CS202374B1 - Process for preparing derivatives of polysaccharides containg quaternary ammonium groups - Google Patents

Description

The present invention relates to a process for producing a strong basic anion exchange resin using a polysaccharide, trimethyl 2-hydroxy 3-chloro-propylammonium chloride in an alkaline medium.

The processes known to date for preparing polysaccharides with a quaternary ammonium group utilized the reaction of the dialysides of the polysaccharides with hydrazides containing quaternary ammonium group fC. L. Mehltretter, T.E. Yeates, G.E. Hamerstrand, Β. T. Hoffreiter and C.E. Rist, Tappi 45, 750 (1962) J. Said preparation process is relatively complicated, since it is a two-step synthesis in which, in the first step, it is necessary to prepare the dialdehyde polysaccharide by periodate oxidation. In addition to this process, quaternary ammonium polysaccharide derivatives can be prepared by reacting the polysaccharide with a mixture of epichlorohydrin-triethylamine and a mixture of epichlorohydrin-triethylamine. triethanolamine in a 3: 1 molar ratio in an alkaline medium (Berni, Ralph J .; Benerito, Ruth R .; Mc Kelvey, John B. United States Dept. of Agriculture US 3, 464,781 Cl. 8-116.2; D 06 m In this process, the epichlorohydrin, which is in excess in the reaction mixture, crosslinks the starting poly3accharide. A very common procedure is the subsequent N-alkylation of tertiary amino group-containing polysaccharide derivatives (DEAE-cellulose and DEAE-Sephadex most commonly known) with alkyl halides and epoxiderivatives, respectively, with the E-cellulose reaction. at 95 ° C quaternary ammonium derivatives CSoignet, Donald M .;

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Benerito, Ruth R .; Ralph H. United States Dept. of Agriculture US 3,494,719 Cl. 8-116; D 06m, 10 Feb 1970, Appl. 16 Jun 1967 3 PP ·) · Cross-linking and diquaternary ammonium derivatives are formed during the reaction. Mono- and di-quaternary ammonium derivatives of cellulose were prepared by reaction of DEAE-cellulose with G ^^ - C ^ alkyl halide, or 0 ₅ ~ ₁₀ 0 alkyldihalogénmi non-aqueous. These reactions achieved a conversion rate of 35%. The use of alkyldihalides leads to cross-linking of DEAE-cellulose. (Perrier, Dorothy M .; Benerito, Ruth R. South. Res. Cent. ARS, New Orleans La. J. Appl. Polym. Sci. 1975 19 (12) 3211-20J,

These drawbacks can be overcome by a novel process which allows the preparation of quaternary ammonium derivatives of polysaccharides with very good parameters, wherein a non-crosslinked or crosslinked polysaccharide can be used as the basic carrier. The principle of the invention is that in the first step the insoluble polysaccharide activates with 17.5% to 25% aqueous NaOH solution; alkali-soluble polysaccharides with solid Na 2 CO 4 or a saturated aqueous solution of NagCO 3 for 30 to 60 min. at 15 to 25 ° C in a molar ratio of polysaccharide / activating base 1 / 0.2 to 3, wherein in the second step it is etherified with 0.1 to 2 mol of trimethyl-2-hydroxy-3-chloropropylammonium chloride at 30 to 80 ° C, preferably 40 to 60 ° C, up to 6 hours. .

The polysaccharide used may be starch or cellulose, respectively. their networked analogues. Depending on the composition of the reaction mixture, preparations in the range of 0.18 to 0.68 meq / g can be prepared. Since DEXTROSIL is a 50% aqueous solution of trimethyl-2-hydroxy-3-chloropropylammonium chloride, it is possible in the case of alkali, resp. of water-soluble activation polysaccharides can be converted with solid Na 2 CO 4, since upon addition of the etherification agent, the activating base dissolves in the reaction medium. The reaction can be carried out in a heterogeneous phase, which is advantageous from a technological point of view. The advantage of the proposed process for the preparation of quaternary ammonium polysaccharide derivatives is that:

- all necessary basic raw materials are produced in FISSR,

- the reaction is carried out in the heterogeneous phase, ensuring a thorough mixing of the mixture in the reactor and a simple washing after completion of the reaction,

- makes it possible to prepare water-dispersible or water-dispersible strong basic anion exchangers with a wide range of interchangeable capacities and possibilities of use.

Example 1

To 162 g of powdered cellulose add 243 ml of 17.5% NaOH. Stir the mixture for 0.5 hour. at 20 ° C. Then add 405 ml of DEXTROSIL to the mixture and react for 4 hours with stirring. at 60 ° C. After completion of the reaction, wash with water until neutral and cycle with 1% NaOH for 1 h. pri lab. temperature. After cycling, wash with water to neutral reaction with acetone and dry to constant weight. The exchange capacity of the resulting ion exchanger is determined by potentiometric titration with 0.1 M HCl. The product exchange capacity is 0.68 meq / g.

Example 2

To 162 g of powdered cellulose add 162 ml of 25% NaOH. Stir the mixture for 0.5 h.

at 20 ° C. Then add 324 ml of DEXTROSIL to the mixture and allow to react with stirring for 2 hours. at 50 ° C. Washing, cycling and titration are as in Example 1. The product exchange capacity is 0.37 meq / g.

Example 3

To 162 g of WHATMAN crosslinked cellulose add 583 ml of 17.5% NaOH. Stir the mixture for 0.5 h. at 20 ° C. Then add 243 ml of Dextrosil to the mixture and react with stirring at 60 ° C for 4 hours. Washing, cycling and titration are as in Example 1. The product exchange capacity is 0.34 meq / g.

Example 4

To 162 g of water-soluble hydroxyethylcellulose are added 12 g of anhydrous Na ₂ CO 4 and 40 ml of DEXTROSIL. The reaction mixture was allowed to react with stirring at 40 ° C for 2 h. After completion of the reaction, wash with 1% ethanolic HCl, acetone and dry. The product contains 0.25% N, which corresponds to a exchange capacity of 0.18 meq / g.

Example 5

To 162 g of cold water-soluble starch, add 12 g of anhydrous NagCO-j and 40 ml of DEXTROSIL. The reaction mixture was allowed to react with stirring for 2 h. at 40 ° C. After completion of the reaction, wash with 1% ethanolic HCl, acetone and dry. The product contains 0.69% N, which corresponds to a exchange capacity of 0.49 meq / g.

Example 6

To 162 g of cold water-soluble starch is added 243 ml of saturated aqueous solution of NagCO3. Stir the mixture for 0.5 h at 20 ° C. Then 162 ml of DEXTROSIL are added to the mixture and the reaction is allowed to react for 2 hours at 50 ° C. After completion of the reaction, wash with 1% ethanolic H31, acetone and dry. The product contains 0.84% N, which corresponds to a exchange capacity of 0.60 meq / g.

Water-soluble derivatives can be used as a flocculant in the flocculation of a cellulosic-type polymeric material, e.g. in the flocculation of waste water from the pulp and paper industry. Water-insoluble derivatives can be used for ionic adsorption of enzymes and other biologically active material, and also as a strong basic anion exchange resin.

Claims (1)

OBJECT OF THE INVENTION Process for the preparation of quaternary ammonium-containing polysaccharide derivatives, characterized in that in the first step the insoluble polyeaeharide is activated with 17.5% to 25% aqueous sodium hydroxide solution, in the case of water and water, respectively. of alkali-soluble polysaccharides with solid sodium carbonate or saturated aqueous sodium carbonate solution for 30 to 60 min. at 15 to 25 ° C and a molar ratio of polysaccharide / activating base of 1 / 0.2 to 3, wherein in the second step it is etherified with 0.1 to 2 molar trimethyl-2-hydroxy-3-chloropropylammonium chloride at a temperature of 30 to 80 ° C, preferably 40 to 60 ° C for 2 to 6 hours.