CS236317B1 - Inorganic carriers modified with (3-phenoxypropyl) -silyl group - Google Patents

Abstract

Inorganic supports modified with a (3-phenoxypropyl)silyl group formed by the interaction of an inorganic porous or non-porous material A, where A represents SiO^, TiOp, AL2Oz or glass with an organosilicon reagent of the general formula, rA (R2)Si(CH2)zOCgH5 where R1 represents chlorine or an alkoxy group of one to four carbon atoms and R2 is R1 or methyl. The inorganic materials prepared in this way are particularly suitable for chromatographic separation of substances and as fillers for polymers.

Description

The invention relates to inorganic materials modified with a (3-phenoxypropyl) silyl group which is bonded to the surface of the support by chemical bonding.

In many technical fields, inorganic materials such as silica gel, alumina, titanium dioxide, porosity glass modified with organosilicon compounds, which introduce various functional groups such as (3-aminopropyl) silyl, octadecyl, (2-phenylethyl) silyl or 3- ( 2-epoxypropoxy) propylsilyl, which are then used as carriers for enzyme fixation, for chromatographic separation of substances, or as fillers for polymers (e.g. E. Grushka: Bonded Stationary Phases in Chromatography, Ann Arbor Science

Publ., Ann Arbor 1974; R.R. Myears, J.S. Long. (eds): Film Making * Composition, Part III, Dekker, New York 1972; J. Gotz (ed.): Survey Papers of the XIth Int. Congress on Glass, ČSTS-Dům techniky, Prague 1977; K.K. Unger: Porous silica, Elsevier 1979).

Carriers modified by phenyl groups on the surface have been used so far, and when prepared, the phenyl group was bound directly to silicon by the cell, or through the ethylidene group (see K.K. Unger Porous silica) due to this binding the electron density of the phenyl group was only slightly increased. However, the inorganic materials according to the invention contain a phenyl group bonded via a silylpropoxy group on the surface and thus the electron density of the aromatic group is greatly increased as a result of the electron donation by the alkoxy group. Thus, these materials are both more efficient donors for charge-transfer interaction and more reactive substrates in electrophilic substitutions.

The essence of the invention include inorganic carriers, modified (3-phenoxypropyl) silyl_skupinou formed by the interaction of the inorganic material A which represents SiO _2, TiO ₂ ^and L ₂ ° 3 or glass organosilicon reagent of formula CRI (R ²⁾ Si (CH "). OC H _c

Wherein R ¹ represents chlorine or alkoxy of one to four 2 L carbon atoms, R represents R or methyl.

Inorganic materials are commercially available and their grain size, surface and pore size are governed by the requirements of their application; for example, for use in liquid chromatography, partially hydrated silica (silicas) having a particle diameter of 3-50 px and preferably spherical shape having a surface area of 30 to 600 m ² / g and a mean pore diameter of 3 to 30 nm are suitable for other applications no porous materials are required for polymer fillers.

The organosilicon reagents required for the preparation of the inorganic materials of the invention can be readily prepared according to the author's certificate.

224,790 by reacting allylphenyl ether with trichlorosilane or methyldichlorosilane.

The interaction between the inorganic material and the organosilicon reagent occurs between the hydroxyl group of the inorganic material and the Si-Cl bond of the organosilicon reagent, which group is sometimes pre-hydrolysed to the silanol group

-OH + Cl-Si- (CH ₂ ) ₃ OC ₆ H ₅ - ^ - O-Si (CH ₂ ) ₃ OC _g H ₅ + HCl

Cl-SiI

(CH ₂ ) ₃ OC _g H ₅ + H ₂ O

I + HO-Si- (CH ₂ ) ₃ OC _g H ₅

HO-Si- (CH _O) -jOC ^ -H, - + HCl 2 3 6 5

-O-Si- (CH 2) _q OC _c H 1 - + H - O 2 3 6 5 2 where it represents the surface of the inorganic carrier A.

The interaction thus produces hydrogen chloride, which should be removed from the reaction. Hydrogen chloride may be partially removed by physical means (e.g., by purging the mixture with an inert gas), but for complete removal, it is preferable to use chemical bonding with a suitable acceptor, e.g. Particularly preferred for this purpose is hexamethyldisilazane, which has the advantage that trimethylsilylates those hydroxyl groups of the surface that have not participated in the interaction with 3-phenoxypropyltrichlorosilane or (3-phenoxypropylmethyldichlorosilane). hydrogen chloride acceptor required.

The actual interaction is preferably carried out in an aprotic solvent, preferably toluene, at a temperature of from 20 ° C to the boiling point of the solvent in the presence of a hydrogen chloride acceptor supplied either in advance,

236 317 simultaneously or after the organosilicon reagent. The ratio of inorganic material to organosilicon is determined by the intended application and by the surface area of the inorganic material.

Assuming a monomolecular coverage of the carrier surface, one 3-phenoxypropylsilyl group will assume about 0.25-1 nm of the available surface.

After the interaction, it is desirable to wash the modified materials with solvents to remove any excess reagent, unreacted hydrogen chloride acceptor, the product of its reaction with hydrogen chloride, and by-products. Very often, it is expedient to dry the modified material. The materials thus prepared contain chemically bonded phenoxypropylsilyl groups (as evidenced by infrared spectroscopy) and are used in a number of fields, especially as carriers in chromatography and as fillers for macromolecular substances.

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

Example 1

325 parts of 3-phenoxypropyltrichlorosilane were dissolved in 8000 parts of toluene and 300 parts of dried silica having a mean pore diameter of 10 nm and a specific surface area of 250 m / g were added. The mixture was allowed to stand for one week, then maintained at boiling for 48 hours, 300 parts of pyridine added, and after a week filtered and washed with toluene, methanol, methanol: water 1: 1, again with methanol and dried.

4.9% C was detected in the product and in the infrared spectrum these bands (KBr tablet) were found to duplicate the valence vibration of the aliphatic CH- group at 2920 and 2950 cm ^-1 , the fe-1 "nyl carbon carbon skeleton at 1599 cm, the complex band at 780 cm corresponding to the elevated deformation vibration CH of the phenyl group.

Example 2

Example 1 was repeated except that hexamethyldisilazane was used instead of pyridine. The product contained 5.1% C and the bands shown in Example 1 were also found in its infrared spectrum.

Example 3

Example 1 was repeated except that 3-phenoxy 4 was substituted

236,317 propyltrichlorosilane was used (3-phenoxypropyl) methyldichlorosilane. The product contained 5.1% C and the bands shown in Example 1 were also found in its infrared spectrum.

Example 4

Example 1 was repeated except that alumina (Al 2 O 4) having a specific surface area of 150 m / g was used instead of silica. The product contained 3.9% C and the bands shown in Example 1 were also found in its infrared spectrum.

Example 5

Example 1 was repeated except that very fine titanium dioxide with a mean particle diameter of 1 µm was used instead of silica. The product contained 0.4% C and the bands shown in Example 1 were found in its infrared spectrum.

Example 6

Example 1 was repeated except that porous glass (Corning Glass CPG 10 type 24O) with a mean pore diameter of 25 nm and a specific surface area of 95 m 2 / g was used instead of silica. The product contained 3% C and the bands shown in Example 1 were found in its infrared spectrum.

Example 7

300 parts of 3-phenoxypropyltrimethoxysilane were dissolved in 6000 parts of toluene and 350 parts of silica having a specific surface area of 250 m / g was added to the mixture. The mixture was allowed to stand for a week, then heated to 70 ° C for 3 h. After washing with toluene and acetone, a 3.1% C material was obtained in which the bands as in Example 1 were found.

Example 8

Example 7 was repeated except that 3-phenoxypropyltris (2-ethoxyethoxy) silane was used instead of 3-phenoxypropyltrimethoxysilane. The material obtained contained 2.9% C and showed the same bands as in Example 1 in the IR spectrum.

Claims (1)

Inorganic carriers modified with (3-phenoxypropyl) silyl_skupinou formed by the interaction of an inorganic, porous or neporesního material A, where A is SiOx, TiC> 2, N, O ^ ^{η θ} ^ ο glass organosilicon reagent of the formula R (R ²⁾ Si ( CH ₂ ) ₃ OC ₆ H ₅ wherein R ^{1 is} chloro or an alkoxy group of one to four 2 × 1 carbon atoms, R is R or methyl.