SU1595851A1 - Method of producing cross-linked polymeric sorbents - Google Patents

Abstract

The invention relates to the field of producing three-dimensional copolymers in the form of spherical particles with high ion-exchange and complex-forming ability, which can be used to extract from aqueous solutions of transition metal cations, as well as a number of metals with amphoteric properties, in the form of anions. The sorbents are obtained by crosslinking water-soluble polymeric quaternary salts N, N 1-diallyl-N, N 1-dimethylammonium with a cross-linking agent N, N 1-methylene bisacrylamide in a water in oil emulsion at a polymer concentration of 25-55% by weight in aqueous or water-alcohol solution containing 68-100 wt.% water. The concentration of the crosslinking agent is 1.64-2.75% by weight. The mixture is stirred at a speed of 200-370 rpm. This allows the sorption capacity of sorbents to be increased to 7.07 mEq / g for CU 2 + ions, to 2.38 meq / g for CO 2+ ions, to 2.71 meq / g for NI 2+ ions, and also to simplify sorbent production process. 2 tab.

Description

The invention relates to the preparation of three-dimensional copolymers in the form of particles of spherical shape with high ion-exchange and complexing ability. Such copolymers can be used to recover from aqueous solutions of transition metal cations, as well as a number of metals with amorphous properties, in the form of anions.

The aim of the invention is to increase the sorption capacity and simplify the process for the preparation of sorbents.

Example 1. 50.0 g of petrolatum oil, 0.11 g of sorbate monooleate and 0.051 g of ammonium persulfate are placed in a glass reactor, stirred at a speed of 200 rpm; a mixture consisting of 4.10 g of poly-N, N-diallyl-K, s-dimethylammonium chloride (PDMDAH) dissolved in 0.90 ml of distilled water and 0.205 g of N, N-methylene bisacrylamide (MBAA) are added, dissolved in 2.50 ml of a water-methanol solution (solvent by volume ratio 1: 1). Continue the reaction with constant stirring in a stream of nitrogen for 5 hours at 70 ° C. After cooling the reaction mass, the resulting granules

coke

00

ate

FILTER by filtration, washed with hex, dried.

A crosslinked PDMDAAH is obtained with a crosslinking degree of 5.1 and a yield of 86%. The average size of the granules is 2 .0.08 mm. The swelling ratio is 2.44.

Total exchange capacity under static conditions (TOR), meq / g: 0.1 n HgSO.4. 6; About NaeMo04.4,6.

PRI mme R 2. The process is carried out - e- | -C analogously to Example 1, the only reason is to concentrate the polymer and use silicone oil instead of vaseline. In the reaction, 3 g of PDMDAAX, dissolved in 2 ml of distilled water, is used.

A crosslinked PDNDAAH is obtained from a staple of 7.2 and a yield of 82. The average granule size is 1.48 + 0.05, the swelling coefficient is 1.83. SOU 0.1 n. N5804 5.9 meq / g.

PRI me R 3. The process is carried out analogously to example 1, the difference is only in the concentration of the polymer (1.86 g, PDMADA dissolved in 3.1 ml of distilled water) and the surfactant used (sorbate monolaurate 0.11 g

A crosslinked PDMDAAH is obtained with a staple of 11.5 and a yield of 85. The average granule size is 0.73 ± 0.05 mm, the swelling coefficient is 1.32, and 0.1 NU of 0.1 NU. . 5.1 mEq / g

0.1 n sorption capacity. pjacTBOpoB metal chlorides (CE) at 6.17 mEq / g.

Example 4 The process is carried out analogously to Example 1, the difference is only in the concentration of the polymer. In the reaction, use 3,012 g PDMDAAH, dissolved in 4.5 ml of distilled water.

A cross-linked PDMDAAH is obtained with a collar degree of 7.15% and a yield of 82. The average polymer granule size is .0.88; f -fO, 05 mm, the swelling ratio is 1.98. Example 5. The process is carried out analogously to the example 1, the difference is Only in the concentration of the polymer. In the reaction, 10 g of a + 0% aqueous solution of PmdaAH is used.

A crosslinked PDMDAAH is obtained with a crosslinking degree of 5.0% and a yield of 92%. the granule size is 1.05 + 0.05 mm, the swelling coefficient is 2.71 VOU at 0.1 n HgSO 7.2 mEq / g, at 0.1 n. H ,, Р04 7.8 meq / g.

;

Q

5 Q

with

five

0

EXAMPLE 6 The process is carried out analogously to Example 1, the only difference being that a mixture consisting of 5 g of a 40% aqueous PDMDAH solution in which 0.141 g of MBAA is dissolved is added to the oil phase. .

A crosslinked PDMDAAH is obtained with a crosslinking degree of 7.4% and a yield of 82%. The average granule size is 0.82 + 0.05 mm, the swelling coefficient is 1.45, the OU is 0.1 n. 5.5 meq / g

EXAMPLE 7 The process is carried out analogously to Example 1, the only difference is that 3 g of poly-N, n-diallyl-N, N-diamethylammonium phosphate (PDMAA) diluted in 2 is used in the reaction. ml of distilled water, and 0.12 g of sorbitan monostearate is used as a surfactant.

A crosslinked PDMDAAF is obtained with a crosslinking degree of 9.9% and a yield of 89%. The average size of the granules is 1.3 + 0.05 mm, the swelling ratio is 1.47, CE by -, 07 mEq / g, by, 38 mEq / g, by N12 2.71 mEq / g.

Example 8. The process is carried out, analogously to Example 1, the difference is that 5 g of a 40% aqueous PDMDAH solution is used, and the stirring speed is 280 rpm.

A crosslinked PDIDAX is obtained with a crosslinking degree of 10.7% and a yield of 88%. The average size of the granules is 0.49 ± 0.03 mm, the swelling coefficient is 1.44, the OU is 0.1 n. 6.31 meq / g.

EXAMPLE 9 The process is carried out analogously to example 1, the difference is in the concentration of the polymer (5 g of a 40% aqueous solution of PDMAAH) and the stirring speed (370 rpm).

A crosslinked PDMDAAH is obtained with a crosslinking degree of 10.7% and a yield of 86%. The average size of the granules is 0.21 + 0.03 mm, the swelling coefficient is 1.60, the OU is 0.1 n. HrjSO 5.9 meq / g, CE in C - 6.77 meq / g.

The effect of the conditions for obtaining a cross-linked polymeric sorbent on the size of the granules and swelling in water is given in Table. one.

In tab. Table 2 shows a comparison of the ion exchange and complexing ability of ion exchangers obtained according to the proposed and known methods.

In order to show that end

H, 2S04 5.5 meq / g, CE according to Cu2

the double bonds of polymeric quaternary salts N, N-diallyl-N, N-dimethyl ammonium, was copolymerized with PDMDAAH with acrylamide.

Example: A PbDa 0% aqueous solution of PmdaAh dissolves 0.130 g of acrylamide and 0.0066 g of ammonium persulfate. The copolymerization is carried out in a stream of nitrogen for 5 hours at.

See the NMR spectra of C and H of the obtained sample. No signals related to residual double bonds were detected in the NMR spectra.

For comparison, the NMR spectra of the kQ% -Horo aqueous solution of PDMDAAX are found, in which the presence of signals is detected: in the NMR spectrum with chemical shifts (Ac 125.2 and 129.7 MD, and in the spectrum 4H (100 accumulations ) with a chemical shift (5 and 5.55–6.30. These signals indicate the presence of terminal double CH CH bonds in the initial solution of PDMAAAC).

Thus, the application of the proposed method allows to increase

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d - 15958516

 the sorption capacity of the obtained sorbents and simplify the process of obtaining sorbents by eliminating a number of stages that are complex in instrumentation.

Claims (1)

Invention Formula The method of obtaining cross-linked polymeric sorbents, including crosslinking polymers with a divinyl cross-linking agent, characterized in that, in order to increase the sorption capacity and simplify the method of producing sorbents, water-soluble polymeric quaternary salts N, N-diallyl-N, K are dimethyl ammonium, as a crosslinking agent is N, N-methylene bisacrylamide, the crosslinking is carried out in a water-in-oil emulsion with a polymer concentration of 25-55% by weight in an aqueous or water-alcohol solution at an alcohol-water ratio by weight 0.13 - 0.46:. 1, the concentration of crosslinker 1,64-2,75% by weight of the mixture while stirring at a speed of 200-370 rev / min. Table 1 By example one 2 3 five 6 7 6.17 , 07 2.38 2.71 1595851 -8 Continued table. 2 .3 7.18 6.20 4.8 5.85 2.00 2.19 2.00 0.30