PROCESS FOR PRODUCING 4,4'-DICHLORODIPHENYL SULFONE

Abstract

The invention relates to a process for producing 4,4′-dichlorodiphenyl sulfone comprising reacting a solution comprising 4,4′-dichlorodiphenyl sulfoxide and at least one linear C.sub.6-C.sub.10 carboxylic acid as solvent with an oxidizing agent to obtain a crude reaction product comprising 4,4′-dichlorodiphenyl sulfone, wherein the concentration of water in the reaction mixture is kept below 5 wt %, the process comprising: (a) adding 0.9 to 1.05 mol oxidizing agent per mol 4,4′-dichlorodiphenyl sulfoxide uniformly distributed to the solution at a temperature in the range from 80 to 105° C. over a period from 1.5 to 5 h in a first step to obtain the reaction mixture; (b) agitating the reaction mixture after completion of the first step at the temperature of the first step for 5 to 30 min without adding oxidizing agent; (c) adding 0.05 to 0.2 mol oxidizing agent per mol 4,4′-dichlorodiphenyl sulfoxide to the reaction mixture at a temperature in the range from 80 to 105° C. over a period of less than 40 min in a second step; (d) agitating the reaction mixture after completion of the second step at the temperature of the second step for 10 to 30 min without adding oxidizing agent, (e) heating the reaction mixture to a temperature in the range from 95 to 110° C. and hold this temperature for 10 to 90 min to obtain a crude reaction product comprising 4,4′-dichlorodiphenyl sulfone.

Claims

1.-14. (canceled)

15. A process for producing 4,4′-dichlorodiphenyl sulfone comprising reacting a solution comprising 4,4′-dichlorodiphenyl sulfoxide and at least one linear C.sub.6-C.sub.10 carboxylic acid as solvent with an oxidizing agent to obtain a crude reaction product comprising 4,4′-dichlorodiphenyl sulfone, wherein the concentration of water in the reaction mixture is kept below 5 wt %, the process comprising: (a) adding 0.9 to 1.05 mol oxidizing agent per mol 4,4′-dichlorodiphenyl sulfoxide uniformly distributed to the solution at a temperature in the range from 80 to 105° C. over a period from 1.5 to 5 h in a first step to obtain the reaction mixture; (b) agitating the reaction mixture after completion of the first step at the temperature of the first step for 5 to 30 min without adding oxidizing agent; (c) adding 0.05 to 0.2 mol oxidizing agent per mol 4,4′-dichlorodiphenyl sulfoxide to the reaction mixture at a temperature in the range from 80 to 105° C. over a period of less than 40 min in a second step; (d) agitating the reaction mixture after completion of the second step at the temperature of the second step for 10 to 30 min without adding oxidizing agent, (e) heating the reaction mixture to a temperature in the range from 95 to 110° C. and hold this temperature for 10 to 90 min to obtain a crude reaction product comprising 4,4′-dichlorodiphenyl sulfone.

16. The process according to claim 15, wherein for keeping the concentration of water below 5 wt % water is stripped from the reaction mixture.

17. The process according to claim 15, wherein the oxidizing agent is aqueous hydrogen peroxide with a concentration of 50 to 85 wt %.

18. The process according to claim 15, wherein the oxidizing agent is added continuously with a feed rate from 0.002 to 0.01 mol per mol 4,4′-dichlorodiphenyl sulfoxide and minute.

19. The process according to claim 15, wherein the temperature in the second step is 3 to 8° C. higher than the temperature in the first phase.

20. The process according to claim 15, wherein the reaction mixture is homogenized during the first step and the second step.

21. The process according to claim 15, wherein the reaction is carried out at a pressure in the range from 10 to 900 mbar(abs).

22. The process according to claim 15, wherein the solution is heated to a temperature in the range from 70 to 110° C. before adding the oxidizing agent.

23. The process according to claim 15, wherein the linear C.sub.6-C.sub.10 carboxylic acid is n-hexanoic acid and/or n-heptanoic acid.

24. The process according to claim 15, wherein an acidic catalyst is added to the reaction mixture.

25. The process according to claim 24, wherein the amount of acidic catalyst added to the reaction mixture is in the range from 0.001 to 0.3 mol per mol 4,4′-dichlorodiphenyl sulfoxide.

26. The process according to claim 15, wherein the reaction mixture is worked up to obtain a crude reaction product comprising 4,4′-dichlorodiphenyl sulfone and carboxylic acid.

27. The process according to claim 26, wherein the carboxylic acid is recycled into the reaction.

28. The process according to claim 15, wherein the process is carried out batchwise.

Description

EXAMPLES

[0052] Example Reaction without Split H.sub.2O.sub.2 Dosage

[0053] 1000.1 g of 4,4′-dichlorodiphenyl sulfoxide were dissolved in 3000 g n-heptanoic acid and heated to 90° C. 1.2 g sulfuric acid were added to the solution. Over a period of 3 h and 15 min 188 g H.sub.2O.sub.2 were added to the solution with a constant feed rate. During the reaction the temperature in the vessel was controlled to 90° C. by wall cooling, whereby the temperature in the reactor was determined to be 96 to 98° C. After completion of the H.sub.2O.sub.2 dosage the temperature of the thus obtained reaction mixture was raised to 98° C. The reaction mixture was stirred for 25 minutes at a temperature of 98° C. The reaction thereby was carried out at a pressure of 500 mbar (abs) and 12 NL/h nitrogen were passed through the reaction mixture for stripping water.

[0054] Subsequently, the reaction mixture was cooled to 20° C. by which the 4,4′-dichlorodiphenyl sulfone crystallized and a suspension formed comprising 4,4′-dichlorodiphenyl sulfone crystals and a mother liquor. The suspension was subjected to a filtration obtaining a filter cake comprising the 4,4′-dichlorodiphenyl crystals and 2999 g mother liquor as filtrate.

[0055] The resulting content of 4,4′-dichlorodiphenyl sulfoxide in the 4,4′-dichlorodiphenyl sulfone crystals was 1050 ppm (determined by gas chromatography).

[0056] The mother liquor obtained by the solid-liquid separation contained 3.15 g 4,4′-dichlorodiphenyl sulfoxide. Thus, the conversion rate of the 4,4′-dichlorodiphenyl sulfoxide was 99.68%.

[0057] Example Reaction with Split H.sub.2O.sub.2 Dosage

[0058] 1111 g of 4,4′-dichlorodiphenyl sulfoxide were dissolved in 2900 g n-heptanoic acid and heated to 90° C. 7.2 g sulfuric acid were added to the solution. Over a period of 3 h and 5 min 197 g 70% H.sub.2O.sub.2 were added to the solution with a constant feed rate. During the reaction the temperature in the vessel was controlled to 90° C. by wall cooling, whereby the temperature in the reactor was determined to be 97 to 99° C. After finishing this step, the thus obtained reaction mixture was stirred for 15 minutes at a temperature of 97° C. Then, a second amount of 10 ml H.sub.2O.sub.2 was added within 10 minutes. After completing the H.sub.2O.sub.2 dosage the temperature of the reaction mixture was raised to 103° C. The reaction mixture was stirred for 20 minutes at this temperature. The reaction thereby was carried out at a pressure of 650 mbar (abs) and 10 NL/h nitrogen were passed through the reaction mixture for stripping water.

[0059] Subsequently, the reaction mixture was cooled to 20° C. by which the 4,4′-dichlorodiphenyl sulfone crystallized and a suspension formed comprising 4,4′-dichlorodiphenyl sulfone crystals and a mother liquor. The suspension was subjected to a filtration obtaining a filter cake comprising the 4,4′-dichlorodiphenyl crystals and 2900 g mother liquor as filtrate.

[0060] The resulting content of 4,4′-dichlorodiphenyl sulfoxide in the 4,4′-dichlorodiphenyl sulfone crystals was below the detection limit (determined by gas chromatography).

[0061] The mother liquor obtained by the solid-liquid separation contained 0.5807 g 4,4′-dichlorodiphenyl sulfoxide. Thus, the conversion rate of the 4,4′-dichlorodiphenyl sulfoxide was 99.95%.