SU596593A1 - Method of obtaining phosphonopropylcellulose - Google Patents

Description

(54) METHOD FOR OBTAINING PHOSPHOPOPROPYLCELLULOSE

I

This invention relates to the chemistry of organophosphorus compounds with a C-P bond, namely to a new process for the preparation of phosphonopropylcellulose of the general formula

/ ml-OCHg (NgSNgR-OV (j)

ABOUT

where fi is hydrogen or lower alkoxy;

k-alkali metal or lower alkyl;

cella - mono link pulp.

Phosphorus-containing cellulose derivatives are widely used in engineering as flame-retardant textile materials that do not shrink, crush, have a strong, antiseptic, and ion-exchange properties, extractants of uranium, plutonium, and other valuable elements. They are also used to purify natural compounds such as proteins.

or VITS1MINOV. A method is known for producing phosphonoalkylated cellulose with a C-P bond by reacting cellulose with salts or esters of hydroxy alkylphosphonic or phosphinic acid. The phosphorus content in the product is 0.7-2% tl

There is also known a method for producing phosphonoalkylated cellulose with C-P-C-bonding by reacting cellulose tosylates with trialkylphosphites or dialkylphosphite salts when heated to a temperature within 5-20 hours. Phosphorus content is 4-12% 2.

However, the method for producing the phosphonopropyl cellulose of formula (1), as well as the compounds themselves, are not described in the literature and are new.

The purpose of the invention is to develop a process for the production of phosphonopropylcellulose, characterized by a high content

5 phosphorus in the molecule and a hydrolytically stable C-P bond.

The goal is achieved by the proposed method of obtaining phosphonopropylcellulose, which is

0 in that allyl cellulose with Jf 80-851 is treated with an alkaline salt of phosphoric acid or dialkylphosphite in the presence of organic peroxide when heated to a temperature of 80-100

5 in the medium of an organic solvent in an inert gas atmosphere.

Claims (2)

As organic peroxides, for example, benzoyl peroxide, tert-butyl peroxide or tert-butyl hydroperoxide can be used. Products with a high phosphorus content are obtained using benzoyl peroxide. In the case of the use of salts of phosphoric acid, njJpuecc are, for example, in water-dioxane, acetic-dioxane medium or in a mixture of dimethylformamide with water. in the case of dialkylphosphite, the process can be carried out in any organic solvent. Target products are recovered by known techniques. v The absence of mechanical impurities of the original phosphorylating agents was proved by paper and thin-layer chromatography. In the IR spectra of the products of the reaction of allyl cellulose with salts of hypophosphorous acid, there are no C-O-P bonds, and there are 0 characteristic P-H groups for the P-0 bond at 1200 cm and P-H at 2400 cm. The method for producing phosphoropropylcellulose is new and has not previously been used for the production of phosphorylated cellulose. The method is characterized by simplicity and allows obtaining phosphonopropyl cellulose resistant to hydrolysis with a phosphorus content up to 7 Example. Sodium salt of phosphonic acid} f-propyl cellulose A mixture of 19.6 g (0.1 mol) of allyl cellulose (YL 85%), 17 g (0.16 mol) of sodium phosphate monohydrate: sodium, 1.21 g (0.005 mol) of benzoyl peroxide stir for 6-7 hours at 90100 ° C in a water-dioxane medium (15 zodas + 50 ml dioxane) in an inert gas atmosphere. The resulting colorless powder is filtered off, washed with a small amount of water, benzene and acetone and dried to a constant weight. Get 23.5 g of phosphorus product with a phosphorus content of 7.27, 4%. . Ex. 2. Sodium or potassium salt of phosphonous acid j — propyl cellulose. A mixture of 1.94 g (0.01 mol) of allyl cel lulose (in 80%), 2.12 g (0.02 mol of sodium phosphate monohydrate (or 2.08 g (Oh, 02 mol) of potassium phosphate and potassium hydroxide, 0.2 G; (0.008 mol) benzoyl peroxide, 2.5 water and 25 ml of dioxane are stirred at 4 at 80 ° C. under an inert gas atmosphere, to obtain 2.4 g of product with a phosphorus content of 6.38% or 6.15% (in the case of phosphorus potassium formate) When a similar reaction is carried out in a water-dimethylformamide medium, I get 2.2 g of a product with a phosphorus content of 4.4-4.5%. Example 3. Sodium salt of phosphonic acid Jf-propyl cellulose A mixture of 1.94 g (0, 01 mole) lylcellulose (JC "80%), 2.12 g (0.02 mol) of sodium phosphate monohydrate, 0.1 g (0.0011 mol) of tert-butyl hydroperoxide, 2.5 ml of acetic acid and 20 MP of dioxane are stirred 8 H at 8 ° C in an inert gas stream. 2.4 g of a product with a phosphorus content of 6.3% is obtained. Under similar conditions, in the presence of 0.15 g (0.001 mol) of tert-butyl peroxide, a product containing phosphorus 5, &;%. PRI me R 4. Diethylphosphonate -propylcellulose. A mixture of 9.7 g (0.05 mol) of acetyl cellulose (in 80%), 20.7 g (0.15 mol) of diethylphosphite, 1.5 g (0.0062 mol) of benzoyl peroxide is stirred for 5 hours at 80-85 С in an inert gas atmosphere. Excess diethylphosphite is distilled off in vacuo. The product is washed with dioxane and benzene and dried in a vacuum desiccator. A pale yellow colored powder is obtained. Weight 12 g. Phosphorus content of 6.2%. EXAMPLE 5 Diethylphosphonate, propyl cellulose .g) A mixture of 1.94 g (0.01 mol) of allyl cellulose (jC 80%), 2.76 g (0.02 mol) of diethyl phosphite, 20 ml of dioxane and 0, 2 g (0.0008 mol) of benzoyl peroxide are stirred for 4 hours at 80-85 ° C in an inert gas atmosphere. The colorless powder is filtered, washed with dioxane, benzene and acetone. Dry to constant weight. 2.85 g of product are obtained with a phosphorus content of 5.85%. Example 6. Dimethylphosphonate -propylcellulose. A mixture of 1.96 g (0.01 mol) of allyl cellulose (85%), 2.2 g (0.02 mol) of dimethyl phosphite, 0.15 g (0.001 mol) of tert-butyl peroxide and 20 ml of dioxane is stirred for 4 hours at 90 -100 ° C in the atmosphere of inert gas. The colorless powder is filtered off, washed with dioxane and acetone and dried to constant weight. 2.4 g of product are obtained with a phosphorus content of 3.6%. Similarly, from 3.9 g (0.0 mol) of dibutyl phosphite, 2.4 g of dibutyl phosphonate in γ-propyl cellulose with a phosphorus content of 2.4% are obtained. The invention The method for producing phosphonopropylcellulose of the general formula j g / gl-OCHgCHjCHgP-OB Where B is hydrogen or lower alkoxy; J B - alkali metal or lower alkyl; Cellulose cellulose, consisting in that allyl cellulose with jf 80-85% is treated with an alkaline hypophosphorous acid salt or dialkyl phosphite in the presence of organic peroxide when heated to a temperature of 80-5 in an organic solvent in an inert gas atmosphere. Sources of information taken into account in the examination: US Patent 3574719, cl. 260-502.4, 1971. 2. Muratova U.M. and others. Foe-derivatives of cellulose, Navy, 1968, 10B, p. 594.