SU1145023A1 - Cobaltcine-containing copolymers as thermostable ionites - Google Patents

Abstract

Cobaltition-containing copolymers of the formula as P colQ heat-resistant ion exchangers.

Description

This invention relates to a new cobaltitinium-containing poly.

measures of the general formula where X is in OH or C, m: n: C: k 2: (17-38) :( 48-76) g (5-12), which have the properties of strongly basic anion exchangers with increased heat resistance. The synthesis of almost all known cobalticinium-containing polymers that exhibit ion-exchange properties is based on the use of 1,1-diatyl talcobalticini as the cobaltocinium-containing component of hexafluorophosphate. Known cobalt-containing polymers are obtained by a polycondensation reaction of 1,1-diacetylcobalticine with Cl 1 oligophenylene or acetic acid polystyrene C23 with ion exchange capacity of 0.27-0.90 mg-eq / g from a neutral solution, but with low thermal stability; at 72 hours, the polymer samples in the OH form lose 60-80% of the total amount of bone ,.-. It also contains heat-resistant cobalt-cyanine-containing polymers based on hexafluorophosphate 1,1-diacetyl. cobalticine and acetophenone with an ion exchange capacity of 0.72-1.27 mg-qky / g from a neutral solution Cz. The disadvantage of these polymers is that they are obtained in the form of a fine powder, which makes it difficult to use as an ion-exchange material without additional granulation and impairs ion-exchange properties (low swelling in water, moisture capacity coefficient, K dYO, 1 g HJO / g. Cationite) . In addition, the use of hexafluorophosphate 1,1 diacetylcobalticine as the cobaltysinium component makes the polymer synthesis method non-technological. 1,1-Diacetyl cobalticine hexafluorophosphate is obtained as one of the oxidation products of 1,1-diethyl cobaltin bromide. The latter is obtained by direct four-step synthesis from sodium cyclopentadienide, ethyl bromide and cobalt salt. The aim of the invention is to synthesize heat-resistant ion exchangers with increased mechanical strength, swelling, and moisture capacity. The goal is achieved by the indicated copolymer structure, which is obtained by reacting styrene iodomethylated copolymer (2% pressure) with cobaltocene followed by treating the product with sulfuric acid by the reaction

4NH2 $ Oi4

1145023

SNg-CH-C rig CH.

SNgL) The use of cobaltocene, which is obtained by a technologically accessible method, and commercial polystyrene as the starting compounds, simplifies the synthesis technology. New cobaltization-containing polymers are obtained with a yield of 70-76%. The cobalt content is 16.1–9.45%. The ion exchange capacity of the neutral solution (pH 7; 5) is 0.770, 80 mEq / g. The theoretical ion exchange capacity is 1.99-2.05 mEq / g. The coefficient of capacity in St-form is 0.90 r HjO / r. anion exchange resin An example of an iodomethylated copolymer of styrene with divinylbenzene (iodine content 50.91%) fed with a threefold amount of dichloroethane (DCE), a solution of 1.54 g of cobaltocene in 150 ml of DCE is added under an argon atmosphere. The reaction mass was kept at this temperature for 5 hours. Then, DCE was removed, the copolymer was terephrated with terahydrofuran (THF) several times, poured over with one THB and left for 1 hour at 4 ° c. A twofold solution in THF was added to the swollen copolymer with a twofold volume and left for a day at this temperature. The resulting product is successively washed with THF, water, and converted into the OH-form by treating the IN with a solution.

J.Z

Co,%

Example, Maon. The polymer yield after drying in vacuum is 70.2%. The ion exchange capacity of the sample from the neutral solution (pH 7.5) is 0.77 mEq / g. The cobalt content is 11.8%. Example 2: Synthesis was carried out analogously to Example 1, but the reaction with 4NHjSO was carried out at. Yield 69.1%. Cobalt content is 9.45%. Ion exchange on the capacity of the sample from a neutral solution (pH 7.6) 0.80 mg-eq / g. The moisture capacity in the C1 form, K (, is equal to 0.90 g-H O / g anion exchanger. The 06 sample in the OH form does not lose its capacity after thermolysis for 72 hours. Example 3. The synthesis is carried out analogously to the example 2, increasing the reaction time from 4NHjS 0 to 48 hours. Yield: 76.12%. Cobalt content: 16.1%. Ion exchange capacity of the sample from the neutral solution is 0.79 mg-eq / g. , equal to 0.52 r "H, jO / r anion exchange resin. The ratio of units in the copolymer is determined by the percentage of Co and J, determined by the method of X-ray fluorescence analysis. and elemental analysis data on C and Table shows data based on the extreme values of cobalt and iodine (example 2 and 3);

The resulting OH-form copolymers are brown granules, which are kept in their present state under a layer of water without changing properties for an unlimited time. The ion exchange capacity is 0.77-0.80 and is maintained when the copolymers are heated for 72 hours. The moisture capacity of these copolymers is 5 to 9 times higher than the moisture capacity of known Z.

The resulting cobaltysinium containing the copolymer is designed for use as ion-exchange} 11th material in the water treatment system on atomic water reactors, where the duration of the work of anion exchangers is determined by their heat resistance. In addition, heat-resistant ion-exchange membranes can be prepared from these compounds for special industrial purposes | when the main factor in membrane operation is the duration of operation due to their thermal stability.

AV-17-8 h anion exchangers used for these purposes (GOST-20302-74) in the CH-form feed 70-80% of their capacity (e 3.0-3,) at 125 ° C for three days.

t The proposed ion exchanger does not lose its capacity for three days.