CS257226B1 - Inorganic materials modified with chemically bound (1-phenylethyl) aminopropyl groups and processes for their preparation - Google Patents

Abstract

Inorganic materials modified by chemically bonded (l-phenylethyl)aminopropyl groups of the general formula Si-(CH9)-NHCH < I i í J R /CÍI3 ^C6H5 where (sX^H represents the surface of a support selected from the group consisting of! silicon dioxide, aluminum oxide, aluminosilicates, · glass and ceramics and R1 is a methyl, methoxy or ethoxy group. These substances are prepared by reacting an inorganic material with an organosilicon reagent of the general formula r1r2si(ch2)3nhch „CH, -X c6H5 where R2 represents a methoxy or ethoxy group and the other symbols have the above-mentioned meaning. The materials prepared in this way can be used as sorbents in chromatography, catalyst and biocatalyst carriers or as fillers for macromolecular substances.

Description

The invention relates to inorganic materials modified with (1-phenylethyl) aminopropyl groups which are bonded to the surface of the support by chemical bonding and to a process for their preparation.

In technical fields such as enzyme immobilization, heterogeneisation of homogeneous catalysts, preparation of filled polymers or chromatography, inorganic materials such as silica gel, alumina, glass, titanium dioxide modified with organosilicon compounds are applied, introducing various functional groups such as octadecyl, phenoxypropyl, 2-cyanopropyl etc. (e.g., E. Grushka: Bonded Stationary Phases in Chromatography, Ann Arbor Science Publ., Ann Arbor 1972; RR Myears, SJ Long (Ed.): Film Forming Compositlons,

Part III by M. Dekker, New York 1972; K. K. Unger: Porous Silica, Elsevier, New York (1979).

Inorganic materials modified with a chemically bonded sec-amino group are still underrepresented in this range of materials. The gap according to the invention suitably fills this gap.

The present invention provides inorganic materials modified with chemically bonded (1-phenylethyl) aminopropyl groups of the formula.

Si- (CH) NHCH o / <i? ^C 6 H ₅ wherein the (S ^ represents the surface of the carrier selected from the group consisting of silica, titania, alumina, aluminosilicates, glass and ceramics, and R ^ is methyl, methoxy, These compounds are prepared by reacting an inorganic material with an organosilicon reagent of the formula

CH, /

RR ₂ Si (CH _{2) 3} NHCH ^XC 6 ^H 5 wherein R ₂ represents a methoxy or ethoxy group, and other symbols are as defined above.

These materials are easy to prepare since the desired organosilicon reagents are described in U.S. Pat. AO No. 252 619 and the necessary inorganic materials are commercially available and their graininess, surface and pore size can be easily selected according to their application.

The interaction between the inorganic carrier and the organosilicon reagent occurs between the hydroxyl group of the inorganic carrier and the alkoxysilyl group of the reagent, optionally the silanol group formed by hydrolysis of the alkoxysilyl group, e.g.

oc ₂ h ₅

+ (C ₂ H ₅ O) ₃ Si (CH ₂ ) ₃ NHCH (CH ₃ ) C ₈ H ₅

Sj-Oš (CH ₂ ) ₃ NHCH (CH ₃ ) C _g H ₅ + 2 C 6 g OH (ch ₃ o) ₂ (CH ₃ ) Si (CH ₂ ) ₃ NHCH (CH ₃ ) C _g H ₅ + 2H ₂ <3 (HO) ₂ CH ₃ Si (CH ₂ ) ₃ NHCH (CH ₃ ) C ₈ H ₅ + 2 CH ₃ OH

O

OH + (HO) ₂ (CH ₃ ) Sl (CH ₂ ) ₃ NHCH (CH ₃ ) C ₉ H ₅ - 4 H-OSi (CH ₃ ) (CH ₂ ) ₃ NHCH (CH ₃ ) C ₉ H ₈ + 2 H ₃ OH where OH represents the surface of the inorganic carrier; Thus, this interaction creates a solid

The OH (most often siloxane) bond between the carrier surface and the organosilicon reagent and the surface is thus modified by 1- (phenylethyl) aminopropyl groups. When the organosilicon reagent is optically active, a chiral center is introduced by this interaction onto the support surface, which can be used, for example, to chromatographically separate racemates or prepare catalysts for enantioselective synthesis.

The interaction itself can be carried out in and without solvents (but this leads to unnecessarily high consumption of the organosilicon reagent). Suitable solvents are in particular aprotic solvents such as tetrahydrofuran, toluene, dioxane, dichloroethane, but other solvents or water may also be used. For modifying inorganic carriers, a temperature of from 15 ° C to the boiling point of the solvent is usually chosen; azeotropic removal of the alcohols or water formed is also preferred.

The ratio of the inorganic material to the organosilicon reagent is controlled by the intended application and by the surface area of the inorganic carrier. With monomolecular surface coverage, one agent molecule is expected to assume approximately 0.25 to nm of the available surface.

After modification, it is advantageous to wash the modified materials with solvents to remove any excess reagent, and it is often convenient to dry the material so prepared.

The materials thus prepared contain (1-phenylethyl) aminopropyl groups chemically bound to the surface and can be used, for example, as sorbents in chromatography, catalyst and biocatalyst supports, as fillers for macromolecular substances, or in other applications.

The following examples characterize the compounds of the invention without limiting or restricting it. The weights are in parts by weight.

He did

200 parts of dried silica (SiO.) With a mean pore diameter of 3.5 nm and a specific surface area

468 m / g was overlaid with 600 parts of toluene and 100 parts of N- [3- (triethoxysilyl) propyl] (- phenylethyl) amine was added. The mixture was heated to boiling for 5 h. Then part of the solvent was distilled off, the silica was washed three times with toluene and dried in vacuo. 9.1% C was found in the product and a weak wide band centered at 2950 cm ^-1 corresponding to the vibration of saturated CH bonds was found in the infrared spectrum.

Example2

200 parts of porous glass having a specific surface area of 300 m / g was overlaid with 500 parts of water and 150 parts of N- [3- (dimethoxymethylsilyl) propyl] (1-phenylethyl) amine was added and left to stand at room temperature for 10 days. Thereafter, the reaction mixture was held at 90 ° C for 5 h. The resulting product was washed with water, dioxane and diethyl ether after suction and dried at 90 ° C. It contained 2.6% C.

Example 3

Example 1 was repeated except that alumina (Al ₂ O ₃ ) was used instead of silica.

with a specific surface area of 150 m / g. The product obtained contained 2% C.

He attaches

Example 1 was repeated except that very fine titanium dioxide with an average particle diameter of 0.1 µm was used instead of silica. The product obtained contained 0.8 i C.

Example5

Example 1 was repeated except that porous ceramic 2 having a specific surface area of 55 m / g was used instead of silica. The product obtained contained 1.2% of carbon.

Example 6

Example 1 was repeated except that Nalsit A 4 molecular sieve was used instead of silica. The product obtained contained 0.4 Ϊ C.

Claims (2)

SUBJECT OF THE INVENTION 1. Inorganic materials modified with chemically bonded (1-phenylethyl) aminopropyl groups of the formula Si - (CH ₂ ) ₃ NHCH wherein O 2 represents the support surface selected from the group consisting of silica, titanium dioxide, alumina, alumosilicates, glass and ceramics and R ¹ is a methyl, methoxy or ethoxy group. 2. A process for the production of inorganic materials of the formula (1), which comprises reacting the inorganic materials with an organosilicon reagent of the formula: XH ₃ R ¹ R ₂ Si (CH ₂ ) ₃ NHCH wherein R ₂ represents a methoxy or ethoxy group and the other symbols have the meanings given above.