PL150377B1 - The method of manufacture of alkylacoxysilane - Google Patents

Description

PATENT DESCRIPTION 150 377

REPUBLIC

POLAND

OFFICE

PATENT

RP

The fifth oxygen

U <· * Patent tr. e tHwH

Additional patent to patent no. - Pending: 86 12 31 / P. 263511 /

Priority Int. Cl. ⁵ C07F 7/18

Application announced: 88 08 18

The patent description was published: 90 07 31

Creators of the invention: Włodzimierz Urbaniak, Zenon Foltynowicz, Bogdan Marciniec

The holder of the patent: Uniwersytet im. Adama Mickiewicza, Poznań / Poland /

METHOD OF MAKING ALKYLALCOXYSILANES

The invention relates to a process for the preparation of alkylalkoxysilanes of general formula I, in who? 3 R and R are lower alkyl groups, R is higher alkyl groups having 5 to 20 carbon atoms and n is an integer ranging from 0 to 2 by hydrosilylating alkenes in the presence of a catalyst. Alkylalkoxysilanes are known compounds and one of the basic methods of their preparation is hydrosilylation, i.e. the attachment of alkyl / alkoxy / silanes containing silicon-hydrogen bonds to the unsaturated carbon-carbon bond in alkenes. This reaction takes place with or without a solvent in the presence of catalysts. Due to the high selectivity and activity as well as mild reaction conditions, the most commonly used catalysts are soluble complexes of transition metals, mainly rhodium and platinum / Hydrosilylation, edited by B. Marciniec, PWN, Warszawa-Poznań, 1982 /. It is also known to use heterogenized catalysts such as hexachloroplatinic acid or rhodium chloride supported on organic polymers containing amino or phosphine groups / Capka M. et all Chem. Indium. 1972, 650, German Patent Specification No. 2,245,187 / and hexachloroplatinic acid or rhodium chloride deposited on silica modified with organosilicon compounds containing amino, thiol groups (Wang L., Jiang Y., J. Crganometal. Chem. 251, 39 (1983) or phosphine (Capka M., Hefflejs S., Coli. Czech. Chem. Com. 39, 154 (1974) or a complex of chlorotris (triphenylphosphine) rhodium (I) supported on silica modified with dialkyl, cycloalkyl, diarylamino groups (Marciniec Β., Kometka Z.Z., Urbaniak W., J. Mol. Catal., 12, 221 (1981).

In the process according to the invention, in the addition of a hydrogen silane of the general formula 2, in which R ^{* 1} , R ² and n are as defined above, to aliphatic alkenes, a heterogenized rhodium (I) complex of the general formula 3 in which L is a ligand was used as catalyst , forming a bond with the rhodium atom, m takes the values 0, 1 or 2, p is an integer having the values 1 to 3, and S is a modified support of the general formula, in which R5 is

150 377 alkyl group, X - halogen, x takes values from 0 to 10, y - from 1 to 10, k is an integer ranging from 1 to 6, and R5 is an alkyl group or a structural element of general formula 5, wherein R f and k are as defined above. Alkenes, alkadienes or cycloalkadienes can be used as the ligand for forming the bond with the rhodium atom, where it is chemically neutral which compounds of the groups mentioned are used. On the other hand, the carrier S defined by the general formula 3 is obtained by silylating asbestos with an organosilicon compound in an acidic environment or silica in an inert anhydrous organic solvent. The addition reaction in the process according to the invention takes place in the liquid phase.

The heterogenized rhodium catalysts used in the invention are new catalysts in the hydrosilylation reaction of alkenes, alkoxy / alkyl / silanes. Compared to the previously used catalysts heterogenized on organic carriers, they are characterized by higher resistance to organic solvents and reagents as well as higher mechanical and thermal resistance. On the other hand, compared to inorganic supports / silicas /, they are characterized by a higher content of readily available coordinating groups per unit area, and thus a higher resistance to detachment of the complex during reactions taking place in the liquid phase, which enables multiple use of the catalyst.

Alkylalkoxysilanes obtained by the method according to the invention are widely used, mainly as organosilicon monomers for modification of fillings used in chromatography, as well as hydrophobizing aids and monomers for the production of organic polymers, especially organosilicon. The process of the invention is illustrated by the following examples.

Example IA A mixture of 12 g of asbestos specific surface area of 10.0 m ² / g and 100 ccm of concentrated hydrochloric acid, 120 cm ^ isopropyl alcohol and 15 cm ^ metylodichloro / 3-chloropropyl / silane heated under reflux for 12 hours at a temperature of 333 to 353 K with constant stirring. After completion of the reaction, the mixture was filtered, and the precipitate was washed with methanol and benzene. After drying in vacuo, the modified asbestos was aminated.

B. Amination was carried out by heating pre-modified asbestos as in paragraph A, in a solution of diallylamine (10 cm3) in methyl alcohol (190 cm) at reflux for 12 hours. After completion of the reaction, the aminated asbestos was filtered off, washed with benzene and methanol, and dried. Elemental analysis showed: 8.74% carbon, 2.85% hydrogen, 4.23% chlorine and 0.51% nitrogen. The specific surface area was 24.7 m ² / g.

Example II. A mixture consisting of 4 g of asbestos specific surface area of 10.8 m ² / g and 100 ccm of glacial acetic acid and 100 ccm of acetone and 5 cm ^ metylodietoksy / 3- / diallylamine / propyl / amine silane as krzemoorganlczną refluxed at a temperature of 320-330 K with constant stirring. After completion of the reaction, the mixture was filtered and the precipitate was washed with acetone and dried in vacuo. Elemental analysis showed 1.16% carbon, 1.88% hydrogen and 0.35% nitrogen. The specific surface area was 31.8 m ² / g.

Example III. The reaction was carried out as in Example 2, using tris (3- (diethoxymethylsilyl) propyl amine as the organosilicon amine. Elemental analysis showed: 1.66% carbon, 1.96% hydrogen and 0.35% nitrogen. The specific surface area was

31.3 ffl ² / g Example IV. A mixture consisting of 4 g of asbestos with a specific surface area

22.4 m ² / g, 100 cm 3 glacial acetic acid, 100 cm 3 acetone and 10 cm 3 methyldichloro (3-chloropropyl) silane were heated to reflux for 12 hours at 320-330 K with constant stirring. After completion of the reaction, the mixture was filtered and the precipitate was washed with acetone and dried in vacuo. Modified asbestos was aminated with diallylamine as in Example 1b. Elemental analysis showed 0.76% carbon, 1.91% hydrogen, 0.37% chlorine and 0.13% nitrogen in aminated asbestos. The specific surface area was 21.8 m ² / g.

EXAMPLE V 13 g of asbestos having a surface area of 13.5 m ² / g and 200 cm &lt; glacial acetic acid and 40 cm ^ of distilled water, stirred vigorously for 1 hour at 293-298 C and then for 0.5 hours at 320-330 K. After cooling, the solution was filtered off, and 100 cm3 of glacial acetic acid, 100 cm3 of acetone, 20 cm3 of water were added to the asbestos.

150 377 and heated at 320-330 K for 6 hours with vigorous stirring. To the mixture was added in three portions every two hours tris 10 cm ⁵ / 3- / dietoksymetylosililo / propyl / amine.

After completion of the reaction, the mixture was left at the temperature of 293-298 K for 12 hours, and then acetic acid, acetone and water were evaporated under reduced pressure. The dry precipitate is heated for 2 hours at 423 K. The solid was then washed on the filter with 200 cm ⁵ acetone and water / 1: 1 / and after transfer to Soxhlet extracted with acetone for 6 hours. The washed modified asbestos was dried under reduced pressure. Elemental analysis showed 15.36% carbon, 3.97% hydrogen and 1.74% nitrogen. The specific surface area was

91.5 m ² / g ·

Example VI. 15 g of silica with a specific surface area of 220 m ^Z / g, dried for 6 hours at 423 K, 50 cm ^{5 of} dried benzene and 20 cm ^{5 of} tris (3- (diethoxymethylsilyl) propyl) amine were heated under reflux for 5 hours at 350-353 K with constant stirring. After completion of the reaction, the precipitate was filtered off and transferred to a Soxhlet apparatus, where it was washed with benzene for 5 hours. The aminated silica was then dried under reduced pressure. Elemental analysis showed 5.26% carbon, 1.65% hydrogen and 2.45% nitrogen.

Example VII. 2 g of the aminated asbestos prepared as in Example 1 was mixed with a solution of 0.125 g of the di - H - chlorotetracyclooctenedirodine complex (1) in 50 ml of chloroform and left at 293-298 K for 24 hours, with occasional stirring. The mixture was then transferred to a foam filter and washed with 100 cm ⁵ chloroform. Elemental analysis showed 1.42% bound rhodium. The ratio of nitrogen to rhodium was 2.64.

Example VIII. The catalyst was prepared as in Example VII, using as the carrier the aminated asbestos prepared as described in Example II. The analysis showed 1.60% rhodium. The ratio of nitrogen to rhodium was 0.69.

Example IX. The catalyst was prepared as in Example VII, using as the carrier the aminated asbestos prepared in Example III. The analysis showed 1.46% of rhodium. The N / Rh ratio was 1.76.

Example 10 The catalyst was prepared as in Example 7, using as the carrier the aminated asbestos prepared according to Example 4. Analysis showed 1.17% rhodium content. The N / Rh ratio was 0.82.

Example XI. The catalyst was prepared as in Example 7, using as the carrier the aminated asbestos prepared as in Example V. The analysis showed 1.27% rhodium. The N / Rh ratio was 10.07.

Example XII. The catalyst was prepared as in Example VII, using as a support aminated silica prepared according to Example VI. The analysis showed 1.5% rhodium content. The N / Rh ratio was 12.

Example XIII. In a glass ampoule with a capacity of 20 cm ⁵ provided 0.01 mol / 1.88 cm ⁵ / triethoxysilane, 0.01 mol / 1.25 cm ^5/1-hexene and 0.1 g of the catalyst prepared according to Example VII. The ampoule was sealed and heated for 2 hours at 353 K. The content of the ampoule after the reaction was analyzed by gas chromatography, revealing 64% of the product in the reaction mixture, which after chromatographic isolation was identified as hexyltriethoxysilane by comparing the retention time with the commercial product.

Example XIV. The reaction was performed as described in Example XIII, using the catalyst prepared as in Example VIII. Hexyltriethoxysilane was obtained in a 67% yield.

Example XV. The reaction was carried out as described in Example XIII, using the catalyst prepared as in Example IX. Hexyltriethoxysilane was obtained in a yield of 70%.

Example XVI. The reaction was carried out as described in Example 13, using the catalyst prepared as in Example X. The hexyltriethoxysilane was obtained in a 72% yield.

Example XVII. The reaction was performed as described in Example XIII, using the catalyst prepared as in Example XI. Hexyltriethoxysilane was obtained in a 67% yield.

150 377

Example XVIII. The reaction was carried out as described in Example XIII, using the catalyst prepared as in Example XII. Eexyltriethoxysilane was obtained in a 71% yield.

Example XIX. The reaction was carried out in a manner analogous to that described in Example 13, using 0.01 mol / 1.88 cm3) of triethoxysilane, 0.01 mol / 1.57 cm3) of octene-1 and 0.1 g of the catalyst prepared according to Example 7. 68% of the product was found in the reaction mixture, which was identified as octyltriethoxysilane in the manner described in Example 13.

Example XX. The reaction was carried out as described in Example XIX, using the catalyst prepared as in Example VIII. Octyltriethoxysilane was obtained in 72% yield.

Example XXI. The reaction was carried out as described in Example XIX, using the catalyst prepared as in Example IX. Octyltriethoxysilane was obtained in 71% yield.

Example XXII. The reaction was carried out as described in Example 19, using the catalyst prepared as in Example 10. The octyltriethoxysilane was obtained in 69% yield.

Example XXIII. The reaction was carried out as described in Example XIX, using the catalyst prepared as in Example XI. Octyltriethoxysilane was obtained in 73% yield.

Example XXIV. The reaction was carried out as described in Example 19, using the catalyst prepared as in Example 12. Octyltriethoxysilane was obtained in a 75% yield.

Example XXV. The reaction was carried out in a manner analogous to that described in Example 13, using 0.01 mol (1.88 cm 3) of triethoxysilane, 0.01 mol (3.20 cm 3) of octadecene-1, and 0.1 g of the catalyst prepared as in Example VII. From the reaction mixture, 64% octadecyltriethoxysilane was isolated and identified as described in Example 13.

Example XXVI. The reaction was carried out as described in Example XXV, using the catalyst prepared as in Example VIII. Octadecyltriethoxysilane was obtained in 69% yield.

Example XXVII. The reaction was carried out as described in Example XXV, using the catalyst prepared as in Example IX. Octadecyltriethoxysilane was obtained in 68% yield.

Example XXVIII. The reaction was carried out as described in Example 25, using the catalyst prepared as in Example 10. Octadecyltriethoxysilane was obtained in 65% yield.

Example XXIX. The reaction was carried out as described in Example XXV, using the catalyst prepared as in Example XI. Octadecyltriethoxysilane was obtained in 67% yield.

Example XXX. The reaction was carried out as described in Example XXV, using the catalyst prepared as in Example XII. Octadecyltriethoxysilane was obtained in 69% yield.

Claims (1)

Patent claim f r 1? A method for the preparation of alkylalkoxysilanes of the general formula I, in which R and R are lower alkyl groups, denote higher alkyl groups having 5 to 20 carbon atoms, and an integer ranging from 0 to 2, by catalytic addition of hydrogen, 12 rosilane of the general formula in formula 2, in which R and R are as defined above for aliphatic alkenes, characterized in that the catalyst is a heterogenized rhodium catalyst of the general formula 3, in which L is a ligand forming a bond with the rhodium atom and takes the values 0, 1 or 2 , p is an integer ranging from 1 to 3, and S is a modified carrier of general formula where R5 is an alkyl group, X - halogen, x - number ranging from 0 to 10, y - number ranging from 1 to 10, k is an integer ranging from 1 to 6, and R ^ denotes an allyl group or a group of general formula 5 in which and R ^ are as defined above. 150 377 mor 4 SiH wzdr 2 RhCLL ^ Sp nsample 3 'X no. I * / 0 | (CHA (CHA \ AND AND O-Sl- 0- Si-0 - -Si-0 ζ 0 \ X 0-StOH Hertz A AND I, - (CH ₂ \ Si — R ⁴ I HZOr 5