SU753363A3 - Method of isolating dimethoxy- or diethoxydithiophosphoric acids - Google Patents

Description

The purification method leads to positive results under laboratory conditions; however, under production conditions, double extraction with diethyl ether due to its explosion hazard and its ability to ignite creates significant difficulties .V.

The closest in technical essence and achievable results to the described method is a method of purification of dimethoxydithiophosphoric acid, according to which a 20% aqueous solution of sodium hydroxide is added to the toluene crude reaction mixture until a pH value of 6-6.5 is reached and an aqueous solution containing sodium the dimethoxythiophosphoric acid salt is separated from the organic phase. Upon cooling, concentrated sulfuric acid is added to the aqueous solution, and as a result, dimethoxythiophosphoric acid is released. This method allows to reduce the amount of impurities up to 5%.

The disadvantage of this method of purification of dimethoxydithiophosphoric acid is an insufficient degree of purification.

The aim of the invention is to increase the degree of purification of dimethoxy- or diethoxydithiophosphoric acids.

This goal is achieved by the described method of separating dimethox or diethoxyphosphoric acids from the reaction mixture obtained by the interaction of phosphorus pentasulfide with methanol or ethanol in a toluene solution by batch or continuous extraction of the reaction mixture with water, taken in an amount of 200-350 parts by weight n 100 weight.h. the reaction mixture, With the subsequent treatment of the aqueous phase with toluene, taken in an amount of 2060 parts by weight. per 100 weight parts the aqueous phase, and containing sodium chloride, taken in an amount of 15-30 weight.h and 100 weight of the aqueous phase.

A distinctive feature of the method is that the reaction mixture is periodically or continuously extracted with water, taken in an amount of 200-350 parts by weight. per 100 weight parts the reaction mixture, followed by treatment of the aqueous phase with toluene, taken in an amount of 20-60 parts by weight. per 100 weight.h of the aqueous phase and containing sodium chloride, taken in the amount of 1530 weight.h. per 100 weight parts the aqueous phase.

The described method allows to increase the degree of purification of dimethoxy- or diethoxyphosphoric acid to 99.599, 8%, and thus reduce the impurity content to 0.2-0.5%.

The described method is simple in technological design, requires a smaller amount of raw materials than in the known method and lower costs for corrosion protection of the equipment.

Both isolated dithiophosphoric acids were obtained using phosphorus pentasulfide of two kinds, which differ in the degree of their contamination. The crude reaction mixture obtained from two types of phosphorus pentasulfide is designated A and B.

P r. I m p 1. Preparation and purification of dimethoxydithiophosphoric acid.

In a 2000 ml round bottom flask equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel, 333 g (1.5 mol) of phosphorus pentasulfide and 375 ml of toluene are placed. The suspension is heated to 80 ° C. At this temperature, 204 g (6.73 mol) of methanol are added over 1 hour. After the addition is complete, the mixture is kept at 90 ° C for 1 hour. Then the crude reaction mixture is cooled to room temperature. The volume of the mixture is 900 ml.

The quality of the used pentasulfide phosphorus.

.The parameters of the crude reaction mixture

BUT

AT

50-60

50-56 8-15

50 ml of the resulting crude reaction mixture is placed in a shaking funnel and mixed with 50 ml of water. After shaking and precipitating, the aqueous phase is separated, the reaction mixture is extracted again, namely 400 ml, then 300 ml, and finally 300 ml of water once more. The volume of the combined aqueous phases is 1700 ml. The aqueous phase, placed in a 2000 ml beaker, is stirred with a mechanical stirrer. 400 g of sodium chloride and 250 ml of pure toluene are added. After stirring for 10 minutes, the reaction mixture is placed in a separatory funnel and after precipitation both phases are separated from each other. The aqueous phase is shaken again in a beaker and mixed with stirring with 50 g of sodium chloride and 100 ml of toluene. After separating the organic phase, the aqueous phase is stirred with 25 g of sodium chloride and 100 ml of toluene and then the toluene is separated. At the end of the extraction, 700 ml of a toluene solution in which dimethoxythiophosphoric acid is contained are obtained. Solution parameters Quality of phospho-A pentasulfide A used. Concentration of dimethoxydithiophenol acid, g / 100 ml Dimethoxydithiophosphorus frequency 99.5-99.8 99.0 acids,% 0.2-0.5 0.5 Impurities,% Example 2. Production and purification ka diethoxydithiophosphoric acid. 360 (1.6 mol) phosphorus pentasulfide and 400 ml of toluene are placed in a 2000 ml round-bottom flask equipped with a stirrer with a thermometer, a reflux condenser and a funnel to add substances. The suspension is heated to 80 ° C. At this temperature, 313 g (6.8 mol) of ethanol is added over 1 hour. At the end of the addition, the smegate at 90 ° C is continued to react for 1 hour. Then the crude reaction mixture is left to room temperature. The volume of the mixture is 900 ml. Parameters crude Quality of the used reactive blended syphosphorus pentasulfide Diethoxydithiophosphoric acid concentration in 60, 0 t, g / 100 ml 6-10. The contaminants,% 450 ml of the resulting crude reaction mixture, are placed in a shaker funnel, mixed with 450 ml of water and extracted by shaking. After separation of the layers, the aqueous phase is separated and the reaction mixture is again extracted: first, add 350 ml, then 300 ml and finally 250 ml of water. The combined aqueous phases have a volume of 1600 ml. The aqueous phase is placed in a beaker with a volume of 2000 ml. While stirring with a mechanical stirrer, 390 sodium chloride and 250 ml of pure toluene are added. After stirring for several minutes, the mixture is placed in a separatory funnel and, after separation of the phases, they are separated. Then the aqueous phase is treated with 50 g of sodium chloride and 100 MP of toluene, after the new separation the organic phase is treated with 25 g of sodium chloride and 100 ml of toluene. At the end of the extraction, 650 ml of a toluene solution is obtained, which contains diethoxy actiophosphoric acid. Parameters Resin quality of thief phosphorus pentasulfide Concentration of diethoxydithiophosphoric acid, g / 100 ml Purity of diethoxydithiophosphoric acid, 99% 6-99.9 99.8-99.3% 0.1-0.4 0.7-1.2 Impurities, % Example 3. The preparation and purification of dimethoxythiophosphoric acid. A 2000 ml round-bottomed flask equipped with a stirrer, thermometers fl, reflux condenser and addition funnel was introduced with 3332 g {1.5 mol) phosphorus pentasulfide and 375 ml of toluene. The suspension is heated to. At this temperature, 204 g (6.73 mol) of methanol are added over an hour. Upon completion of the reaction, the mixture is incubated for 1 h at 90 s. Then the crude reaction mixture is cooled to room temperature. Its volume reaches 9000 ml. Quality of application. Raw phosphate phosphorus A wet raw pentasulfide parameters. Dimethoxythiophosphoric acid concentration, g / 100 ml Impurity,% 750 ml of the resulting crude reaction mixture placed in a shaking funnel and mixed with 500 ml water. After extraction, the aqueous phase is separated by shaking and settling, the reaction mixture is re-extracted with 400 ml, then 300 ml and one more time with 300 ml of water. The volume of the combined aqueous phase reaches 1800 ml. The aqueous phase transferred to a 2500 ml beaker is stirred with an engine driven stirrer. 400 g of sodium chloride and 250 ml of pure toluene are added. After 10 minutes of stirring, they are placed in a separatory funnel, where both phases are separated. The aqueous phase is re-shaken in a beaker and mixed with stirring with 50 g of sodium chloride and 200 ml of toluene. After the organic phase is again separated, the aqueous phase is mixed with 25 g of sodium chloride and 100 ml of toluene. Upon completion of the extraction, 800 ml of a toluene solution are obtained in which dimethoxythiophosphoric acid is contained. Parameters of rast- Quality use of phosphorus A b anti-pentasulfide Concentration of dimethoxydithiophosphoric acid, g / 100 ml 40-45 39-44 Purity of dimethoxyditophosphoric acid,% 99.5-99.8 99.0-99 Impurities,% .0.2- 0.5 0.5-1 Example 4. Purification of dimethox dithiofophosphoric acid. 430 ml of the crude reaction mixture prepared according to Example 3 was mixed in a shaking funnel with 500 ml of water. After extraction, the aqueous phase is separated by shaking and settling, the reaction mixture is re-extracted with 400 ml, then 300 ml and one more time with 300 ml of water. The volume of the combined aqueous phase is 1650 ml. The aqueous phase transferred to a 2500 ml beaker is stirred. 400 g of sodium chloride and 250 ml of toluene are added. After 10 minutes of stirring, the mixture is fed to a separatory funnel and, after settling, the phases are separated. The aqueous phase is re-shaken in a beaker and mixed with 50 g of sodium chloride and 200 ml of toluene. After the organic phase is again separated, the aqueous phase is stirred with 25 g of sodium chloride and 100 ml of toluene. At the end of the extraction, 650 ml of a toluene solution is obtained in which dimethoxythiothiophosphoric acid is contained. Parameters are grown. Quality of phosphorus pentasulfide A B Dimethoxythiophosphoric acid concentration, g / 100 ml 30-34 29-33 99.5 you,% 0.5-0.1 0.5-1.0 Impurities,%. Example 5. Preparation and purification of diethoxydithiophosphoric acid. B equipped with a stirrer, a thermometer, a reflux condenser and an addition funnel, a 2000 ml round-bottom flask was added 360 g (1.6 mol) of phosphorus pentasulfide and a suspension of 400 g of toluene was prepared. The suspension is heated to. At this temperature, 313 g (6.8 mol of ethanol is added over the course of one hour. After the addition is complete, the mixture is kept for one hour. Then the crude reaction mixture is cooled to room temperature. The volume reaches 900 ml. Raw parameters The quality of the photonosyram A pentasulfide used is The concentration of dystoxydithiophosphoric acid, g / 100 ml 58-60 58-58, .Obder impurities,% 6-10 10-15 650 ml of the resulting crude reaction mixture is placed in an agitated funnel. 350 ml, then 300 ml and 250 ml of water. The combined aqueous phase has a volume of 1700 ml. The aqueous phase is transferred to a 2500 ml chemical beaker. The aqueous phase is stirred, 390 g of sodium chloride and 250 ml of pure toluene are added. the separating funnel is separated and the phases are separated after settling.The aqueous phase is treated with 50 g of sodium chloride and 100 ml of toluene, after the organic phase is separated again, the aqueous phase is treated with 25 g of sodium chloride and 100 ml of toluene. At the end of the extraction, 750 ml of a toluene solution is obtained, which contains diethoxydithiophosphoric acid. Mix Parameters Quality of Phosphorus Pentasulfide Used Concentration of Diethoxydithiophosphoric Acid, 41.5-45.5 38-43. g / 100 ml Purity of diethoxydactiophosphoric acid, 9-1.2 0.2-0.5 lots,% 0.9-1.2 0.2-0.5 Impurities,% P r and m e p 6. Purification of diethoxydithiophosphorus acid. 380 ml of the crude reaction mass prepared according to Example 5 is placed in a shaking funnel, stirred with 450 ml of water. After settling, the aqueous phase is separated, and the reaction mixture is re-extracted, first with 350 ml, then 300 ml and 250 ml of water. The combined aqueous phase has a volume of 1500 ml. The aqueous phase is placed in a 2500 ml beaker. With stirring, 390 g of sodium chloride and 250 ml of pure toluene are added. After several minutes of stirring the mixture, the mixture is fed to a separatory funnel and, after settling, the phases are separated. Then the aqueous phase is treated with 50 g of sodium chloride and 100 ml of toluene, after re-separation of the phases, 25 g of sodium chloride and 100 ml of toluene are treated. After the completion of the extraction, 600 ml of a toluene solution are obtained, which contain diethoxydithiophosphoric acid.

Parameters of rast- Quality of the used thief pentasulfide phosphor

AT

33-362

30-322 99, 5-99.8 98.8-99.3 0.2-0.5 0.7-1.2

Example 7. Preparation and purification of dimethoxythiothiophosphoric acid.

Into a 2000 ml round-bottomed flask equipped with a stirrer, thermometer, reflux condenser and addition funnel, 333 g (1.5 mol) of phosphorus pentasulfide and 375 ml of toluene are added. The suspension is heated to 80 ° C. At this temperature, 204.2 g (6.73 mol) of methanol are added over an hour. After the addition is complete, the mixture is maintained for 1 hour. Then the crude reaction mixture is cooled to room temperature. Its volume reaches 900 ml.

Parameters crude Quality of using emulsified blended hypophosphorus pentasulfide

AT

50-56

58-60 8-15 4-8

750 ml of the resulting crude reaction mixture is placed in a shaking funnel and mixed with 500 ml of water. After extraction, the aqueous phase is separated by shaking, the reaction mixture is re-extracted with 400 ml, then 300 ml and once again with 300 ml of water. The volume of the combined aqueous phase reaches 1800 ml. The aqueous phase transferred to the beaker is stirred with an engine driven stirrer. 190 g of sodium chloride and 250 ml of toluene are added. After 10 minutes of stirring, the mixture is fed to a separatory funnel and after settling, both phases are separated from each other. The aqueous phase is treated in a beaker with stirring 50 g of sodium chloride and 200 ml of toluene. After re-separating the organic phase, 30 g of sodium chloride and 2 100 ml of toluene are added to the aqueous phase and then the toluene is separated. Upon completion of the extraction, 800 ml of a toluene solution are obtained in which dimethoxythiophosphoric acid is contained.

1Q Parameters rasta- Quality of the applied thief phosphorus penta-sulphide

AT

Concentration of dimethoxy-5thiophosphoric acid, g / 100 ml

38-43

37-42 Purity of dimethoxydithiophosphoric acid99, 5-99.8 99.0-99.5%, 0.2-0.5 0.5-1.0 Impurities,%

Example 8. Purification of dimethoxythiophosphoric acid.

750 ml of the crude reaction mixture prepared according to Example 7 is placed in a shaking funnel and mixed with 500 ml of water. After extraction by shaking and settling, the aqueous phase is separated, the reaction mixture is re-extracted with 400 ml, then 300 ml and one more time with 300 ml of water. The volume of the combined aqueous phase is 1800 ml. It is transferred to the chemical

cue cup with a volume of 2500 ml of the aqueous phase is stirred with a stirrer working from the engine. 330 g of sodium chloride and 250 ml of toluene are added. After 10 min stirring the mixture

placed in a separatory funnel, and after settling, both phases are separated from each other. The aqueous phase is loaded into a beaker and 50 g of sodium chloride and 200 ml of toluene are mixed with stirring. After the organic phase is separated again, the aqueous phase is stirred with 30 g of sodium chloride and 100 ml of toluene. Upon completion of the extraction, 800 ml of a toluene solution are obtained in which dimethoxythiophosphoric acid is contained.

Parameters of rasta- Quality of the used thief

A b

55

38-43

39-44

99.5-99.8 99.0-99.5 0.2-0.5 0.5-1.0 Example 9. Production and purification of diethoxydithiophosphoric acid. 360 g (1.6 mol) of phosphorus pentasulfide and 400 ml of toluene are placed in a 2000 ml round-bottom flask equipped with a stirrer, thermometer, reflux condenser and addition funnel. The suspension is heated to 80 ° C. 313 are added at this temperature for one hour. g (6.8 mol) of ethanol. After completing the addition, the mixture is kept at 90 ° C. Then the crude reaction mixture is cooled to room temperature. Parameters crude Quality of use of the reaction mixture of pulsed phosphorus pentasulfide Diethoxydithiophosphoric acid concentration, g / 100 ml 58-60, 0 Impurities,% 6- 10 650 ml of the resulting crude reaction mixture is placed in an agitated funnel, mixed with water and extracted by shaking. After settling, the aqueous phase is separated and the reaction mixture is re-extracted with 350 ml, then 300 ml and 250 ml of water. the volume is 1700 ml. The aqueous phase is introduced into a chemical station with a volume of 2500 ml. With stirring, 180 g of sodium chloride and 250 ml of toluene are added with a stirrer. After a few minutes of stirring. the mixture is placed in a separatory funnel where it is divided into phases. The aqueous phase is treated with 50 g of sodium chloride and 100 ml of toluene. After the organic phase is again separated, the aqueous phase is treated with 25 g of sodium chloride and 100 ml of toluene. After completion of the extraction, 750 ml of a toluene solution are obtained, which contain diethoxydithiophosphoric acid. Parameters of plant - Quality of use of pentasulfide phospho A B thief Concentration of diethoxydithiophosphoric acid, g / 100 ml 40-45 36-41 Purity of diethoxydithiophosphoric Acid,% 99.4-99.8 98.7-99, Impurities,% 0.2-0 , 6 0.9-1.3 Example 10. Purification of diethox dithiophosphoric acid. 650 MP of the crude reaction mixture prepared according to Example 9, placed in an agitated funnel, 450 ml of water are added and extraction is carried out by shaking. - After settling, the aqueous phase is separated, and the reaction mixture is re-extracted first with 350 ml, then 300 ml and 250 ml of water. The combined aqueous phases have a volume of 1700 ml. The aqueous phase is introduced into a 2500 ml beaker. When grinding with a stirrer, 310 g of sodium chloride and 250 ml of pure toluene are added. After several minutes of stirring, the mixture is fed to a separatory funnel, where it separates into phases. The aqueous phase is then treated with 50 g of sodium chloride and 100 ml of toluene, after separation the organic aqueous phase is treated with 30 g of sodium chloride and 100 ml of toluene. At the end of the extraction, 750 ml of a toluene solution are obtained, which contain diethoxydithiophosphoric acid. Parameters of growth - Quality of applied phosphorus pentasulfide AV Concentration. . , diethoxy dithiophosphoric acid, g / 100 ml 40-44 37-42 The purity of diethoxydithiophosphoric acid,%. 99.5-99.8 98.8-99.1 Impurities,% 0.2-0.5 0.9-1.2 Example 11. Purification of dimethoxythiothiophosphoric acid. 750 ml of the crude reaction mixture prepared according to Example 7 is placed in a shaking funnel and mixed with 500 ml of water. After the extraction is performed by shaking and settling, the aqueous phase is separated, the reaction mixture is extracted again with 400 ml, then 300 ml and once more with 300 ml of water. The volume of the combined aqueous phases reaches 1800 ml. The aqueous phase transferred to a 2500 ml beaker is stirred with a stirrer. 400 g of sodium chloride and 160 ml of toluene are added. After 10 minutes of stirring, the mixture is fed to a separatory funnel, where, after settling, both phases are separated from each other. The aqueous phase is again loaded into a beaker and mixed with stirring with 50 g of potassium chloride and 100 ml of toluene. After the organic phase is again separated, the aqueous phase is mixed with 25 g of sodium chloride and 100 ml of toluene. After the completion of the extraction, 600 ml of a toluene solution in which dimethoxythiophosphoric acid is contained are obtained.

Claims (1)

. The method of separation of dimethoxy- or diethoxydithiophosphoric acids from the reaction mixture obtained by the interaction of phosphorus pentasulfide with methanol or ethanol in a toluene solution, characterized in that, in order to increase the degree of purification, the reaction mixture is periodically or continuously extracted with water taken in an amount of 200350 weight.h . per 100 parts by weight the reaction mixture, followed by treatment of the aqueous phase with toluene, taken in an amount of 20-60 parts by weight per 100 parts by weight aqueous phase, and containing sodium chloride, taken in the amount of 1530 parts by weight per 100 parts by weight water phase. Sources of information taken into account during the examination