DE2245187A1 - PROCESS FOR PRODUCING ORGANIC SILICONE COMPOUNDS BY REACTION OF ORGANIC SILICON HYDRIDS WITH UNSATURATED ORGANIC COMPOUNDS - Google Patents

Description

The invention relates to a method for producing organosilicon compounds by reacting organosilicon compounds Hydrides with unsaturated organic compounds.

It is known from the literature that this reaction, which results in the addition of a Si-H group of the organosilicon Hydrides on the "C = C" or "C - C" bond or the "C = C" or "C - C bonds of the unsaturated compounds based, a suitable method for the preparation of Si-Liciumorganischer Compounds with the silicon-carbon bond or with several of these bonds represent.

767l) -Tp-r (8)

13/1201

The aforementioned addition reaction, also called hydrosilylation, can be carried out under very different conditions be e.g. B. by heating a mixture of the organosilicon hydride and the unsaturated compound under atmospheric or higher pressures to high temperatures (GB-PS 746 510), by irradiating the mixture with UV light (GB-PS 684 597) or with the ^ radiation of Co (US-PS 2 570 642), with triggering with organic Peroxides (GB-PS 769 496), optionally with others Initiators for radical reactions, in the presence of catalysts such as tertiary amines or phosphines (U.S. Patent 3,057,902), of aluminum, boron and tin chlorides (FR-PS 1 155 997), of metals on carriers, ζ. Π. of platinum on activated carbon (DT-PS 1 126 391) or on soluble ones Group VIII metal complexes, e.g. B. iron (BE-PS 668 907), cobalt (US-PS 3,271,362), nickel (J. Chem. Soc. / D /, 1970, 611), ruthenium (FR-PS 1 520 444), palladium (j. Chem. Soc. / D /, 1969, I61), Iridium (j. Chem. Soc. / A /, 1969, 683), platinum and rhodium.

However, the previously known methods have a number of disadvantages. Thus, the thermal additions are only at high temperatures, resulting in a reduction of its selectivity and leads to the formation of by-products. In the case of dissolution by light or by radiochemical means, the addition of the organosilicon hydrides cannot be carried out in the case of unsaturated organic compounds which can easily undergo polymerization. Metals distributed on supports are then only relatively effective catalysts. When they are used, the reaction must be ictierwc; can be carried out at higher temperatures (over 150 C).

SAD ORfQINAL

309813/120! ^ *

- sr -

- I.

They also have other disadvantages that also occur with other heterogeneous catalysts: Sensitivity to catalytic poisons, dependence on activity on the method of preparation and fluctuations in the activity between the individual catalyst batches. Your advantage is there in that they form a heterogeneous phase in the reaction medium, so that they can easily be removed from the reaction mixture can be separated.

It is known that the aforementioned disadvantages can be eliminated to a considerable extent by carrying out the hydrosilylation in the presence of salts or complexes of the transition metals. Of these, platinum and rhodium complexes in particular enable the addition to be carried out under relatively mild conditions with high stereospecificity and high yields. The best-known catalysts of this type are hexachloroplatinum / IV / acid (US Pat. No. 2,283,218), the most widely used industrial hydrosilylation catalyst to date, and phosphine complexes of rhodium such as / (C ₆ H ₅ ) P / ₂ RhCl (US Pat. No. 3,546 266), / (C ₆ H ₅ ) -P / ₂ RH (CO) Cl (J · Chem. Soc. / A /, 1966, 1711), / (C ₆ H ₅ O ₃ P / Rh (CO) H (J. Organometal. Chem. 21, 207/1970 /), olefinic complexes of rhodium (GB-PS 1 0 ^ 1 237, FR-PS 1 366 279) and mixed rhodium carbonyls, e.g. / RhCl (C0) ₂ / ₂ (j. Organometal. Chem. 21, 207/1970 /). Despite numerous advantages, however, these catalysts also have a number of deficiencies: In the case of catalysis with hexachloroplatinum / IV / acid, their reduction often occurs in the course of the reaction due to the hydride present when platinum is precipitated, the catalytic activity of which is significantly lower than that of the catalyst originally used.

309813/1201

sung relatively inconsistent and go into catalytically inactive forms over * A common disadvantage ... of all the above connections is also their high price. Because of this, their regeneration and repeated Possibility of use highly desirable, but very much in view of their solubility in the reaction medium difficult, often without any loss of their katiilytlechlin 'activity not possible.

The process for preparing organosilicon compounds under the conditions set out in this invention 'eliminates many of these disadvantages of the previously used processes and the catalytic systems used. The essence of the invention resides in carrying out the hydrosilylation reaction under mild conditions in the presence of catalysts, which in itself the advantages more homogeneous and heterogeneous catalysts, calibrated by ei « ne are characterized by high catalytic activity and easily separated from the reaction mixture and reused can be. The catalysts described in the context of this invention make it possible to carry out the reaction both in liquid form as well as in the gas phase.

It has been found that catalysts with the aforementioned properties by the action of hexachloroplatinum / IV / acid or from rhodium trichloride to polymeric organic Substances that carry phosphine, phosphite, amino or nitrile groups are produced in such an environment can, in which the compounds listed dft * transition metals are soluble, with advantage in hydroxyliethenic solutions medium, most advantageously in aqueous or absolute Ethyl alcohol. The reaction can be achieved by simply standing

309813/1201

leaving the reaction mixture for a sufficiently long period of time or by heating, advantageously up to the boiling point of the solvent, but not more than 120 ° C, completed will. Catalysts prepared in this way are distinguished by the fact that the metal contained in them adapts to the active ones Groups of the polymeric substance is coordinated.

It was also found that in addition to the hexachloroplatinum / IV / acid for the preparation of these catalysts, their salts, eg. B. NaHPtClg.nHgO, KHPtCl ₆ .nHgO, KgPtClg.nE ^ O (n = 0-6), optionally olefinic platinum complexes of the type HPtCl "(olefin) prepared from these compounds can be used. In some cases it is advantageous to carry out the preparation in a medium containing an inorganic or organic acid, the dissociation capacity of which in the medium used is comparable to or higher than the dissociation capacity of hexachloroplatinum / IV / acid, advantageously using hydrochloric acid .

Similarly, in the preparation of catalysts of the type described above, in addition to the rhodium trichloride Rhodium complexes are used, which under the specified conditions with the organic polymer compounds of general formula L RhX, Y Z, form, in which L one

abcd

polymeric phosphine-containing ligand, X a phosphine of the type PR R R ^J (R and R are identical or different C _{1 -C O} -alkyl-, Gß -Cg-aryl-, C ^ -Cg -cycloalkyl- or C.-C. "-Alkyl groups and hydrogen or a combination thereof, R then a Cs - C _1f) aryl group, advantageously a phenyl or a substituted phenyl group), Y a

309813/1201

Carbonyl group or a % ■ -coordinated alkene (with advantage the ethylene, cyclooctadiene) and Z represents a hydrogen atom or a halogen, where a is at least 1, b = 1 or 2, c = 1 or 2, d = 1 or 2 and a + b + c + d = 4.

For the purposes of the invention, any polymeric substance can be used any organic compound can be used whose molecular weight and structure have the appropriate mechanical properties « shafts (satisfactory strength, small deformability at temperatures up to 150 C), which forms a heterogeneous phase in the reaction medium and the phosphine, Contains phosphite, amino or cyano groups or these groups in a suitable combination. To this end you can z. B. the following polymers are used: polystyrene, copolymers of styrene with divinylbenzene or allyl chloride, Polyvinyl chloride, polymethacrylate and their copolymers with bifunctional monomers, etc., which are linked to the groups listed either directly or via carbon chains,

z. B. via (-CH ₀ -), are substituted. Particular advantages

It is liable when it comes to so-called macroreticulars Polymers, d. H. to substances with an abundantly developed porous internal structure and thus with a large specific surface even when not swollen.

It has also been found that in certain cases it is advantageous to reduce the activity of the catalysts mentioned by the action of SnCl ", secondary or tertiary phosphines or to vary amines on the already prepared catalysts, possibly also in such a way that the hydrosilylation reaction after adding these substances - is carried out at a maximum molar ratio to metal of 5: 1.

3098 13/1201

In the case of catalysis with the platinum and rhodium complexes described above, which are coordinatively bound to polymeric organic substances, the addition of organosilicon hydrides, advantageously of the R ^ SiH (n = 1 - 3) type, with R being the same or different, can be carried out under mild conditions C - C g-alkyl-, Gs - C ^^ krylL- ₁ substituted C ₁ - C g-alkyl-, substituted C ^ - C ^ -aryl-, C ^ - Cg-cycloalkenyl-, C "- C" - Alkenyl, C1 -C6 alkynyl, organoxy, acyloxy, carboxy, siloxy, germoxy, stanoxy and silyl groups and halogen atoms or combinations thereof, with unsaturated compounds with a “C = C” or “C” - C "bond or with" C = C "or" C ^ C "bond

~ h *> 6 7 ** h -

gen, with advantage of the type R rC = C R R 'and of the type R C-C

5 4 5 6 7

R are carried out, where R, R, R and R an ¥ hydrogen atom, a C - C g -alkyl, a C / - C "-Cycloalkyl-, a C, - - C ₂ -aryl, a C ₇ - C.-g-aralkyl-, a substituted C ₁ - Cjo-alkyl-, a substituted Cg - C "-aryl-, a C ₂ - C" -alkenyl-, a substituted C "- C ₁ " -alkenyl-, mean a cyano, organoxy, acyloxy, carboxy, siloxy, germal, stanyl and phosphino group and halogen atoms or a combination thereof.

In the liquid phase, the hydrosilylation according to the Invention with advantage by heating the mixture of both reactants in the presence of a catalyst to a suitable one Temperature, advantageously in the range of 20-15 ° C, under normal or increased pressure, advantageously from 1 to 15 atm, while to achieve the desired conversion the starting components can be realized in the products in the required time. The relative amounts of the silicon-containing The hydride and the unsaturated organic compound can be varied within wide limits. Although this

309813/1201

ratio in general by the stoichiometry of the reaction is determined

-Si-H + C = C > -Si-CCH

/ X - I I

- d. H. a Si-H bond corresponds to a C = C bond or half of a C - C bond - it is in some ways Cases advantageous to work with an excess of one of the reactants, which leads to the desired conversion leads in less time; this way you can too Products with several "C = C" or Si-H bonds can be obtained.

The amount of catalyst can also be varied within wide limits. The platinum and rhodium complexes according to the Invention provide effective catalysts in the order of 1 gram atom of metal per 10 mol of unsaturated Groups represent; the maximum amount of catalyst results primarily from economic considerations. It was determined, that in order to achieve suitable reaction rates it is advantageous to use catalyst concentrations from 1 gram atom of metal to work from 100 to 10,000 moles of unsaturated groups.

In certain cases, especially when at least one of the reactants tends to polymerize or one If the substance is viscous or solid, it is advantageous to carry out the reaction in the presence of a solvent perform. Any substance that interacts with the reactants can be used as the solvent does not react and does not cause a decrease in its catalytic activity by acting on the catalyst.

3098 13/1201

Aromatic hydrocarbons are particularly suitable for this purpose, z. B. benzene, toluene, xylene or various ethers, e.g. B. tetrahydrofuran or dioxane and the like, preferably in a weight ratio of 100-1000: 1, based on the catalyst.

With the method described above, the corresponding products can be obtained in good yields. To Completion of the reaction, the catalyst from the reaction mixture can easily, for. B. by decanting, filtration, or, in the case of low-boiling products, by distilling them off. The catalyst recovered in this way can be used again. The process can also be carried out continuously in the liquid phase, by contacting the reaction mixture with a bed of catalyst at a suitable rate.

When using low-boiling starting raw materials, the discontinuous as well as the continuous implementation of the reaction in the liquid phase requires work under increased pressure, which places higher demands on the equipment to be used and in many cases also increases the operational risks. This is especially true for syntheses that use acetylene as a raw material. It has been found that in these cases the reaction can also be successfully carried out with gaseous reactants by contacting their vapors with the complexes bound to a polymer according to the invention. The platinum complexes are particularly active here. Suitable reaction conditions are: atmospheric or slightly elevated pressure (up to 3 atm); the temperature range results

3098 13/1201

from the dew point of the reaction mixture, since the condensation of the starting substances and the products on the catalyst must be prevented, and from the thermal stability of the catalyst, ie it is between 30 and 230 ⁰ C; the molar reactant ratio is 0.1 to 10, and the contact times correspond to space velocities of 5 to 500 mol of the reaction mixture per hour and kilogram of the catalyst. In this way, the hydrosilylation reaction can also be carried out with reactants whose volatility is sufficient that they have a vapor pressure of at least 70 torr at the reaction temperature. The installation of an apparatus for carrying out this reaction with gaseous starting components hardly differs from the usual systems for heterogeneously catalyzed reactions in a catalytic fixed bed reactor.

Another option that takes advantage of operating at atmospheric pressure or just slightly elevated pressure retains and has advantages especially when one of the starting components is only slightly volatile, consists in Use of a continuous falling film reactor. The less volatile phase flows down along the catalyst layer, the more volatile component is in this reactor in the Introduced cocurrent or countercurrent as gas. The less volatile phase can be dissolved in a suitable solvent be, with advantage in an aromatic hydrocarbon or a cyclic ether. What the reaction conditions as far as is concerned, the same applies as in the case that both components are present in the gaseous phase; only the lower temperature limit is lower, down to -20 C.

3 0 a H 1 3/1 2 0 1 OWOlNAL INSPECTED

The following examples show the implementation options of the invention without wishing to restrict or limit it in any way:

example 1

A mixture of 20.6 g of a styrene-divinylbenzene copolymer (prepared by copolymerizing styrene with divinylbenzene in a weight ratio of h : 1, by chlorination and reaction with diphenylphosphinolithium) with 5.1 $ phosphorus, bound in the form of -CH -P (CgH -) "groups, and from 7 g of RhCl" .3HpO, dissolved in 2 ^ 0 ml of ethyl alcohol, was brought to a moderate boil for 12 hours. After separation of the polymer from the solution by filtration at 50 ⁰ C, its through washing with 50 ml of ethyl alcohol χ 6 and drying, 26 g of a catalyst having won $ 11 Rh.

Example 2

6 g of the compound prepared according to Example 1 were added to a mixture of 200 ml of benzene and 200 ml under nitrogen Ethyl alcohol is weighed, after which 16 hours in this mixture long ethylene was introduced. After filtration, washing with 3 200 ml ethyl alcohol and 3 χ 200 ml benzene and drying obtained 5 »2 g of a catalyst bound to rhodium Contains ethylene.

Example 3

The catalyst was obtained by reacting 27 g of the copolymer used in Example 1 under nitrogen

3Q.9Ö13 / 1201

with 5 g RhCl / P (C ₆ H ₅ ) / in 500 ml CH ₂ Cl ₂ . The reaction mixture was left to stand for 48 hours and then shaken on a vibrator for 2 hours. After filtration, washing with 2 × 250 ml of CH ₂ Cl ₂ and drying, 28 g of a product with 7.6 # Rh were obtained.

example k

A mixture of 11 g makroretikularem poly (Cyanoäthylmethakrylat), 7 g Rhodiumtrichiorid and 80 ml of ethanol was heated for 7 hours at 80 ⁰ C. The polymer was separated off by filtration after the reaction mixture had cooled; after washing it through with 5 × 100 ml of ethyl alcohol and drying it, a catalyst with $ 4.62 Rh was obtained.

Example 5 ''

17 g of a macroreticular styrene-divinylbenzene copolymer from Example 1, which contained 4.6 t N in the form of -CH ₂ N (CH ") ₂ groups, and 9 g of RhCl" .3H ₃ O, dissolved in 100 ml of ethyl alcohol , were ^{heated to 80 °} C. for 6 hours. The polymer was filtered off, washed through with 6 ac 100 ml of ethyl alcohol and dried. A catalyst containing 2 _{tons of} 15 $ Rh was obtained.

Example 6

16 g of macroreticular poly (2-dimethylaminoethylinethacrylate), 8 g of RhCl .3H ₂ O and 90 ml of water were left to stand for 2k hours at room temperature. After separation

3 0 9 8 13/1201

of the polymer by filtration, washing it through with 5 × 100 ml of water and drying, a catalyst with 10.53 f> Rh was obtained.

Example 7

A mixture of 10 g of the macroreticular styrene-divinylbenzene copolymer described in Example 1 and 4.7 g of hexachloroplatinum / IV / acid, dissolved in 50 ml of ethyl alcohol, was ^{heated to 80 °} C. for 7 hours. After cooling, separation of the polymer from the solution by filtration and washing it with 5 × 100 ml of ethyl alcohol and drying, a catalyst with 8.0 $ Pt was obtained.

Example 8

A mixture of 3H makroretikularem g poly (2-cyano äthylmethakrylat), 11 g of hexachloroplatinic / IV / acid and 100 ml ethyl alcohol was heated for 6 hours at 80 ⁰ C. The cooled reaction mixture was filtered; After washing through with 6 χ 100 ml of ethyl alcohol and drying, 37 g of a catalyst with 3.1 $ Pt were obtained.

Example 9

15 g of a macroreticular styrene-divinylbenzene copolymer containing k, 6 $> N in the form of -CH ₂ N (CH ,,) ,, - groups, and 5 g of hexachloroplatinum / IV / acid, dissolved in 70 ml of ethyl alcohol Heated to 80 ° C for 7 hours. The polymer was filtered off from the solution, washed through with 5 × 80 ml of ethyl alcohol and dried. 17 g of a catalyst with \ k.6 $> Pt were obtained.

309613/1201

22AB187

Example 10

21 g of macroreticular poly (2-dimethylaminoethyl methacrylate), 7 g of hexachloroplatinum / ivy acid and 120 ml of water were left to stand for 2k hours at room temperature. After the usual further processing, 23 g of a catalyst with 21 # platinum were obtained.

Example 11

A mixture of the macroreticular styrene-divinylbenzene copolymer from Example 9 and 6 g of hexachloroplatinum / IV / acid, dissolved in 100 ml of water, was left to stand for 2k hours. After separation of the polymer and its usual further processing and drying, a catalyst with $ 14.2 platinum was obtained.

Example 12

By boiling 10 g of hexachloroplatinic / IV / acid with 120 ml of ethyl alcohol for four hours, H (C ₂ H.PtCl_) was obtained. 35 β of the macroreticular styrene-divinylbenzene copolymer from Example 1, which contained -CH ₂ P (CgH-) ₂ groups, were added to the complex prepared in this way. After standing for twenty-four hours, the polymer was separated off by filtration, washed through with 3 × 200 ml of ethyl alcohol and dried. One won k \ g of a catalyst with 9.2 ^ plaCin.

Example 13

In "in R" action, 720 g * weight * t »ile tri

309813/1201

propylsilane, 810 parts of 1-hexene, 1100 parts of benzene and 10 Parts of the catalyst prepared according to Example 5 are given. The reaction mixture was heated to boiling point for four hours; after the catalyst has been separated off the reaction mix, through. Filtration was gained by distillation n-Hexyltripropylsilane in 83 percent yield.

Example 14

A mixture of 700 parts of triethoxysilane and 750 parts 1-hexene and 10 parts of a catalyst according to Example 6 were left to stand at room temperature for 20 hours. After the catalyst had been separated off, 95% of the n-hexyltriethoxysilane were obtained by distillation. The separated catalyst was reintroduced into the reaction vessel, and the reaction was repeated under the same conditions. The yield of the product was $ 92 · in another

Repetition of the reaction felled the n-hexyltriethoxysilane in an 87 percent yield.

Example 15

A mixture of 810 parts of triethoxysilane, 790 parts of 1-hexene and 10 parts of a catalyst according to Example 7 was allowed to stand at room temperature for four hours. After separating the catalyst by filtration, it was obtained one 97 $ of n-hexyltriethoxysilane. The isolated catalyst was again together with 810 parts of triethoxysilane and 790 parts of 1-hexene were added to the reaction vessel. After standing for four hours at room temperature, n-hexyltriethoxysilane was obtained in the same yield. One more-

3 0 9 8 13 / f 2 0 1

- rf ..

Repeating the reaction times under the same conditions gave the product in 9-6 percent yield.

Example 16

800 parts of triethylsilane, 850 parts of 1-octene, 10 parts of a catalyst according to Example 11 and 20 parts of triphenylphosphine were placed in a reaction vessel. The reaction mixture was heated to 90 ° C. for four hours. After removal of the catalyst is won by distillation 59 <jo n-Oktyltriäthylsilans.

Example 17

810 parts of triethoxysilane, 800 parts of 1-hexene, 10 parts of a catalyst according to Example 11 and 10 parts of tin / I / Z chloride were placed in a reaction vessel. After four hours of heating the reaction mixture to 80 ⁰ C and separation of the catalyst were recovered, through distillation n-Hexyltriäthoxysilan in 71prozentiger Ausbeut "

Example 18

In a reactor (diameter 3 cm, length 50 cm), the with 30 g of the catalyst from Example 9 and ceramic Rings was filled, a mixture of triethylsilane and was at 75 ° C at a rate of 65 ml / h 1-hexene (molar ratio 1: 1) metered. It got a 65 percent Sales of the reaction mixture in n-hexyltriethylsilane achieved.

3 0 Β ö 1 3/1 2 0 1

Example 19

A mixture of an organosilicon hydride, one unsaturated compound and 10 parts of a catalyst was placed in a reaction vessel, which was sealed and caused the reaction mixture to react. After the catalyst had been separated off by filtration, the products were obtained by distillation in yields which together with the reaction conditions are compiled in the table below.

Example 20

About 3 g of a catalyst, which was prepared from a macroreticular, -CH_N (CH) "- groups-bearing styrene-divinyl copolymer and from hexachloroplatinum / IV / acid (platinum content in the catalyst 8.1 $), was at 110 ⁰ C 1, 3-butadiene and trichlorosilane passed at rates of 0.14 mol / h and 0.06 mol / h. Sales of trichlorosilane in butenyltrichlorosilane reached $ 70 »in addition, 1,4-bis (trichlorosilyl) butane was produced in small quantities.

Example 21

6 of a catalyst which was prepared from a macroreticular, on its surface -CH_CN groups tra'genden styrene Divinylbenzolmischpolymerisat and from hexachloroplatinic / / IV / g acid (platinum content in the catalyst 1.45 #) were at 100 ⁰ C Acetylene and trichlorosilane at speeds of 0.0? Mol / h and 0.03 mol / h passed. Sales in vinyltrichlorosilane were $ 95 .

309813/1201

Silicon-containing unsaturated hydride compound

Share ^parts Tabel

React React Kataly functional ions sator, temp. Time preparation ⁰ C Hours. according to example

Product yield,

Trichlorosilane 930

Trichlorosilane 950

Trichlorosilane

f # 915

J Srrichlorosilane

Z 860

> Jr i chiors i1an - 680

O ^ riethoxysilan

_ ·. 800

Triethoxysilane 850

Triethoxysilane 850

Triethoxysilane 670

Triethoxysilane 780

Triethylsilane 890

Triethylsilane

820 triethylsilane

91O

Vinyl tri chiorsilan

1-heptene 1050

1-heptene

Styrene

Allyl chloride

1 witches

Ethyl vinyl ether

Ethyl vinyl ether

Acrylonitrile 690

Vinyl acetate

1 witches

1-hexene 860 1 cyclohexene 970 k

100

80

80

100

90 80 80 80 80 100 20

80 120

7 2 2 2 3 5 24

20 6

(2-trichlorosilylethyl) trichlorosilane, 85

n-heptyl trichlorosilane, 73

n-heptyl trichlorosilane, 79

1- and 2-phenyltrichlorosilane (1 : 1), 37

3-chloropropyltrichlorosilane,

n-hexyltriethoxysilane, 90

( 2-ethoxyethyl ) triethoxysilane, 50

( 2-ethoxyethyl ) triethoxysilane, 90

( 1-cyanoethyl ) triethoxysilane, 19

(Triethoxysilyl) ethyl acetate, 17

n-hexyl triethylsilane, 92

n-Hexyltriethylsilane, 49 n-Cyclohexyltriethylsilan, ö9

22Fig.187

Example 22

About 3 g of a catalyst according to Example 21 were at 70 C acetylene and methyldichlorosilane at speeds of 0.133 mol / h and 0.057 mol / h. Sales in methylvinyldichlorosilane reached $ 90.

Example 23

Acetylene and triethoxysilane were passed over 3 g of a catalyst according to Example 21 at 100 ° C. at rates of 0.077 mol / h and 0.033 mol / h. The conversion in triethoxyvinylsilane was 90%.

example 2k

About 7 g of a catalyst, which consists of a macroreti calular copolymer of 2-cyanoethyl methacrylate and of ethylene dimethacrylate and of hexachloroplatinum / IV / acid was prepared (platinum content in the catalyst 0.7 $ trickled at 50 ° C. at a rate of 0.025 Mol / h of liquid triethoxysilane. In countercurrent, a flow of acetylene gas rose at a rate of 0.075 Moles / h. The product contained 90 # triethoxyvinylsilane.

30 above sea level V 1 20 1

Claims (2)

Claims 1. Process for the production of organo-alcium bonds by reaction of organosilicon hydrides, the contain at least one hydrogen atom bonded to a silicon atom, with unsaturated organic compounds, the aliphatic, with at least one double * · or one Contain triple bond bonded carbon atoms, since * characterized by that the reaction is catalyzed with platinum and rhodium compounds, in which the netall is coordinatively bound to polymeric * organic substances, which are phosphine, phosphite, amino or contain cyano groups or combinations thereof, the reaction being discontinuous in the liquid phase in the presence of a solvent or without a solvent or is realized continuously or under conditions in which at least one of the reactants is a gas occurs. 2. The method according to claim 1, characterized in that the used in the preparation of the catalyst polymeric substance containing the phosphine, phosphite, araino or carries cyano groups or combinations of these groups and to which the metal is coordinated, polystyrene, a copolymer of styrene with divinylbenzene or allyl chloride, polyvinyl chloride or polymethacrylate or a copolymer of the same is then preferably with a richly developed porous internal structure, and that the platinum and rhodium compounds hexachloroplatinum / IV / acids, their salts or complexes of the type HPtClO./olefin/, where ethylene or cyclohexene is the preferred olefin, 309813/1201 or rhodium complexes, which by interaction with of the polymeric substance lead to compounds of the general formula L RhX, Y Z, in which L is a phosphine group of the ora D c d Ganischen polymer means, X is a phosphine of the type PR RR ^J (R and R are the same or different C ₁ - C ₁₀ -alkyl, C ₆ - C _g -aryl, Cg - Cg-Cycloalkyl.- or C ₁ - C_ -Alkoxy groups or hydrogen atoms or their combination, R is a Cg - C _1o -aryl group, advantageously a phenyl or a substituted phenyl), Y is a carbonyl group or a TT-coordinated alkene, advantageously an ethylene, a cyclohexene or a cyclooctadiene and Z. is a hydrogen atom or a halogen, where a minimum 1, b, c and d are 1 or 2 and a + b + c + d = 4. 3. Process according to claims 1 and 2, characterized in that the organosilicon hydride is preferably selected from the group of compounds of the general formula R. SiH (n = 1, 2), in which R are identical or different C ₁ - Cjg- Alkyl-, Cg-Cg-cycloalkyl-, C / -C "-aryl-, substituted C- Cg-alkyl-, substituted Cg-C" -aryl-, Cg-Cg-cycloalkyl-, C _{2 -Cg-alkynyl} -, organoxy *, acyloxy, carboxy, siloxy, germoxy, stanoxy and silyl groups and halogen atoms or a combination thereof, and the organic unsaturated compound advantageously from the groups of compounds of the general | i ί 6 7 h _ ti Formula R RX = CR R 'and the formula RC - CR- ^ is selected, in which R, R, H and R are a hydrogen atom, a C - C..g-alkyl-, a Cg - Cg-cycloalkyl-, a Cg - C ₁₂ aryl, a Cg - C "aralkyl, a C" - C ₁ "alkenyl, a substituted C" - C ₁ "alkenyl, a cyano, organoxy, acyloxy, Mean carboxy, siloxy, silyl, germyl, stanyl or a phosphino group or halogen atoms or a combination thereof. , 30 9813/1201