SU907007A1 - Process for preparing polyampholytes - Google Patents

Description

I

The invention relates to methods for producing fibrous ion-exchange materials containing phosphoric acid and amino groups, and can be used in textile enterprises in purification processes (sorption of large organic ions, surfactants, dyes) and in the sorption processes of the mining and metallurgical industry for trapping non-ferrous metal ions both from individual solutions and from mixtures.

There are several known methods for the preparation of phospho-containing granular ion exchangers. All of them, as a rule, are multi-stage and long in time, have low values of capacity for metals, and the time for establishing sorption equilibrium is 24 hours,

A known method of producing polyampholyte containing phosphoric acid groups by copolymerizing dichloroethyl ester of vinylphosphonic acid, vinylpyridine, and divinylbenzene, followed by

by saponification or by treating nitrogen-containing monomors with phosphorus derivatives tl and 2.

Closest to the invention in. It is a method for the production of polnamfolit by treating a nitrogen-containing polymer, which uses the product of the ammonolysis of cross-linked copolymers of alkyl esters of acrylic and methacrylic acid, phosphorous acid and formalin in an acidic medium (per 1 wt. h.

10 aminopolymer taken 1.5-2 weight. including phosphorous acid, 0.5-1 wt. including hydrochloric acid and 1-1,5 weight. including formalin). The result is am (}) ozone ionite,

15 containing phos () yuric acid and amino groups.

The ratio of the components for carrying out the reaction polymer - H3PO2 - HCE SNlo 1: 2: 1: 1.5. The exchange capacity of the obtained ion exchanger over the copper cation from. 0, O5 n. CuSO solution, v reaches 34 mg-eq / g (in an acidic environment) 3J. The disadvantage of this method lies in its duration, determined mainly by slow swelling of the ion exchanger. In addition, the use of the obtained polyampholyte is difficult when carrying out sorption from slurries and viscous solutions. The working area of pH during the sorption of copper by the synthesized ion exchanger is rather narrow (1.5-4). In addition, due to the large number of crosslinks in the starting polymer, the sorption rate of the copper cation is rather small (the time for establishing the sorption equilibrium is 24 hours). The purpose of the invention is to increase the serption properties of polyampholyte and simplify the process of its production. The goal has been achieved by a method for producing polyampholytes by treating a nitrogen-containing: polymer material with a phosphorous cue and formalin in an acidic medium, moreover, as a nitrogen-containing; Polymeric material uses polyacrylonitrile fiber modified with water-soluble polyamines with an amino group content of 4–4.5 mg eq / g. The starting material was obtained by treating polyacrylonitrile fiber with polyethylene with polyamine and high molecular weight polyethylenimine in the presence of hydroxylamine at pH 9-9.5. The desired pH is achieved by a certain ratio of hydroxylamine and the corresponding polyamine. It is necessary to strictly observe the indicated pH values, since when obtaining the initial fiber with and, 5 the number of ashgroups in the fiber is extremely small. Processing fiber specified mixture results in anion resin containing primary and vtog. amine amino groups. The synthesized anion exchange resin is treated with: phosphorous acid and formalin in the presence of HC2 at a ratio of - 1: (1-1.2); (0.8-1) for 2-5 hours at 80-100 ° C without prior swelling. As a result, polyampholyte is obtained, which has more high-energy exchange capacity for the copper cation of 3.2-4.2 mg eq / g. The whole process takes no more than 6 hours. The synthesized polyampholyte has high sorption l kinetic properties with respect to metal cations , cobalt, nickel, since copper sorption ends in 10-ZOmin and is selective with respect to copper cations at sorption of the mixture; and, and is also capable of extracting significant amounts of nonionic surfactants (OP-7, OP-f). in a relatively simple way, N would be l obtained polyampholyte containing amino and phosphoric acid groups with satisfactory physicomechanical indicators (strength 15-18 cN / tex), capable of sorbing metal cations and large organic ions. , in the OH form with an amino group content of 4.0 ivir-eq / g, is treated with a mixture containing 22.5 g of phosphorous acid; 22.5 g of formalin; 22.5 g of concentrated hydrochloric acid and 230 ml of water, for 5 hours at 100 C. After the completion of the reaction, the polyampholyte is washed successively with 0.1N. NdOH; 0.1 and. ASC and water until the absence in the washings of FS-; odds. The synthesized papiampholyte has a copper OED concentration of 4.1 mEq / g. Example2. South of ion-exchange polyacrylonitrile fiber treated with high molecular weight polyethylene-polyamine at pH 9.5, in the OH form with the content of amino groups: 4.5 mg eq / g is treated as in Example 1 at 80 ° C for 2 hours. Polyampholyte has an EUC on copper of 4.2 mg eq / g. Example 3. South of ion-exchange polyacrylonitrile fiber treated with high molecular weight polyethylene polyamine at pH 9.2, in OH-form with an amino group content of 4.15 mg-eq / g is treated with a mixture containing 22.5 g of phosphorous ACID} 27 g of formalin; 20 g of concentrated hydrochloric acid and 221 ml of water, for 4 hours at 9 ° C. At the end of the reaction, the polyamfolite is washed successively with O, 1N. NciOH; 0.1 n. HC2 and water until absent in the washings of phosphorus. The synthesized polyampholyte has a copper SOY of 4.15 mEq / g. Example 4. South of ion-exchange polyacrylonitrile fiber treated with high molecular weight polyethylenimine in the OH form with an amino group content of 4.5 mEq / g is treated with a mixture containing 22.5 g of phosphorous {syllot; 22.5 g of formalin; 22.5 g of concentrated hydrochloric acid and 230 ml of water for 3 hours at. At the end of the reaction, the panyampholyte is washed successively with 0.1 N. HqOH;

0.1 n. NSV and water until absent in pum Bt.1kh waters of phosphorus. The quilted polyampholyte has a copper OED 4.3 oq / g.

The table shows the data on the sorption of metals (Co, Co, K) from salt solutions and from mixtures at different pH values, as well as data on the sorption of ionic surfactants

As can be seen from the table, the proposed method provides a reduction of the polyamphophyte synthesis process from 24 hours to 6 hours and a significant improvement in the sorption properties associated with a decrease in the duration of the process of metal sorption to 30 minutes (by a known method 24 hours). The obtained fibrous sorbent, podoliampholit, when testing the sorption of non-ferrous metal ions from sulphate and ammonia solutions with a concentration of salts of metals 0, O5 n. it has a copper capacity of 4.22 mEq / g, nickel 2, 82 mEq / g, and cobalt - 1.77 mg eq / g, and the rate of sorption equilibrium is 48 times higher than in the case of using granular sorbents.

Synthesized polyampholyte is capable of extracting metals (copper, cobalt, nickel) not only in the acid, but also in the alkaline region.

Taking into account the complex composition of mine waters and the low content of metal cations in solutions of processing non-ferrous ores, polyampholyte synthesized by the proposed method was tested for sorption of Ktnon T13 solutions of the ternary mixture Su, Co, Nt and showed high selectivity to copper cations.

During sorption from a mixture of cations of Cb, Col and a concentration of 2 g / l of each component, the synthesized polyampholyte absorbs up to 3.1 m1-eq / g of copper, 0.2 mEq / g nickel and 0.16 mg eq / g cobalt. This can be used for the separation of non-ferrous metals from both technological solutions and wastewater from hydro-metallurgical enterprises.

The use of this invention significantly reduces the duration of the production process of an ion-exchange material with higher kinetic and selective properties.

9 & 0700710

Claims (2)

Formula isotop fiber with amino groups The method of obtaining the piamfopito. By Sources of information, of processing nitrogen-containing polymer into consideration when examining a material with phosphorous acid and forma- s1- Author's testimony of the USSR Linom in an acidic environment, I-No. 271012, cl. From 226/06, 1968. shopping center and with the fact that, in order to increase 2. USSR author's certificate sorption properties of polyampholyte and upro-no. 339555, cells, С O8F 212/14, 8 / ОО, the process of its production, as 08 J 5/20, 1970. nitrogen-containing polymeric material 103. USSR Copyright Certificate use of modified water-.№ 481629, cl. C 08 F 212/14, 1974 Roman polyamines polnacrylonitrile- (prototype). 4-4.5 mEq / g.