CS223256B1 - A process for the preparation of cellulose comprising 3-N-aminoarylamino-2-hydroxypropyl functional groups - Google Patents

Abstract

The purpose of the invention was to prepare a previously unknown cellulose modification that would be a suitable chromatographic carrier and a starting intermediate for the preparation of chelating sorbents. The stated purpose was achieved by using a domestic raw material — epichlorohydrin — as a connecting bridge between cellulose and an aromatic diamine. First, epichlorohydrin is reacted with a primary aromatic diamine, one of whose amino groups is protected by an acyl group. The resulting 3- -chloro-2-hydroxypropyl derivatives are converted by the action of an alkali metal hydroxide into glycidyl derivatives, which then react in an alkaline environment with the hydroxyl groups of cellulose. Other fields of application may be: energy, research institutions, food industry.

Description

The invention relates to a process for preparing cellulose containing 3-N-aminoarylamino-2-hydroxypropyl functionalities.

Sorbents with primary aromatic amino groups find wide application in laboratory and industrial practice either directly as such or as a starting material for the preparation of selective ion exchangers. A variety of materials of this type have been prepared, primarily of a hydrophilic nature, based on polysaccharides, dextran gels, synthetic acrylamide gels, or copolymers of hydroxyalkyl methacrylates with divinyl comonomers.

Numerous procedures have been developed for introducing aminoaryl residues into polysaccharide macromolecules. Most preferred are those in which the desired products are formed by a one-step reaction. This includes the addition of aminoaryl vinyl sulfones to the hydroxyl groups of cellulose to form the corresponding ethers. This process for the preparation of cellulose with an aminoaryl residue in a cellulose macromolecule is the subject of US Pat. The disadvantage of this method of preparing celluloseCellulose - O - CH _{2 -} CH - CH _{2 -} NH - Ar - NH - Ac

AND

OH where

Ac is an acyl monobasic organic acid,

Ar is a benzene ring, optionally substituted with C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, nitro, wherein the position of the -NH-Ac group may be in the 2, 3 or 4 position consisting of the primary aromatic diamine, one amino group is protected with an acyl group, and 1-chloro-2,3-epoxypropane is reacted in a separate step with stirring in an environmentally water-miscible organic solvent preferably selected from the group consisting of acetone, tetrahydrofuran, 1,4-dioxane; 3-dimethoxyethane at 40 to 70 ° C for 3 to 10 hours, and then the crude reaction mixture is added under stirring to a suspension of cellulose and alkali metal hydroxide in a water-immiscible organic solvent preferably selected from the group consisting of chlorobenzene, white spirit toluene, whereupon the newly formed reaction mixture is heated at 60 to 130 ° C for 3 to 12 hours, whereby the organic The water-miscible solvent is distilled off during the first hour of heating, and then the cellulose is separated from the suspension by filtration and washed with a water-miscible organic solvent, preferably methanol, ethanol and acetone.

Microcrystalline cellulose, fibrous cellulose, but preferably spherical cellulose prepared according to the A.A.

172,640 (1976). The advantage of this spherical cellulose is that it is highly porous, as the primary aromatic amino groups in the side chain of the cellulose with aminoarylvinylsulfones are difficult to synthesize by using pure raw materials, especially aminoarylvinylsulfone, and accurately adjusting the pH during the reaction. whereas the reaction takes place in a non-aqueous medium. The multi-step synthesis of cellulose with primary aromatic amino groups, such as the preparation of p-nitrobenzyl cellulose by p-nitrobenzyl chloride and its subsequent reduction, presents the disadvantages of a low degree of conversion both in the actual preparation of p-nitrobenzyl cellulose and the subsequent reduction. result in low concentration of primary aromatic amino groups in the cellulose macromolecule ranging from 0.15 to 0.20 mmol / / g ·

We have now found that the above disadvantages can be overcome by a process for preparing cellulose containing 3-N-aminoarylamino-2-hydroxypropyl groups of the formula of up to 90% by volume of water in the swollen state. This high porosity also causes its higher reactivity.

The primary aromatic diamine whose one amino group is protected by an acyl group is an aromatic diamine whose acyl amino group is in the 2- or 3-position or 4-position on the aromatic ring relative to the primary, unprotected amino group.

In the reaction of a primary aromatic diamine, one amino group of which is protected by an acyl group, with 1-chloro-2,3-epoxypropane, the molar ratio to each other is selected in the range of 1: 1 to 2, depending on the physical and chemical properties it should have the resulting product, preferably a molar ratio of 1: 1.1 to 1.5.

Of the alkali metal hydroxides, sodium hydroxide or potassium hydroxide is usually used in an amount of 90 to 110% of theory, based on the content of 1-chloro-2,3-epoxypropane and cellulose.

The advantage of the process according to the invention is that it is possible to prepare cellulose with a substantially higher content of primary aromatic amino groups (0.2 to 1.53 mmol g ^-1 ) over the prior art process using p-nitrobenzyl chloride and subsequent reduction of the resulting p-nitrobenzyl cellulose. , 15 to 0.20 mmol g ¹ .

Cellulose prepared according to this patent containing 3-N-aminoarylamino-2-hydroxypropyl groups has not been prepared yet.

A further advantage of the process according to the invention is the possibility to obtain cross-linked cellulose using 1-chloro-2,3-epoxypropylene in an amount higher than equimolar to the starting diamine.

Example 1

15.0 g of p-aminoacetanilide are dissolved in 30 ml of acetone and 11.1 g of 1-chloro-2,3-epoxypropane are added dropwise over 15 minutes at 50 ° C. Stir at the same temperature for 5 hours. The crude reaction mixture thus prepared was poured into a suspension of 14.58 g of spherical cellulose in 30 ml of white spirit with 8.4 g of sodium hydroxide in 8.5 ml of water. While stirring, the temperature of the reaction mixture was maintained at 71 ° C at which acetone was distilled off. After distillation, the mixture was heated to 130 ° C and stirred at 130 ° C for 3 hours. The product obtained is washed with acetone, then with water until the filtrate is neutral and finally dried at 45 ° C.

The product contains 1.432 mmol of 1- (N-p-aminophenyl) amino-2-hydroxypropyl groups / g cellulose.

Example 2

18.0 g of oxalyl-m-phenylenediamine are dissolved in 30 ml of 1,4-dioxane and 13.8 g of 1-chloro-2,3-epoxypropane are added dropwise at 70 DEG C. over 15 minutes. Stir at the same temperature

B hours. The crude reaction mixture thus prepared was poured into a suspension of 14.6 g of fibrous cellulose in 30 ml of chlorobenzene with 9.6 g of potassium hydroxide in 10 ml of water. While stirring, the temperature of the reaction mixture was maintained at 85 ° C for 12 hours. The product is then washed with acetone, water to neutralize the filtrate and finally dried at 45 ° C.

The product obtained contained 0.796 mmol of 1- (N-aminophenyl) amino-2-hydroxypropyl groups / g cellulose.

Example 3

13.6 g of formyl-o-phenylenediamine are dissolved in 30 ml of acetone and 9.3 g of 1-chloro-2,3-epoxypropane are added dropwise at 40 ° C over 15 minutes. Stir at the same temperature for 10 hours. The crude reaction mixture was then poured into a suspension of 14.6 g of microcrystalline cellulose in 30 ml of toluene with 7.6 g of sodium hydroxide in 8 ml of water. Acetone was distilled off at 85 ° C, then the temperature was raised to 100 ° C and stirred for 6 hours. The product obtained is washed with acetone, then with water until the filtrate is neutral and finally dried at 45 ° C.

The product contains 0.947 mmol of 1- (N-o-aminophenyl) amino-2-hydroxypropyl groups / g cellulose.

Claims (1)

OBJECT OF THE INVENTION Process for the preparation of cellulose-containing 3-N-aminoarylamino-2-hydroxypropyl functional groups Cellulose formula -O-CH ₂ -CH-CH ₃ -NH-Ar-NH-Ac OH where Ac is an acyl monobasic organic acid, Ar is a benzene ring, optionally substituted with C1-C4 alkyl, C1-C4 alkoxy, halogen, nitro, wherein the position of the —NH — Ac group may be in the 2, 3 or 4 position, characterized in that the primary aromatic diamine is one amino group is protected with an acyl group, and 1-chloro-2,3-epoxypropane is first reacted in a separate, water-miscible organic solvent, preferably in a separate step, with stirring, preferably selected from acetone, tetrahydrofuran, 1,4-dioxane, 1,3-dimethoxyethane, at 40 to 70 ° C for 3 to 10 hours, and then the crude reaction mixture is added under stirring to a suspension of cellulose and alkali metal hydroxide in a water-immiscible organic solvent preferably selected from the group consisting of chlorobenzene, naphtha, toluene, whereupon the newly formed reaction mixture is heated to 60 to 130 ° C for 3 to 12 hours while the organic The water-miscible solvent is distilled off during the first hour and then the cellulose is separated from the suspension by filtration and washed with a water-miscible organic solvent, preferably methanol, ethanol and acetone.