The method of obtaining di-(-chloroethyl)vinylphosphonate

 

(57) Abstract:

The invention relates to the chemistry of organophosphorus compounds, specifically to methods for di (chloroethyl)vinylphosphonate (Vinnitsa) by dehydrochlorination di (chloroethyl)- -chloroethylphosphonic (isomerate) in the presence of a nucleophilic reagent by heating. The purpose of the invention is the simplification of the existing method, improved manufacturability. This is accomplished by using in the synthesis of Vinitsa as a nucleophilic reagent anhydrous sodium carbonate in a molar ratio of isomerizate:Na2CO3=1:1.1 to 1.4. The reaction dehydrochlorinating carried out at 115-125oC for 5-7 h 1 table.

The invention relates to the chemistry of organophosphorus compounds, specifically to methods for di (chloroethyl)-vinylphosphonate structural formula:

< / BR>
shows the properties of a reactive monomer flame retardant, known as the "vinito".

Ways of getting Vinitsa based on the dehydrochlorination di (chloroethyl)(b-chloroethylphosphonic (isomerate) in the presence of various nucleophilic reagents [1-4] In most cases as nucleophilic reagents used carbonates or bicarbonates society nucleophilic reagent may use aqueous solutions of KOH or NaOH [4] Reaction dihydrochloride was carried out at 25-225oC, usually in the presence of catalysts AcCOOH, PhCOOH, dialkylphosphate, salts of organic acids. Often for the method of obtaining Vinitsa using solvent either in the synthesis or for washing; the reaction is carried out in the stream of nitrogen.

Closest to the claimed is a method of obtaining Vinitsa, in which [5] as a nucleophilic reagent used carbonate or sodium bicarbonate in a molar ratio of isomerizate:sodium bicarbonate 1:about 0.6-0.7. As catalysts for use phenols or organic acids, the reaction is carried out in the presence of a solvent [5] this method of obtaining Vinitsa is difficult to implement, catalysts, solvent requires washing and additional purification of the final product.

The aim of the invention is to simplify the way, improving its maintainability.

The objective is achieved by the fact that, as the nucleophilic reagent used is anhydrous sodium carbonate (soda ash) in a molar ratio of isomerizate:sodium carbonate is 1:1.2 to 1.4 and reaction are 5-7 PM

The reaction equation:

< / BR>
The synthesis is carried out at a temperature of 115-125oC. Dry soda ash load when razmeshenie; mode mixing turbulent, the Reynolds criterion centrifugal Rey50. After exposure of the reaction mass is distilled water at 10-30 mm RT.article and 90-100oC for 1 h After cooling to 25-30oC the mass is filtered at POST=20-30 mm RT. Art. from the precipitate salts. The finished product is a colorless mobile liquid, soluble in water and common organic solvents: alcohol, benzene, acetone, chloroform. The structure and personality of the obtained compounds were confirmed by elemental analysis, titration to the double bond using a acetate mercury and using IR spectroscopy.

Using the proposed method allows us to simplify the process of obtaining Vinitsa by eliminating the use of catalyst and solvent, which in turn allows us to simplify the selection of the target product, which does not require additional purification.

The decrease in the molar ratio of sodium carbonate to the isomerized product below 1.1 and the reaction time less than 5 hours leads to lower output <90% Increase in same molar ratio above 1.4 and reaction time more than 7 hours leads to resinification of the target product with a color change to 10 Hazen units.

Example 1. In Chernogo isomerate then, while stirring 46,5 g (0,439 mole) of dry soda ash. Raise the temperature to 120oC and incubated the reaction mass with stirring and this temperature for 5 hours Mode of turbulent mixing (Rey50). After the exposure temperature is reduced to 110-115oC, stirring off and distilled from the reaction mass of water at 20-30 mm RT.article within 1 h after cooling to 25-30oC mass filter for P leave 20 mm RT.article on a glass filter from SCHOTT precipitate salts. The finished product is a colorless mobile liquid. The product yield in the synthesis 108,5, the Content of Vinitsa on the results of the titration on the double bond using acetate of mercury in terms of winits of 76.5 wt. The output in terms of isomerizate is 99%

C6H4Cl2O3P.

Found, P 12,94.

Calculated P 13,30.

nD201,4690;

d240=1,3945

IR spectrum (cm-1):

The color scale Hazen, Hazen units: 1.

Examples 2-7. The process is conducted analogously to example 1, by changing the ratio of reagents and time of the reaction. The completeness of the reaction was determined by the residual isomerate in the reaction mass chromatogr amosorb WHP", stationary phase methanesiliconic elastomer brand E-301. Identification of the final product was carried out by gas chromatography-infrared spectroscopy on the complex, including a gas chromatograph Perkin-Elmer 8700 and IR-spectrometer with Fourier transform "Perkin-Elmer 1720X".

The results are presented in the table.

The resulting winits can be used as a feedstock in the synthesis of oligomeric products intended for use as components of various polymers.

The sources of information.

1. Di b-chlorotalonil ether vinylphosphonic acid. Gefter B. L. P. Moshkin A. Zhuravlev S. S. getter chem. chemicals", Vol. 18. M. Chemistry, 1969, S. 108-11.

2. U.S. patent N 3584040, class C 07 F 9/38, publ. 15.12.70.

3. About how to obtain bis -(b-chloroethyl)vinylphosphonate. Abramov I. A. Balyasnikov I.e. Gefter E. L. Zhuravleva HP Raev E. F. I. Rogachev A. - Journal of applied chemistry, 1974, 47, N 3, 676-677.

4. Japan's bid N 52-31853, class C 07 F 9/40, publ. 17.08.77.

5. U.S. patent N 3694527, class C 07 F 9/40 publ. 26.09.72 (prototype).

The method of obtaining di-(chloroethyl)-vinylphosphonate the dehydrochlorination di-chloroethyl--chloroethylphosphonic at 115 125oIn the presence of anhydrous carb and di-chloroethyl--chloroethylphosphonic and sodium carbonate 1 1,1 1,4 within 5 to 7 PM

 

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