Polymerisation of ethylene and alpha-olefins with pyrrol-iminophenol complexes

1. An active catalyst system consisting essentially of:

a metallic complex represented by general formula I

wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently selected from hydrogen, C 1 to C 20 hydrocarbyls or inert functional groups and wherein two or more of those groups can be linked together to form rings, M is a metal of Group 3 to 10 of the Periodic Table, Y is O, each X is independently selected from halogens, m is zero or an integer from 1 to 3, (n+2) is the valence of M; and

wherein

and

an activating agent that is an aluminum-containing complex, wherein the active catalyst system comprises an Al/M ratio ranging from 100 to 3000, wherein at least one of R 1 , R 6 and R 7 is not hydrogen.

2. The active catalyst system of claim 1 , wherein m is zero and R 2 , R 3 , R 4 , R 8 , R 9 and R 11 are the same and are hydrogen.

3. The active catalyst system of claim 1 , wherein R 1 , R 5 , R 6 , R 7 , R 10 and R 12 are each independently selected from hydrogen, alkyl groups, aryl groups, halogen, nitro or cyano groups.

4. A method for preparing the active catalyst system of claim 1 comprising:

providing the metallic complex represented by general formula I;

activating the metallic complex with the activating agent having ionising action;

optionally adding a cocatalyst; and

retrieving an active oligomerisation or polymerisation catalyst system.

5. A method for oligomerising or homo- or co-polymerising ethylene and alpha-olefins comprising:

injecting the active catalyst system of claim 1 into a reactor;

injecting a monomer and optional comonomer into the reactor;

maintaining under polymerisation conditions; and

retrieving oligomers or polymer.

6. The method of claim 5 , wherein the monomer or optional comonomer are selected from ethylene, propylene or 1-hexene.

7. An active catalyst system consisting essentially of:

a metallic complex represented by general formula I

wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently selected from hydrogen, C 1 to C 20 hydrocarbyls or inert functional groups and wherein two or more of those groups can be linked together to form rings, M is a metal of Group 3 to 10 of the Periodic Table, Y is O, each X is Cl, m is zero or an integer from 1 to 3, (n+2) is the valence of M; and

wherein

and

an activating agent that is an aluminum-containing complex, wherein the active catalyst system comprises an Al/M ratio ranging from 100 to 3000.

8. A method for preparing the active catalyst system of claim 7 comprising:

providing the metallic complex represented by general formula I;

activating the metallic complex with the activating agent having ionising action;

optionally adding a cocatalyst; and

retrieving an active oligomerisation or polymerisation catalyst system.

9. A method for oligomerising or homo- or co-polymerising ethylene and alpha-olefins comprising:

injecting the active catalyst system of claim 7 into a reactor;

injecting a monomer and optional comonomer into the reactor;

maintaining under polymerisation conditions; and

retrieving oligomers or polymer.

10. An active catalyst system consisting essentially of:

a metallic complex represented by general formula I

wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently selected from hydrogen, C 1 to C 20 hydrocarbyls or inert functional groups and wherein two or more of those groups can be linked together to form rings, M is a metal of Group 3 to 10 of the Periodic Table, Y is O, each X is independently selected from halogens, m is zero or an integer from 1 to 3, (n+2) is the valence of M; and

wherein

and

an activating agent that is an aluminum-containing complex, wherein the active catalyst system comprises an Al/M ratio ranging from 100 to 3000, wherein at least one of R 1 , R 10 and R 12 is not hydrogen.

11. A method for preparing the active catalyst system of claim 10 comprising:

providing the metallic complex represented by general formula I;

activating the metallic complex with the activating agent having ionising action;

optionally adding a cocatalyst; and

retrieving an active oligomerisation or polymerisation catalyst system.

12. A method for oligomerising or homo- or co-polymerising ethylene and alpha-olefins comprising:

injecting the active catalyst system of claim 10 into a reactor;

injecting a monomer and optional comonomer into the reactor;

maintaining under polymerisation conditions; and

retrieving oligomers or polymer.

13. An active catalyst system consisting essentially of:

a metallic complex represented by general formula I

wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently selected from hydrogen, C 1 to C 20 hydrocarbyls or inert functional groups and wherein two or more of those groups can be linked together to form rings, M is a metal of Group 3 to 10 of the Periodic Table, Y is O, each X is independently selected from halogens, m is zero or an integer from 1 to 3, (n+2) is the valence of M; and

wherein

and

an activating agent that is an aluminum-containing complex, wherein the active catalyst system comprises an Al/M ratio ranging from 100 to 3000, wherein the aluminum-containing complex is triisobutyl aluminum, triethyl aluminum, or aluminoxane.

14. The active catalyst system of claim 13 , wherein the aluminum-containing complex is triisobutyl aluminum or aluminoxane.

15. A method for preparing the active catalyst system of claim 13 comprising:

providing the metallic complex represented by general formula I;

activating the metallic complex with the activating agent having ionising action;

optionally adding a cocatalyst; and

retrieving an active oligomerisation or polymerisation catalyst system.

16. A method for oligomerising or homo- or co-polymerising ethylene and alpha-olefins comprising:

injecting the active catalyst system of claim 13 into a reactor;

injecting a monomer and optional comonomer into the reactor;

maintaining under polymerisation conditions; and

retrieving oligomers or polymer.

17. An active catalyst system consisting essentially of:

a metallic complex represented by general formula I

wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently selected from hydrogen, C 1 to C 20 hydrocarbyls or inert functional groups and wherein two or more of those groups can be linked together to form rings, wherein M is Ti, Cr, Zr or Fe, wherein Y is O, each X is independently selected from halogens, m is zero or an integer from 1 to 3, (n+2) is the valence of M; and

wherein

and

an activating agent that is an aluminum-containing complex, wherein the active catalyst system comprises an Al/M ratio ranging from 100 to 3000.

18. The active catalyst system of claim 17 , wherein M is Zr.

19. A method for preparing the active catalyst system of claim 17 comprising:

providing the metallic complex represented by general formula I;

activating the metallic complex with the activating agent having ionising action;

optionally adding a cocatalyst; and

retrieving an active oligomerisation or polymerisation catalyst system.

20. A method for oligomerising or homo- or co-polymerising ethylene and alpha-olefins comprising:

injecting the active catalyst system of claim 17 into a reactor;

injecting a monomer and optional comonomer into the reactor;

maintaining under polymerisation conditions; and

retrieving oligomers or polymer.

21. An active catalyst system consisting essentially of:

a metallic complex represented by general formula I

wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently selected from hydrogen, C 1 to C 20 hydrocarbyls or inert functional groups and wherein two or more of those groups can be linked together to form rings, M is Ti, Cr, Zr or Fe, Y is O or NR*, with R* being alkyl or aryl group having from 1 to 12 carbon atoms, each X is independently selected from halogens, m is zero or an integer from 1 to 3, (n+2) is the valence of M; and

wherein

an activating agent that is an aluminum-containing complex, wherein the active catalyst system comprises an Al/M ratio ranging from 100 to 3000; and

a co-catalyst.

22. The active catalyst system of claim 21 , wherein m is zero and R 2 , R 3 , R 4 , R 8 , R 9 and R 11 are the same and are hydrogen.

23. The active catalyst system of claim 21 , wherein R 1 , R 5 , R 6 , R 7 , R 10 and R 12 are each independently selected from hydrogen, alkyl groups, aryl groups, halogen, nitro or cyano groups.

24. The active catalyst system of claim 21 , wherein at least one of R 1 , R 6 , and R 7 is not hydrogen.

25. The active catalyst system of claim 21 , wherein X is Cl.

26. The active catalyst system of claim 21 , wherein at least one of R 1 , R 10 and R 12 is not hydrogen.

27. A method for preparing the active catalyst system of claim 21 comprising:

providing the metallic complex represented by general formula I;

activating the metallic complex with the activating agent having ionising action;

optionally adding a cocatalyst; and

retrieving an active oligomerisation or polymerisation catalyst system.

28. A method for oligomerising or homo- or co-polymerising ethylene and alpha-olefins comprising:

injecting the active catalyst system of claim 21 into a reactor;

injecting a monomer and optional comonomer into the reactor;

maintaining under polymerisation conditions; and

retrieving oligomers or polymer.

29. An active catalyst system consisting essentially of:

a metallic complex represented by general formula I

wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently selected from hydrogen, C 1 to C 20 hydrocarbyls or inert functional groups and wherein two or more of those groups can be linked together to form rings, M is a metal of Group 3 to 10 of the Periodic Table, Y is O, each X is independently selected from halogens, m is zero or an integer from 1 to 3, (n+2) is the valence of M; and

wherein

and

an activating agent that is a boron containing complex, wherein the boron containing complex is selected from a triphenylcarbenium boronate or a boron containing complex of the formula:

[L′-H]+[BAr 1 Ar 2 X 3 X 4 ]—

wherein L′ is a neutral Lewis base; H is a hydrogen atom; [L′-H]+ is a Bronsted acid; B is boron in a valence state of 3; Ar 1 and Ar 2 are the same or different aromatic or substituted-aromatic hydrocarbon radicals containing from 6 to 20 carbon atoms; and wherein X 3 and X 4 are radicals independently selected from the group consisting of hydride radicals, halide radicals with the proviso that only one of X 3 or X 4 can be a halide radical, hydrocarbyl radicals containing from 1 to 20 carbon atoms, substituted-hydrocarbyl radicals, and hydrocarbyl-substituted metal radicals.

30. The active catalyst system of claim 29 , wherein the boron containing complex is tetrakis-pentafluorophenyl-borato-triphenylcarbenium.

31. A method for preparing the active catalyst system of claim 29 comprising:

providing the metallic complex represented by general formula I;

activating the metallic complex with the activating agent having ionising action;

optionally adding a cocatalyst; and

retrieving an active oligomerisation or polymerisation catalyst system.

32. A method for oligomerising or homo- or co-polymerising ethylene and alpha-olefins comprising:

injecting the active catalyst system of claim 29 into a reactor;

injecting a monomer and optional comonomer into the reactor;

maintaining under polymerisation conditions; and

retrieving oligomers or polymer.

33. An active catalyst system consisting essentially of:

a metallic complex represented by general formula I

wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently selected from hydrogen, C 1 to C 20 hydrocarbyls or inert functional groups and wherein two or more of those groups can be linked together to form rings, M is Ti, Cr, Zr or Fe, Y is O or NR*, with R* being alkyl or aryl group having from 1 to 12 carbon atoms, each X is independently selected from halogens, m is zero or an integer from 1 to 3, (n+2) is the valence of M; and

wherein

an activating agent that is a boron containing complex, wherein the boron containing complex is selected from a triphenylcarbenium boronate or a boron containing complex of the formula:

[L′-H]+[BAr 1 Ar 2 X 3 X 4 ]—

wherein L′ is a neutral Lewis base; H is a hydrogen atom; [L′-H]+ is a Bronsted acid; B is boron in a valence state of 3; Ar 1 and Ar 2 are the same or different aromatic or substituted-aromatic hydrocarbon radicals containing from 6 to 20 carbon atoms; and wherein X 3 and X 4 are radicals independently selected from the group consisting of hydride radicals, halide radicals with the proviso that only one of X 3 or X 4 can be a halide radical, hydrocarbyl radicals containing from 1 to 20 carbon atoms, substituted-hydrocarbyl radicals, and hydrocarbyl-substituted metal radicals; and

a co-catalyst.

34. The active catalyst system of claim 33 , wherein the boron containing complex is tetrakis-pentafluorophenyl-borato-triphenylcarbenium.

35. A method for preparing the active catalyst system of claim 33 comprising:

providing the metallic complex represented by general formula I;

activating the metallic complex with the activating agent having ionising action;

optionally adding a cocatalyst; and

retrieving an active oligomerisation or polymerisation catalyst system.

36. A method for oligomerising or homo- or co-polymerising ethylene and alpha-olefins comprising:

injecting the active catalyst system of claim 33 into a reactor;

injecting a monomer and optional comonomer into the reactor;

maintaining under polymerisation conditions; and

retrieving oligomers or polymer.