according to ISO 1520). This excellent value is proof of the elasticity of the Paint film.

With rapid deformation (ball impact according to ASTM D 2794-93) a value becomes reached by 20 inch-pound.

The process according to the invention is illustrated by the examples below explained.

However, the invention is not limited to the examples.

Embodiments Preliminary note

All reactions were carried out using Schlenk technology under argon or in vacuo carried out. All solvents used were made according to the usual Laboratory methods dried before use and used distilled under argon. Commercial educts were not subjected to any further purification.

1 H NMR spectra were proton decoupled at 400 and 500 MHz, respectively 13 C spectra recorded at 100 MHz with the AMX 500 from Bruker. The Varian XR 300 spectrometer from Varian was used at 60 MHz for the Recording of proton decoupled ²⁹Si spectra used. The mass spectra were used in Maldi measurements with Krat os Maldi 3 from Shimatzu and at CI measurements made with Finnigan's MAT 800/230.

Commercially available starting materials, such as chlorodimethylsilane and tetravinylsilane, were without further cleaning used. The purity of the tetravinyl silane used was 96%.

The synthesis of Si [(CH₂) ₂Si [(CH₂) ₂Si (C₂H₃) ₃] ₃] ₄ was carried out as they are in Organometallics 1994, 13, 2682.

The synthesis of phenyltrivinylsilane from phenyltrichlorosilane and vinyl magnesium Chloride was made as described in J. Org. Chem. 1957, 22, 1200-1202 is described.

A 0.1% solution of hexachloro was used as the hydrosilylation catalyst platinic acid used in absolute isopropanol.

example 1 Synthesis of Si [(CH₂) ₂SiClMe₂] ₄

5 drops of the platinum catalyst were added at room temperature to a mixture of 5 g (36.7 mmol) of tetravinylsilane, 20.8 g (220.1 mmol) of chlorodimethylsilane and 20 ml of THF. The mixture was then stirred for 30 min at room temperature and heated to 45 ° C to 50 ° C. A violent exothermic reaction started after a few minutes, and the heating bath might have to be removed. As the temperature dropped, the mixture was heated to 45 ° C. to 50 ° C. for a further 2 hours. After cooling to room temperature, the mixture was stirred for a further 20 h and all volatile constituents were removed in vacuo. The product was obtained as a colorless wax.
NMR: (CDCl₃)
1 H: δ = 0.42 ppm (s, 6H, SiCH₃); 0.59 ppm and 0.68 ppm (m, each 2H, SiCH₂).
13 C {1 H}: δ = 0.93 ppm (s, SiCH₃); 2.06 ppm (s, SiCH₂); 11.26 ppm (s, Cl SiCH₂).

Example 2 Synthesis of Si [(CH₂) ₂Si [(CH₂) ₂SiClMe₂] ₃] ₄

To the reaction mixture consisting of 3 g (5.20 mmol) Si [(CH₂) ₂Si (C₂H₃) ₃] ₄, 7.8 g of chlorodimethylsilane and 20 ml of THF were added to 5 drops of the platinum Catalyst and initially stirred at room temperature for 30 min. Then you warmed up to 45 ° C to 50 ° C; the reaction that started after a few minutes was essential less exothermic than that described in Example 1. Then it was warmed up for 2 hours 45 ° C, then cooled again to room temperature and stirred for a further 20 h. To removing the volatiles in vacuo gave the product as colorless solid.

Elemental analysis (C, H)

C₅₆H₁₃₆Cl₁₂Si₁₇
M = 1712.580 g / mol
NMR: (CDCl₃)
1 H: δ = 0.39 ppm (s, 22H, Si (CH₃) ₂ and Si (CH₂) ₂Si); 0.60 ppm (m, 12H, Si (CH₂) ₂SiCl).
13 C {1 H}: δ = 1.00 ppm (s, SiCH₃); 1.97 ppm, 2.29 ppm and 2.82 ppm (s, SiCH₂); 11.47 ppm (s, ClSiCH₂).

Example 3 Synthesis of Si [(CH₂) ₂Si (OH) Me₂] ₄

To 8.5 g (84.0 mmol) of triethylamine and 1.62 g (90.0 mmol) of water in 300 ml A solution of 10.0 g was added dropwise to diethyl ether within 30 minutes (19.5 mmol) Si [(CH₂) ₂SiClMe₂] ₄ from Example 1 in 20 ml diethyl ether. The ge triethylamine hydrochloride formed as a white precipitate. After The addition was stirred for a further 1 h and then the solid was filtered off. The filtrate was freed from solvent in vacuo. The colorless solid thus obtained was dissolved in THF and slowly added dropwise to 500 ml of hexane with vigorous stirring. The Product was obtained as a fine, white precipitate, which after filtering off and once washing with hexane no longer needed to be cleaned.

A stable solid was obtained.
Mp: 144 ° C.

Elemental analysis

C₁₆H₄₄O₄Si₅
M = 440.951 g / mol
NMR: (DMSO-d₆)
1 H: δ = 0.0 ppm (s, 6H, SiCH₃); 0.39 ppm (m, 4H, Si (CH₂) ₂Si); 5.21 ppm (s, 1H, SiOH).
13 C {1 H}: δ = -0.63 ppm (s, SiCH₃); 1.93 ppm (s, Si (CH₂) ₄); 9.77 ppm (s, Si (OH) CH₂).
²⁹Si {¹H}: δ = 14.26 ppm (s, Si (CH₂) ₄); 16.33 ppm (s, SiOH).
MS: (CI)
m / e = 337 (Si [(CH₂) ₂Si (OH) Me₂] ₃⁺)
IR: (Nujol trituration)
3160 cm ^-1 , very wide (νO-H).

Example 4 Synthesis of Si [(CH₂) ₂Si [(CH₂) ₂Si (OH) Me₂] ₃] ₄

To a mixture of 20.7 g (30.4 mmol) triethylamine, 3.65 g (32.7 mmol) Water and 700 ml of diethyl ether were 4 g (2.34 mmol) within 30 min. Si [(CH₂) ₂Si [(CH₂) ₂SiClMe₂] ₃] ₄ from Example 2 was added dropwise in 40 ml of diethyl ether. After the addition was complete, the reaction mixture was stirred for a further 1 h and then filtered the precipitate of triethylamine hydrochloride. The filtrate was freed from volatile constituents in vacuo and the semi-crystalline colorless residue taken up in THF. This solution was dissolved in 300 ml of hexane dripped. The product was thus obtained as a colorless precipitate. When this at When it was left to become oily, the solvent was decanted off and stirred oily product with some diethyl ether. The cleaned fine crystalline product was filtered off and dried in vacuo.

A stable solid was obtained.

Elemental analysis (C, H)

C₅₆H₁₄₈O₁₂Si₁₇
M = 1491.239 g / mol
NMR: (DMSO-d₆)
1 H: δ = 0.06 ppm (s, 18H, SiCH₃); 0.46 ppm (m, 16H, SiCH₂); 5.31 ppm (s, 3H, SiOH).
13 C {1 H}: δ = -0.42 ppm (s, SiCH₃); 1.89 ppm (s, Si (OH) CH₂CH₂Si); 2.23 ppm and 2.43 ppm (s, Si (CH₂) ₂Si), 9.99 ppm (s, Si (OH) CH₂CH₂Si).

Example 5 Synthesis of C₆H₅Si [(CH₂) ₂SiClMe₂] ₃

25.0 g were added to 12.3 g (66.1 mmol) of phenyltrivinylsilane in 50 ml of THF (264.5 mmol) chlorodimethylsilane and a few drops of the Pt catalyst. Man warmed the reaction mixture to 45-50 ° C for 20 h, then cooled to room temperature  temperature and removed all volatile components in vacuo. You got one colorless oil, which is reacted according to Example 6 without further purification has been.

Example 6 Synthesis of C₆H₅Si [(CH₂) ₂Si (OH) Me₂] ₃

To a solution of 34.5 ml (247.7 mmol) of triethylamine and 4.8 ml (264.9 mmol) water in 1.2 l tert. Butyl methyl ether was added dropwise within 2 h 26.9 g (57.4 mmol) of C₆H₅Si [(CH₂) ₂SiClMe₂] ₃ from Example 5 in 30 ml of diethyl ether. After the addition, the mixture was stirred at room temperature for another hour and filtered then the white precipitate of triethylamine hydrochloride. The colorless The filtrate was freed of volatile components on a rotary evaporator. The way The white solid obtained was dissolved in 30 ml of THF and, with stirring, in 400 ml Dropped hexane. The product precipitated out as a fine white precipitate. This was suction filtered, washed twice with 50 ml of hexane and finally in dyna for 20 h mix vacuum dried. A stable solid was obtained.

Elemental analysis (C, H)

C₁₈H₃₈O₂Si₄
M = 414.840 g / mol
NMR: (DMSO-d₆)
1 H: δ = -0.11 ppm (s, 18H, SiCH₃); 0.32 ppm and 0.70 ppm (m, each 6H, SiCH₂); 5.27 ppm (s, 3H, SiOH); 7.35 ppm and 7.44 ppm (m, 5H, SiC₆H₅).
13 CC {1 H}: δ = -0.43 ppm (s, SiCH₃); 2.52 ppm (s, Si (CH₂) ₄); 9.91 ppm (s, Si (OH) CH₂); 127.85 ppm, 128.84 ppm, 134.19 ppm and 137.32 ppm (s, SiC₆H₅).

Example 7 Synthesis of Si [(CH₂) ₂Si (OH) Me₂] ₄ in tert. Butyl methyl ether

94.3 g (183.4 mmol) Si [(CH₂) ₂SiClMe₂] ₄ were dissolved in 100 ml diethyl ether and at room temperature with vigorous stirring to a solution of 110.3 ml (792.3 mmol) triethylamine, 15.3 ml (850 mmol) water and 3 630 ml tert.  Dropped butyl methyl ether. The triethylamine hydrochloride that formed immediately fell as a white solid. The dropping took place so quickly that the reaction temperature was between 25 ° C and 30 ° C. After the addition was complete stirred for an hour and then the precipitate was filtered off through a frit. After removing the volatile constituents in vacuo at about 35 ° C the crude product as a white solid. This was done in as little as possible THF was taken up and added dropwise to 3 l of hexane with vigorous stirring. The way The fine white precipitate obtained was filtered off and washed once with hexane and then dried in vacuo.

The resulting tert implementation. Butyl methyl ether was used without further ado Cleaning used for a second, analog reaction. The course of the reaction, and the quality of the fine product remained unchanged.

General regulation for the production of lacquer solutions

To the carbosilane dendrimers Si [(CH₂) ₂Si (OH) Me₂] ₄, Ph-Si [(CH₂) ₂Si (OH) Me₂] ₃ or Si [(CH₂) ₂Si [(CH₂) ₂Si (OH) Me₂] ₃] ₄ in the corresponding solvent one tetraethoxysilane (TEOS) and finally the catalyst formic acid. The The reaction mixture was stirred until it was absolutely clear, and then left until good workability is given. The exact Experimental data for the preparation of the coating solutions 1 to 6 are in Table 1 summarized. The molar, volume ratios and concentrations of the The substances used are summarized in Table 2.

General regulations for the production of paint films

Before coating, all surfaces were carefully rubbed off with Acetone cleaned. The approximate amount of each paint solution 1 until 6 was used with a four-fold film drawing frame from Erichsen, model 360, applied to the surface. The surfaces used had the following dimensions:

Table 3

Dimensions of the surfaces used

The information about the type of surface, film thickness and drying conditions conditions are summarized in Table 4. The results of the lead tests Pen hardness, cross hatch test and solvent resistance can be found in Table 5. Physico-chemical properties of the paint solution 1 pre parried films are given in Table 6, while the mechanical eigen properties of the lacquer film 1/5 are shown in Table 7.  

Table 4

Production of paint films from the paint solutions 1, 2, 3, 5 and 6. (The paint solution 4 was cured in a plastic vessel to form a shaped body / film 0.8 mm thick).

Table 5

Preliminary tests of paint films 1 to 18

Table 6

Physico-chemical properties of paint films of the paint solution 1

Table 7

Mechanical properties of the lacquer film 1/5

Example 8 Covering powdered activated carbon with H₂PtCl₆ (Cat I)

49.5 g of activated carbon Norit CN 1 were placed in 300 ml of double-distilled water slurries and with 200 ml of an aqueous H₂PtCl₆ solution, the 0.5 g Pt - just net as metal - contained, offset. The mixture was stirred for 10 minutes and sucked Catalyst on a filter. The water-moist raw product (153 g) was dried at 0.1 Pa and 110 ° C and stored under argon. The catalyst Cat I contained 1% Pt.

Example 9 Activation of lumpy activated carbon with H₂PtCl₆ (Cat II)

49.5 g (= 114.6 ml) of activated carbon extrudates Norit ROX 0.8 were mixed with 33.9 ml an aqueous H₂PtCl₆ solution containing 0.5 g Pt - calculated as metal - soaked. The crude product was first at 110 ° C in a stream of nitrogen dried, then dried at 0.1 Pa and 110 ° C and under argon stored. The catalyst contained 1% Pt.

Example 10 Coating of powdered SiO₂ with H₂PtCl₆ (Cat III)

49.5 g SiO₂ (Merck 657) were mixed with 132 ml of an aqueous H₂PtCl₆ solution Contained 0.5 g Pt - calculated as metal - pasted. The water-moist raw product was first dried at 110 ° C in a drying cabinet, then at 0.1 Pa and dried at 110 ° C and stored under argon. The catalyst contained 1% Pt.

Example 11 Coating of powdered Al₂O₃ with H₂PtCl₆ (Cat IV)

49.5 g of γ-Al₂O₃ (Rhone-Poulenc, SPH 509) were mixed with 40 ml of an aqueous H₂PtCl₆ solution containing 0.5 g Pt - calculated as metal - pasted. The what The raw, moist product was first dried in a drying cabinet at 110 ° C. then dried at 0.1 Pa and 110 ° C and stored under argon. Of the Catalyst contained 1% Pt.  

Example 12 Coating of powdered TiO₂ with H₂PtCl₆ (Cat V)

49.5 g of TiO₂ (Bayer) were mixed with 70 ml of an aqueous H₂PtCl₆ solution containing 0.5 g Pt - calculated as metal - contained, pasted. The water-moist raw product was first dried at 110 ° C in a drying cabinet, then at 0.1 Pa and dried at 110 ° C and stored under argon. The catalyst contained 1% Pt.

Example 13 Synthesis of Si [(CH₂) ₂SiClMe₂] ₄ with 5 g of cat

867 g (9.17 mol) of chlorodimethylsilane and 5 g of the dried catalyst I were added to 250 g (1.84 mol) of tetravinylsilane in 600 ml of THF. With vigorous stirring, the mixture was then heated to about 40 ° C. until the clearly exothermic reaction started after a few minutes and then the external heat source was removed. The reaction was maintained for about 30 minutes with vigorous reflux. With the reflux becoming weaker, the reaction was heated to 55 to 60 ° C. for only 15 h and then cooled to room temperature. The supported catalyst was filtered off through a frit. The colorless solution was concentrated in vacuo. The product spontaneously crystallized out as a colorless solid. This was then dried in vacuo for a further 20 h.
Yield: 861.5 g corresponding to 92% of theory. Th.

Example 14 Synthesis of Si [(CH₂) ₂SiClMe₂] ₄ with 4 g of cat

The reaction was carried out analogously to Example 2, but only with 4 g of the supported catalyst Cat I. The mixture of THF and excess chlorodimethylsilane which had been condensed off after the filtration was used again in Example 3.
Yield: 854.3 g corresponding to 91% of theory. Th.

Example 15 Synthesis of Si [(CH₂) ₂SiClMe₂] ₄ with 4 g of cat

To 250 g (1.84 mol) of tetravinylsilane and the condensate from Example 3, consisting of THF and chlorodimethylsilane, 729 g (7.71 mol) of chlorodimethylsilane and 4 g of the dried catalyst I were added. With vigorous stirring, the mixture was then warmed up approx. 40 ° C until the clearly exothermic reaction started after a few minutes and then removed the external heat source. The reaction was maintained for about 60 minutes with vigorous reflux. When the reflux became weaker, the mixture was heated to 55 to 60 ° C. for a further 15 h and then cooled to room temperature. Now the supported catalyst was filtered off over a frit and the colorless solution was concentrated in vacuo. The product spontaneously crystallized out as a colorless solid. This was then dried in vacuo for a further 20 h.
Yield: 849.0 g; corresponding to 90% of theory Th.

Example 16 Synthesis of Si [(CH₂) ₂SiClMe₂] ₄ with Cat II

34.7 g (366.7 mmol) of chlorodimethylsilane and 200 mg of the supported catalyst Cat II were added to 10 g (73.3 mmol) of tetravinylsilane in 30 ml of THF. The reaction mixture was warmed to 40 ° C. and, after the onset, the mixture was removed exother men reaction the external heat source. The temperature then rose automatically to approx. 60 ° C; after the exothermic reaction had ended, the mixture was heated to 40 ° C. for a further 15 h and then cooled to room temperature. The catalyst was filtered off and the colorless solution was freed from volatile constituents in vacuo. The product was obtained as a white solid.
Yield: 32.5 g corresponding to 86% of theory

Example 17 Synthesis of Si [(CH₂) ₂SiClMe₂] ₄ with Cat III

34.7 g (366.7 mmol) of chlorodimethylsilane and 200 mg of the supported catalyst Cat III were added to 10 g (73.3 mmol) of tetravinylsilane in 30 ml of THF. The reaction mixture was heated to 40 ° C and, after the onset of the exothermic reaction, the external heat source was removed. The temperature then rose automatically to approx. 65 ° C; after the exothermic reaction had ended, the mixture was heated to 50 ° C. for a further 2 h and then cooled to room temperature. The catalyst was filtered off and the colorless solution was freed from volatile constituents in vacuo. The product was obtained as a white solid.
Yield: 34.6 g corresponding to 92% of theory

Example 18 Synthesis of Si [(CH₂) ₂SiClMe₂] ₄ with Cat IV

86.8 g (917.0 mmol) of chlorodimethylsilane and 0.5 g of the catalyst Cat IV were added to 25 g (183.4 mmol) of tetravinylsilane in 60 ml of THF. The mixture was slowly warmed to 40 ° C., after about 30 min started a strong exothermic reaction. The reaction mixture heated up to 65 ° C and had to be cooled in the meantime with a cold bath (acetone / dry ice). After the end of the exothermic reaction, the mixture was heated at 50 ° C. for a further 2 h and then stirred at room temperature for a further 20 h. The catalyst was then filtered off via a frit and the filtrate was freed of volatile constituents in vacuo.
Yield: 80.8 g corresponding to 86% of theory. Th.

Example 19 Synthesis of Sit (CH₂) ₂SiClMe₂] ₄ with Kat V

To 25 g (183.4 mmol) of tetravinylsilane in 60 ml of THF were added 86.8 g (917.0 mmol) of chlorodimethylsilane and 0.2 g of the catalyst V. It was slowly warmed to 40 ° C. and the external heat source was removed as soon as possible the exothermic reaction started. The reaction mixture quickly warmed up to 60 ° C. After the end of the exothermic reaction, the mixture was heated at 50 ° C. for a further 2 h and then stirred at room temperature for a further 20 h. The catalyst was then filtered off via a frit and the filtrate was freed of volatile constituents in vacuo.
Yield: 70 g corresponding to 74% of theory. Th.

Example 20 Synthesis of Si [(CH₂) ₂SiClMe₂] ₄ with cat I in tert. Butyl methyl ether

To 125 g (0.92 mol) of tetravinylsilane in 300 ml of tert. Butyl methyl ether was added to 509 ml (433.7 g; 4.59 mol) of chlorodimethylsilane and 2 g of the catalyst I. The mixture was heated to 40 to 45 ° C. and the external heat source was removed as soon as the exothermic reaction started. The temperature rose slowly to 55 ° C due to the consumption of the low boilers (chlorodimethylsilane) and fell again after about 30 minutes with the end of the exothermic reaction. The mixture was then heated to 50 ° C. for a further 2 hours, then cooled to room temperature and the catalyst was removed by filtration through a frit. (Product crystallized in the frit was easily transferred by heating with a hair dryer). The colorless filtrate was freed from volatile constituents in vacuo and the product was obtained as colorless crystals.
Yield: 435 g corresponding to 92% of theory. Th.

Claims (31)

1. Functional carbosilane dendrimers of the general formula R _4-i Si [(CH₂) _n SiX _a R _3-a ] _i with i = 3.4, n = 2-6 and R = alkyl and / or aryl, where n can be the same or different within the molecule and the other radicals have the following meaning

• a) X = OH with a = 1

or

• b) X = [(CH₂) _n Si (OH) R₂] with a = 1 to 3

or

• c) X = [(CH₂) _n SiR _3-a [(CH₂) _n Si (OH) R₂] _a ] with a = 1 to 3

or

• d) X = [(CH₂) _n SiR _3-a [(CH₂) _n SiR _3-a [(CH₂) _n Si (OH) R₂] _a ] _a ] with a = 1 to 3.

2. Functional carbosilane dendrimers according to claim 1, characterized indicates that the values of the indices n are the same within the molecule.   3. A process for the preparation of the carbosilane dendrimers according to one of claims 1 to 2, characterized in that dendrimers of the formula R _4-i [Si (CH₂) _n SiZ _c R _3-c ] _i with i = 3.4, n = 2 to 6 and R = alkyl and / or aryl, in which n can be the same or different within the molecule and the other radicals have the following meaning:

• a) Z = Cl, Br, I, OR

with c = 1,
or

• b) Z = [(CH₂) _n SiWR₂]

with c = 1 to 3 and
W in the following has the meaning of Cl, Br, I or OR
or

• c) Z = [(CH₂) _n SiR _3-c [(CH₂) _n SiWR₂] _c ] with c = 1 to 3,

or

• d) Z = [(CH₂) _n SiR _3-c [(CH₂) _n SiR _3-c [(CH₂) _n SiWR₂] _c ] _c ] with c = 1 to 3,

in the presence of a base with water in a non-polar solvent be hydrolyzed.   4. A process for the preparation of carbosilane dendrimers according to claim 3, characterized in that triorganoamines are used as bases. 5. Process for the preparation of carbosilane dendrimers according to one of the Claims 3 to 4, characterized in that as a non-polar solution medium aliphatic ethers are used. 6. Process for the preparation of compounds of the formula R _4-i Si [(CH₂) _p SiZ _e R _3-e ] _i with p = 2-10, e = 1-3, i = 3, 4 and R = alkyl and / or aryl, where p can be the same or different within the molecule and the other radicals have the following meaning:

• a) Z = halogen, OR

or

• b) Z = [(CH₂) _p SiW _e R _3-e ] with W = halogen, OR or
• c) Z = [(CH₂) _p SiR _3-e [(CH₂) _p SiW _e R _3-e ] _e ] with W = halogen, OR, characterized in that alkenylsilanes of the formula R _4-i Si [(CH₂) _{p -2} Q] _i with p = 2-10, i = 3, 4, R = alkyl and / or aryl and
• a) Q = C₂H₃ or
• b) Q = [(CH₂) _p Si (C₂H₃) _e R _3-e ] with e = 1-3 or
• c) Q = [(CH₂) _p SiR _3-e [(CH₂) _p Si (C₂H₃) _e R _3-e ] _e ] with e = 1-3 with hydridosilanes of the formula HSiP _e R _3-e with e = 1- 3, P = halogen, OR and R = alkyl and / or aryl in the presence of heterogeneous catalysts.

7. The method according to claim 6, characterized in that as a heterogeneous Catalyst is used as a catalyst that is catalytically active Part of platinum or a platinum compound and as a carrier material Has carbon. 8. The method according to claim 7, characterized in that as a heterogeneous Catalyst hexachloroplatinic acid is used on activated carbon. 9. The method according to any one of claims 6 to 8, characterized in that the reaction is carried out batchwise in a solvent. 10. The method according to any one of claims 6 to 9, characterized in that used as alkenylsilane tetravinylsilane and as hydridosilane HSiClMe₂ becomes. 11. Organic-inorganic hybrid materials, obtainable by the reaction of carbosilane dendrimers of the formula R _4-i Si [(CH₂) _n SiX _a R _3-a ] _i with i = 3, 4, n = 2-6 and R = Alkyl and / or aryl, where n can be the same or different within the molecule and the other radicals have the following meaning

• a) X = OH with a = 1

or

• b) X = [(CH₂) _n Si (OH) R₂] with a = 1 to 3,

or

• c) X = [(CH₂) _n SiR _3-a [(CH₂) _n Si (OH) R₂] _a ] with a = 1-3,

or

• d) X = [(CH₂) _n SiR _3-a [(CH₂) _n SiR _3-a [(CH₂) _n Si (OH) R₂] _a ] _a ] with a = 1-3,

with metal alkoxides of the formula M (OR ′) _x with M = Si, Ge, Sn, B, Al, Ga, In, Ti, Zr, Hf, V, Nb or Ta, R¹ = an unbranched or branched C₁-C₅ alkyl radical and x, corresponding to the oxidation state of M, 3 or 4, with water and in the presence of a catalyst. 12. Organic-inorganic hybrid materials according to claim 11, characterized ge indicates that the catalyst is an organometallic compound or is organic or inorganic acid. 13. A process for the preparation of coatings, characterized in that carbosilane dendrimers of the formula R _4-i Si [(CH₂) _n SiX _a R _3-a ] _i with i = 3.4, n = 2-6 and R = Alkyl and / or aryl, where n can be the same or different within the molecule and the other radicals have the following meaning

• a) X = OH

with a = 1
or

• b) X = [(CH₂) _n Si (OH) R₂] with a = 1 to 3, preferably a = 3

or

• c) X = [(CH₂) _n SiR _3-a [(CH₂) _n Si (OH) R₂] _a ] with a = 1-3,

or

• d) X = [(CH₂) _n SiR _3-a [(CH₂) _n SiR _3-a [(CH₂) _n Si (OH) R₂] _a ] _a ] with a = 1-3,

with metal alkoxides of the formula M (OR ′) _x with M = Si, Ge, Sn, B, Al, Ga, In, Ti, Zr, Hf, V, Nb or Ta, R ′ = an unbranched or branched C₁-C₅- Alkyl radical and x, corresponding to the oxidation state of M, 3 or 4, are reacted with water and in the presence of a catalyst and optionally a solvent. 14. Use of the carbosilane dendrimers according to one of claims 1 to 2 as a carrier for connecting metal connections. 15. Use of the organic-inorganic hybrid materials according to claim 11 as paint.