Haloaluminoxane compositions, their preparation, and their use in catalysis

1. A haloaluminoxane composition wherein the halogen is fluorine, chlorine, or bromine, wherein the amount of halogen atoms present in said composition is in the range of about 0.5 mole % to about 10 mole % relative to aluminum atoms, and wherein said composition is formed from an aluminoxane and at least one halogenation agent.

2. A composition according to claim 1 wherein said composition is formed from components comprising

(a) at least one aluminoxane and

(b) at least one halogenation agent which is

(i) at least one halohydrocarbon of the formula R n CX 4-n , where n=1–3, X is, independently, fluorine, chlorine or bromine, and where R is, independently, a hydrogen atom or a hydrocarbyl group having from one to about twenty carbon atoms;

or

(ii) at least one siloxane having at least one labile halogen atom in the molecule, wherein each halogen atom is, independently, fluorine, chlorine, or bromine;

or

(iii) at least one silane of the formula R′ n SiX 4-n , where n=1–3, X is, independently, fluorine, chlorine or bromine, and where R′ is, independently, a hydrocarbyl group having from one to about twenty carbon atoms,

or

(iv) at least one tin compound of the formula R′ n SnX 4-n , where n=1–3, X is, independently, fluorine, chlorine or bromine, and where R′ is, independently, a hydrocarbyl group having from one to about twenty carbon atoms;

or

(v) at least one hydrocarbyl aluminum halide of the formula R″ m AlX 3-m , where m=1 or 2, where X is, independently, fluorine, chlorine or bromine, and where R″ is, independently, a hydrocarbyl group having from one to about twenty carbon atoms;

or

(vi) mixtures of any two or more of (i)–(v).

3. A composition according to claim 1 wherein the amount of halogen atoms present in said composition is in the range of about 2 mole % to about 10 mole % relative to aluminum atoms.

4. A composition according to claim 2 wherein the halogen is fluorine.

5. A composition according to claim 2 wherein (b) is at least one halohydrocarbon.

6. A composition according to claim 2 wherein the amount of halogen atoms present in said haloaluminoxane composition is in the range of about 2 mole % to about 10 mole % relative to aluminum atoms.

7. A composition according to claim 6 wherein (b) is at least one siloxane, silane, tin compound, or hydrocarbyl aluminum halide.

8. A composition according to claim 2 wherein the hydrocarbyl groups of said aluminoxane are saturated, and have from one to about twenty carbon atoms.

9. A composition according to claim 2 wherein said aluminoxane is methylaluminoxane, ethylaluminoxane, n-butylaluminoxane, or isobutylaluminoxane.

10. A composition according to claim 5 wherein said halohydrocarbon is one in which at least one R is an aryl group.

11. A composition according to claim 10 wherein said halohydrocarbon is α,α,α-trifluorotoluene.

12. A composition according to claim 5 wherein said aluminoxane is methylaluminoxane, ethylaluminoxane, n-butylaluminoxane, or isobutylaluminoxane, and wherein said halohydrocarbon is one in which at least one R is an aryl group.

13. A composition according to claim 5 wherein said aluminoxane is methylaluminoxane, ethylaluminoxane, n-butylaluminoxane, or isobutylaluminoxane, and wherein said halohydrocarbon is α,α,α-trifluorotoluene.

14. A composition according to claim 13 wherein the amount of halogen atoms present in said haloaluminoxane is in the range of about 2 mole % to about 10 mole % relative to aluminum atoms.

15. A composition according to claim 13 wherein the amount of halogen atoms present in said haloaluminoxane is in the range of about 2 mole % to about 6 mole % relative to aluminum atoms.

16. A composition according to claim 7 wherein said halogenation agent is a silane.

17. A composition according to claim 7 wherein said halogenation agent is a silane, and wherein said silane is triphenylfluorosilane or trimethylfluorosilane.

18. A composition which comprises a haloaluminoxane composition as in claim 2 supported on a catalyst support or carrier.

19. A composition as in claim 18 wherein said inorganic support or carrier is silica, alumina, or silica-alumina.

20. A composition according to claim 18 wherein said aluminoxane is methylaluminoxane, ethylaluminoxane, n-butylaluminoxane, or isobutylaluminoxane.

21. A composition according to claim 18 wherein (b) is at least one halohydrocarbon, and wherein said halohydrocarbon is one in which at least one R is an aryl group.

22. A composition according to claim 18 wherein said aluminoxane is methylaluminoxane, ethylaluminoxane, n-butylaluminoxane, or isobutylaluminoxane, wherein (b) is at least one halohydrocarbon, and wherein said halohydrocarbon is one in which at least one R is an aiyl group.

23. A composition according to claim 22 wherein said halohydrocarbon is α,α,α-trifluorotoluene, and wherein said catalyst support or carrier is silica.

24. A composition according to claim 7 wherein said aluminoxane is methylaluminoxane, ethylaluminoxane, n-butylaluminoxane, or isobutylaluminoxane; wherein said halogenation agent is a siloxane; and wherein said siloxane is a trisiloxane or a tricyclosiloxane.

25. A composition according to claim 7 wherein said halogenation agent is a siloxane, and wherein said siloxane is 3,3,3-trifluoropropyiheptamethyltrisiloxane, 3,3,3-trifluoropropyiheptamethylcyclotrisiloxane, or poly[methyl(3,3,3-trifluoropropyl)siloxane].

26. A composition according to claim 25 wherein said aluminoxane is methylaluminoxane, ethylaluminoxane, n-butylaluminoxane, or isobutylaluminoxane.

27. A composition according to claim 18 wherein the amount of halogen atoms present in said haloaluminoxane composition is in the range of about 2 mole % to about 10 mole % relative to aluminum atoms.

28. A composition according to claim 27 wherein said aluminoxane is methylaluminoxane, ethylaluminoxane, n-butylaluminoxane, or isobutylaluminoxane, and wherein said inorganic support or carrier is silica, alumina, or silica-alumina.

29. A composition according to claim 27 wherein said aluminoxane is methylaluminoxane, ethylaluminoxane, n-butylaluminoxane, or isobutylaluminoxane; wherein said halogenation agent is a siloxane; and wherein said siloxane is a trisiloxane or a tricyclosiloxane.

30. A composition according to claim 27 wherein said halogenation agent is a siloxane, and wherein said siloxane is 3,3,3-trifluoropropylheptamethyltrisiloxane, 3,3,3 -trifluoropropylheptamethylcyclotrisiloxane, or poly[methyl(3,3,3-trifluoropropyl)siloxane].

31. A composition according to claim 30 wherein said aluminoxane is methylaluminoxane, ethylaluminoxane, n-butylaluminoxane, or isobutylaluminoxane.

32. A composition according to claim 27 wherein said aluminoxane is methylaluminoxane; wherein said halogenation agent is a siloxane, wherein said siloxane is poly[methyl(3,3,3-trifluoropropyl)siloxane], and wherein said support is silica.