SU1740379A1 - Method of cobalticinium-containing polymers production - Google Patents

Abstract

Usage: cobaltcinium-containing polymers possess ion-exchange ability and can be used as a heat-resistant highly basic anion exchange resin. SUMMARY OF THE INVENTION: Cobalt-tycinium-containing polymers are obtained by polycondensation of isophthalic or terephthalic aldehyde and hexator phosphate 1.1-diacetylcobalticine or a mixture of hexafluorophosphate 1,1-diacetyl cobalticinium and mixtures of an acetyl derivative, which is used for hexafer-artifrale – artifrale – artiframe – artiframe – artiframe – artiframe – artiframe – artiframe – olerate. the ratio of the latter to the hexafluorophosphate of 1,1-diacetylcobalticine is 1: 4-1: 1.5 and the reaction is carried out in a solution of ethyl alcohol at the boiling point of the reaction mixture using Ora KOH with the content in the reaction solution 1 5-2.0% 1 table. (L C vj 4 O GJ VI O

Description

The invention relates to methods for producing cobalt-cyanine-containing polymers that possess ion-exchange ability, can be used as a heat-resistant highly basic anionite and belong to the class of polyalkones.

A known method for the preparation of cobaltysinium-containing polymers by reacting the sodium derivative of cyclopentadiene with a, sodibromoalkanes, followed by the interaction of the resulting sodium derivative, dicyclopentadienyl alkane, with a cobalt salt. A similar ferrocene polymer was obtained under similar conditions from the sodium derivative of the nd -dicyclopentadienyl alkane and the iron salt with a very low yield of 0.02-0.05%

A method is described for the preparation of cobalticycin-containing polymers by the interaction of hexafluorophosphate 1 .G-diacetylcobaltsine with oligophenyl (mol.m. 10001400) with terminal acetyl groups in a melt at 200-210 ° C in a stream of argon in the presence of p-toluenesulfonic acid as a catalyst. The polymers are obtained with a yield of 64-90%. Cobalt content in polymers 4.75–9.10%; Ion exchange capacity 0.27-0.93 mEq / g.

A method is known for producing cobalt-cynium-containing polymers by reacting 1,1-diacetyl-cobalticine hexafluorophosphate with acetylated polystyrene in a melt in an argon flow at 120–200 ° C in the presence of triethyl orthophosphate as a ketalization agent and p-toluenesulfonic acid as a catalyst. The polymers are obtained with a yield of 68-96%. The cobalt content in polymers is 6.0–8.8%. Ion exchange capacity 0.31-0.90 mg-eq / g.

Also known are cobalt-tsini-containing copolymers based on iodomethylated polystyrene and cobaltocene obtained with a yield of 70-76% and having an ion-exchange capacity of 0.8 mEq / g at pH 7.5.

The closest to the proposed method is the production of cobalt-cine-containing polymers by polycondensation of 1,1-diacetyl cobalticini hexafluorophosphate or a mixture of unsubstituted cobalticini hexafluorophosphates. acetyl- and 1 L of ciacetylco-balticine with acetophenone in the presence of anhydrous zinc chloride at 200 ° C; Cobalt content in the polymer is 9.7%; ion exchange capacity: 0.7 mg-eq / g;

The disadvantage of this method is the low polymer yield, 30-50% and carrying out the reaction under harsh conditions at 200 ° C and in an inert atmosphere.

The aim of the invention is to reduce the reaction temperature, increase the yield and ion-exchange capacity of cobalt-cyanine-containing polymers.

This aim is achieved in that in Preparation kobaltitsiniysoder--containing polymers by polycondensation hexafluorophosphate 1.1 -diatsetilkobaltitsini hexafluorophosphate or mixtures of 1 V -diatsetilkobaltitsini kobaltitsini with acetyl derivative in the presence of a catalyst, as the acetyl derivative kobaltitsini geksaftor- using 1-acetyl phosphate, 1 -ethylcobalticine at a ratio to 1,1-diacetylcobalticine 1,1: diacetylcobalticine to hescafluorophosphate, isophthalic or terephthalic aldehyde is used as a comonomer iju carried out in a solution of ethanol at reflux of the reaction mass by using KOH as a catalyst to the content in the reaction solution 1.5- 2.0%.

When polymers are prepared by reacting 1,1-diacetyl cobalticini hexafluorophosphate with isophthalaldehyde, the reaction proceeds as follows:

+ ONS-r t-CHO M

iyj ao ° c

COCH CHj-n

where OH and SG, n - cross-linked polymer

Polycondensation of acetyl derivatives of cobalticin is carried out with isophthalic (TU 15P-756-71) and terephthalic (TU 6-09-11-593-75) aldehydes.

Hexafluorophosphate 1 1 -diacetylcobalticine was obtained by oxidation of hexafluorophosphate 1 1: -diethylcobalticine with a five-fold excess of potassium permanganate in an acidic medium.

By oxidation of 1,1-diethylcobalticinium bromide by a sevenfold excess of potassium permanganate in an acidic medium, after recrystallization of the product isolated by column adsorption chromatography from the water, a mixture of acetyl cobalticinium derivatives is obtained with a yield of 11% (according to the PMR spectra, the mixture contains 76% 1.V-diacetylcobalticin and 24% 1-acetyl, T-ethylcobaltiticini). 4% of a mixture of hexafluorophosphates of 1,1-diacetylcobalticine (50% in a mixture) and 1-acetyl, G-ethylcobalticinini (50% in a mixture) are separated from one stripped off filtrate. By oxidizing 1,1-diethylcobalticinium bromide with an 8-fold excess of KMpOg, a mixture of acetyl derivatives is obtained in 6% yield, consisting of 84% 1, G-diacetylcobalticini and 16% 1-acetyl. 1-ethyl-cobalticinium After double recrystallization of this mixture, a product is obtained with the content of 1 1-diacetyl cobalticini 93-96%, m.p. 200-202 ° C.

Cobalt-cine-containing polymers are obtained in a yield of 64-93%. The cobalt content of the polymers is 5.26-13.51%. ion exchange capacity - 0.37-1 51 mg-eq / g

According to the data of dynamic TGA, in air polymers lose in the mass of 5% at a temperature of 100-130 ° C 10% - at 220-250 ° C, 50% - at 400 ° C, the residue at 800 ° C is 20%.

The PC spectra of the polymers contain bands in the region of 560, 1030-1070, 3100, characteristic of the system are cobalticine cations, 840, related to the PFe anion, 710, 1600 cm, related to benzene, 1690 cm, related to to C 0, 1380 cm - to CH bonds of the terminal acetyl group.

PRI me R 1. In a single-neck flask equipped with a reflux condenser, 0.2750 g (0.0006 M) of 1,1-diacetyl-cobalticini hexafluorophosphate (mp 200–202 ° C) and 0.0882 g (0.0006 M) of isophthalaldehyde in 15 ml of absolute ethanol before boiling (80 ° C) with stirring until the initial reagents are almost completely dissolved. A solution of 0.35 g of KOH in 6 ml of absolute ethanol is added to this mixture at 80 ° C with stirring through a refrigerator. After the catalyst was added, a black precipitate of polymer precipitated from the solution. Stirring is continued for 8 hours. The obtained polymer precipitate is filtered, washed with ethyl alcohol, a mixture of acetone and water (15: 1 ratio) until neutral, with acetone and alcohol. The dark brown polymer is dried under vacuum. The yield is 0.327 g. 93%. The cobalt content is 11.15%. The experimental ion exchange capacity at pH 7.5 is 0.88 mEq / g, at pH 6.0-1.37 mEq / g, and at pH 7.0-1.08 mEq / g. repeated ion-exchange capacity of 0.65 mEq / g; theoretical ion-exchange capacity — 1.94 mg-eq / g. The polymer is insoluble in water, tetrahydrofuran, acetone, dioxane. chloroform. Properties are listed in the table.

Example 2. In a single-neck flask (as in Example 1), 0.5 g (0.0012 M) of a mixture of hexafluorophosphates of 1.1-diacetylcobalticine and 1-acetyl, 1 -hgilcobalticini (4: 1) and 0.16 g are heated (0,0012 M) isophthaldehyde aldehyde in 17 ml of absolute ethanol. 0.64 g of KOH in 8 ml of ethanol is added to this mixture. Stirring while heating is continued for 7 hours. The polymer was isolated as in Example 1. The yield was 0.54 g, 84.6%. The experimental ion exchange capacity at pH 7.5 was 1.10 mg eq / g. The cobalt content is 11.42%. Properties are listed in the table.

Example 3. Under the conditions of example 1, 0.3 g (0.0007 M) of a mixture of hexafluorophosphates of 1,1-diacetyl- and 1-acetyl, 1-ethyl-cobalticycin (in a ratio of 3: 1) and 0.1 g ( 0.0007 M) terephthalic aldehyde in 24 ml of absolute ethanol, 0.4 g of KOH in 5 ml of absolute ethanol is added and heated at the boiling point of the reaction mixture for 10 hours. The resulting polymer is isolated as in Example 1. Exit 0 , 36 g, 93%. The cobalt content is 13.00%. The experimental ion exchange capacity at pH 7.5 is 0.96 mEq / g. Repeated ion exchange capacity at pH 6.0–0.21 mg-eq / g. The properties are listed in the table. Example 4. Under the conditions of Example 1, 0.25 g (0.0006 M) of a mixture of hexafluorophosphates is heated. 1.1 g-diacetyl and 1-acetyl, 1-ethyl-cobalticini (2: 1 ratio) and 0.8 g (0.0006 M) of isophthalic aldehyde in 15 ml of absolutized ethyl alcohol, 0.41 g of KOH is added. in 8 ml of absolute ethanol and heated at boiling of the reaction mixture for 10 hours. The resulting polymer is treated as in example 1. Yield 0.22 g, 66%. The cobalt content is 13.51%. The experimental ion exchange capacity at pH 7.0 is 1.51 meq / g, the repeated ion exchange capacity at pH 6.5-0.51 meq / g. Properties are listed in the table.

Example 5. Under the conditions of Example 1, 0.2 g (0.0005 M) of a mixture of 1,1-diacetyl- and 1-acetyl, 1-ethyl-cobalticini hexafluorophosphates (in a ratio of 1: 5: 1) and 0.065 g (0.0005 M) isophthalaldehyde in 14 ml of absolute ethanol, 0.26 g of KOH in 5 ml of absolute ethanol is added and heated at boiling for 7 hours. The polymer obtained is isolated in Example 1. Cobalt content 9 is 93%. Yield 0.24 g, 94%. The experimental ion exchange capacity at pH 7.5 is 0.86 mEq / g. Properties are listed in the table.

Example 6. Under the conditions of example 1, 0.87 g (0.002 M) of a mixture of hexafluorophosphates of 1,1-diacetylcobaltizini and 1-acetyl T-ethyl cobalticini (1: 1) and 0.28 g (0.002 M) of isophthalic aldehyde in 30 ml are heated absolutized ethyl alcohol. 0.8 g of KOH in 10 ml of ethanol is added to this mixture. Stirring while heating is continued for 10 hours. The polymer is isolated as in Example 1. Yield 0.71 g. 64%. The cobalt content is 5.26%. The experimental ion exchange capacity of the sample at pH 7.5 is 0.37 mg-eq / g. Properties are listed in the table.

Analogously to examples 1. 6, 3, cobalt-cyanine-containing polychalcones with a different concentration and at 50 ° C were obtained. Examples are given:; in the table.

Claims (1)

Claims of the Invention A method for producing cobaltZenium-containing polymers by polycondensation of hexafluorophosphate of 1,1-diacetylcobalticine or a mixture of hexafluorophosphate of 1,1-diacetylcobaltizini and acetyl derivative of cobalticycin in the presence of a catalyst, which, in order to reduce the reaction temperature, to increase the tebaltocini derivative, in the presence of a catalyst, in order to reduce the reaction temperature, to increase the cost of raising cobalticycin, in the presence of a catalyst, to increase the campaign temperature, to raise the temperate, to reduce the reaction temperature, to increase the campaign cost, to increase the reaction temperature, to increase the cost of the reaction. and increase the ion exchange capacity as 1-acetyl hexafluorophosphate and 1-ethylcobalticini hexafluorophosphate at a ratio of 1,1-diacetylcobalticine 1: 4-1: 1.5 to hexafluorophosphate; and additional isophthalic aldehyde is used as a comonomer, and the reaction is carried out ethanol solution at boiling of the reaction mass, when using KOH as a catalyst with a content of 1.5-2.0% in the reaction solution. Properties of cobaltysin-containing polychalcones  Note. Examples 6-8 beyond, DAK - hexafluorophosphate 1, I1-diacetylcobalticine, AEC - hexafluorophosphate 1-acetyl, 1J-ethylcobalticine, AND / T FA - iso-, terephthalic aldehyde, AK - acetylcobalticine, AF - acetophenone