DD296853A5 - METHOD FOR PRODUCING SURFACE-FUNCTIONALIZED TRAWER MATERIALS - Google Patents

Abstract

The invention relates to a process for the preparation of surface-functionalized carrier materials which can be used as separation media, chromatography materials, ion exchangers, solid phase synthesis materials or as catalyst carriers. The preparation of surface-functionalized carrier materials is achieved by the chemical fixation of mixtures of epoxidized polydienes or polydiene copolymers with reactive organic compounds or reaction products of epoxidized polydienes or polydiene copolymers with reactive organic compounds such as amines, carboxylic acids, amino acids and their derivatives on the surface of inorganic solids, such as pulverized amorphous or ceramized glasses, fumed or pyrogenic silicas and main and Nebengruppenmetalloxiden. The surface-functionalized traeger materials are characterized in particular by complete surface modification, high pressure and dimensional stability, high stability in the p H range 2-12 and high biological stability. {Carrier material; chromatography; Ion exchanger; Solid phase synthesis material; p H stability; Druckstabilitaet; Formstabilitaet; polysilicic acid; oxides; polydienes; diene copolymers; epoxy; Oberflaechenfunktionalitaet; amines}

Description

Field of application of the invention

The invention relates to a process for the preparation of surface-functionalized carrier materials which, on account of their properties, can be used as separation media, chromatography materials, ion exchangers, solid phase synthesis materials or as catalyst carriers.

Characteristic of known technical solutions

Starting materials for the production of surface-functionalized carrier materials are special biopolymers such as, for example, cellulose and derivatives thereof ("Affinity Chromatography Principles and Methods", Pharmacia Fine Chemicals AB, Sweden 1984), synthetic, highly crosslinked polymer particles, for example divinylbenzene crosslinked polystyrenes (STEWART, YOUNG, " Solid Phase Peptide Syntheses ") and inorganic solids that are surface-functionalized by silane modification (Schutijser, Europapatent B 10043159). The possible uses of materials based on special biopolymers are limited in particular by their high swellability, low pressure stability and by non-excludable chemical and biological decomposition reactions materials based on crosslinked

Synthetic polymers have increased stability to chemical reagents and biodegradation processes. The possible applications are also limited by the low pressure and dimensional stability.

The silane modification of inorganic solids leads to surface-functionalized support materials with comparatively high chemical and biological resistance as well as good printing and dimensional stability. To prevent non-specific interactions with the inorganic solid surface several manufacturing steps are required in the known methods, which is disadvantageous to evaluate (endcapping).

The production of inorganic-organic composites by reaction of epoxidized diene polymers with inorganic solid surfaces to form particle aggregations is described in DD 256141 A1.

The production of surface-functionalized support materials based on epoxidized polymers and inorganic solids is already known, whereby functionalization of the organic surface of the resulting materials takes place only after the inorganic solid surface has been coated with polymers in an additional process step.

Object of the invention

The aim of the invention is the preparation of surface-functionalized support materials with good biological and chemical resistance and high pH and pressure stability, which can be used as separation media, chromatography materials, ion exchangers, solid phase synthesis materials or as a catalyst support.

Explanation of the essence of the invention

The object of the invention is the development of a process for the preparation of surface-functionalized carrier materials which, on account of their properties, can be used as separation media, chromatography materials, ion exchangers, solid phase synthesis materials or as catalyst carriers.

According to the invention the object is achieved in that the surface-functionalized support materials by adsorption of mixtures of epoxidized polydienes or diene copolymers and reactive organic compounds or reaction products of epoxidized polydienes or diene copolymers with reactive organic compounds or the reaction products of epoxidized polydienes diene copolymers and reactive organic compounds in admixture with epoxidized polydienes or diene copolymers and reactive organic compounds from solvents having polymer contents of 1-30 wt .-% of inorganic solid surfaces and subsequent thermal treatment of the adsorbates at temperatures between 4O ⁰ C and 200 ⁰ C, preferably between 50 ⁰ C and 80 ⁰ C, to be obtained.

As the polymer component can epoxidized polydienes, especially polybutadiene, with average molecular weights M _n of between 500 and 25000дтоГ ', preferably between 2000 and БОООдтоГ ^1, or epoxidized diene copolymers, preferably polybutadiene copolymers, with amounts of aliphatic and aromatic comonomers between 1 and 80%, and average molecular weights M _n between 500 and гбОООдтоІ " ¹ .

As reactive organic compounds, aliphatic and aromatic carboxylic acids, dicarboxylic acids, carboxylic acid or dicarboxylic acid halides, carboxylic acid or dicarboxylic acid anhydrides or compounds containing one or more free or activated carboxylic acid groups, or aliphatic and aromatic amines, diamines or compounds containing one or more amino groups , Use.

Inorganic solids are according to the invention pulverized amorphous or ceramized glasses, precipitated or pyrogenic silicas and main and Nebengruppenmetalloxide such as Al2O3, CaO, MgO, SnO, TiO ₂ , Fe ₂ O 3 and mixtures thereof, preferably spherical polysilicic acid particles with BET surface areas between 50 and 500 m ² g ~ 'and average particle diameters between 1 and δΟΟμιη.

By adsorption of the epoxidized polymer component and the reactive organic compounds or the reaction products of epoxidized polymer and reactive organic compound on the surface of the inorganic solid, this surface is completely covered. In the subsequent thermal treatment of the adsorbates is a chemically irreversible linkage of polymer component, reactive organic compound and inorganic solid or inorganic solid and reaction products of epoxidized polymer and reactive organic compound and thus an introduction of surface functionality.

The properties of the surface-functionalized support materials can be according to the inorganic solids used and their properties such as specific surface area, porosity, particle diameter, particle shape, according to the characteristics of the polymer component used such as average molecular weight, degree of epoxidation, polymer uniformity or the corresponding properties of the copolymers used and by proportion and Type of organic reactive compound used vary widely and depending on the purpose.

According to the invention, the surface-functionalized support materials are distinguished, in particular, by complete modification of the surface of the inorganic solid, high pressure and dimensional stability, pH stability in aqueous electrolyte solutions or mixtures of aqueous electrolyte solutions with organic compounds in the pH range from 2 to 12, and high biological stability Resistant to microorganisms. Because of their properties, the surface-functionalized support materials can be used as separation media, chromatography materials, ion exchangers, solid phase synthesis materials, catalyst supports or as materials for immobilizing biologically active substances or substances used to prepare, separate, purify or immobilize biologically active material.

embodiments

example 1

5 g of a poly silicic acid (0 _BET = 260m ² g ~ \ d = 200 μηι) are heated for 6 hours under high vacuum at 400 ⁰ C and under inert conditions a solution of 2.5 g of a Polybutadienepoxids (Epoxidäquivalientgewicht = 70g · тоГ ¹ , M _n = 2300 g mol " ¹ ) and 3.0 g of tert-butyloxycarbonylglycine in 50 ml of dry 1,2-dichloroethane The mixture is dispersed for 5 minutes in an ultrasonic bath and then left for 144 hours at 25 ° C. Thereafter, the adsorbate is transferred under inert conditions aspirated a G4 frit and subsequently tempered at 80 ⁰ C. After 24 hours of hot extraction with 1,2-dichloroethane and vacuum drying a functionalised support material with completely shielded surface remains (Obet = 13Om Zg ²⁾ and an amino acid content of 1,07mmol g ~ \

Example 2

A solution of 2.5 g of a Polybutadienepoxids (Epoxidäquivientgewicht = 70g · mol " ¹ , M _n = 2300g · mol" ¹ ) and 3.0 g of tert-butyloxycarbonylglycine in 50ml of 1,2-dichloroethane is stirred for 4 hours at 65 ° C. 5 g of a thermally pretreated polysilicic acid are then added to the reaction mixture at room temperature, dispersed in an ultrasonic bath for 5 min and the mixture is left at 25 ° C. for 144 hours. Thereafter, the adsorbate is filtered under inert conditions over a G 4 frit and then annealed at 80 ° C for 3 hours. After 24 hours of hot extraction with 1,2-dichloroethane and vacuum drying remains a functionalized anorg.-org. Composite with fully screened surface Obet = 115m ² g ~ ¹ and an amino acid content of 1.27mmol g " ¹ .

Example 3

2.5 g of a polysilicic acid (Obet = 317m ² g ~ \ d = 50μηι) are heated 6 hours in a high vacuum at 400 ⁰ C and then treated with a solution of 0,428g ethylenediamines and 5g Polybutadienepoxid (M _n = гЗООдтоГ ^1, Epoxidäquivaientgewicht = 70дтоГ ¹ ) in 50 ml of benzene and dispersed in an ultrasonic bath for 5 minutes. Subsequently, the mixture is left for 144 hours at room temperature. The adsorbate is filtered off, annealed for 4 hours at 80 ⁰ C and subjected to a 24-hour hot extraction with benzene. After vacuum drying, a functionalized carrier material containing І.ОЭттоІд " ¹ ethylenediamine and fully shielded surface remains (Obet = 180t ² д ^-1 ).

Example 4

0.428 g of ethylenediamine and 5 g of polybutadiene epoxide (M _n = 2300 × ¹ epoxide equivalent weight = 70 × 10 9) are dissolved in 50 ml benzene and refluxed for 48 hours with exclusion of moisture. The cooled reaction mixture is added to 2.5 g of a thermally pretreated polysilicic acid (Obet = 317m ² g ~ ¹ , d = 50μπι) and then dispersed for 5 minutes in an ultrasonic bath. After 144 hours at room temperature, the adsorbate is filtered off, annealed for 4 hours at 8O ⁰ C and subjected to a 24-hour hot extraction with benzene. After vacuum drying, a functionalized support material with a content of ^{1: 1} mmol / l ethylenediamine and completely shielded surface = 175 m ² g ") remains.

Claims (7)

1. A process for the preparation of surface-functionalized carrier materials, characterized in that the surface-functionalized carrier materials by adsorption of mixtures of epoxidized polydienes or diene copolymers with reactive organic compounds or reaction products of epoxidized polydienes or diene copolymers and reactive organic compounds or the reaction products of epoxidated polydienes or diene copolymers and reactive organic compounds in the mixture with the epoxidized polydienes and diene copolymers and reactive organic compounds from solvents having polymer contents of 1 to 30 wt .-% to surfaces of inorganic solids and subsequent thermal treatment of the adsorbates at temperatures between 40 ⁰ C and 200 ⁰ C, preferably between 5O ⁰ C and 80 ^° C. 2. The method according to claim 1, characterized in that the polymer component epoxidized polydienes, preferably polybutadienes, with average molecular weights M _n between 500 and 25000dтоГ \ or epoxidized diene copolymers, preferably polybutadiene copolymers, with proportions of aliphatic and aromatic comonomers between 1 and 80% and middle Molar mass M _n between 500 and гбОООдтоГ ¹ are used. 3. The method according to claim 1, characterized in that as reactive organic compounds aliphatic and aromatic carboxylic acids, dicarboxylic acids, carboxylic acid or Dicarbonsäurehalogenide, carboxylic acid or dicarboxylic anhydrides or compounds containing one or more free or activated carboxylic acid groups, such as free, protected or activated amino acids or amino acid derivatives. 4. The method according to claim 1, characterized in that as reactive organic compounds aliphatic and aromatic amines, diamines or compounds containing one or more amino groups are used. 5. The method according to claim 1, characterized in that as an inorganic solid powdered amorphous or ceramed glasses, precipitated or fumed silicas and main and Nebengruppenmetalloxide such as Al ₂ O ₃ , CaO, MgO, SnO, TiO ₂ , Fe ₂ O ₃ or their mixtures, preferably spherical polysilicic acid particles with BET surface areas between 50 and 500m ² g ~ ¹ and average particle diameters between 1 and 500μηη be used. 6. The method according to claim 1, characterized in that the surface-functionalized carrier materials complete modification of the surface of the inorganic solid, high pressure and dimensional stability, pH stability in aqueous electrolyte solutions or mixtures of aqueous electrolyte solutions with organic compounds in the pH range of 2 to 12 and have a high biological resistance to microorganisms. 7. The method according to claim 1, characterized in that the surface-functional support materials due to their properties as separation media, chromatography materials, ion exchangers, solid phase synthesis materials, catalyst support or as materials for immobilizing biologically active substances or substances that are biologically active for the preparation, separation, purification or immobilization Serve materials are used.