Method for producing bisphenol catalysts and bisphenols

1. A method for producing a catalyst composition which catalyzes the formation of bisphenols from aromatic hydroxy compounds and carbonyl containing compounds, said method comprising the step of attaching a poly-sulfur mercaptan promoter component to a solid acid support component comprising a protic acid functionality, said poly-sulfur mercaptan promoter component having the following structure (I),

wherein R1 is a benzothiazole functionality;

wherein a is between about 0 and about 11;

wherein b is between about 1 and about 11;

wherein c is between about 1 and about 11;

wherein d is between about 1 and about 5;

wherein X is a linking functionality which is one member selected from the group consisting of a linear aliphatic chain comprising between about 1 and about 11 carbon atoms, a cyclic aliphatic ring comprising at least 5 carbon atoms, a cyclic aromatic ring comprising at least 6 carbon atoms, a cyclic aliphatic heterocycle comprising at least 3 carbon atoms, and a cyclic aromatic heterocycle comprising at least 3 carbon atoms;

wherein Y is a linking functionality which is one member selected from the group consisting of a linear aliphatic chain comprising between about 1 and about 11 carbon atoms, a cyclic aliphatic ring comprising at least 5 carbon atoms, a cyclic aromatic ring comprising at least 6 carbon atoms, a cyclic aliphatic heterocycle comprising at least 3 carbon atoms, and a cyclic aromatic heterocycle comprising at least 3 carbon atoms; and

wherein R2 is one member selected from the group consisting of a hydrogen, a secondary aliphatic functionality, a tertiary aliphatic functionality, an ester functionality, a carbonate functionality, and a benzyl functionality which is attached via the benzylic methylene carbon.

2. The method of claim 1 , wherein said tertiary aliphatic functionality is one member selected from the group consisting of a branched aliphatic functionality, and a cyclic aliphatic functionality.

3. The method of claim 1 , wherein said R 2 functionality is one member selected from the group consisting of an isopropyl functionality, an isobutyl functionality, a tertiary butyl functionality, a tertiary amyl functionality, a cyclopentyl functionality, a benzyl, a 4-methoxybenzyl functionality, a 1-methylcyclohexyl functionality, and a cyclohexyl functionality.

4. The method of claim 1 , wherein said ester functionality is one member selected from the group consisting of an acetate functionality, a propionate functionality, and a benzoate functionality.

5. The method of claim 1 , wherein said carbonate functionality is one member selected from the group consisting of an alkyl carbonate functionality, and an aromatic carbonate functionality.

6. The method of claim 1 , wherein the bisphenol which is being formed is 4,4′-isopropylidenediphenol.

7. The method of claim l, wherein the carbonyl containing compound is a ketone or in aldehyde.

8. The method of claim 1 , wherein the aromatic hydroxy compound is phenol, and the carbonyl containing compound is acetone.

9. The method of claim 1 , wherein the attachment step is performed in an aqueous solution comprising water.

10. The method of claim 1 , wherein said solid acid comprises at least one member selected from the group consisting of polystyrene, a zeolite, and silica.

11. A method for producing a catalyst composition which catalyzes the formation of bisphenols from aromatic hydroxy compounds and carbonyl containing compounds, said method comprising the step of attaching a poly-sulfur mercaptan promoter component to a polymeric resin component comprising a protic acid functionality, wherein said poly-sulfur mercaptan promoter component is a functionalized benzothiazole mercaptan.

12. The method of claim 11 , wherein said a functionalized benzothiazole mercaptan has the structure (IV),

wherein l is between about 0 and about 11;

wherein m is between about 1 and about 11;

wherein n is between about 1 and about 11;

wherein X is a linking functionality which is one member selected from the group consisting of a linear aliphatic claim comprising between about 1 and about 11 carbon atoms, a cyclic aliphatic ring comprising at least 5 carbon atoms, a cyclic aromatic ring comprising at least 6 carbon atoms, a cyclic aliphatic heterocycle comprising at least 3 carbon atoms, and a cyclic aromatic heterocycle comprising at least 3 carbon atoms;

wherein Y is a linking functionality which is one member selected from the group consisting of a linear aliphatic chain comprising between about 1 and about 11 carbon atoms, a cyclic aliphatic ring comprising at least 5 carbon atoms, a cyclic aromatic ring comprising at least 6carbon atoms, a cyclic aliphatic heterocycle comprising at least 3 carbon atoms, and a cyclic aromatic heterocycle comprising at least 3 carbon atoms;

wherein R 15 is a hydrogen atom or a sulfur-protecting functionality which is one member selected from the group consisting of an aliphatic functionality comprising at least about 4 carbon atom, an ester functionality comprising between about 1 and about 11 carbon atoms, a carbonate functionality comprising between about 1 and about 11 carbon atoms, and a benzylic functionality comprising at least about 7 carbon atoms which is attached to the terminal sulfur atom via the benzylic methylene carbon; and

wherein each of R 16 , R 17 , R 18 , and R 19 are independently one member selected from the group consisting of a hydrogen, a fluoride, a bromide, a chloride, an iodide, a vinyl group, a hydroxide, an alkoxide functionality comprising between about 1 and about 11 carbon atoms, an aryloxide functionality comprising at least about 6 carbon atoms, an aliphatic functionality comprising between about 1 and about 11 carbon atoms, an aromatic functionality comprising at least about 6 carbon atoms, a cycloaliphatic ring comprising at least about 5 carbon atoms, said cycloaliphatic ring being fused to the benzothiazole arene ring through an adjacent ring substituent, and a cycloaromatic ring comprising at least about 6 carbon atoms, said cycloaromatic ring being fused to the benzothiazole arene ring through an adjacent ring substituent.

13. The method of claim 11 , wherein the bisphenol which is being formed is 4,4′-isopropylidenediphenol.

14. The method of claim 11 , wherein the carbonyl containing compound is a ketone or an aldehyde.

15. The method of claim 11 , wherein the aromatic hydroxy compound is phenol, and the carbonyl containing compound is acetone.

16. The method of claim 11 , wherein the attachment step is performed in an aqueous solution comprising water.

17. The method of claim 11 , where in said polymeric resin comprises at least one member selected from the group consisting of polystyrene, a zeolite, and silica.

18. The method of claim 17 , wherein said polymeric resin further comprises divinylbenzene.

19. The method of claim 18 , wherein the amount of divinylbenzene is up to about 12 percent of the total weight of the polymeric resin.

20. The method of claim 11 , wherein said protic acid functionality comprises at least one member selected from the group consisting of a sulfonic acid functionality, a phosphonic acid functionality, and a carboxylic acid functionality.

21. The method of claim 12 , wherein the linking functionality X, is the same as the linking functionality Y.

22. The method of claim 12 , wherein the bisphenol is 4,4′-isopropylidenediphenol, the aromatic hydroxy compound is phenol, the carbonyl containing compound is acetone, and said promoter component is,

wherein R 33 is a hydrogen atom or a sulfur-protecting functionality which is one member selected from the group consisting of an aliphatic functionality comprising at least about 4 carbon atom, an ester functionality comprising between about 1 and about 11 carbon atoms, a carbonate functionality comprising between about 1 and about 11 carbon atoms, and a benzylic functionality comprising at least about 7 carbon atoms which is attached via the benzylic methylene carbon; and

wherein y is 3 or 6.

23. A method for forming bisphenols, comprising the step of reacting an aromatic hydroxy compound with a carbonyl containing compound in the presence of a catalyst composition, said catalyst composition comprising a solid acid component and a poly-sulfur mercaptan promoter component having the following structure (I),

wherein R1 is a benzothiazole functionality;

wherein a is between about 1 and about 11;

wherein b is between about 1 and about 11;

wherein c is between about 1 and 11;

wherein d is between about 1 and about 5;

wherein X is a linking functionality which is one member selected from the group consisting of a linear aliphatic chain comprising between about 1 and about 11 carbon atoms, a cyclic aliphatic ring comprising at least 5 carbon atoms, a cyclic aromatic ring comprising at least 6 carbon atoms, a cyclic aliphatic heterocycle comprising at least 3 carbon atoms, and a cyclic aromatic heterocycle comprising at least 3 carbon atoms;

wherein Y is a linking functionality which is one member selected from the group consisting of a linear aliphatic chain comprising between about 1 and about 11 carbon atoms, a cyclic aliphatic ring comprising at least 5 carbon atoms, a cyclic aromatic ring comprising at least 6 carbon atoms, a cyclic aliphatic heterocycle comprising at least 3 carbon atoms, and a cyclic aromatic heterocycle comprising at least 3 carbon atoms; and

wherein R2 is one member selected from the group consisting of a hydrogen, a secondary aliphatic functionality, a tertiary aliphatic functionality, an ester functionality, a carbonate functionality, and a benzyl functionality which is attached via the benzylic methylene carbon.

24. The method of claim 23 , wherein said tertiary aliphatic functionality is one member selected from the group consisting of a branched aliphatic functionality, and a cyclic aliphatic functionality.

25. The method of claim 23 , wherein said R 2 is one member selected from the group consisting of a, an isopropyl functionality, an isobutyl functionality, a tertiary butyl functionality, a tertiary amyl functionality, a cyclopentyl functionality, a benzyl, a 4-methoxybenzyl, a 1-methylcyclohexyl functionality, and a cyclohexyl functionality.

26. The method of claim 23 , wherein said ester functionality is one member selected from the group consisting of an acetate functionality, a propionate functionality, and a benzoate functionality.

27. The method of claim 23 , wherein said carbonate functionality is one member selected from the group consisting of an alkyl carbonate functionality, and an aromatic carbonate functionality.

28. The method of claim 23 , wherein the bisphenol which is being formed is 4,4′-isopropylidenediphenol.

29. The method of claim 23 wherein the aromatic hydroxy compound is phenol.

30. The method of claim 23 , wherein the carbonyl containing compound is a ketone or an aldehyde.

31. The method of claim 30 wherein the ketone is acetone.

32. The method of claim 23 , wherein said solid acid comprises at least one member selected from the group consisting of polystyrene, a zeolite, and silica.

33. The method of claim 23 , wherein said solid acid is a sulfonic acid functionalized polymeric resin.

34. The method of claim 23 , wherein said polymeric resin further comprises divinylbenzene.

35. The method of claim 34 , wherein the amount of divinylbenzene is up to about 12 percent of the total weight of the polymeric resin.

36. The method of claim 23 , wherein said solid acid component comprises at least one member selected from the group consisting of a sulfonic acid functionality, a phosphonic acid functionality, and a carboxylic acid functionality.

37. The method of claim 23 , wherein the linking functionality X, is the same as the linking functionality Y.

38. A method for forming bisphenols, comprising the step of reacting an aromatic hydroxy compound with a carbonyl containing compound in the presence of a catalyst composition, said catalyst composition comprising a polymeric resin component comprising a protic acid functionality, and a poly-sulfur mercaptan promoter component, wherein said poly-sulfur mercaptan promoter component is a functionalized benzothiazole mercaptan.

39. The method of claim 38 , wherein said functionalized benzothiazole mercaptan has the structure (IV),

wherein l is between about 0 and about 11;

wherein m is between about 1 and about 11;

wherein n is between about 1 and about 11;

wherein X is a linking functionality which is one member selected from the group consisting of a linear aliphatic chain comprising between about 1 and about 11 carbon atoms, a cyclic aliphatic ring comprising at least 5 carbon atoms, a cyclic aromatic ring comprising at least 6 carbon atoms, a cyclic aliphatic heterocycle comprising at least 3 carbon atoms, and a cyclic aromatic heterocycle comprising at least 3 carbon atoms;

wherein Y is a linking functionality which is one member selected from the group consisting of a linear aliphatic chain comprising between about 1 and about 11 carbon atoms, a cyclic aliphatic ring comprising at least 5 carbon atoms, a cyclic aromatic ring comprising at least 6 carbon atoms, a cyclic aliphatic heterocycle comprising at least 3 carbon atoms, and a cyclic aromatic heterocycle comprising at least 3 carbon atoms,

wherein R 15 is a hydrogen atom or a sulfur-protecting functionality which is one member selected from the group consisting of an aliphatic functionality comprising at least about 4 carbon atom, an ester functionality comprising between about 1 and about 11 carbon atoms, a carbonate functionality comprising between about 1and about 11 carbon atoms, and a benzylic functionality comprising at least about 7 carbon atoms which is attached to the terminal sulfur atom via the benzylic methylene carbon; and

wherein each of R 16 , R 17 , R 18 , and R 19 are independently one member selected from the group consisting of a hydrogen, a fluoride, a bromide, a chloride, an iodide, a vinyl group, a hydroxide, an alkoxide functionality comprising between about 1 and about 11 carbon atoms, an aryloxide functionality comprising at least about 6 carbon atoms, an aliphatic functionality comprising between about 1 and about 11 carbon atoms, an aromatic functionality comprising at least about 6 carbon atoms, a cycloaliphatic ring comprising at least about 5 carbon atoms, said cycloaliphatic ring being fused to the benzothiazole arene ring through an adjacent ring substituent, and a cycloaromatic ring comprising at least about 6 carbon atoms, said cycloaromatic ring being fused to the benzothiazole arene ring through an adjacent ring substituent.

40. The method of claim 39 , wherein the bisphenol which is being formed is 4,4′-isopropylidenediphenol.

41. The method of claim 39 , wherein the aromatic hydroxy compound is phenol.

42. The method of claim 39 , wherein the carbonyl containing compound is a ketone or an aldehyde.

43. The method of claim 42 , wherein the ketone is acetone.

44. The method of claim 39 , wherein said polymeric resin comprises at least one member selected from the group consisting of polystyrene, a zeolite, and silica.

45. The method of claim 44 , wherein said polymeric resin further comprises divinylbenzene.

46. The method of claim 45 , wherein the amount of divinylbenzene is up to about 12 percent based on the total weight of the polymeric resin.

47. The method of claim 39 , wherein said protic acid functionality comprises at least one member selected from the group consisting of a sulfonic acid functionality, a phosphonic acid functionality, and a carboxylic acid functionality.

48. The method of claim 39 , wherein the linking functionality X, is the same as the linking functionality Y.

49. The method of claim 38 , wherein the bisphenol is 4,4′-isopropylidenediphenol, the aromatic hydroxy compound is phenol, the carbonyl containing compound is acetone, and said promoter component is,

wherein R 33 is a hydrogen atom or a sulfur-protecting functionality which is one member selected from the group consisting of an aliphatic functionality comprising at least about 4 carbon atom, an ester functionality comprising between about 1 and about 11 carbon atoms, a carbonate functionality comprising between about 1 and about 11 carbon atoms, and a benzylic functionality comprising at least about 7 carbon atoms which is attached to the terminal sulfur atom via the benzylic methylene carbon; and

wherein y is 3 or 6.