CS257525B1 - Inorganic materials modified by chemically bound complexone moieties - Google Patents

Abstract

Inorganic materials with a surface modified by chemically bound complexone groups are described, characterized in that they consist of an inorganic porous or non-porous material selected from the group consisting of silica, alumina, titania and glass, the surface of which is modified by chemically bound complexone groups of the general formula I and IX -Si-CH,CH,CH,NHCOCH, CH..COOH CH COOH I 2 2 2 2 I 2 / 2 (CH,CH,N)—CH-CH-N (I) / 2 2 n 2 2 v hococh2 xh2cooh I . -Si-CH.,CH_CH^NIICCCřI i 2 2 2 N(CH„CH„N)-CH,CH,N 2 2 n 2 2 HOCOCH CH2CONHCH2-CH2-CH2-Si- 'CH2COOH (II) / / where η = 1 or 0. The essence of the preparation of the materials lies in the reaction of the above inorganic porous or non-porous material with organosilicon agents of the general formula III and IV (EO)3sích2ch2ch2nhcoch; < > HOCOCH. (RO) 3SiCH2CH2CH2NHCOCH. HOCOCH. N (CH.,CHnN|—OLOLN Z Z Jl Z Z ■\ / N(CH2CH2N^CH2CH2N (III) C^OONHC^O^a^Si(OR) 3 (IV) where R = methyl, ethyl and n = 0 or 1.

Description

The present invention relates to inorganic materials modified by a complexone moiety which is bound to their surface by chemical bonding,

Inorganic materials such as silica gel, porous glass, alumina, titanium dioxide modified with organosilicon compounds, which introduce various organic functional groups on their surface, are used in technical fields such as liquid chromatography, immobilization of enzymes, heterogeneous catalysis, preparation of filled polymers or laminates. (see, for example, KK Unger: Porous Silica, Elsevier, New York 1979).

This wide range of materials still lacks inorganic materials modified by the complexone group based on ephenylenediaminetetraacetic acid (EDTA) or diethylenetriaminepentaacetic acid (DTPA). This is because, to date, a suitable alkoxysilyl (or chlorosilyl) modified complexone compound has not been known which would allow the easy preparation of such materials.

Inorganic materials with a chelating group of ethylenediamine or 8-hydroquinoline type are known because available alkoxysilanes bearing the appropriate groups exist for their preparation (Pleuddemann E.P .: Silane Coupling Agents, Plenum Press, New York, 1980). Their main drawback is low chelating ability compared to EDTA or DTPA. Neither the preparation of inorganic materials with chelating groups EDTA, respectively. DTPA-modification with commercially available silanes such as 3-aminopropyltriethoxysilane or 3-glycidyloxypropyltrimethoxysilane followed by polymer-analogous reaction with a suitable EDTA derivative, respectively. DTPA - not yet described.

We have found that this procedure does not produce good results because the polymeranalogical reaction is lengthy, does not proceed quantitatively, the resulting surface is always very heterogeneous in terms of interactions and only low chelating capacities are achieved. On the other hand, there are polymeric complexones that carry EDTA or DTPA moieties (see, for example, U.S. Patent No. 211,634).

A general disadvantage of these materials is that they swell and some contain functional groups in the mass, not just on the surface. As a result, in addition to poor mechanical stability, a slow equilibrium in cation chelation is also achieved.

These disadvantages are solved by the inorganic materials according to the invention. The present invention provides inorganic materials having a surface modified by chemically bonded complexone groups characterized in that they consist of an inorganic porous or non-porous material selected from the group consisting of silica, alumina, titanium dioxide and glass, the surface of which is modified by chemically bonded complexone groups of formula and II

HOCOCH _n

N (CH _n CH _n N -) - CH _O CH _O N <2 2 n 2 2 (I)

-s-ch ₂ ch ₂ ch ₂ nhcoch ₂

HOCOCH _n (CH _o CH _n N) —CH _n CH _o N _K 2 2 n 4 2 (II) where η = 1 or 0.

Summary preparation of materials according to the invention comprises reacting the inorganic porous or non-porous material selected from the group consisting of silica, alumina, titanium dioxide or glass, with organosilicon compounds of general Formula III and IV (RO) ₃ sich ₂ CH ₂ CH ₂ NHCOCH ₂

HOCOCH, 'N (CH.CH _o N ·) -CH.CH.jN o

2 n ^{2 2} / (III) (RO) ₃ SiCH ₂ CH ₂ CH ₂ NHCOCH ₂

CH, COOH, CH ₉ CONHCH ₂ CH ₂ CH ₂ Si (OR)

N (CH ₂ CH ₂ N) -CH ₂ CH ₂ N (IV)

HOCOCH where R = methyl, ethyl and n = 0 or 1.

These materials are easy to prepare in a single operation (followed by hydrolysis), with only groupings I and II bound to the surface by a solid chemical bond. The organosilicon reagents III and IV required for the preparation of the materials of the invention can be readily prepared according to U.S. Pat. AO 256 456 by reaction of 3-trialkoxysilylpropylamine with complex dianhydrides in anhydrous medium.

The necessary inorganic materials are commercially available and their choice depends on the application requirements. For example, silica gel with an average particle size of 3 to 50 µm and a specific surface area of 5 to 600 m / g is suitable for liquid chromatography.

The reaction between the carrier and the organosilicon reagent takes place between the hydroxyl groups of the carrier and the alkoxy group, respectively. hydroxyl (formed by hydrolysis) of reagents III, optionally. IV. Thus, in the case of n = 0:

g-OH + III ->> 10-Si- (CH ₂ ) j NHCOCH,

CH.CO \ «2 ° NCH _of CH ² _N ² .0 N \ / ' -O-Si- (CH -) NHCOCH- .CH.COOII,. 3 3 ¹ ^ nch ₂ ch ₂ n.

HOCOCH ₂ ' ^/ 1' CH ₂ COOH

OH

OH + IV - OH

-OH ° X ^X (CH 2).

HOCOCH _n

NCH-OkN 2 Z from Si-OCH _n CONH (CH ₂ ) |

This creates a strong chemical bond to the surface of the carrier and the surface comprises groupings I and II.

The reaction can be carried out in polar solvents such as alcohols, dimethylformamide, pyridine, water at temperatures from 15 ° C to the boiling point of the solvent. After the reaction, it is preferable to wash the modified materials with solvents to remove excess reagents and to dry the resulting material.

The following examples characterize the compounds of the invention without limiting it.

Example 1

To a solution of a mixture of silanes III and IV (R ... ethyl, n = 0? 15 g) in methanol (300 mL) was added 2 g of silica gel having a particle size of 10 µm, a specific surface area of 450 m / g. The mixture was allowed to react with stirring at room temperature for 240 hours. The resulting product is suction washed with methanol, water, methanol and dried at 85 ° C for 3 hours.

Exchange capacity: 0.63 mmol Cu ⁺⁺ / g.

Example 2

The silane mixture as in Example 1 (13 g) was dissolved in 300 ml of distilled water at 45 ° C and silica gel (13 g, identical to Example 1) was added. The mixture was heated at 80 ° C for 8 hours. The product was filtered off with suction, washed with water, methanol and dried at 85 ° C for 3 hours.

Exchange capacity: 0.51 mmol Cu ⁺⁺ / g.

Example3

As in Example 1 except that porous glass is used instead of silica gel.

Example 4

As in Example 2, except that alumina was used instead of silica gel.

Example 5

As in Example 1, except that titanium dioxide was used instead of silica gel.

Claims (2)

1. Inorganic materials modified by chemically bonded complexone groupings, characterized in that they consist of inorganic porous or non-porous material selected from the group consisting of silica, alumina, titanium dioxide and glass, the surface of which is modified by chemically bonded complexone groups of formulas I and II -Si-CH ₂ -CH ₂ -CH ₂ NHCOCH ₂ HOCOCH ch ₂ cooh ch ₂ cooh (I) AND -Si -CH ₂ CH ₂ CH ₂ NHCOCH ₂ HOCOCH ₂ CH-COOH I ² N (CH-CH _n N) —CH 2 CH _n N 2 Z n 2 2 ch ₂ conhch ₂ -ch ₂ -ch ₂ -sCH ₂ COOH (II) where η = 1 or 0. 2. A process for preparing inorganic materials modified komplexonovým array according to claim 1, wherein the inorganic material as in step 1, is reacted with organosilicon compounds of general Formula III and IV (RO) ₃ sich ₂ CH ₂ CH ₂ NHCOCH ₂ HOCOCH " COOH CH "CO / ² \ CH _O N _O CH ^{2 2} \ / CH ₂ CO (III) (RO) ₃ SiCH ₂ CH ₂ CH ₂ NHCOCH ₂ CH ₂ CONHCH ₂ CH ₂ CH ₂ Si (OR) ₃ .N (CH ₀ CHN) -CH, CH ₀ N 2 ZZ Z _n where n = 0 or 1 and R = methyl, ethyl. Severography, n. P., MOST