CS240634B1 - Inorganic materials modified with cyclopentadienylsilyl group - Google Patents

Abstract

Inorganic materials modified with a cyclopentadienylsilyl group, formed by the interaction of an inorganic porous or non-porous material A, where A represents SiO2, TiO2, Al2O3, glass, ceramic or aluminosilicate with organosilicon agents of the general formula Cj-H^ (CH2) nSiR^Rj_m and where n represents an integer from 1 to 12, m an integer from 0, 1 or 2, R1 an alkyl of one to ? four carbon atoms, R" an alkoxy group of one to four carbon atoms, a chlorine or bromine atom. The materials prepared in this way contain chemically bound cyclopentadienyl groups and can be used as sorbents in chromatography, carriers of heterogeneous homogeneous catalysts and as fillers of macromolecular substances.

Description

The invention relates to inorganic materials modified with cyclopentadienyl groups which are chemically bonded to the surface of the support.

In a number of technical fields, inorganic materials such as silica gel, alumina, titanium dioxide, porous glass modified with organosilicon compounds, which introduce various functional groups to their surface (e.g. E. Grushka: Bouded stationary phases in ohromatography, Ann Arbor Science Publ., Ann Arbor) 1972, K. K. Unger: Porous silica, Elsevier, New York 1979). The inorganic materials thus treated are used to heterogeneize homogeneous catalysts, as carriers for enzyme fixation, in liquid chromatography or as polymer fillers.

The present invention relates to cyclopentadienylsilyl modified inorganic supports formed by the interaction of an inorganic porous or non-porous material selected from the group consisting of silica, alumina, titanium dioxide, glass, ceramic or alumosilicate with an organosilicon reagent of the formula

C, -H, (CH 2) SiR 2b 2 n m d-m wherein n represents an integer of 1 to 12, m an integer of 0, 1, or 2, r 1; alkyl of one to four carbon atoms; and 2

R is alkoxy of one to four carbon atoms, chlorine or bromine.

These materials are readily transportable and the cyclopentadienylsilyl groups are firmly bound to the surface by chemical bonding.

The necessary inorganic materials are commercially available and their grain size, surface and pore size are governed by the requirements of their application. The organosilicon reagents required to prepare the inorganic materials of the invention can be readily prepared.

The interaction between the inorganic carrier and the organosilicon reagent occurs between the hydroxyl group of the inorganic carrier and the R-Si bond or HO-Si bond formed by hydrolysis of the R-Si bond, e.g.

-OH + (C _o H _c O) -Si (CH _o ) C _c H _c -> -O-Si- (CH C, H, + CH _c OH b J 2 no 5 2 noo 2b

OH + C1 _O Si _(CH) C _C H _C -> -O-Si- (CH) C _C H _C + HCl

2 n b b 2 n b b where

-OH represents the surface of the inorganic carrier. Thus, this interaction creates a strong chemical bond between the carrier surface and the organosilicon reagent, and the surface is thus modified by homogeneous groups.

The interaction of the carrier with the alkoxysilanes yields an alcohol which is desirably removed from the reaction mixture by azeotropic distillation with a solvent. In the case of chlorosilanes, hydrogen chloride is released which can be partially removed by physical means, for example by purging the reaction mixture with an inert gas, but for complete removal it is advantageous to use chemical bonding with a suitable acceptor. Particularly preferred for this purpose is the use of hexamyldisilazane, which has the advantage that trimethylsilylizes those hydroxyl groups of the surface which have not been involved in the interaction with the strong cyclopentadienyl.

The actual interaction can be carried out in a solvent such as toluene or tetrahydrofuran from 15 ° C to the boiling point of the solvent in the presence of a hydrogen chloride acceptor supplied before, simultaneously or after the organic reagent.

After the interaction itself, it is desirable to wash the modified materials with solvents to remove excess reagent, unreacted hydrogen chloride acceptor, its reaction product with hydrogen chloride and by-products. Very often, it is expedient to dry the modified material.

The materials thus prepared contain chemically bonded cyclopentadienyl groups and can be used as sorbents in chromatography, carriers of heterogeneous homogeneous catalysts and as fillers for macromolecular substances.

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

Example 1

300 parts of dried silica having a mean pore diameter of 3.5 nm and a specific surface area of 468 m ² / g were overlaid with 600 parts of toluene and 15 parts of 3-cyclopentadienylpropyltriethoxysilane were added. The mixture was heated to boiling for 4 h. Then the solvent was distilled off, the silica was washed three times with toluene and dried in vacuo. 7 parts of hexamethyldisilazane were added to the treated oil. The reaction mixture was shaken for 3 h and the silica was washed with toluene until completely decolorised and then dried under vacuum. The product was found to 3% of C and infrared spectrum are the bands 3040 and 2970 cm ^1, which is attributable to vibration of the cyclopentadienyl ring.

Example 2

Example 1 was repeated except that 3-cyclopentadienylpropyltriethoxysilane was used instead of 3-cyclopentadienylpropyltriethoxysilane. The product contained 3.5% C and the same bands as in Example 1 were also found in its infrared spectrum.

Example 3

Example 1 was repeated except that silica was used instead of alumina (Al _o 0 _o) with a specific surface of 150 m / g. The product obtained contained 2% C and its infrared spectrum showed the same bands as in Example 1.

Example 4

Example 2 was repeated except that very fine titanium dioxide with a mean particle diameter of 1 µm was used instead of silica. The product contained 1.1% C, in its infrared spectrum bands were found as in Example 1.

Example 5

Example 1 was repeated except that porous glass (Corning Glass CPG 10 type 240) with a mean pore diameter of 25 nm and a specific surface area of 95 m / g was used instead of silica, and cyclopentadienylmethyltribromosilane was used instead of 3-cyclopentadienylpropyltriethoxysilane. The product contained 1.3% C and bands as in Example 1 were found in its infrared spectrum.

Example 6

Example 3 was repeated except that 5-cyclopentadienylpentyldimethylbutoxysilane was used instead of 3-cyclopentadienylpropyltriethoxysilane. The product obtained contained 2.1% C and showed the same bands as in Example 1 in the IR spectrum.

Example 7 parts of cyclopentadienyldimethylchlorosilane were dissolved in 700 parts of toluene and 250 parts of silica having a specific surface area of 250 m / g was added to 2 mixtures. The mixture was allowed to stand for a week, then heated to 120 ° C for 2 h and washed with toluene and acetone to give a 2.5% C material with bands as in Example 1 found in the IR spectrum.

Example 8

Example 7 was repeated except that cyclopentadienyl (dodecylmethoxydibutylsilane) was used instead of cyclopentadienyldimethylchlorosilane. The product contained 4% C and its infrared spectrum showed the same bands as in Example 1.

Example 9

Example 7 was repeated except that a ceramic porous with a grain size of 0.1 to 0.2 mm was used instead of silica. The product contained 5.1% C and its infrared spectrum showed bands similar to Example 1.

Example 10

Example 7 was repeated except that molecular sieve 4A was used instead of silica. A 3.7% C material was obtained in which the bands as in Example 1 were found in the IR spectrum.

Claims (1)

SUBJECT OF THE INVENTION Inorganic materials modified with cyclopentadienylsilyl, formed by the interaction of inorganic porous or non-porous material A, wherein A is SiO ₂ , TiO 2, Al ₂ O 3, Glass, ceramic or alumosilicate, with organosilicon agents of the general formula 12 1 C _K Hc (CH ₀ ) SiR R, where n is an integer of 1 to 12, m is an integer of 0, 1 or 2, R is 13 m and has 2 alkyl of one to four carbon atoms, R is alkoxy of one to four four carbon atoms, chlorine or bromine atom.