Production of hexabromocyclododecane of enhanced gamma isomer content

• US 20020045783A1
• Filed: 10/18/2001
• Published: 04/18/2002
• Est. Priority Date: 02/22/1999
• Status: Active Grant

• Current Assignee: Albemarle Corporation
• Original Assignee: Albemarle Corporation
• Inventors: Kendall, John K.
• Granted Patent: US 6,506,952 B2
• Time in Patent Office: Days
• US Class Current: 570/101
• CPC Class Codes: C07C 17/02 to unsaturated hydrocarbons
• CPC Class Codes: C07C 23/02 Monocyclic halogenated hydrocarbons

Abstract

Hexabromocyclododecane with enhanced gamma isomer content is produced by brominating cyclododecatriene in a liquid medium comprised of (1) at least 50 wt % of at least one liquid inert organic solvent other than 1,4-dioxane having a solubility in water of at least 1 wt % at 25° C., and (2) water in an amount of up to about 40 wt %, in the presence of (3) about 0.5 to about 30 wt % of bromide ion (Br⁻), each wt % being based on the total weight of the liquid portion of the liquid medium.

Claims

1. A process which comprises brominating cyclododecatriene in a liquid medium comprised of (1) at least 50 wt % of at least one liquid inert organic solvent other than 1,4-dioxane having a solubility in water of at least 1 wt % at 25°

C., and (2) water in an amount of up to about 40 wt %, in the presence of (3) about 0.5 to about 30 wt % of bromide ion (Br⁻

), whereby hexabromocyclododecane is produced, each wt % being based on the total weight of the liquid portion of the liquid medium.

2. A process according to claim 1 wherein the bromination is conducted at one or more temperatures in the range of about 0°

C. to about 60°

C.

3. A process according to claim 1 wherein the bromination is conducted at one or more temperatures in the range of about 20°

C. to about 55°

C.

4. A process according to claim 1 wherein the bromination is performed using preexisting elemental bromine.

5. A process according to claim 1 wherein the bromination is performed using bromine formed in situ.

6. A process according to claim 1 wherein said at least one liquid inert organic solvent consists essentially of (a) at least one halogen-free aprotic solvent containing at least two oxygen atoms or at least one nitrogen atom in the molecule other than 1,4-dioxane, or (b) at least one liquid polyalkylene glycol in which the alkylene groups each contain two or three carbon atoms and in which the average molecular weight of the polyalkylene glycol is at least about 150 and/or at least one liquid monoalkyl ether thereof, or (c) a combination of (a) and (b).

7. A process according to claim 6 wherein in (a) said at least one halogen-free aprotic aprotic solvent containing at least one nitrogen atom is at least one halogen-free aprotic solvent that contains only one nitrogen atom in the molecule, wherein in (b) said at least one liquid polyalkylene glycol in which the alkylene groups each contain two or three carbon atoms is at least one liquid polyalkylene glycol in which the alkylene groups each contain only two carbon atoms, and wherein in (b) said average molecular weight of said polyalkylene glycol is at least about 200.

8. A process according to claim 7 wherein in (b) said average molecular weight of said polyalkylene glycol is in the range of about 200 to about 400.

9. A process according to claim 6 wherein the liquid inert organic solvent that is used in said process consists essentially of (I) at least one liquid polyethylene glycol, (II) at least one liquid polyethylene glycol monoether, (III) at least one liquid polyethylene glycol dimethyl ether, or any mixture of two or more of (I), (II), and (III), wherein each of (I), (II) and (III) has an average molecular weight in the range of about 200 to about 400.

10. A process according to claim 6 wherein the liquid inert organic solvent that is used in said process consists essentially of at least one liquid polyethylene glycol dimethyl ether having an average molecular weight in the range of about 200 to about 400.

11. A process according to claim 6 wherein the liquid inert organic solvent that is used in said process consists essentially of a combination of at least (A) at least one liquid polyalkylene glycol in which the alkylene groups each contain two or three carbon atoms having an average molecular weight above about 400 and/or a mono- or dialkyl ether thereof, and (B) at least one other liquid inert organic solvent that reduces the viscosity of said liquid medium.

12. A process according to claim 6 wherein the liquid inert organic solvent that is used in said process consists essentially of at least one liquid inert organic ester.

13. A process according to claim 6 wherein the liquid inert organic solvent that is used in said process consists essentially of at least one liquid inert nitrile.

14. A process according to claim 12 wherein said liquid inert organic ester consists essentially of ethyl acetate, ethylene glycol diacetate, ethylformate, or a mixture of any two or all three of them.

15. A process according to claim 13 wherein said liquid inert nitrile consists essentially of acetonitrile.

16. A process according to claim 1 wherein the process is conducted so that a batch of reaction mass containing hexabromocyclododecane has been formed upon completion of the bromination, and wherein said batch of reaction mass is subjected to a thermal finishing step at one or more temperatures in the range of about 70 to about 90°

C.

17. A process according to claim 16 wherein said one or more temperatures in the range of about 70 to about 90°

C. are maintained for a period in the range of about 1 to about 60 minutes.

18. A process according to claim 17 wherein the bromination is conducted at one or more temperatures in the range of about 0°

C. to about 60°

C.

20. A process according to claim 19 wherein in (b) said average molecular weight of said polyalkylene glycol is in the range of about 200 to about 400.

21. A process according to claim 19 wherein the liquid inert organic solvent that is used in said process consists essentially of (I) at least one liquid polyethylene glycol, (II) at least one liquid polyethylene glycol monoether, (III) at least one liquid polyethylene glycol dimethyl ether, or any mixture of two or more of (I), (II), and (III), wherein each of (I), (II) and (III) has an average molecular weight in the range of about 200 to about 400.

22. A process according to claim 19 wherein the liquid inert organic solvent that is used in said process consists essentially of at least one liquid polyethylene glycol dimethyl ether having an average molecular weight in the range of about 200 to about 400.

23. A process according to claim 19 wherein the liquid inert organic solvent that is used in said process consists essentially of at least one liquid inert organic ester.

24. A process according to claim 19 wherein the liquid inert organic solvent that is used in said process consists essentially of at least one liquid inert nitrile.

25. A process according to claim 23 wherein said liquid inert organic ester consists essentially of ethyl acetate, ethylene glycol diacetate, ethylformate, or a mixture of any two or all three of them.

26. A process according to claim 24 wherein said liquid inert nitrile consists essentially of acetonitrile.

27. A process according to claim 19 wherein the process is conducted so that a batch of reaction mass containing hexabromocyclododecane has been formed upon completion of the bromination, and wherein said batch of reaction mass is subjected to a thermal finishing step at one or more temperatures in the range of about 70 to about 90°

C. for a period in the range of about 1 to about 60 minutes.

28. A process according to claim 27 wherein the bromination is conducted at one or more temperatures in the range of about 0°

C. to about 60°

C.

30. A process according to claim 29 wherein the liquid inert organic solvent that is used in said process consists essentially of (I) at least one liquid polyethylene glycol, (II) at least one liquid polyethylene glycol monoether, (III) at least one liquid polyethylene glycol dimethyl ether, or any mixture of two or more of (I), (II), and (III), wherein each of (I), (II) and (III) has an average molecular weight in the range of about 200 to about 400.

31. A process according to claim 29 wherein the liquid inert organic solvent that is used in said process consists essentially of at least one liquid polyethylene glycol dimethyl ether having an average molecular weight in the range of about 200 to about 400.

32. A process according to claim 29 wherein the liquid inert organic solvent that is used in said process consists essentially of at least one liquid inert organic ester.

33. A process according to claim 29 wherein the liquid inert organic solvent that is used in said process consists essentially of at least one liquid inert nitrile.

34. A process according to claim 32 wherein said liquid inert organic ester consists essentially of ethyl acetate, ethylene glycol diacetate, ethylformate, or a mixture of any two or all three of them.

35. A process according to claim 33 wherein said liquid inert nitrile consists essentially of acetonitrile.

37. A liquid reaction medium according to claim 36 wherein the liquid inert organic solvent that is present in said medium consists essentially of (I) at least one liquid polyethylene glycol, (II) at least one liquid polyethylene glycol monoether, (III) at least one liquid polyethylene glycol dimethyl ether, or any mixture of two or more of (I), (II), and (III), wherein each of (I), (II) and (III) has an average molecular weight in the range of about 200 to about 400.

38. A liquid reaction medium according to claim 36 wherein the liquid inert organic solvent that is present in said medium consists essentially of at least one liquid polyethylene glycol dimethyl ether having an average molecular weight in the range of about 200 to about 400.

39. A liquid reaction medium according to claim 36 wherein the liquid inert organic solvent that is present in said medium consists essentially of at least one liquid inert organic ester.

40. A liquid reaction medium according to claim 36 wherein the liquid inert organic solvent that is present in said medium consists essentially of at least one liquid inert nitrile.

41. A liquid reaction medium according to claim 39 wherein said liquid inert organic ester consists essentially of ethyl acetate, ethylene glycol diacetate, ethylformate, or a mixture of any two or all three of them.

42. A liquid reaction medium according to claim 40 wherein said liquid inert nitrile consists essentially of acetonitrile.

43. A liquid reaction medium according to claim 36 wherein said reaction medium also contains cyclododecatriene as a component thereof.

19. A process which comprises bringing together in a reactor or reaction zone components comprising (i) cyclododecatriene, (ii) a brominating agent, (iii) a liquid inert organic solvent that is (a) at least one halogen-free aprotic solvent containing in the molecule at least two oxygen atoms or at least one nitrogen atom other than 1,4-dioxane, or (b) at least one liquid polyalkylene glycol in which the alkylene groups each contain two or three carbon atoms and in which the average molecular weight of the polyalkylene glycol is at least about 150, and/or at least one liquid monoalkyl ether thereof, or (c) a combination of (a), (b), and (c) or a combination of any two of (a), (b), and (c), (iv) water, and (v) a source of bromide ion (Br⁻

), wherein any of (i), (ii), (iii), (iv), and (v) are fed into the reactor or reaction zone (A) concurrently, substantially concurrently, or in any sequence, and (B) in any subcombination or subcombinations of (i), (ii), (iii), (iv), or (v), with the provisos that (i) and (ii) are not brought together in the same feed or in the absence of (iii), (iv), and (v), and that at least (i) and (ii) are fed separately but concurrently or substantially concurrently into said reactor or reaction zone, whereby hexabromocyclododecane is produced.

29. A process which comprises bringing together in a reactor or reaction zone components comprising (i) cyclododecatriene, (ii) a brominating agent, (iii) a liquid inert organic solvent that is (a) at least one halogen-free aprotic solvent containing in the molecule at least two oxygen atoms or at least one nitrogen atom other than 1,4-dioxane, or (b) at least one liquid polyalkylene glycol in which the alkylene groups each contain two or three carbon atoms and in which the average molecular weight of the polyalkylene glycol is at least about 150, and/or at least one liquid monoalkyl ether thereof, or (c) a combination of (a) and (b), (iv) water, and (v) a source of bromide ion (Br⁻

), wherein at least (i) and (ii) are brought together by feeding (i) and (ii) separately but concurrently or substantially concurrently into the reactor or reaction zone already containing (iii), (iv), (v), and optionally a small amount of (ii).

36. A liquid reaction medium comprised of:

1) about 50 to about 99 wt % of a liquid inert organic solvent that is (a) at least one halogen-free aprotic solvent containing in the molecule at least two oxygen atoms or at least one nitrogen atom other than 1,4-dioxane, or (b) at least one liquid polyalkylene glycol in which the alkylene groups each contain two or three carbon atoms and in which the average molecular weight of the polyalkylene glycol is at least about 150, and/or at least one liquid monoalkyl ether thereof, or (c) a combination of (a) and (b); and

2) up to about 40 wt % of water;

said medium containing about 0.5 to about 30 wt % of bromide ion (Br⁻

) based on the total weight of the liquids in the reaction medium.

44. A process which comprises brominating cyclododecatriene in a liquid medium comprised of at least 50 wt % of diethyl ether in the presence of about 0.5 to about 30 wt % of bromide, whereby hexabromocyclododecane is produced, each wt % being based on the total weight of the liquid portion of the liquid medium.

45. A process according to claim 44 wherein no water is deliberately introduced into said medium.

46. A process according to claim 44 wherein water is deliberately introduced into said medium such that said medium contains up to about 40 wt % of water during bromination.

47. A process according to claim 44 wherein no organic solvent other than the diethyl ether is used in the bromination.

48. A process according to claim 47 wherein no water is deliberately introduced into said medium.

49. A process according to claim 47 wherein water is deliberately introduced into said medium such that said medium contains up to about 40 wt % of water during bromination.

50. A process according to claim 44 wherein the bromination is conducted at one or more temperatures in the range of about 0°

C. to about 60°

C.

51. A process according to claim 44 wherein the bromination is conducted at one or more temperatures in the range of about 20°

C. to about 55°

C.

52. A process according to claim 44 wherein the bromination is performed using preexisting elemental bromine.

53. A process according to claim 44 wherein the bromination is performed using bromine formed in situ.

54. A liquid reaction medium comprised of about 50 to about 100 wt % of diethyl ether and optionally up to about 40 wt % of water, said medium containing cyclododecatriene and about 0.5 to about 30 wt % of bromide based on the total weight of the liquids in the reaction medium.

55. A liquid reaction medium according to claim 54 wherein said medium contains no deliberately added water.

56. A liquid reaction medium according to claim 54 wherein said medium does contain said up to about 40 wt % of water.

57. A liquid reaction medium according to claim 54 wherein no organic solvent other than the diethyl ether is present in said medium.