SU653891A1 - Method of obtaining anion exchanger - Google Patents

Description

This invention relates to the synthesis of highly permeable polyfunctional anion exchangers, which can be used to isolate and purify antibiotics, enzymes, alkaloids, sorption, concentration and separation of metals in hydrometallurgy.

A known method of producing anion exchangers by aminating halogen-methylated copolymers of mono- and divinyl compounds with alkyl substituted diamines.

As a polymer matrix, a copolymer of styrene and divinylbenzene (DBB) is used, which, at best, as a result of the modification, may become macroporous with limited swelling and, therefore, limited permeability.

In addition, the amination is carried out at the boiling point of amines (such

the amines are boiled at IZO-I C C) for 2 hours in the case of N, N-tetramethylethylenediamine and 8 c in the case of dimethylaminoethyltrimethylammonium iodide. After amination and distillation, in both cases, it is passed under a pressure of 35 mm Hg. at kS ° C, methylene chloride for k h, which complicates the entire synthesis of ion exchangers. The total duration of the synthesis of such ion exchangers 6-12 Cho

There is also known a method of producing anion exchangers by aminating with ethylene dimine or propylene diamine chloromethyl styrene copolymers with divi yl benzene.

This method is characterized by the duration of the synthesis (H-10 h), the relatively low exchange capacity of the anion exchangers obtained, the inability to form 1 complex compounds with metals from us, which is due to the lack of complexing properties of the functional groups of these ion exchangers, as well as low permeability of the polymer matrix. The purpose of the invention. - production of highly permeable polyfunctional anionites with high selectivity and improved kinetic characteristics. This goal is achieved by using halogen-methylated styrene copolymers with long chain dienes as the initial copolymers, and ionic groups are introduced by aminating these copolymers S, M-dimethylpropane diamine or N-methyl propane diamine. The amino groups of N, K-dimethyl and N-methyl propane diamine are separated by three methylene groups, which reduces the g4 effect of conjugation, resulting in an increase in their ability to donor acceptor interaction with sorbed ions with the realization of both ionic and coordination bonds. The high permeability of the starting halogen-methylated copolymers makes it possible to carry out the amination reaction in 1.5-2.0 hours. The synthesized anion exchangers are characterized by rather high chemical and thermal resistance. The chemical resistance of ion exchangers was studied, such as 5 n, with solutions. or NaOH for 30 min, and also with 10 solution at room temperature for 48 h. O6 loss (of the anionite capacity after contact with the acid solution does not exceed 3.7%, and with alkali solution 4.2 Hydrogen peroxide reduces the exchange capacity 21% of the ion exchanger. Example: 10 g of a chloromethylated styrene copolymer with 8% diisopropenyl derivatives of diphenyloxide or diphenylmethane and 30 ml of dioxano are loaded into the reactor. d 100 ° C in flow After cooling to room temperature, the anion exchanger is separated by filtration, washed with distilled water, treated with 5% NaOH solution and washed with distilled water until neutrality of the filtrate. The nitrogen content in the polymer is 10.99% , exchange capacity for 0.1 But to a solution of HCl 6.8 mgo equiv / g, the swelling ratio in water is 2.3, Example: 10 g of chloromethylated styrene copolymer with 8% diisopropenyl derivatives: diphenyloxide or diphenylmethane and 30 ml are loaded into the reactor. dioxane. After swelling for 2 hours, 50 ml of N-methylpropanediamine are added to the reactor and heated to 11) 0 ° C with stirring for 1.5 hours. After cooling to room temperature, the a-nionite is separated by filtration, washed with distilled water, treated 5% NaOH solution and washed with distilled water until neutral wash water. The nitrogen content of the polymer is 11. exchange capacity 0.1 n. a solution of HC1 6.66 mg, eq / g, the coefficient of swelling in water is 2.2. Analogously to Examples 1 and 2, the aminations of the halogen-methylated styrene copolymers with the diisopropenyl derivatives of diphenyl, diphenyl sulfide or diphenyl sulfone are reacted; halomethylated styrene copolymers. with N, N-alkylenedimethacrylamide, with bis- (p-vinylphenyl) alkanes, with N, N-x-butylene methacrylamides of dimethacrylic esters of dioxydiphenylsulfoxide, dioxydiphenylsulfone, hydroquinone, dioxydiphenylpropane or dioxydiphenylmethane The physicochemical characteristics of the synthesized ion exchangers are given in the table. As can be seen from the data presented in the table, the duration of amination in the proposed method is 1.5 Mo. Synthesized anion exchangers are able to sorb nickel and cobalt ions with a sufficiently high capacity (up to 3.5 mg.eq / g). Sorption of these ions was carried out from 0.05 n. solutions of nickel sulphate or cobalt under static conditions at room temperature. It should be noted that the proposed polyfunctional anion exchangers are characterized by a high capacity for metal ions at low swelling rates tH3,

note: eOE (calculated on the nitrogen content, ESR is determined from potentiometric titration curves. DNPDA - anion exchanger based on N, Ndimethylpropanediamine, NAPA - based on N-netilpropandiamina.

Claims (1)

METHOD FOR PRODUCING Anion exchange resins by amination galogenmetilirovannyh copolymers of styrene with divipilnymi monomers, characterized in that, in order to obtain high permeability polyfunctional anioniuov with improved selectivity and improved kinetic characteristics, as starting copolymers used galogenmetilirovannye copolymers of styrene with long chain dienes and amination carried Ν, Ν ¹ - dimethylpropanediamine or N-methylpropanediamine.