CS258081B1 - The process for preparing high-porous bead celluloe is amine-phenylethyl sulfone groups - Google Patents

Abstract

The aim of the solution is a method for preparing highly porous pearl cellulose containing aminophenylethylsulfone groups of the general formula R - 0 (-CHgCHg SO2 -<<K where the symbols -H, -NH2 and n have the meaning given in the description. The aim is achieved by reacting pearl cellulose or its hydroxylalkyl derivative with 3 or 4-aminophenylsulfatoxyethylsulfone in a mixture of pyridine and water in the presence of an alkali metal hydroxide at a temperature of 30 to 80 C for 1 to 8 hours.

Description

The invention relates to a method for preparing highly porous pearl cellulose containing amine-phenylethylsulfone groups.

Sorption materials containing primary aromatic amino groups find wide application in various fields of chemistry and chemical technology, either directly as such, or after their diazotization for enzyme immobilization, or as a starting material for the preparation of chelating sorbents.

A number of procedures have been developed for the introduction of aminoacyl residues into polysaccharide macromolecules. The most commonly used include the reaction of p-nitrobenzyl chloride with agarose or dextran-based polysaccharides and the subsequent reduction of the resulting p-nitrobenzyl polysaccharide, as well as the addition of aminoaryl vinyl sulfones to the hydroxyl groups of cellulose in a dimethyl sulfoxide environment at 75 °C for 15 hours in the presence of sodium hydroxide (2.7% N, 1.95 mmol N). A higher degree of addition of aminoaryl vinyl sulfones to cellulose can be achieved in a chlorobenzene environment with prior drying of cellulose from pyridine. The actual binding of the aminoaryl vinyl sulfone is carried out at 80 °C for 5 hours (3.5% N,

X o'

2.5 mmol<g J.

It is an attempt to achieve the highest possible degree of binding of the aminoaryl residue to the cellulose macromolecule (expressed in moles of primary aromatic amino groups bound per gram of dry cellulose), because this determines the maximum achievable exchange capacity of the subsequently prepared sorbents. The degree of addition depends not only on the quality of the cellulose itself, the type of reaction medium and all other reaction conditions, but also to a large extent on the pretreatment of the starting cellulose (dewatering or drying of pearl cellulose).

The porosity of sorbents is of great importance for their sorption behavior. The starting pearl cellulose is a highly porous material and has up to 90% of volumetric pores and contains up to 5.6 g of water/g of cellulose dry matter. Due to this high water content in pearl cellulose, pearl cellulose cannot be used in its original state, because this water dilutes the reaction mixture and thus products with low exchange capacity are obtained or a large excess of reagents must be used. If water is removed from pearl cellulose directly by evaporation, complete loss of porosity occurs.

Good results of binding aminoaryl residues into the pearl cellulose macromolecule are achieved when using pre-dried pearl cellulose from an organic solvent environment. Although this method achieves a high degree of binding of the aminoaryl residue into the pearl cellulose, drying the pearl cellulose partially leads to an irreversible reduction in porosity, because drying the pearl cellulose from an organic solvent environment also leads to a greater or lesser irreversible reduction in porosity.

This partially irreversible loss of porosity compared to the porosity of the starting pearl cellulose is a major disadvantage of the process for preparing pearl cellulose with bound aminoaryl vinyl sulfone according to AO 216 393, because the chelating derivatives prepared from these semi-finished products show slow sorption kinetics (Ostsorb salicyl, i.e. pearl cellulose containing chemically bound salicylic acid shows an exchange half-life of 118 seconds for a CuSO^ solution with a concentration of c = 0.05 mol.l*'?' at a pH of this solution of 4.4).

High porosity of the final product is also necessary for the successful sorption of high molecular weight substances, for the sorption of immunoglobulins and other biologically active substances when using this pearl cellulose derivative as a carrier in affinity chromatography.

The above-mentioned disadvantages of aminoaryl derivatives of pearl cellulose containing aminophenylethylsulfone groups can be eliminated by the preparation method according to the present invention.

The essence of the method for preparing highly porous pearl cellulose containing aminophenylethylsulfone groups consists in reacting pearl cellulose or its hydroxyalkyl derivative with 3 or 4-aminophenylsulfatoxyethylsulfone in a mixture of pyridine and water in a volume ratio of 1:1 to 1:3 in the presence of an alkali metal hydroxide at a temperature of 30 to 80 °C for 1 to 8 hours. After neutralizing the reaction mixture, the product is isolated and washed with water. The process according to the invention achieves an addition degree of up to 2.5.10 ^J mol.g of cellulose with a water content in the product of up to 77% by weight.

The greater effect of the invention, compared to the current state of the art, lies in the fact that the starting pearl cellulose does not need to be drained or dried, so that irreversible loss of porosity cannot occur, _and moreover, by adding water to the reaction medium, the consumption of pyridine is reduced, which is of not only economic but also ecological importance. Furthermore, the resulting pearl cellulose containing aminophenylethylsulfone groups exhibits a higher water content and thus a higher pore content than the pearl cellulose prepared according to AO 216 393. A comparison of the properties of the pearl cellulose containing p-aminophenylethylsulfone groups prepared according to the present invention and according to AO 216 393 is shown in Table 1.

Table 1

login ex. • 1 1 by 1 216,393 type of cellulose, starting SPG ⁺ HE>T ⁺⁺ SFC+ HET ⁴ * ⁴ · % water in the product 73.99 77.22 63.89 69.50 pore volume, cnr/g dry. 2.84 3.39 1.77 2.28 mmol II / g. dry cell 2.62 2.34 2.03 1.66

+ basic pearl cellulose ++ pearl hydroxyethyl cellulose

Example 1 g of aspirated pearl cellulose is stirred in a mixture of 27 ml of pyridine and 27 ml of water, in which 23.6 g of 4-aminophenylsulfatoxyethylsulfone is previously dissolved. After addition of 7.8 g of sodium hydroxide, the mixture is stirred at 80 °C for one hour. The reaction mixture is now acidified with 50 ml of 7/ hydrochloric acid, the product is filtered off and washed with water.

The obtained cellulose with 4-aminophenylsulfoethyl groups contains 3.67 wt. % N, which corresponds to 2.62 . 10“^mol.g“^, the water content in the product is 73.99%, the pore volume is 2.84 cm^.g ¹ .

Example 2 g of suction-dried pearl hydroxyethyl cellulose is stirred in a mixture of 14 ml of pyridine and 42 ml of water, in which 24.0 g of 3-aminophenylsulfatoxyethylsulfone is previously dissolved. After addition of 8 g of potassium hydroxide, the mixture is stirred at 40 °C for 8 hours. The reaction mixture is now acidified with 50 ml of 7% hydrochloric acid, the product is suction-dried and washed with water.

The obtained hydroxyethyl cellulose with 3-aminophenylsulfoethyl groups contains 3.28 wt. % N, which corresponds to 2.34.10“”^ raol/g, the water content in the product is 77.22%, the pore volume is 3.39 cm\g“\

Claims (1)

A process for the preparation of highly porous pearl oeluloses containing aminophenylethylsulfone groups of the general formula R 0 - (- CH ₂ 0H ₂ - O) _n - S0 ₂ NH, where R is a bead cellulose residue, the -NHg group is in the 3-position on the benzene ring. or 4 and n is 0 or lysed by reacting the bead cellulose or its hydroxyalkyl derivative with 3 or 4-aminophenylsulfatoxyethylsulfone in a 1: 1 to 1: 3 mixture of pyridine and water in the presence of an alkali metal hydroxide at a temperature of 30 to 30 80 ^P C for 1 to 8 hours ·