CS199329B1 - Process for preparing organosilicon compounds - Google Patents

Description

The invention relates to a process for the preparation of organosilicon compounds by addition of silicon hydrides to unsaturated organic compounds.

It is known that this reaction, consisting of the addition of a Si-H group of organosilicon hydrides to the C = C or C2C bond or linkage of organic compounds, is an industrially used process for preparing organosilicon containing Si-C type linkages or bonds.

This process, also called hydrosilylation, occurs with compounds containing a C = C bond in the sense of the equation:

_x of II = Si-H + JC = C _X -> = Si-C-CH.

^z II

This process can be carried out under very diverse conditions (E.J. Lukevits, MG Voronkov: Gidrosilirovanie, gidrogermylirovanije, gidrostanilirovanije. Izd. Akad. Nauk Latvijskoj SSR, Riga, 1964). Preferred catalysts are transition metal complexes. The catalyst most commonly used to date is chloroplatinic acid (U.S. Pat. No. 2,823,218). Also suitable are rhodium complexes such as ((C ₆ H ₅ P) / R R Cl (US Patent 3,546,266), ((C ₆ H ₅ ) ₃ P / ₃ Rh (CO) H (J. Organometal. Chem. 21, 207) (C ₆ H ₅ ) ₃ P / ₂ Rh (CO) Cl (J. Chem.

Soc. (A) 1966, 1711), (Rh (CO) ₂ Cl / ₂ (J. Organometal. Chem. 21, 207 (1970)) and rhodium complexes with coordinated olefin (British Patent 1,041,237, French Patent 1,366) 279).

Although these catalysts make it possible to carry out hydrosilylation under relatively mild conditions, usually with high selectivity and good yields, they are not entirely without drawbacks. Their main ··· ·,> *

199 329

The disadvantage is the high price, which makes their recovery and reuse highly economically desirable. Because of the solubility of these complexes in the reaction medium, their isolation is difficult, and in many cases impossible without a decrease in their catalytic activity.

It is further known that this lack of soluble hydrosilylation catalysts based on transition metal complexes, while retaining their advantages, can be overcome by binding these compounds to organic polymeric materials, such as styrene-divinylbenzene copolymers.

This is done through such active groups which are capable of forming coordinate bonds with a metal, for example by -P (CGH _{5) 2} · Advantages of this method are limited to those substances whose structure ensures their insolubility under conditions hydroeilylační reaction. Moreover, these carriers exhibit considerable deformability at higher temperatures, which makes it difficult to use them at reaction temperatures of about 120 ° C. Another disadvantage is the fact that they have to be produced by a multi-stage process.

According to the present invention can produce organosilicon compounds by the addition of silica hydrldů general formula ^R 4-n ^S1H n 'where denotes R is the same or different alkyl groups having 1-8 carbon atoms, aryl having 6 to 12 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkenyl of 2 to 6 carbon atoms, siloxy or halogen atoms, e.g. fluorine, chlorine or bromine and n is 1 or 2, to unsaturated organic compounds of the formulas

R ¹ R ² C = CR ³ R ⁴ or R 6 CbCR ² ,

Where R, R, R and R are hydrogen, (C 1 -C 16) alkyl, (C 6 -C 8) cycloalkyl, (C 6 -C 12) aryl, (C 7 -C 10) cycloalkenyl, alkoxy or alkenoxy group; These groups being optionally substituted by silyl, siloxy or alkoxy groups having 1 to 6 carbon atoms, aryloxy groups having 6 to 12 carbon atoms, cyano groups or halogens, for example fluorine, chlorine, in the presence of rhodium complex catalysts wherein the reaction is carried out in the presence of rhodium complex catalysts formed from soluble rhodium complexes of the general formula

Rh X Y. Z ',

O C where denote

X a tertiary or di-tertiary phosphine group, e.g. a triphenylphosphine group,

Y is a halogen atom such as chlorine, bromine or iodine, hydrogen or a combination thereof when b = 2,

Z is a carbonyl or C 2 -C 8 alkenyl group, a is 0, 1, 2 or 3, b is 1, 2 or 3, c is 0, 1 or 2 and the sum of a + b + c is 3, 4 or 5, and organic liquids containing a coordination group having a boiling point above 150 ° C and inorganic carriers, the resulting metal content of the catalyst being in the range of 0.01 to 22 weight percent. %.

199 929

The group-coordinated organic liquid is poly (methyl-3-cyanopropylsiloxane), mannitol hexa-β-cyanoethyl ether, ethylene glycol bis (ε-cyanoethyl ether), 1,5,9-cyclododecatriene, or poly (dimethylsiloxane).

The catalyst is activated carbon, sillcagel, γ-alumina or porous glass.

The reaction between silica hydride and an unsaturated organic compound is carried out at 20 to 150 ° C and a pressure of 1 to 15 at, optionally in the presence of solvents such as aromatic hydrocarbons such as benzene, toluene, optionally xylene or an ether such as tetrahydrofuran.

The relative amounts of silica hydride and the unsaturated organic compound can be varied within a wide range. Although this ratio is generally determined by the stoichiometry of the reaction, i.e. one C-C bond per C-C bond and one C-C bond per 1/2 of the Si-H bond, it is sometimes advantageous to work with an excess of one of the reactants.

The amount of catalyst can also be varied within wide limits. The catalysts are already active in amounts of the order of 1 gram gram of metal per 10 ⁵ moles of unsaturated compound. However, to achieve the desired re-action rate, it is preferred to work with concentrations of 1 gram gram of metal per 10-10 moles of unsaturated compound. After completion of the reaction, catalysts which form a heterogeneous phase in the reaction medium and exhibit high catalytic activity can be readily separated from the reaction mixture, for example by decanting, filtering or, in the case of low-boiling products, by distillation thereof, and reused. The process of the invention thus combines the advantages of homogeneously and heterogeneously catalysed processes.

The organosilicon compounds prepared according to the invention can be used as hydrophobising agents, binders between inorganic fillers and organic materials, as intermediates for the preparation of other organosilicon derivatives or as monomers for the preparation of lacquers, resins, oils or rubbers.

The following examples illustrate the practice of the invention without limiting or limiting it.

Examples

Example 1

In other examples, the activated carbon was heated with 10% nitric acid for 5 hours, then the acid was removed by evaporation and the activated carbon was washed with distilled water until neutral. It was then heated with a 5% aqueous ammonia solution, the solution was evaporated and the activated carbon washed with distilled water for neutral reaction. After drying at 120 ° C, the activated carbon was still heated to 300 ° C under argon for several days. The reactions described below were carried out under anaerobic conditions in a 250 ml three-neck flask equipped with a stirrer, a dropping funnel and a reflux condenser.

Example 2

To 20 g of activated carbon of Example 1 was added 12.28 g of polynitrilsiloxane in 100 ml of benzene and the mixture was heated to boiling for 2 hours. To the mixture was further added 3.88 g · Rh (CO) ₂ Cl / ₂ and heating was continued for a further 2 hours. Then the benzene was distilled off, the charcoal was thoroughly washed with benzene and the remainder of the solvent was distilled off again. Thus

The 1SI 329 4 catalyst prepared contained 2.96% Rh.

Example 3

In this example, the same procedure as in Example 2 was used. To 2 g of RhCl 3. 3 H 10, 4 ml of cyclododecatriene in 100 ml of ethanol were added and the mixture was stirred at 70 ° C for 3 hours. To this mixture was then added 13 g of activated carbon from Example 1 and the mixture was heated to 70 ° C with stirring for an additional 3 hours. Thereafter, the impregnated activated carbon was thoroughly washed with ethanol and the alcohol removed by distillation. The catalyst contained 3.79% Rh.

Example 4

Example 3 was repeated except that 2 g of Bh ₃ CO ₃ -Cl ₃ was used instead of RhCl 3.3 H ₃ O. The catalyst contained 5.22% Rh.

Example 5

To 100 ml of absolute toluene was added 10 ml (4.7 g) of activated carbon and 1 g of mannit-hexa- (β-cyanoethyl ether). The mixture was heated at 80 ° C for 1 hour and then 1 g Rh ₂ (CO) ₄ Cl ₂ was added. After heating at reflux for 2 hours, the solid was filtered off and the residue distilled. The catalyst contained 4.29% Rh.

Example 6

The carrier used was γ-alumina, which was dried for 5 hours at 200 ° C under vacuum. To a mixture of 10 ml (7.2 g) of γ-alumina and 1 g of polynitrilsiloxane in 100 ml of toluene heated to boiling for 1 hour was added 1 g / Rh (CO> ₂ Cl / ₂₎ and heated to boiling for a further The solid was then filtered off, washed with toluene and the solvent was distilled off, after freeze drying of the catalyst, containing 6.24% Rh.

Example 7

Soda lime vacuum dried at 200 ° C for 5 hours was used as carrier. 0.5 g of Rh ₂ (CO) ₄ Cl was added to a mixture of 10 ml (8.8 g) of soda lime and 1.5 g of ethylene glycol bis- (β-cyanoethyl ether) in 100 ml of toluene heated to boiling for 1 hour. ₂ and the mixture was further heated to boiling for 2 hours. The solid was filtered off, washed and freeze-dried. The catalyst contained 2.34% Rh.

Example 8

Porous glass vacuum dried at 200 ° C for 5 hours was used as carrier. To a mixture of 10 ml (4.1 g) of porous glass and 1.5 g of ethylene-bis (β-cyanoethyl ether) and 100 ml of toluene, boiled for 1 hour, was added 0.5 g of Rh ₂ (CO ₄ ) Cl ₂ and reaction the mixture was heated to boiling for an additional 2 hours. The solid was filtered off, washed thoroughly with toluene and the remainder of the solvent was distilled off. After freeze-drying, the catalyst contained 3.32% Rh.

199 329

Example 9

Zeolite vacuum dried at 300 ° C for 5 hours was used as carrier. To a mixture of 10 ml (5.9 g) of zeolite and 5 g of polynitrilsiloxane in 200 ml of toluene, heated to boiling for 1 hour, was added 1 g of RH / CClHg / P / CH2Cl2, and the mixture was further heated to boiling for 2 hours. The solid was filtered off, washed, and the remainder of the solvent was distilled off. After freeze-drying, the catalyst contained 0.08% Rh.

Example 10

Mixture 380 weights. parts of 1-hexene, 365 wt. parts of triethoxysilane and the catalyst described in Examples 2 to 9 in the amounts below were heated to 80 ° C for 2.5 hours. After cooling the reaction mixture and separating the catalyst, n-hexyltriethylsilane was found in the reaction mixture in these yields (based on triethylsilane). Example catalyst Yield% (20) 77 (15) 65 (40) 55 (55) 78 (60) 77 (40) 85 (40) 84 (60) 63

Example 11

Mixture 380 weights. parts of 1-hexene, 438 wt. parts of triethoxysilane and the catalyst described in Examples 2-9 in the amount given below were heated to the indicated temperature for a given period of time. After cooling the reaction mixture and separating the catalyst, n-hexyltriethoxysilane was found in the reaction mixture in the following yields (based on triethoxysilane):

Example catalyst (parts by weight) temperature reaction Noc: 2 ° C time reaction throw yield % 2 (55) 80 2.5 84 2 (30) 25 24 47 3 Italy (25) 80 2.5 76 3 Italy (20) 25 24 83 4 Italy (20) 80 2.5 78 5 (50) 80 2.5 81 6 (50) 80 2.5 82 7 (40) 80 2.5 85 8 (35) 80 2.5 ⁸⁶ 9 (55) 80 2.5 85

329 ⁰

Example 12

Mixture 350 weights. parts of 1-heptene, 675 weight. parts of trichloroslanine and catalyst in the amount given below were heated to the indicated temperature for 3 hours. After cooling the reaction mixture and separating the catalyst, n-heptyltrichlorosilane was found in the reaction mixture in these yields (based on 1-heptene). Catalyst from Example reaction temperature yield (parts by weight) ° C%

2 (35) 150 57 3 (40) 150 10 5 (.40) 120 57 6 (50) 120 61 7 (50) 120 77 8 (60) 120 31 9 (55) 120 51

Example 13

Mixture 380 weights. parts of 1-hexene, 438 wt. parts of trlethoxysilane and 30 weights. parts of the catalyst described in Example 2 were heated at 80 ° C for 2 hours. After cooling, the reaction mixture was filtered and n-hexyltriethoxysilane was found in the filtrate in 81% yield; the separated catalyst was washed twice with 500 weight. parts of benzene and after separation of the solvent reused to catalyze the same amount of 1-hexene and trlethoxysilane. After carrying out the reaction under the same conditions as for the first use of the catalyst, a 65% yield of n-hexyltriethoxysilane was found}. The catalyst was filtered again, washed and used to catalyze under the same conditions again, this time a 35% yield of n-hexyltriethoxyailane.

Example 14

Mixture 380 weights. parts of 1-hexene, 438 wt. parts of trlethoxysilane and a given amount of solvent and catalyst of Example 3 were heated at 80 ° C for 3 hours. After cooling the reaction mixture, the following yields of n-hexyltriethoxysilane (relative to triethoxysilane) were found:

Catalyst (weight parts) solvent (parts by weight) yield % Italy (25) tetrahydrofuran (400) 84 (15) benzene (440) 87 (40) diethyl ether (350) 82 (24) chlorobenzene (550) 85

Example 15

An appropriate amount of silica hydride, an unsaturated compound and a catalyst prepared according to Example 2 or 3 were introduced into the reaction vessel. Yields of individual products determined by gas chromatography7

199 329 phi and related to silica hydrides, the same as the experimental conditions of the individual experiments are shown in the table:

silica hydride unsaturated compound catalyst reaction reaction product of example temperature time

(weight parts) (weight parts) (weight parts) Noc: 2 ° C throw % triethoxysilane (438) trans-2hexene (380) 3 Italy (25) 80 2 n-hexyltriethoxysllan, 15 triethylsilane (365) cis-2 / hexene (380) 3 Italy (25) 80 2 n-hexyltriethylsilane, 31 triethoxysilane (438) cyclohexene (410) 3 (50) 80 8 cyclohexyltriethoxysilane, 9 trichlorsilane (675) allyl chloride (460) 3 (60) 150 '5 3-chloropropyltrichlorosilane, 10 triethoxysilane (438) vinylethylet- games (380) 2 (30) 80 3 (2-ethoxyethyl) triethoxysilane, 69 triethoxysilane (438) allylcyanide (420) 2 (40) 80 6 3-cyanopropyltriethoxysilane, 11 triethylsilane (365) 1-Heptin (390) 2 (50) 80 2 mixture of heptenyltriethylsilanes, 20 triethoxysilane (438) 1,3-butadiene (340) 3 (40) 80 3 butenyl-

triethoxysilanes, 82 • SCOPE OF THE INVENTION

Claims (4)

OBJECT OF THE INVENTION 1. A process for preparing organosilicon compounds by the addition of silicate hydride of the formula ^R 4-n ^S1H n 'wherein R denotes identical or different alkyl groups having 1-8 carbon atoms, aryl having 6 to 12 carbon atoms, alkoxy having 1 to 4 carbon atoms, with alkenvlskupiny 2 to 6 carbon atoms, siloxy or halogen atoms, for example fluorine, chlorine or bromine; and n is 1 or 2, to unsaturated organic compounds of the formulas R ^{* 1} R ² C = CR ³ R ⁴ or R ⁵ Cs ² R ² , where they denote R 1, R ² , R ³ and R ^{4 are} hydrogen, C 1 -C 16 alkyl, C 6 -C 8 cycloalkyl, C 6 -C 12 aryl, C 7 -C 10 cycloalkenyl, alkoxy or alkenoxy These groups being optionally substituted by silyl, siloxy or alkoxy groups having 1 to 6 carbon atoms, aryloxy groups having 6 to 12 carbon atoms, cyano groups or halogens, for example fluorine, chlorine, in the presence of rhodium complex catalysts characterized in that the reaction is carried out in the presence of rhodium complex catalysts formed from soluble rhodium complexes of the formula 198 329 where they indicate X a tertiary or di-tertiary phosphine group, for example a triphenylphosphine group, Y is a halogen atom such as chlorine, bromine or iodine, hydrogen or a combination thereof when b = 2, Z is a carbonyl group or an alkenyl group of 2 to 8 carbon atoms, a is 0, 1, 2 or 3, b is 1, 2 or 3, c is 0, 1 or 2 and the sum of aH + + c is 3, 4 or 5, and organic liquids containing a coordinating capable group and boiling above 150 ° C and inorganic carriers, the resulting metal content of the catalyst being in the range 0.01 to 22 weight. %. 2. The process of claim 1 wherein the coordinated organic liquid is poly (methyl-3-cyanopropylsiloxane), mannitol-bexa-p-cyanoethyl ether, ethylene glycol bis (e-cyanoethyl ether), 1,5,9-cyclododecatriene. or poly (dimethylsiloxane). 3. The process of claim 1 wherein the carrier is activated carbon, silica gel, γ-alumina or porous glass. 4. Process according to claim 1, characterized in that the reaction between the silica hydride and the unsaturated organic compound is carried out at 20 to 150 [deg.] C. and a pressure of 1 to 15 at, optionally in the presence of solvents such as aromatic hydrocarbons such as benzene, toluene or xylene or ether, for example tetrahydrofuran. Printed by Moravian Printing Works, plant 12, Leninova 15, Olomouc Price: 2,40 Kčs