Carbosilane-dendrimers, carbosilane-hybrid materials, methods for manufacturing them and a method for manufacturing coatings from the carbosilane-dendrimers

The present invention relates to novel functional carbosilane-dendrimers, organic-inorganic carbosilane-hybrid materials, methods for manufacturing them, methods for manufacturing coatings from the functional carbosilane-dendrimers and the use thereof.

The present invention relates to novel functional carbosilane-dendrimers, 
organic-inorganic carbosilane-hybrid materials, methods for manufacturing 
them, methods for manufacturing coatings from the functional 
carbosilane-dendrimers and the use thereof. 
The term "dendrimers" is applied to highly branched molecules with a highly 
ordered, mostly three-dimensional structure, whose molecular weight lies 
in the range of those of oligomers or polymers. 
Dendrimers have the advantage, however, that they can be synthesized 
deliberately with an exactly uniform molecular weight, whereas the 
conventional polymers always have a particular molecular weight 
distribution. In addition, particular functional dendrimers, such as those 
with vinyl terminal groups, can be manufactured with a defined number of 
such reactive groups. 
The carbosilane-dendrimers known to date are synthesized starting from an 
initiator core by alternate hydrosilylation and Grignard reaction (U.S. 
Pat. No. 5,276,110, Adv. Mater. 1993, 5, 466-468, Macromolecules 1993, 26, 
963-968, J. Chem. Soc., Chem. Commun. 1994, 2575-2576 und Organometallics 
1994, 13, 2682-2690). For example, the initiator molecule tetravinylsilane 
is reacted with HSiCl.sub.2 CH.sub.3 in thf under Pt catalysis. A 
vinylsilane is synthesized once again, by reaction with vinylmagnesium 
halide, and is available for further hydrosilylation. 
It has been impossible to date, however, to produce high-molecular weight 
carbosilane-dendrimers with a defined number of functional Si--OH terminal 
groups. 
Si--OH-functional carbosilane-dendrimers permit, however, a large number of 
reactions, for example bonding to metal compounds, as per Equation 1 
##STR1## 
with M=metal and X=alkyl, alkoxy, halogeno or hydrido and are therefore of 
great interest. Thus, for example, the bonding of catalytically active 
metal compounds, e.g. for their immobilization or else for the manufacure 
of organic-inorganic hybrid materials, is extremely important. It is 
already known from WO 94/06807 that organic-inorganic hybrid materials can 
be manufactured by reacting carbosilanes containing trialkoxysilane groups 
with water and a catalyst or a carboxylic acid in a suitable solvent. Very 
thin, transparent films can be obtained crack-free by dipping suitable 
substrates in these solutions (dip coating). These carbosilane- dendrimers 
containing Si--O-alkyl terminal groups are subjected to hydrolysis slowly 
in the presence of humidity. Moreover, the reactivity of individual metal 
alkoxides to hydrolysis and condensation varies widely. Alkoxides of 
titanium, zirconium or aluminium react far more rapidly with water than 
the corresponding silicon alkoxides. Cocondensation of the above-mentioned 
alkoxides is very difficult, since the reactive species react with water 
at such a rate that they often cannot be embedded into a homogeneous 
network, but instead form precipitates from the corresponding metal 
(hydroxy) oxides. To prevent this, the concentration of water in the 
reaction solution must be as low as possible. 
There was therefore a major requirement for Si--OH-functional 
carbosilane-dendrimers that can be reacted with reactive metal alkoxides 
without the system having in addition to contain water. 
An adequate shelf-life of functional carbosilane-dendrimers is furthermore 
desirable for the application as a coating resin. 
The object of the present invention is therefore the production of high 
molecular-weight functional carbosilane-dendrimers which possess a defined 
number of terminal Si--OH groups and can therefore be reacted without the 
presence of water with metal alkoxides, such as Ti(OR).sub.4, 
Zr(OR).sub.4, Al(OR).sub.3 or else Si(OR).sub.4, to form 
carbosilane-dendrimers with O-metal bonds, which during hydrolysis with 
water do not display the disadvantages described above of precipitate 
formation by metal (hydroxy) oxides and which form homogeneous networks. 
In addition the carbosilane-dendrimers are to have an unlimited shelf 
life. In addition the compounds should be simple to manufacture. 
Surprisingly it has now been found that carbosilane-dendrimers containing 
terminal Si--OH groups, which are stabilized with alkyl and/or aryl 
groups, fulfil these requirements. 
The present invention therefore provides functional carbosilane-dendrimers 
with the formula 
EQU R.sub.4-i Si(CH.sub.2).sub.n SiX.sub.a R.sub.3-a !.sub.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 inside the molecule and where the 
other groups stand for the following 
a) X=OH 
with a=1 or 
b) X=(CH.sub.2).sub.n Si(OH)R.sub.2 ! 
with a=1 to 3, preferably a=3 or 
c) X=(CH.sub.2).sub.n SiR.sub.3-a (CH.sub.2).sub.n Si(OH)R.sub.2 !.sub.a 
! 
with a=1-3, preferably a=3 or 
d) X=(CH.sub.2).sub.n SiR.sub.3-a (CH.sub.2).sub.n SiR.sub.3-a 
(CH.sub.2).sub.n Si(OH)R.sub.2 !.sub.a !.sub.a ! 
with a=1-3, preferably a=3. 
The alkyl groups R in the context of the invention are preferably linear or 
branched, optionally substituted C.sub.1 -C.sub.5 alkyl groups. 
The term "substituted" in the context of the invention includes all common 
substituents, such as halogen, alkyl, amine etc. 
The aryl groups R in the context of the invention are preferably optionally 
substituted C.sub.6 rings. 
When fully formulated, the carbosilane-dendrimers according to the 
invention correspond to formulae (Ia-d) 
EQU R.sub.4-i Si(CH.sub.2).sub.n Si(OH)R.sub.2 !.sub.i or (Ia) 
EQU R.sub.4-i Si(CH.sub.2).sub.n SiR.sub.3-a (CH.sub.2).sub.n Si(OH)R.sub.2 
!.sub.a !.sub.i or (Ib) 
EQU R.sub.4-i Si(CH.sub.2).sub.n SiR.sub.3-a (CH.sub.2).sub.n SiR.sub.3-a 
(CH.sub.2).sub.n Si(OH)R.sub.2 !.sub.a !.sub.a !.sub.i or(Ic) 
EQU R.sub.4-i Si(CH.sub.2).sub.n SiR.sub.3-a (CH.sub.2).sub.n SiR.sub.3-a 
(CH.sub.2).sub.n SiR.sub.3-a (CH.sub.2).sub.n Si(OH)R.sub.2 !.sub.a 
!.sub.a !.sub.a !.sub.i, (Id) 
In a preferred form of embodiment of the present invention the values of 
the indices n inside the molecule are the same. 
Carbosilane-dendrimers with the formulae 
Si(CH.sub.2).sub.2 Si(OH)Me.sub.2 !.sub.4, Si(CH.sub.2).sub.2 
Si(CH.sub.2).sub.2 Si(OH)Me.sub.2 !.sub.3 !.sub.4 or Si(CH.sub.2).sub.3 
Si(OH)Me.sub.2 !.sub.4, where Me is a methyl group, 
are particularly preferred. 
The outstanding shelf-life of the carbosilane-dendrimers according to the 
invention is also worth noting. The colourless powders can also be stored 
in humid air for many months without undergoing changes. In contrast to 
already known carbosilane-dendrimers with functional terminal groups, such 
as Si-vinyl, Si--O-alkyl or Si--Cl, there is available only for the novel 
carbosilane-dendrimers an effective purification step which, unlike 
chromatographic methods, can also be performed on a commercial scale. 
Exceptionally pure and hence uniform carbosilane-dendrimers can be 
supplied in large quantities. Carbosilane-dendrimers with O-metal bonds 
are also obtainable from these Si--OH-functional carbosilane- dendrimers 
by reaction with metal alkoxides in the presence of a catalyst. In 
addition it has been found that the latter produce, after hydrolysis with 
water and crosslinking by condensation using a sol-gel process, 
organic-inorganic hybrid materials with outstanding properties. The latter 
are used as coatings for the transparent coating of surfaces. Particular 
mention should be made here of the high scratch-resistance combined with 
flexibility, transparency, good thermal stability and chemical resistance. 
The present invention in addition provides a method for manufacturing the 
carbosilane-dendrimers according to the invention of formula (I), 
according to which the dendrimers of formula (II) 
EQU R.sub.4-i Si(CH.sub.2).sub.n SiZ.sub.c R.sub.3-c !.sub.i (II) 
with i=3, 4, preferably i=4, n=2 to 6, preferably n=2 and R=alkyl and/or 
aryl, where n can be the same or different inside the molecule and where 
the other groups stand for the following: 
a) Z=Cl, Br, I, OR 
with c=1, or 
b) Z=(CH.sub.2).sub.n SiWR.sub.2 ! 
with c=1 to 3, preferably c=3 and W stands for Cl, Br, I or OR or 
c) Z=(CH.sub.2).sub.n SiR.sub.3-c (CH.sub.2).sub.n SiWR.sub.2 !.sub.c ! 
with c=1 to 3, preferably c=3, W stands for Cl, Br, I or OR or 
d) Z=(CH.sub.2).sub.n SiR.sub.3-c (CH.sub.2).sub.n SiR.sub.3-c 
(CH.sub.2).sub.n SiWR.sub.2 !.sub.c !.sub.c ! 
with c=1 to 3, preferably c=3, W stands for Cl, Br, I or OR 
is hydrolysed in a non-polar solvent with water in the presence of a base. 
Bases in the context of the invention are preferably triorganic amines, 
wherein the organic groups include all common alkyl, aryl and phenyl 
groups, linear or branched and optionally substituted, preferably trialkyl 
amines, particularly preferably alkyl corresponds to a C.sub.1 -C.sub.3 
group. Preferably water and also trialkyl amine are used to excess. 
Preferably the method according to the invention is carried out at 
temperatures.gtoreq.room temperature, particularly preferably at 
25.degree. to 50 .degree. C., more particularly preferably at 30.degree. 
C. Non-polar solvents in the context of the invention are aliphatic 
ethers, preferably tert.-butylmethylether. 
The educts can be mixed in any order. In a preferred form of embodiment of 
the present invention a compound of formulae (IIa-d) dissolved in a 
non-polar solvent is added drop-wise with stirring to a mixture consisting 
of base, water and non-polar solvent at temperatures.gtoreq.room 
temperature and then stirred for at least one further hour. 
The compounds of formula (IIa) can be manufactured according to 
conventional methods by the reaction of a suitable unsaturated silane with 
a hydridosilane, such as e.g. an alkoxysilane or a halogenated silane, in 
the presence of a catalyst, e.g. hexachloroplatinic acid in isopropanol, 
in a non-polar solvent. 
The silanes of formula (IIa) obtained in this way can be reacted in a 
further step in a Grignard reaction with an alkenylmagnesium halide in 
aliphatic ether to obtain compounds with alkenylsilane functionality. The 
above-mentioned steps can be repeated to manufacture the compounds of 
formulae (IIb), (IIc) and (IId). 
General instructions for manufacturing the compounds IIa to IId are in 
addition described in U.S. Pat. No. 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. 
Hexachloroplatinic acid and a bisdivinyltetramethylsiloxane!platinum(O) 
complex (Karstedt catalyst) are described in the above-mentioned 
literature inter alia as catalysts for the manufacture of compounds of 
formula (III) by the hydrosilylation of alkenylsilanes of formula (IV) 
with hydridosilanes of formula (V). They are used dissolved e.g. in 
alcohols or in xylene. 
In many hydrosilylations these catalysts supply very good results as 
regards regioselectivity and yield, but it has been found that 
disadvantages are also associated with the latter. This becomes clear 
particularly if it is desired to convert reactions on a laboratory scale 
to an industrial scale. 
Mention can be made here as an example of the reaction of tetra-vinylsilane 
with chlorodimethylsilane, as described in DE-A-19 717 839 and 
Organometallics 1995, 28, 6657-6661. The catalysis with hexachloroplatinic 
acid in isopropanol or with the Karstedt catalyst supplies the desired 
Si(CH.sub.2).sub.2 SiClMe.sub.2 !.sub.4 in good yield. The addition takes 
place regioselectively and the formation of Markoffnikov products takes 
place, if at all, only in insignificant amounts. 
The reactions of tetravinylsilane with HSiCl.sub.3, HSiCl.sub.2 Me or 
HSiClMe.sub.2, in which four Si--C-bonds are linked in each case, are all 
strongly exothermal. As described in Macromolecules 1993, 26, 963-968, it 
is often necessary, even with preparations of only a few grams, to cool 
the reaction vessel with a cold bath, since a reflux condenser on its own 
can no longer recondense the low-boiling chlorosilane. 
In addition to the strong development of heat it is in addition very 
difficult to estimate when exactly the reaction will commence. If all the 
educts have been purified extremely thoroughly and fresh catalyst has been 
prepared prior to the reaction, the reaction sometimes starts on its own 
without additional heating. In most cases, however, the supply of heat is 
required. When the reaction has started, the pre-heated mixture is then 
all the more difficult to control, for example by cooling. Both traces of 
impurities in the educts (water, HCl), and also modified catalyst 
activity, could be regarded as responsible for this. 
In Adv. Organometallic Chem. 1979, 17, 407-409 this reaction behaviour is 
described as the "induction period", and is attributed to the formation of 
the catalytically active species itself during this "induction period". 
Such an unpredictable reaction course is unsuitable for an industrial 
application. The rapid cooling after the start of the exothermal reaction, 
where it is possible at all, is so only at great expense in technical 
terms. 
A further disadvantage of the homogeneous catalysis lies in the fact that 
the catalyst, even if only in small concentration, remains in the product. 
In addition to the fact that valuable precious metal is lost, harmful 
effects on subsequent products usually result from the inclusion. 
It has now been found that the regioselective addition of hydfidosilanes to 
alkenylsilane with formation of the desired anti-Markoffnikov products 
takes place without the above-mentioned disadvantages and in high yield 
(typically about 90% (purity of the alkenylsilane used not included)), if 
this reaction is catalysed heterogeneously. 
This heterogeneous catalyst has furthermore the advantage that partial 
substitution products (remaining alkenyl groups) and Markoffnikov products 
are either not found at all or, if they are, only in very small mounts. 
It is possible with the heterogeneous catalysts used in the method 
according to the invention for the reaction course of the hydrosilylation 
and also the heat evolution to be controlled reliably by means of the 
catalyst content. A reduced catalyst concentration leads directly to a 
reduced heat evolution. Simple large-scale implementation of the method is 
thus possible. 
In addition, the preliminary purification of the educts often becomes 
unnecessary through the use of the catalyst according to the invention. 
A further advantage of the heterogeneous products used in the method 
according to the invention for an industrial application is the fact that 
the hydrosilylation can be conducted optionally in continuous operation, 
which increases the space-time yield considerably. 
The separation of the supported catalyst is possible in continuous and 
discontinuous operation, e.g. by filtration, without any difficulty. 
Products which are free from catalyst residues are obtained both in 
continuous and in discontinuous operation. 
In addition the supported catalysts, unlike the homogeneous catalysts known 
according to the prior art, such as hexachloroplatinic acid in 
isopropanol, can be stored without loss of activity and without particular 
measures. 
The invention therefore provides a method for manufacturing 
carbosilane-dendrimers of formula (III), 
EQU R.sub.4-i Si(CH.sub.2).sub.p SiZ.sub.e R.sub.3-e !.sub.i (III) 
with p=2-10, e=1-3, i=3,4 and R=alkyl and/or aryl, where p can be the same 
or different, preferably the same, inside the molecule, and where the 
other groups stand for the following: 
Z=halogen, OR, preferably Z=Cl or 
b) Z=(CH.sub.2).sub.p SiW.sub.e R.sub.3-e ! with W=halogen, OR, preferably 
W=Cl, or 
c) Z=(CH.sub.2).sub.p SiR.sub.3-e (CH.sub.2).sub.p SiW.sub.e R.sub.3-e 
!.sub.e ! with W=halogen, OR, preferably W=Cl, 
characterised in that alkenylsilanes of formula (IV) 
EQU R.sub.4-i Si(CH.sub.2).sub.p-2 Q!.sub.i 
with p=2-10, i=3,4, R=Alkyl and/or aryl and 
a) Q=C.sub.2 H.sub.3 or 
b) Q=(CH.sub.2).sub.p Si(C.sub.2 H.sub.3).sub.e R.sub.3-e ! with e=1-3 or 
c) Q=(CH.sub.2).sub.p SiR.sub.3-e (CH.sub.2).sub.p Si(C.sub.2 
H.sub.3).sub.e R.sub.3-e !.sub.e ! with e=1-3 
are reacted with hydridosilanes of formula (V) 
EQU HSiP.sub.e R.sub.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 preferably used as the alkenylsilane and HSiCl.sub.3, 
HSiCl.sub.2 Me or HSiClMe.sub.2, where Me is a methyl group, as the 
hydridosilane. 
Tetravinylsilane and HSiClMe.sub.2 are particularly preferably used. 
The heterogeneous catalyst consists preferably of platinum or a platinum 
compound, which can be applied to a wide range of support materials. 
Substances based on carbon or metal oxides or metal oxide mixtures may be 
mentioned as examples of support materials. The support materials can be 
of synthetic or natural origin, i.e. consist for example of clay minerals, 
pumice, kaolin, bleaching earths, bauxite, bentonite, kieselguhr, asbestos 
or zeolite. In a preferred form of embodiment of the invention the 
catalytically active component is used applied to a carbon-containing 
support such as activated carbon, carbon black, graphite or coke, wherein 
activated carbon is preferred. 
The supported catalyst can be used both in powder form and in lumps, e.g. 
as balls, cylinders, rods, hollow cylinders or rings. 
The catalyst used in the method according to the invention is preferably 
applied to a suitable support. Its reactive component consists, preferably 
when in the reactive state, of a platinum halide or of a complex compound 
containing a platinum halide, which can in addition contain for example 
olefins, amines, phosphines, nitriles, carbon monoxide or water, such as 
A.sub.2 Pthal.sub.6, where A stands for example for H, Li, Na, K, 
NH.sub.4, Rb, Cs, NR.sub.4 with R: organic group C.sub.6 - to C.sub.10 
-aryl-, C.sub.7 - to C.sub.12 -aralkyl- and/or C.sub.1 - to C.sub.20 
-alkyl group, and hal for a halogen, for example F, Cl, Br, I. Complex 
platinum compounds of this kind containing halogen are known in principle. 
In a preferred form of embodiment of the invention the catalyst used in the 
method according to the invention is generated in situ. For this the 
platinum halide or the complex compound containing the platinum halide is 
produced in situ on the support during the preparation stage from a 
suitable halogen-free metal platinum compound and a halide-containing 
compound. Platinum nitrate, platinum oxide, platinum hydroxide, platinum 
acetylacetonate and other compounds familar to the skilled man are for 
example considered as halogen-free metal platinum compounds. 
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 of the rare earth metals (atomic 
numbers 58-71) are considered as halide-containing compounds. NaBr, NaCl, 
MgBr.sub.2, AlCl.sub.3, NaPF.sub.6, MnCl.sub.2, CoBr.sub.2, CeCl.sub.3, 
SmI.sub.2, CuCl.sub.2, Na.sub.2 ZnCl.sub.4, TiCl.sub.4 are examples. 
The amount of the platinum halide or that of the complex compound 
containing the platinum halide in the reactive state preferably comes to 
0.01 to 15 wt %, particularly preferably 0.05 to 10 wt %, calculated as 
platinum metal and referred to the total weight of the catalyst. 
The following are mentioned e.g. as preferred solvents for the manufacture 
of supported catalysts according to the invention: 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, isopropanol, n-butanol, isobutanol, t-butanol, cumyl alcohol, 
iso-amyl alcohol, diethylene glycol, etc., ketones, such as acetone, 
2-butanone, methyl isobutyl ketone, acetylacetone etc., ethers, such as 
diethylether, diisopropylether, methyl-t-butylether, 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., 
dimethyl acetamide, N-methylpyrrolidinone and tetramethyl urea. Mixtures 
of such solvents can naturally also be used. 
The manufacture of a catalyst to be used according to the invention takes 
place according to methods that in principle are known to the skilled man. 
Thus platinum-containing solutions and the above-mentioned 
halide-containing compounds can be precipitated on the catalyst support to 
be used according to the invention by soaking, adsorption, immersion, 
spraying, impregnation and ion exchange. It is also possible to fix 
platinum and the above-mentioned halide-containing compounds to the 
support with a base. NaOH, Li.sub.2 CO.sub.3 and potassium phenolate are 
considered as bases. Platinum and the halide-containing compound can be 
applied to the support either successively in any order or simultaneously. 
In the case of the application of the platinum by soaking with a 
platinum-containing solution the period of soaking depends to a certain 
extent on the platinum compound used, the form and porosity of the support 
used and the solvent. The latter comes preferably to a few minutes to some 
hours, for example 0.01 to 30 h, particularly preferably 0.05 to 20 h, 
more particularly preferably 0.1 to 15 h. 
The mixture can be stirred during the soaking. It may also be advantageous, 
however, to allow the mixture to stand or to shake it, so that any moulds 
used are not damaged by a stirrer. 
After the soaking the supported catalyst should be separated, e.g. by 
filtration, sedimentation or centrifuging. Surplus solvent can be 
separated by distillation at the same time. 
After the soaking the supported catalysts so obtained are dried. This can 
take place in the air, under vacuum or in a gas current. Suitable gases 
for the drying of the supported catalyst in a gas current are e.g. 
nitrogen, oxygen, carbon dioxide or noble gases, as well as any mixtures 
of the above-mentioned gases, preferably e.g. air. The drying preferably 
takes place at 20.degree. to 200.degree. C., particularly preferably at 
40.degree. to 180.degree. C., more particularly preferably at 60.degree. 
to 150.degree. C. 
The drying depends e.g. on the porosity of the support used and on the 
solvent used. It comes preferably to a few hours, for example 0.5 to 50 h, 
particularly preferably 1 to 40 h, more particularly preferably 1 to 30 h. 
After the drying the dried supported catalysts can be calcined. This can 
take place in the air, under a vacuum or in a gas current. Suitable gases 
for the calcination of the supported catalyst in a gas current are e.g. 
nitrogen, oxygen, carbon dioxide or noble gases, as well as any mixtures 
of the above-mentioned gases, preferably e.g. air. The calcination 
preferably takes place at 100.degree. to 800.degree. C., particularly 
preferably at 100.degree. to 700.degree. C., more particularly preferably 
at 100.degree. to 600.degree. C. 
The calcination time preferably comes to 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 mouldings and be 
separated from the reaction mixture e.g. by filtration, sedimentation or 
centrifuging. 
The present invention also provides for organic-inorganic hybrid materials 
that are obtainable by the reacting of the carbosilane-dendrimers 
according to the invention according to formula I 
EQU R.sub.4-i Si(CH.sub.2).sub.n SiX.sub.a R.sub.3-a !.sub.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 inside the molecule and where the 
other groups stand for the following 
a) X=OH 
with a=1 or 
b) X=(CH.sub.2).sub.n Si(OH)R.sub.2 ! 
with a=1 to 3, preferably a=3 or 
c) X=(CH.sub.2).sub.n SiR.sub.3-a (CH.sub.2).sub.n Si(OH)R.sub.2 !.sub.a 
! 
with a=1-3, preferably a=3, or 
d) X=(CH.sub.2).sub.n SiR.sub.3-a (CH.sub.2).sub.n SiR.sub.3-a 
(CH.sub.2).sub.n Si(OH)R.sub.2 !.sub.a !.sub.a ! 
with a=1-3, preferably a=3, 
with metal alkoxides of the formula 
EQU M(OR').sub.x 
with M=Si, Ge, Sn, B, Al, Ga, In, Ti, Zr, Hf, V, Nb or Ta, R'=an unbranched 
or branched C.sub.1 -C.sub.5 alkyl group and x stands for 3 or 4 depending 
on the oxidation number of M, with water and in the presence of a 
catalyst. 
The alkyl groups R in the context of the invention are preferably linear or 
branched, optionally substituted C.sub.1 -C.sub.5 alkyl groups. 
The aryl groups in the context of the invention are preferably optionally 
substituted C.sub.6 rings. 
In a preferred form of embodiment of the present invention the values for 
the indices n inside the molecule are the same. Particularly preferably 
n=2 and i=4. 
In a preferred form of embodiment of the present invention M=Si, Al, Ti or 
Zr, R' is an unbranched or branched alkyl residue and x, depending on the 
oxidation number of M, is 3 or 4. 
Particularly preferably the metal alkoxide corresponds to the formula 
Si(OEt).sub.4, where Et is an ethyl group. 
Catalysts in the context of the invention are inorganic or organic acids, 
preferably organic acids or organometallic compounds, such as e.g. zinc 
octoate. 
The concentration of the catalyst in the total mixture preferably comes to 
0.1 to 5 mol/l, particularly preferably 0.1 to 1.0 mol/l. 
In a preferred form of embodiment of the present invention the reacting of 
the functional carbosilane-dendrimers of Formulae Ia to Id with the metal 
alkoxide takes place in the presence of a catalyst in a solvent. 
The ratio of carbosilane-dendrimers to metal alkoxide is determined by the 
number of silanol groups. 1 to 4 mol, preferably one mole, of the metal 
alkoxide can be used per mole of silanol group. 
The present invention provides in addition a method for manufacturing 
coatings, characterised in that carbosilane-dendrimers of formula (I) 
EQU R.sub.4-i Si(CH.sub.2).sub.n SiX.sub.a R.sub.3-a !.sub.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 inside the molecule and where the 
other groups stand for the following 
a) X=OH 
with a=1 or 
b) X=(CH.sub.2).sub.n Si(OH)R.sub.2 ! 
with a=1 to 3, preferably a=3 or 
c) X=(CH.sub.2).sub.n SiR.sub.3-a (CH.sub.2).sub.n Si(OH)R.sub.2 !.sub.a 
! 
with a=1-3, preferably a=3 or 
d) X=(CH.sub.2).sub.n SiR.sub.3-a (CH.sub.2).sub.n SiR.sub.3-a 
(CH.sub.2).sub.n Si(OH)R.sub.2 !.sub.a !.sub.a ! 
with a=1-3, preferably a=3, 
are reacted with metal alkoxides of formula 
EQU M(OR').sub.x 
with M=Si, Ge, Sn, B, Al, Ga, In, Ti, Zr, Hf, V, Nb or Ta, particularly 
preferably Si, Al, Ti, R'=an unbranched or branched C.sub.1 -C.sub.5 alkyl 
group and x, depending on the oxidation number of M, stands for 3 or 4, 
with water and in the presence of a catalyst in a solvent. 
The alkyl groups R in the context of the invention are preferably linear or 
branched, optionally substituted C.sub.1 -C.sub.5 alkyl groups. 
The aryl groups in the context of the invention are preferably optionally 
substituted C.sub.6 rings. 
In a further preferred form of embodiment of the present invention the 
values of the indices n inside the molecule are the same. Particularly 
preferably n=2 and i=4. 
In a preferred form of embodiment of the present invention M=Si, Al, Ti or 
Zr, R' is an unbranched or branched alkyl group and x, depending on the 
oxidation number of M, is 3 or 4. 
Particularly preferably the metal alkoxide corresponds to the formula 
Si(OEt).sub.4, where Et is an ethyl group. 
Catalysts in the context of the invention are preferably inorganic or 
organic acids, preferably organic acids or organometallic compounds, such 
as e.g. zinc octoate. 
The concentration of the catalyst in the total mixture preferably comes to 
0.1 to 5 mol/l, particularly preferably 0.1 to 1.0 mol/l. 
In a preferred form of embodiment of the present invention the reacting of 
the functional carbosilane-dendrimers of Formulae Ia to Id with the metal 
alkoxide takes place in the presence of a catalyst in a solvent. 
The solvent not only ensures a homogeneous solution, but can also influence 
the reaction rate to a considerable extent. The gel formation should be 
sufficiently slow for the coating solution to be able to be worked for a 
few hours. Solvents in the context of the invention are e.g. alcohols. 
Aqueous alcohols are preferred. Ethanol or isopropanol with a water 
content of 5 to 25%, preferably 20%, may be mentioned as particularly 
preferred. 
The ratio of carbosilane-dendrimer to metal alkoxide is determined by the 
number of silanol groups. 1 to 4 mol, preferably one mole, of the metal 
alkoxide can be used per mole of silanol group. 
The method according to the invention is preferably carried out so that the 
carbosilane-dendrimer according to one of formulae Ia to Id is dissolved 
or suspended in the suitable mount of aqueous alcohol and mixed with the 
metal alkoxide. The catalyst is then added, whereupon an optionally 
present suspension becomes homogeneous in a few minutes. It can be 
ascertained by spreading a drop of the coating solution on a microscope 
slide if the viscosity is high enough for good processing. 
The present invention in addition provides the use of the Si--OH-functional 
carbosilane-dendrimers according to the invention as supports for the 
bonding of catalytically active metal compounds. 
The present invention also provides the use of the functional 
carbosilane-dendrimers with O-metal bond as coatings. 
The coating can be applied to a wide range of surfaces by the conventional 
methods. For example it can be applied by means of a knife or by dipping 
(dip coating) in the coating solution, which results in very thin layers 
(a few .mu.m). 
The coating solution applied to the surface is preferably cured in the air 
at a suitable temperature. 
Before a forced drying takes place at higher temperature, the bulk of the 
volatile components are preferably evaporated at room temperature. 
Suitable temperatures for the curing of the coating films lie in the 
temperature range from 15.degree. C. to 250.degree. C. In the case of wet 
film thicknesses of 120 .mu.m and more, complete curing at room 
temperature is obtained only after a few days. A temperature range of 
50.degree. C. to 120.degree. C., which guarantees curing in a few hours, 
is preferred here. 
The properties will be described in detail below for a coating consisting 
of Si(CH.sub.2).sub.2 Si(OH)Me.sub.2 !.sub.4 and Si(OEt).sub.4 (1:4). 
The coating films produced in this way are absolutely transparent and have 
a high gloss. The absorbance is less than 0.002 in the range from 360 to 
560 nm and about 0.03 in the range from 560 to 810 nm. 
Determination of the scratch resistance by means of pencil hardness to ASTM 
3363 shows that a 27 .mu.m film on a glass surface, which has been cured 
at 20.degree. C. for 24 h, cannot be scratched by a pencil with a hardness 
of 5H. The same result is obtained for a similarly coated steel plate. 
The adhesion of the coatings was tested to ISO 2409. The best possible 
classification "O" was obtained both on glass and on steel, iron, 
aluminium or silicon. 
The solvent resistance was tested by vigorous, five-minute rubbing of the 
coating with a cotton-wool ball soaked in solvent. The coating was not 
modified in any way by any of the solvents used, namely ethanol, acetone, 
dimethyl formamide, toluene, chloroform or n-butylacetate. 
Thermogravimetric analysis (TGA) in air shows no decrease in weight up to 
210.degree. C., i.e. the film is thermally stable up to this temperature 
at least for a short time. Above 210.degree. C. a weight decrease of 
approx. 10% is observed, which stems mainly from escaping solvent or 
post-curing. Only between 230.degree. C. and 450.degree. C. does 
decomposition (oxidation) of the organic component take place. 
TGA under nitrogen shows that a weight decrease of approx. 4% occurs up to 
235.degree. C., compared with only approx. 3% between 235.degree. C. und 
490.degree. C. This weight decrease can be attributed only to components 
which are included in the coating (e.g. solvents) or are formed at this 
temperature by post-curing. It is remarkable that the film can at least 
for a short time even be thermally stressed up to 490.degree. C. without 
decomposing. Above 490.degree. C. the organic component in the coating is 
broken down. 
Also surprising is the surface tension of 28.5 mN/m determined from contact 
angle measurements, wherein the non-polar portion comes to 25.0 mN/m and 
the polar portion to 3.4 mN/m. The non-polar portion predominates 
strongly, which is unusual for a system containing many siloxane and 
silanol groups. The carbosilane skeleton consequently has a great 
influence on these parameters. 
The coefficient of thermal expansion is also surprisingly high at 
63.times.10.sup.-6 /K. Conventional gels produce, even where silanes with 
a high organic content, such as n-octyl groups, are used, coefficients of 
expansion in the range of only 1 to 22.times.10.sup.-6 /K, as described in 
Mat. Res. Symp. Proc. 1988, 121, 811-816. 
The expansion coefficient determined for the coating according to the 
invention agrees very closely with that of e.g. polycarbonate (about 
60.times.10.sup.-6 /K). It follows from the surface tension that the 
wetting of plastics materials should also prove satisfactory. 
Mechanical testing of a coating applied to an iron slab produces a value of 
11 mm for a slow deformation (indentation test to ISO 1520). This 
excellent value is evidence of the elasticity of the coating. 
With rapid deformation (ball impact to ASTM D 2794-93) a value of 20 
inch-pound is obtained.

The method according to the invention will be explained in detail by means 
of the following examples. 
The invention is not however limited to the examples. 
EXAMPLES 
Preliminary remarks: 
All reactions were carried out with the use of Schlenk technique under 
argon or in a vacuum. All the solvents used were dried prior to use by the 
conventional laboratory methods and used distilled under argon. Commercial 
educts were not subjected to further purification. 
.sup.1 H-NMR spectra were recorded at 400 and 500 MHz, proton-decoupled 
.sup.13 C spectra at 100 MHz with the AMX 500 of the company Bruker. The 
spectrometer XR 300 of the company Varian was used at 60 MHz for the 
recording of the proton-decoupled .sup.29 Si spectra. The mass spectra 
were in the case of Maldi measurements obtained with Kratos Maldi 3 of the 
company Shimatzu and in the case of CI measurements with MAT 800/230 of 
the company Finnigan. 
Commercial educts such as chlorodimethylsilane and tetravinylsilane were 
used without further purification. The purity of the tetravinylsilane used 
came to 96%. 
The synthesis of Si(CH.sub.2).sub.2 Si(CH.sub.2).sub.2 Si(C.sub.2 
H.sub.3).sub.3!.sub.3 !.sub.4 was carried out as described in 
Organometallics 1994, 13, 2682. 
The synthesis of phenyltrivinylsilane from phenyltrichlorosilane and 
vinylmagnesium chloride was carried out as described in J. Org. Chem. 
1957, 22, 1200-1202. 
A 0.1% solution of hexachloroplatinic acid in absolute isopropanol was used 
as the hydrosilylation catalyst. 
Example 1 
Synthesis of Si(CH.sub.2).sub.2 SiClMe.sub.2 !.sub.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 whole was stirred initially for 
30 min at room temperature and heated to 45.degree. C. to 50.degree. C. A 
violent exothermal reaction occurred after a few minutes, the heating bath 
having to be removed in certain circumstances. When the temperature 
dropped, heating to 45.degree. C. to 50.degree. C. for a further 2 h took 
place. After cooling to room temperature stirring took place for a further 
20 h and all volatile components were removed under vacuum. The product 
was obtained as a colourless wax. 
NMR: (CDCl.sub.3) 
.sup.1 H: .delta.=0.42 ppm (s, 6H, SiCH.sub.3); 0,59 ppm and 0.68 ppm (m, 
2H in each case, SiCH.sub.2). 
.sup.13 C{.sup.1 H}: .delta.=0.93 ppm (s, SiCH.sub.3); 2.06 ppm (s, 
SiCH.sub.2); 11.26 ppm (s, ClSiCH.sub.2). 
Example 2 
Synthesis of Si(CH.sub.2).sub.2 Si(CH.sub.2).sub.2 SiClMe.sub.2 !.sub.3 
!.sub.4 
5 drops of the platinum catalyst were added to the reaction mixture 
consisting of 3 g (5.20 mmol) of Si(CH.sub.2).sub.2 Si(C.sub.2 
H.sub.3).sub.3 !.sub.4, 7.8 g of chlorodimethylsilane and 20 of thf and 
the whole was stirred initially for 30 min at room temperature. Heating to 
45.degree. C. to 50.degree. C. then took place; the reaction that started 
after a few minutes was far less exothermal than that described in Example 
1. Further heating to 45.degree. C. for 2 h, followed by renewed cooling 
to room temperature and stirring for a further 20 h, then took place. 
After removal of the volatile components under vacuum, the product was 
obtained as a colourless solid. 
Elemental analysis (C, H): 
______________________________________ 
C H 
______________________________________ 
Calcd.: 39.28% 8.00% 
Found: 40.0% 8.0% 
______________________________________ 
C.sub.56 H.sub.136 Cl.sub.12 Si.sub.17 
M=1712.580 g/mol 
NMR: (CDCl.sub.3) 
.sup.1 H: .delta.=0.39 ppm (s, 22H, Si(CH.sub.3).sub.2 and 
Si(CH.sub.2).sub.2 Si); 0.60 ppm (m, 12H, Si(CH.sub.2).sub.2 SiCl). 
.sup.13 C{.sup.1 H}: .delta.=1.00 ppm (s, SiCH.sub.3); 1.97 ppm, 2.29 ppm 
and 2.82 ppm (s, SiCH.sub.2); 11.47 ppm (s, ClSiCH.sub.2). 
Example 3 
Synthesis of Si(CH.sub.2).sub.2 Si(OH)Me.sub.2 !.sub.4 
A solution of 10.0 g (19.5 mmol) of Si(CH.sub.2).sub.2 SiClMe.sub.2 
!.sub.4 from Example 1 in 20 ml of diethyl ether was added drop-wise 
within 30 minutes to 8.5 g (84.0 mmol) of triethylamine and 1.62 g (90.0 
mmol) of water in 300 ml of diethylether. The triethylamine hydrochloride 
formed was obtained as a white precipitate. After the addition, stirring 
took place for a further hour and the solid was then filtered off. The 
filtrate was freed of the solvent in a vacuum. The colourless solid so 
obtained was dissolved in tiff and dripped slowly into 500 ml of hexane 
with vigorous stirring. The product was obtained as a free, white 
precipitate, which did not have to be purified further after filtering off 
and a single washing with hexane. 
A stable solid was obtained. 
Melting point: 144.degree. C. 
Elemental analysis: 
______________________________________ 
C H O Si 
______________________________________ 
Calcd.: 43.58% 10.06% 14.51% 31.85% 
Found: 43.6% 10.1% 14.2% 32.1% (diff.) 
______________________________________ 
C.sub.16 H.sub.44 O.sub.4 Si.sub.5 
M=440.951 g/mol 
NMR: (dmso-d.sub.6) 
.sup.1 H: .delta.=0.0 ppm (s, 6H, SiCH.sub.3); 0.39 ppm (m, 4H, 
Si(CH.sub.2).sub.2 Si); 5.21 ppm (s, 1H, SiOH). 
.sup.13 C{.sup.1 H}: .delta.=-0.63 ppm (s, SiCH.sub.3); 1.93 ppm (s, 
Si(CH.sub.2).sub.4); 9.77 ppm (s, Si(OH)CH.sub.2). 
.sup.29 Si{.sup.1 H}: .delta.=14.26 ppm (s, Si(CH.sub.2).sub.4); 16.33 ppm 
(s, SiOH). 
MS: (CI) 
m/e=337 (Si(CH.sub.2).sub.2 Si(OH)Me.sub.2 !.sub.3.sup.+) 
IR: (Nujol trituration) 
3160 cm.sup.-1, very broad (.nu.O--H). 
Example 4 
Synthesis of Si(CH.sub.2).sub.2 Si(CH.sub.2).sub.2 Si(OH)Me.sub.2 !.sub.3 
!.sub.4 
4 g (2.34 mmol) of Si(CH.sub.2).sub.2 Si(CH.sub.2).sub.2 SiClMe.sub.2 
!.sub.3 !.sub.4 from Example 2 in 40 ml of diethyl ether were added 
drop-wise within 30 min to a mixture of 20.7 g (30.4 mmol) of 
triethylamine, 3.65 g (32.7 mmol) of water and 700 ml of diethyl ether. On 
completion of the addition, the reaction mixture was stirred for a further 
hour and the precipitate of triethylamine hydrochloride was then filtered 
off. The filtrate was freed of volatile components in a vacuum and the 
partly crystalline colourless residue was dissolved in thf. This solution 
was dripped into 300 ml of hexane. The product was obtained in this way as 
a colourless precipitate. When the latter became oily on standing, the 
solvent was decanted off and the oily product stirred with some diethyl 
ether. The after-purified finely crystalline product was filtered off and 
dried in a vacuum. 
A stable solid was obtained. 
Elemental analysis (C, H): 
______________________________________ 
C H 
______________________________________ 
Calcd.: 45.10% 10.00% 
Found: 44.8% 9.7% 
______________________________________ 
C.sub.56 H.sub.148 O.sub.12 Si.sub.17 
M=1491.239 g/mol 
NMR: (dmso-d.sub.6) 
.sup.1 H: .delta.=0.06 ppm (s, 18H, SiCH.sub.3); 0.46 ppm (m, 16H, 
SiCH.sub.2); 5.31 ppm (s, 3H, SiOH). 
.sup.13 C{.sup.1 H}: .delta.=-0.42 ppm (s, SiCH.sub.3); 1.89 ppm (s, 
Si(OH)CH.sub.2 CH.sub.2 Si); 2.23 ppm and 2.43 ppm (s, Si(CH.sub.2).sub.2 
Si), 9.99 ppm (s, Si(OH)CH.sub.2 CH.sub.2 Si). 
Example 5 
Synthesis of C.sub.6 H.sub.5 Si(CH.sub.2).sub.2 SiClMe.sub.2 !.sub.3 
25.0 g (264.5 mmol) of chlorodimethylsilane and some drops of the Pt 
catalyst were added to 12.3 g (66.1 mmol) of phenyltrivinylsilane in 50 ml 
of thf. The reaction mixture was heated to 45-50.degree. C. for 20 h, then 
cooled to room temperature, and all volatile components were removed in a 
vacuum. A colourless oil was obtained, which was reacted further according 
to Example 6 without further purification. 
Example 6 
Synthesis of C.sub.6 H.sub.5 Si(CH.sub.2).sub.2 Si(OH)Me.sub.2 !.sub.3 
26.9 g (57.4 mmol) of C.sub.6 H.sub.5 Si(CH.sub.2).sub.2 SiClMe.sub.2 
!.sub.3 from Example 5 in 30 ml of diethyl ether were added drop-wise 
within 2 h to a solution of 34.5 ml (247.7 mmol) of triethylamine and 4.8 
ml (264.9 mmol) of water in 1.2 1 of tert.-butylmethylether. After the 
addition, stirring took place for a further hour at room temperature and 
the white precipitate of triethylamine hydrochloride was then filtered 
off. The colourless filtrate was freed of volatile components on a rotary 
evaporator. The white solid so obtained was dissolved in 30 ml of thf and 
dripped into 400 ml of hexane with stirring. The product was obtained as a 
fine white precipitate. The latter was filtered off, washed twice with 50 
ml of hexane and finally dried under a dynamic vacuum for 20 h. A stable 
solid was obtained. 
Elemental analysis (C, H): 
______________________________________ 
C H 
______________________________________ 
Calcd.: 52.11% 9.23% 
Found: 52.3% 8.7% 
______________________________________ 
C.sub.18 H.sub.38 O.sub.2 Si.sub.4 
M=414.840 g/Mol 
NMR: (dmso-d.sub.6) 
.sup.1 H: .delta.=-0.11 ppm (s, 18H, SiCH.sub.3); 0.32 ppm and 0.70 ppm (m, 
6H in each case, SiCH.sub.2); 5.27 ppm (s, 3H, SiOH); 7.35 ppm and 7.44 
ppm (m, 5H, SiC.sub.6 H.sub.5). 
.sup.13 C{.sup.1 H}: .delta.=-0.43 ppm (s, SiCH.sub.3); 2.52 ppm (s, 
Si(CH.sub.2).sub.4); 9.91 ppm (s, Si(OH)CH.sub.2); 127.85 ppm, 128.84 ppm, 
134.19 ppm and 137.32 ppm (s, SiC.sub.6 H.sub.5). 
Example 7 
Synthesis of Si(CH.sub.2).sub.2 Si(OH)Me.sub.2 !.sub.4 in tert.- 
butylmethylether 
94.3 g (183.4 mmol) of Si(CH.sub.2).sub.2 SiClMe.sub.2 !.sub.4 were 
dissolved in 100 ml of diethyl ether and added drop-wise with vigorous 
stirring at room temperature to a solution of 110.3 ml (792.3 mmol) of 
triethylamine, 15.3 ml (850mmol) of water and 3 630 ml of 
tert.-butylmethylether. The triethylamine hydrochloride formed 
precipitated immediately as a white solid. The rate of the drop-wise 
addition was such that the reaction temperature lay between 25 .degree. C. 
and 30.degree. C. On completion of the addition, stirring took place for a 
further hour and the precipitate was then filtered off through a frit. 
After the removal of the volatile components under vacuum at approx. 
35.degree. C., the crude product was obtained as a white solid. The latter 
was dissolved in as little thf as possible and dripped into 3 l of hexane 
with vigorous stirring. The fine, white precipitate so obtained was 
filtered off, washed once with hexane and then vacuum-dried. 
The tert.-butylmethylether and the excess chlorodimethylsilane obtained 
after the above reaction was used for a second, similar reaction without 
further purification. The reaction course, as well as the quality of the 
fine product, remained unchanged. 
General Instructions on the Manufacture of Coating Solutions 
There were added to the carbosilane-dendrimers Si(CH.sub.2).sub.2 
Si(OH)Me.sub.2 !.sub.4, Ph-Si(CH.sub.2).sub.2 Si(OH)Me.sub.2 !.sub.3 or 
Si(CH.sub.2).sub.2 Si(CH.sub.2).sub.2 Si(OH)Me.sub.2 !.sub.3 !.sub.4, in 
the corresponding solvent, tetraethoxysilane (teos) and finally the 
catalyst formic acid. The reaction mixture was stirred until it was 
absolutely dear, and then stood until good processability was obtained. 
The exact test data for the manufacture of coating solutions 1 to 6 are 
listed in Table 1. The molar ratios, proportions by volume and 
concentrations of the substances used are listed in Table 2. 
TABLE 1 
__________________________________________________________________________ 
Manufacture of coating solutions 1 to 6. 
Coating 
solution 
Carbosilane-dendrimer Amount 
TEOS Amount 
Solvent 
HCOOH 
Water 
no. (mol) (mol) Amount 
Amount 
Amount 
Time*) 
__________________________________________________________________________ 
1 Si(CH.sub.2).sub.2 Si(OH)Me.sub.2 !.sub.4 
1 ml 
(4.49 mmol) 
Isopropanol 
0.44 ml 
0.06 ml 
40 min 
500 mg (1.13 mmol) 1 ml 
2 Si(CH.sub.2).sub.2 Si(OH)Me.sub.2 !.sub.4 
0.4 ml 
(1.8 mmol) 
Isopropanol 
0.03 ml 
0.1 ml 
70 min 
200 mg (0.46 mmol) 0.5 ml 
3 Si(CH.sub.2).sub.2 Si(OH)Me.sub.2 !.sub.4 
0.4 ml 
(1.8 mmol) 
Ethanol 
0.03 ml 
0.1 ml 
75 min 
200 mg (0.46 mmol) 0.5 ml 
4 Si(CH.sub.2).sub.2 Si(CH.sub.2).sub.2 Si(OH)Me.sub.2 !.sub.3 
!.sub.4 1.8 ml 
(8.06 mmol) 
Methanol 
1.06 ml 
0.14 ml 
-- 
1 g (0.67 mmol) 3 ml 
5 Ph--Si(CH.sub.2).sub.2 Si(OH)Me.sub.2 !.sub.3 
0.4 ml 
(1.8 mmol) 
Ethanol 
0.1 ml 
0.1 ml 
45 min 
200 mg (0.48 mmol) 0.5 ml 
6 Ph--Si(CH.sub.2).sub.2 Si(OH)Me.sub.2 !.sub.3 
0.32 ml 
(1.44 mmol) 
Ethanol 
0.1 ml 
0.1 ml 
45 min 
200 mg (0.48 mmol) 0.5 ml 
__________________________________________________________________________ 
*)Time after which good processability has been obtained. 
TABLE 2 
__________________________________________________________________________ 
Molar amounts and molar ratios of coating solutions 1 to 6. 
Coating 
solution 
Carbosilane-dendrimer 
TEOS Solvent 
Water HCOOC Solids 
no. mmol!/V**) mmol!/V**) 
mmol!/V**) 
mmol!/V**) 
mmol!/V**) 
content*) 
__________________________________________________________________________ 
1 Si(CH.sub.2).sub.2 Si(OH)Me.sub.2 !.sub.4 
4.49/4 
Isopropanol 
3.3/2.9 
11.7/10.4 
31% 
1.13/1 13.1/11.6 
2 Si(CH.sub.2).sub.2 Si(OH)Me.sub.2 !.sub.4 
1.80/4 
Isopropanol 
5.6/12.1 
0.8/1.7 
30% 
0.46/1 6.6/14.4 
3 Si(CH.sub.2).sub.2 Si(OH)Me.sub.2 !.sub.4 
1.80/4 
Ethanol 
5.6/12.2 
0.8/1.7 
30% 
0.46/1 6.6/18.7 
4 Si(CH.sub.2).sub.2 Si(CH.sub.2).sub.2 Si(OH)Me.sub.2 !.sub.3 
!.sub.4 8.06/12 
Methanol 
7.8/11.6 
28.2/42.1 
25% 
0.67/1 74.0/110.4 
5 Ph--Si(CH.sub.2).sub.2 Si(OH)Me.sub.2 !.sub.3 
1.80/3,8 
Ethanol 
5.6/11.7 
2.7/5.6 
28% 
0.48/1 8.6/17.9 
6 Ph--Si(CH.sub.2).sub.2 Si(OH)Me.sub.2 !.sub.3 
1.44/3 
Ethanol 
5.6/11.7 
2.7/5.6 
28% 
0.48/1 8.6/17.9 
__________________________________________________________________________ 
*)Carbosilane-dendrimer and SiO.sub.2 in total solution. 
**)Molar ratio of the components used, referred to carbosilandendrimer 
General Instructions on the Manufacture of Coating Films 
Prior to coating all the surfaces were cleaned carefully by rubbing with 
acetone. The approximate mount of the respective coating solution 1 to 6 
required was then applied to the surface with a four-fold film casting 
frame of the company Erichsen, Model 360. The surfaces used had the 
following dimensions: 
TABLE 3 
______________________________________ 
Dimensions of the surfaces used 
______________________________________ 
Glass 80 .times. 115 .times. 2.77 mm 
Iron 65 .times. 210 .times. 0.48 mm 
Aluminium 80 .times. 150 .times. 2.00 mm 
Steel 80 .times. 150 .times. 1.47 mm 
Silicon 114 .times. 114 .times. 0.38 mm 
______________________________________ 
The data on the nature of the surfaces, film thicknesses and drying 
conditions are given in Table 4. The results of the tests on the pencil 
hardness, the cross-cut adhesion test and the solvent resistance are 
contained in Table 5. Physical-chemical properties of films prepared from 
coating solution 1 are given in Table 6, while the mechanical properties 
of the coating film 1/5 are shown in Table 7. 
TABLE 4 
______________________________________ 
Manufacture of coating films from coating 
solutions 1, 2, 3, 5 and 6. (Coating 
solution 4 was cured in a plastics vessel to 
a moulding/film of 0,8 mm thickness). 
Coating 
solution Wet film Dry film 
film no. 
Surface thickness 
thickness 
Drying conditions 
______________________________________ 
1/1 Glass 120 .mu.m 
27 .mu.m 
24 h R.T. 
1/2 Glass 120 .mu.m 
22 .mu.m 
3 h R.T., 2 h 105.degree. C., 19 
h R.T. 
1/3 Glass 240 .mu.m 
64 .mu.m 
24 h R.T. 
1/4 Glass 240 .mu.m 
33 .mu.m 
3 h R.T., 2 h 105.degree. C., 19 
h R.T. 
1/5 Iron 120 .mu.m 
9 .mu.m 
24 h R.T. 
1/6 Iron 120 .mu.m 
8 .mu.m 
3 h R.T., 1 H 50.degree. C., 4 h 
80.degree. C. 
1/7 Iron 120 .mu.m 
10 .mu.m 
24 h R.T., 2 h 105.degree. C. 
1/8 Iron 240 .mu.m 
38 .mu.m 
24 h R.T. 
1/9 Iron 240 .mu.m 
39 .mu.m 
3 d 60.degree. C., 2 h R.T. 
1/10 Alumin- 120 .mu.m 
23 .mu.m 
24 h R.T. 
ium 
1/11 Alumin- 120 .mu.m 
19 .mu.m 
17 h R.T., 2 h 105.degree. C. 
ium 
1/12 Steel 120 .mu.m 
18 .mu.m 
24 h R.T. 
1/13 Steel 120 .mu.m 
18 .mu.m 
17 h R.T., 2 h 105.degree. C. 
1/14 Silicon 120 .mu.m 
4 .mu.m 
24 h R.T. 
2/15 Glass 120 .mu.m 
15 .mu.m 
20 d R.T. 
3/16 Glass 120 .mu.m 
34 .mu.m 
20 d R.T. 
5/17 Glass 120 .mu.m 
10 .mu.m 
15 d R.T. 
6/18 Glass 120 .mu.m 
9 .mu.m 
15 d R.T. 
______________________________________ 
TABLE 5 
______________________________________ 
Preliminary tests on coating films 1 to 18. 
Coat- 
ing Cross-cut Solvent resistance*.sup.) 
film Pencil hardness to 
adhesion test 
acetone, toluene, CHCl.sub.3, 
no. ASTM D 3363 to ISO 2409 
ethanol, butylacetate, DMF 
______________________________________ 
1 &gt;5H 0-1 No change 
2 &gt;5H 0-1 No change 
3 &gt;5H 0-1 No change 
4 &gt;5H 0-1 No change 
5 n.a. 0-1 No change 
6 n.a. 0-1 No change 
7 n.a. 0-1 No change 
8 n.a. 0-1 No change 
9 n.a. 0-1 No change 
10 n.a. 1 No change 
11 n.a. 0-1 No change 
12 &gt;5H 0-1 No change 
13 &gt;4H 0-1 No change 
14 n.a. 0-1 No change 
15 &gt;5H 0-1 No change 
16 &gt;5H 0-1 No change 
17 &gt;5H 0-1 No change 
18 &gt;5H 0-1 No change 
______________________________________ 
*.sup.) Tested by fiveminute rubbing of the coating films with a 
cottonwool ball soaked in solvent or by dipping the surface in the 
solvent. 
n.a. = Test not applicable on rough or soft surfaces (used iron and 
aluminium plates) 
TABLE 6 
______________________________________ 
Physical-chemical properties of coating films of coating solution 1. 
Coating films of coating 
solution 1 
______________________________________ 
Roughness, R.sub.A value 
31 nm +/- 5 nm 
Roughness, R.sub.A value 
21 nm +/- 4 nm 
(after cleaning) 
Surface tension 28.5 mN/m 
Surface tension 28.7 mN/m 
(after cleaning) 
Heat resistance (air) 
210-230.degree. C.*.sup.) 
Heat resistance (N.sub.2) 
490.degree. C.*.sup.) 
Absorbance in the UV/visual range 
360 to 560 nm &lt;0.002 
560 to 810 nm .ltoreq.0.03 
Refractive index (.lambda. = 633 nm) 
1,4642 +/- 0.0002 
______________________________________ 
*.sup.) From TGA, i.e. decomposition of the organic component occurs abov 
this temperature. 
TABLE 7 
______________________________________ 
Mechanical properties of coating film 1/5. 
______________________________________ 
Indentation test to ISO 1520 
11 mm 
Ball impact test to 20 inch-pound 
ASTM D 2794-93 
______________________________________ 
Example 8 
Treatment of Activated Carbon in Powder Form with H.sub.2 PtCl.sub.6 (Cat 
I) 
49.5 g of activated carbon Norit CN 1 were suspended in 300 ml of 
double-distilled water and mixed with 200 ml of an aqueous H.sub.2 
PtCl.sub.6 solution containing 0.5 g Pt calculated as metal. Stirring took 
place for 10 minutes and the catalyst was then extracted on a nutsch 
filter. The water-moist crude product (153 g) was dried at 0.1 Pa and 
110.degree. C. and stored under argon. The catalyst Cat I contained 1% Pt. 
Example 9 
Treatment of Lumpy Activated Carbon with H.sub.2 PtCl.sub.6 (Cat II) 
49.5 g (=114.6 ml) of activated carbon extrudate Norit ROX 0.8 were soaked 
with 33.9 ml of an aqueous H.sub.2 PtCl.sub.6 solution containing 0.5 g Pt 
calculated as metal. The crude product was first of all dried in a 
nitrogen current at 110.degree. C., then dried at 0.1 Pa and 110.degree. 
C. and stored under argon. The catalyst contained 1% Pt. 
Example 10 
Treatment of SiO.sub.2 with H.sub.2 PtCl.sub.6 (Cat III) 
49.5 g of SiO.sub.2 (Merck 657) were made into a paste with 132 ml of an 
aqueous H.sub.2 PtCl.sub.6 solution containing 0.5 g Pt calculated as 
metal. The water-moist crude product was first of all dried in a drying 
cabinet at 110.degree. C., then dried at 0.1 Pa and 110.degree. C. and 
stored under argon. The catalyst contained 1% Pt. 
Example 11 
Treatment of Al.sub.2 O.sub.3 in Powder Form with H.sub.2 PtCl.sub.6 (Cat 
IV) 
49.5 g of .gamma.-Al.sub.2 O.sub.3 (Rhone-Poulenc, SPH 509). were made into 
a paste with 40 ml of an aqueous H.sub.2 PtCl.sub.6 solution containing 
0.5 g Pt calculated as metal. The water-moist crude product was first of 
all dried in a drying cabinet at 110.degree. C., then dried at 0.1 Pa and 
110.degree. C. and stored under argon. The catalyst contained 1% Pt. 
Example 12 
Treatment of TiO.sub.2 in Powder Form with H.sub.2 PtCl.sub.6 (Cat V) 
49.5 g of TiO.sub.2 (Bayer) were made into a paste with 70 ml of an H.sub.2 
PtCl.sub.6 containing 0.5 g Pt calculated as metal. The water-moist crude 
product was first of all dried in a drying cabinet at 110.degree. C., then 
dried at 0.1 Pa and 110.degree. C. and stored under argon. The catalyst 
contained 1% Pt. 
Example 13 
Synthesis of Si(CH.sub.2).sub.2 SiClMe.sub.2 !.sub.4 with 5g of Cat I 
867 g (9.17 mol) of chlorodimethylsilane and 5 g of the dried catalyst Cat 
I were added to 250 g (1.84 mol) of tetravinylsilane in 600 ml of thf. 
Heating took place with vigorous stirring until the clearly exothermal 
reaction started after a few minutes and the external heat source was then 
removed. The reaction supported itself for approx. 30 min under vigorous 
reflux. When the reflux became weaker, heating took place for a further 15 
h to 55.degree. to 60.degree. C., followed by cooling to room temperature. 
The supported catalyst was filtered off through a frit. From the 
colourless solution all the volatiles were removed in vacuo. In so doing 
the product crystallized out spontaneously as a colourless solid. The 
latter was then vacuum-dried for a further 20 h. 
Yield: 861.5 g corresponding to 92% of theoretical. 
Example 14 
Synthesis of Si(CH.sub.2).sub.2 SiClMe.sub.2 !.sub.4 with 4 g of Cat I 
The reaction took place similarly to Example 2, but with only 4 g of the 
supported catalyst Cat I. The mixture of thf and surplus 
chlorodimethylsilane condensed out after the filtration was used again in 
Example 3. 
Yield: 854.3 g corresponding to 91% of theoretical. 
Example 15 
Synthesis of Si(CH.sub.2).sub.2 SiClMe.sub.2 !.sub.4 with 4 g of Cat I 
729 g (7.71 mol) of chlorodimethylsilane and 4 g of the dried catalyst Cat 
I were added to 250 g (1.84 mol) of tetravinylsilane and to the condensate 
from Example 3 consisting of thf and chlorodimethylsilane. The whole was 
heated under vigorous stirring to approx. 40.degree. C. until the clearly 
exothermal reaction started after a few minutes and the external heat 
source was then removed. The reaction supported itself for approx. 60 min 
under vigorous reflux. When the reflux became weaker, heating took place 
for a further 15 h to 55.degree. to 60.degree. C., followed by cooling to 
room temperature. The supported catalyst was then filtered off through a 
frit and from the colourless solution all the volatiles were removed in 
vacuo. In so doing the product crystallized out spontaneously as a 
colourless solid. The latter was then vacuum-dried for a further 20 h. 
Yield: 849.0 g corresponding to 90% of theoretical. 
Example 16 
Synthesis of Si(CH.sub.2).sub.2 SiClMe.sub.2 !.sub.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 heated to 40.degree. C. and the 
external heat source removed after the start of the exothermal reaction. 
The temperature then rose spontaneously to approx. 60.degree. C.; on 
completion of the exothermal reaction, heating for a further 15 h to 
40.degree. C. took place, followed by cooling to room temperature. The 
catalyst was filtered off and the colourless solution freed from volatile 
components in vacuo. The product was obtained as a white solid. 
Yield: 32.5 g corresponding to 86% of theoretical. 
Example 17 
Synthesis of Si(CH.sub.2).sub.2 SiClMe.sub.2 !.sub.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.degree. C. and the 
external heat source removed after the start of the exothermal reaction. 
The temperature then rose spontaneously to approx. 65.degree. C.; on 
completion of the exothermal reaction, heating for a further 2 h to 
50.degree. C. took place, followed by cooling to room temperature. The 
catalyst was filtered off and the colourless solution freed from volatile 
components in vacuo. The product was obtained as a white solid. 
Yield: 34.6 g corresponding to 92% of theoretical. 
Example 18 
Synthesis of Si(CH.sub.2).sub.2 SiClMe.sub.2 !.sub.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. 
Heating took place slowly to 40.degree. C., and after about 30 min a 
strongly exothermal reaction started. In so doing the reaction mixture 
heated up to 65.degree. C. and had to be cooled in the meantime with a 
cooling bath (acetone/dry ice). After the end of the exothermal reaction 
heating took place for a further 2 h to 50.degree. C., followed by 
stirring for a further 20 h at room temperature. The catalyst was then 
filtered off through a frit and the filtrate freed of volatile components 
in vacuo. 
Yield: 80.8 g corresponding to 86% of theoretical. 
Example 19 
Synthesis of Si(CH.sub.2).sub.2 SiClMe.sub.2 !.sub.4 with Cat V 
86.8 g (917.0 mmol) of chlorodimethylsilane and 0.2 g of the catalyst Cat V 
were added to 25 g (183.4 mmol) of tetravinylsilane in 60 ml of thf. 
Heating took place slowly to 40.degree. C. and the external heat source 
was removed as soon as the exothermal reaction started. In so doing the 
reaction mixture heated up rapidly to 60.degree. C. After the end of the 
exothermal reaction heating took place for a further 2 h to 50.degree. C., 
followed by stirring for a further 20 h at room temperature. The catalyst 
was then filtered off through a frit and the filtrate freed of volatile 
components in vacuo. 
Yield: 70 g corresponding to 74% of theoretical. 
Example 20 
Synthesis of Si(CH.sub.2).sub.2 SiClMe.sub.2 !.sub.4 with Cat I in 
tert.-butylmethylether 
509 ml (433.7 g; 4.59 mol) of chlorodimethylsilane and 2 g of the catalyst 
Cat I were added to 125 g (0.92 mol) of tetravinylsilane in 300 ml of 
tert.-butylmethylether. Heating took place to 40.degree.-45.degree. C. and 
the external heat source was removed as soon as the exothermal reaction 
started. The temperature rose slowly to 55.degree. C. due to the 
consumption of the low boiler (chlorodimethylsilane) and dropped again 
after about 30 min with the end of the exothermal reaction. Heating then 
took place for a further 2 h to 50.degree. C., followed by cooling to room 
temperature and removal of the catalyst by filtration through a frit. 
(Product crystallized in the frit was easily transferred by heating with a 
hair-drier). The colourless filtrate was freed of volatile components in 
vacuo and the product was obtained as colourless crystals. 
Yield: 435 g corresponding to 92% of theoretical.