CS225503B1 - Complexon derivatives of the pearl cellulose - Google Patents

Description

The present invention relates to complexone derivatives of pearl cellulose and to a process for their preparation.

Polymeric complexones have found application in various fields of chemistry and chemical technology, and polystyrene resins based on iminodiacetic acid are already commercially available. Polycomplexons can be prepared in practically only two ways. It is possible to either immobilize the ready-to-use complexons or their derivatives on a suitable polymeric backbone (e.g., OM.4crik) or to synthesize a complexone group on a polymeric backbone gradually (J. Chromatogr. 14, 244 (1964); Acta Chim. Acad. Sci. Hung 99 »

363 (1979); USSR AO 555 117 (1977)) Both have advantages and disadvantages. The first method provides a more uniform product, but is synthetically more demanding. Therefore, this route is more suitable for the production of polycomplexones for scientific use, for example in analytical chemistry for metal separation. The second way is easier, but the product tends to be very heterogeneous. The products thus formed are more suitable for technical use, for example in hydrometallurgy.

Until now, styrene-divinylbenzene copolymer has been used almost exclusively as a polymer backbone for the construction of a complexone moiety. A disadvantage of these scaffolds is the low rate of metal sorption, which is due to the slow metal ion hole by the hydrophobic polystyrene gel. Another drawback lies in the preparation of the needed chloromethylated styrene-divinylbenzene copolymers, which work with carcinogenic methyl chloromethyl ether. These drawbacks do not have the polymeric complexones of the invention in which the complexone moiety is anchored and built on bead cellulose as a carrier,

The present invention provides bead cellulose complexone derivatives of the general formula R N (CH CH N) R, wherein at least one R is a cellulose derivative.

225 503 box residue, the others being either CH ₂ COOH or H and η = 1 - 10. The complex bead cellulose derivatives are prepared according to the invention by treating the oligo (ethyleneimine) bead cellulose derivative with a solution of chloroacetic acid or a salt thereof. and neutralizing the carboxymethylation acidity. It is preferred to carry out the carboxymethylation of the oligo (ethyleneimine) bead cellulose derivative (prepared according to No. 225376 by an excess of alkali chloroacetate in an aqueous or aqueous-organic solution at a temperature of 30,100 ° C.

Even a chloroacetic acid solution partially neutralized with sodium carbonate and control the reaction by maintaining the pH of the reaction mixture at 8/10 by the gradual addition of sodium carbonate. However, alkaline hydroxide solutions can also be used for neutralization and for the reaction itself, under conditions in which chlorine in chloroacetic acid is not hydrolyzed. Carboxymethylation utilizes considerably higher reactivity of amino groups compared to hydroxyl groups; however, O-carboxymethylation taking place in parallel to a small extent to form cellulose ethers cannot be excluded.

Strongly hydrophilic and porous pearl cellulose as a complexone carrier causes unusual acceleration of metal sorption and easy availability of all active groups. The complex bead cellulose derivatives of the present invention can be used as sorbents for trapping or separating heavy metals in analytical chemistry, hydrometallurgy, waste water treatment, and the like.

Example 1

Mixture of about 15 ml wet diethylenetriamine derivative of pearl cellulose containing 1.63 mmol of bound diethylenetriamine / g dry matter and a solution of 9.6 g of chloroacetic acid and 5.3 g of carbonate>

Sodium carbonate in 20 ml of water was heated to 80 [deg.] C. The pH of the reaction mixture was maintained at 7-8 by addition of sodium carbonate during heating. The product was then aspirated, washed successively with water, 2N HCl and water. i.e., 1.27 mmol bound complexone / g dry matter and has a sorption capacity for copper of about 6.6 mg Cu ⁺⁺ / ml wet product.

Example 2 _enn

225 503

100 ml of aspirated bead diethylenetriamine derivative (10.2 mmol of bound diethylenetriamine) was added to a solution of 53.3 g of chloroacetic acid in 170 ml of water with stirring. 30.5 g of sodium carbonate are added in portions, then 15.2 g of sodium carbonate are added in one portion and the reaction mixture is heated to 75 DEG C. After stirring at this temperature for 15 hours, 15.2 g of sodium carbonate are added. and stirred for an additional 3 hours. The product is filtered off with suction and washed with water. Capacity for Cu ⁺⁺ : 11.6 mg Cu / ml wet product.

Example 3

100 g of aspirated bead diethylenetriamine derivative (12.8 mmol of bound diethylenetriamine) was added to 138 ml of acetone and the mixture was stirred at room temperature for 30 minutes. Stirring is discontinued, the cellulose is allowed to sit, and 50 ml of aqueous acetone is drawn off. 50 ml of acetone are added and after 30 minutes, 50 ml of aqueous acetone are again withdrawn. Then 8.2 g of 50% aqueous sodium hydroxide solution were added, after stirring for 30 minutes 9.7 g of chloroacetic acid and the reaction mixture was heated to 50 ° C for 1 hour. stirring was continued for 2 hours. The product is filtered off with suction and washed with water. Capacity for Cu ⁺⁺ 58.9 mg Cu / g dry product.

Example 4

A solution of 29.3 g of chloroacetic acid in 125 ml of water is neutralized with stirring at a temperature below 20 DEG C. with 24.8 g of 50% aqueous solution.

if 225 503 sodium hydroxide solution. To this solution was added 100 g of aspirated triethylenetetramine bead cellulose derivative (30.95 mmol of bound triethylenetetramine) and the reaction mixture was stirred at rt

0 for 5 hours. The pH is maintained at 10.5 / H by successive addition of 20% sodium hydroxide solution. The product is filtered off with suction and washed with water. Capacity for Cu ⁺⁺ : 40.0 mg Cu / g dry product.

Claims (2)

SCOPE OF THE INVENTION 225,503 Complexone derivatives of pearl cellulose of the general formula R 2 N (dT CH_N) R, wherein at least one R is a cellulose residue and 2 2 n R 1 others are CH 2 COOH or Η, n = 1 → 10. 2. A process for producing complex bead cellulose derivatives wherein the oligo (ethyleneimine) bead cellulose derivative is treated with an excess of a solution of chloroacetic acid or a salt thereof and neutralizing the acidity formed during the reaction.