Catalyst preparation method

• US 6,656,866 B2
• Filed: 12/04/2000
• Issued: 12/02/2003
• Est. Priority Date: 12/04/2000
• Status: Expired due to Term

• Current Assignee: Univation Technologies LLC (Dow, Inc.)
• Original Assignee: Univation Technologies LLC (Dow, Inc.)
• Inventors: Wenzel, Timothy T., Schreck, David James
• Primary Examiner(s): Bell, Mark L.
• Assistant Examiner(s): BROWN, JENNINE M
• Application Number:
  US09/729,842
• Publication Number:
  US 20020119890A1
• Time in Patent Office: 1,093 Days
• Field of Search: 502/117
• US Class Current: 502/117
• CPC Class Codes: B01J 2531/0252 Salen ligands or analogues, e.g. derived from ethylenediamine and salicylaldehyde
• CPC Class Codes: B01J 2531/0258 Flexible ligands, e.g. mainly sp3-carbon framework as exemplified by the "tedicyp" ligand, i.e. cis-cis-cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane
• CPC Class Codes: B01J 2531/46 Titanium
• CPC Class Codes: B01J 2531/48 Zirconium
• CPC Class Codes: B01J 2531/49 Hafnium
• CPC Class Codes: B01J 2531/56 Vanadium
• CPC Class Codes: B01J 31/14 of aluminium or boron
• CPC Class Codes: B01J 31/143 of aluminium
• CPC Class Codes: B01J 31/146 of boron
• CPC Class Codes: B01J 31/1616 Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts catalysts comprising molecular sieves B01J29/00
• CPC Class Codes: B01J 31/1805 the ligands containing nitrogen
• CPC Class Codes: B01J 31/2243 At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
• CPC Class Codes: B01J 31/2295 Cyclic compounds, e.g. cyclopentadienyls
• CPC Class Codes: B01J 35/0006 Catalysts containing parts with different compositions
• CPC Class Codes: B01J 35/19 Catalysts containing parts with different compositions
• CPC Class Codes: B01J 37/0045 Drying a slurry, e.g. spray drying
• CPC Class Codes: C08F 10/00 Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• CPC Class Codes: C08F 10/02 Ethene
• CPC Class Codes: C08F 110/02 Ethene
• CPC Class Codes: C08F 210/08 Butenes
• CPC Class Codes: C08F 210/14 : Monomers containing five or more carbon atoms
• CPC Class Codes: C08F 210/16 : Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• CPC Class Codes: C08F 2410/06 : Catalyst characterized by its size
• CPC Class Codes: C08F 4/65904 : in combination with another component of C08F4/64
• CPC Class Codes: C08F 4/65912 : in combination with an organoaluminium compound
• CPC Class Codes: C08F 4/65916 : supported on a carrier, e.g. silica, MgCl2, polymer
• CPC Class Codes: C08F 4/65925 : two cyclopentadienyl rings being mutually non-bridged
• CPC Class Codes: C08F 4/65927 : two cyclopentadienyl rings being mutually bridged

Abstract

The present invention relates to a method of preparing a supported catalyst system, the method including combining 1) a first supported catalyst system comprising a support, an activator and a metal catalyst compound, and 2) a second supported catalyst system comprising a support, an activator and a metal catalyst compound and thereafter spray-drying the combination.

Claims

1. A method of preparing a supported catalyst system comprising combining 1) a first supported catalyst system comprising a support, an activator and a metal catalyst compound, and 2) a second supported catalyst system comprising a support, an activator and a metal catalyst compound;

and thereafter spray-drying the combination of

     1) and

     2); and

wherein the particle size of the first supported catalyst system is different from the particle size of the second supported catalyst system.

2. The method of claim 1 wherein the first catalyst compound is different from the second catalyst compound.

3. The method of claim 1 wherein the activator of the first supported catalyst system is different from the activator of the second supported catalyst system.

4. The method of claim 1 wherein the combination to be spray dried is prepared by combining a two different supported activators with a catalyst compound.

5. The method of claim 1 wherein the combination to be spray dried is prepared by combining a two or more different supported catalyst compounds with an activator.

6. The method of claim 1 wherein at least one of the activators is selected from the group consisting of alumoxanes, modified alumoxanes, non-coordinating ionic activators and ionizing activators.

7. The method of claim 1 wherein at least one of the activators is selected from the group consisting of:

trimethylammonium tetraphenylborate,

triethylammonium tetraphenylborate,

tripropylammonium tetraphenylborate,

tri(n-butyl)ammonium tetraphenylborate,

tri(t-butyl)ammonium tetraphenylborate,

N,N-dimethylanilinium tetraphenylborate,

N,N-diethylanilinium tetraphenylborate,

N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate,

trimethylammonium tetrakis(pentafluorophenyl)borate,

triethylammonium tetrakis(pentafluorophenyl)borate,

tripropylammonium tetrakis(pentafluorophenyl)borate,

tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,

tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate,

N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,

N,N-diethylanilinium tetrakis(pentafluorophenyl)borate,

N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate,

trimethylammonium tetrakis-(2,3,4,6-tetrafluorophenylborate,

triethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,

tripropylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,

tri(n-butyl)ammonium tetrakis-(2,3,4,6-tetrafluoro-phenyl)borate,

dimethyl(t-butyl)ammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,

N,N-dimethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,

N,N-diethylanilinium tetrakis-(2,3,4,6-tetrafluoro-phenyl)borate, and

N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate;

di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate,

dicyclohexylammonium tetrakis(pentafluorophenyl)borate;

triphenylphosphonium tetrakis(pentafluorophenyl)borate,

tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate,

tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate, methyl alumoxane,

and modified methyl alumoxane.

8. The method of claim 1 wherein at least one of the two or more different catalyst compounds comprises a bulky ligand metallocene compound.

9. The method of claim 1 wherein one or more of the catalyst compounds is selected from the group consisting of:

bis(cyclopentadienyl)titanium dimethyl,

bis(cyclopentadienyl)titanium diphenyl,

bis(cyclopentadienyl)zirconium dimethyl,

bis(cyclopentadienyl)zirconium diphenyl,

bis(cyclopentadienyl)hafnium methyl and diphenyl,

bis(cyclopentadienyl)titanium di-neopentyl,

bis(cyclopentadienyl)zirconium di-neopentyl,

bis(cyclopentadienyl)titanium dibenzyl,

bis(cyclopentadienyl)zirconium dibenzyl,

bis(cyclopentadienyl)vanadium dimethyl,

bis(cyclopentadienyl)titanium methyl chloride,

bis(cyclopentadienyl)titanium ethyl chloride,

bis(cyclopentadienyl)titanium phenyl chloride,

bis(cyclopentadienyl)zirconium methyl chloride,

bis(cyclopentadienyl)zirconium ethyl chloride,

bis(cyclopentadienyl)zirconium phenyl chloride,

bis(cyclopentadienyl)titanium methyl bromide,

cyclopentadienyl titanium trimethyl,

cyclopentadienyl zirconium triphenyl,

cyclopentadienyl zirconium trineopentyl,

cyclopentadienyl zirconium trimethyl,

cyclopentadienyl hafnium triphenyl,

cyclopentadienyl hafnium trineopentyl,

cyclopentadienyl hafnium trimethyl,

pentamethylcyclopentadienyl titanium trichloride,

pentaethylcyclopentadienyl titanium trichloride;

bis(indenyl)titanium diphenyl or dichloride,

bis(methylcyclopentadienyl)titanium diphenyl or dihalide,

bis(1,2-dimethylcyclopentadienyl)titanium diphenyl or dichloride,

bis(1,2-diethylcyclopentadienyl)titanium diphenyl or dichloride,

bis(pentamethylcyclopentadienyl)titanium diphenyl or dichloride;

dimethyl silyldicyclopentadienyl titanium diphenyl or dichloride,

methyl phosphine dicyclopentadienyl titanium diphenyl or dichloride,

methylenedicyclopentadienyl titanium diphenyl or dichloride,

isopropyl(cyclopentadienyl)(fluorenyl)zirconium dichloride,

isopropyl(cyclopentadienyl)(octahydrofluorenyl)zirconium dichloride,

diisopropylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,

diisobutylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,

ditertbutylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,

cyclohexylidene(cyclopentadienyl)(fluorenyl)zirconium dichloride,

diisopropylmethylene(2,5-dimethylcyclopentadienyl)(fluorenyl)zirconium dichloride,

isopropyl(cyclopentadienyl)(fluorenyl)hafnium dichloride,

diphenylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride,

diisopropylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride,

diisobutylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride,

ditertbutylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride,

cyclohexylidene(cyclopentadienyl)(fluorenyl)hafnium dichloride,

diisopropylmethylene(2,5-dimethylcyclopentadienyl)(fluorenyl)-hafnium dichloride,

isopropyl(cyclopentadienyl)(fluorenyl)titanium dichloride,

diphenylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride,

diisopropylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride,

diisobutylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride,

ditertbutylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride,

cyclohexylidene(cyclopentadienyl)(fluorenyl)titanium dichloride,

diisopropylmethylene(2,5 dimethylcyclopentadienyl fluorenyl)titanium dichloride,

racemic-ethylene bis(1-indenyl)zirconium(W)dichloride,

racemic-ethylene bis(4,5,6,7-tetrahydro-1-indenyl)zirconium(IV)dichloride,

racemic-dimethylsilyl bis(1-indenyl)zirconium(IV)dichloride,

racemic-dimethylsilyl bis(4,5,6,7-tetrahydro-1-indenyl)zirconium(IV)dichloride,

racemic-1,1,2,2-tetramethylsilanylene bis(1-indenyl)zirconium(IV)dichloride,

racemic-1,1,2,2-tetramethylsilanylene bis(4,5,6,7-tetrahydro-1-indenyl)zirconium(IV)dichloride,

ethylidene(1-indenyl tetramethylcyclopentadienyl)zirconium(IV)dichloride,

racemic-dimethylsilyl bis(2-methyl-4-t-butyl-1-cyclopentadienyl)zirconium(IV)dichloride,

racemic-ethylene bis(1-indenyl)hafnium(IV)dichloride, racemic-ethylene bis(4,5,6,7-tetrahydro-1-indenyl)hafnium(IV)dichloride,

racemic-dimethylsilyl bis(1-indenyl)hafnium(IV)dichloride,

racemic-dimethylsilyl bis(4,5,6,7-tetrahydro-1-indenyl)hafnium(IV)dichloride,

racemic-1,1,2,2-tetramethylsilanylene bis(1-indenyl)hafnium(IV)dichloride,

racemic-1,1,2,2-tetramethylsilanylene bis(4,5,6,7-tetrahydro-1-indenyl)hafnium(IV)dichloride,

ethylidene(1-indenyl-2,3,4,5-tetramethyl-1-cyclopentadienyl)hafnium(IV)dichloride,

racemic-ethylene bis(1-indenyl)titanium(IV)dichloride, racemic-ethylene bis(4,5,6,7-tetrahydro-1-indenyl)titanium(IV)dichloride,

racemic-dimethylsilyl bis(1-indenyl)titanium(IV)dichloride,

racemic-dimethylsilyl bis(4,5,6,7-tetrahydro-1-indenyl)titanium(IV)dichloride,

racemic-1,1,2,2-tetramethylsilanylene bis(1-indenyl)titanium(IV)dichloride

racemic-1,1,2,2-tetramethylsilanylene bis(4,5,6,7-tetrahydro-1-indenyl)titanium(IV)dichloride,

ethylidene(1-indenyl-2,3,4,5-tetramethyl-1-cyclopentadienyl)titanium(IV)dichloride,

indenyl zirconium tris(diethylcarbamate),

indenyl zirconium tris(pivalate),

indenyl zirconium tris(p-toluate),

indenyl zirconium tris(benzoate), (1-methylindenyl) zirconium tris(pivalate),

(2-methylindenyl)zirconium tris(diethylcarbamate),

(methylcyclopentadienyl)zirconium tris(pivalate),

cyclopentadienyl tris(pivalate),

(pentamethylcyclopentadienyl)zirconium tris(benzoate),

bis(pentamethylcyclopentadienyl)zirconium dichloride,

bis(pentamethylcyclopentadienyl)zirconium dimethyl,

(indenyl)(pentamethylcyclopentadienyl)zirconium dichloride, and

(indenyl)(pentamethylcyclopentadienyl)zirconium dimethyl.

10. The method of claim 1 wherein at least one of the two or more different catalyst compounds comprises a catalyst compound selected from the group consisting of:

bis(N-methyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-ethyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-iso-propyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-t-butyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-benzyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-hexyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-phenyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-methyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-benzyl-3,5-di-t-butylsalicylimino)zirconium(IV)dichloride;

bis(N-benzyl-3,5-di-t-butylsalicylimino)zirconium(IV)dipivalate;

bis(N-benzyl-3,5-di-t-butylsalicylimino)titanium(IV)dipivalate;

bis(N-benzyl-3,5-di-t-butylsalicylimino)zirconium(IV)di(bis(dimethylamide));

bis(N-iso-propyl-3,5-di-t-amylsalicylimino)zirconium(IV)dibenzyl;

bis(N-iso-propyl-3,5-di-t-octylsalicylimino)zirconium(IV)dibenzyl;

bis(N-iso-propyl-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-iso-propyl-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)titanium(IV)dibenzyl;

bis(N-iso-propyl-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)hafnium(IV)dibenzyl;

bis(N-iso-butyl-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-iso-butyl-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)zirconium(IV)dichloride;

bis(N-hexyl-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-phenyl-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-iso-propyl-3,5-di-(1′

-methylcyclohexyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-benzyl-3-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-benzyl-3-triphenylmethylsalicylimino)zirconium(IV)dibenzyl;

bis(N-iso-propyl-3,5-di-trimethylsilylsalicylimino)zirconium(IV)dibenzyl;

bis(N-iso-propyl-3-(phenyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-benzyl-3-(2′

,6′

-di-iso-propylphenyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-benzyl-3-(2′

,6′

-di-phenylphenyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-benzyl-3-t-butyl-5-methoxysalicylimino)zirconium(IV)dibenzyl;

bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)zirconium(IV)dibenzyl;

bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)zirconium(IV)dichloride;

bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)zirconium(IV) di(bis(dimethylamide));

bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1′

,1′

-dimethylbenzyl)phenoxide)zirconium(IV)dibenzyl;

bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)titanium(IV)dibenzyl;

bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1′

,1′

-dimenthylbenzyl)phenoxide)titanium(IV)dibenzyl;

bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1′

,1′

-dimenthylbenzyl)phenoxide)titanium(IV)dichloride;

bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1′

,1′

-dimenthylbenzyl)phenoxide)hafnium(IV)dibenzyl;

(N-phenyl-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)zirconium(IV)tribenzyl;

(N-(2′

,6′

-di-iso-propylphenyl)-3,5-di-(1′

,1′

-dimenthylbenzyl)salicylimino)zirconium(IV)tribenzyl;

(N-(2′

,6′

-di-iso-propylphenyl)-3,5-di-(1′

,1′

-dimenthylbenzyl)salicylimino)titanium(IV)tribenzyl; and

(N-(2′

,6′

-di-iso-propylphenyl)-3,5-di-(1′

,1′

-dimenthylbenzyl)salicylimino)zirconium(IV) trichloride.

11. The method of claim 1 wherein at least one of the two or more different catalyst compounds comprises a catalyst compound represented by the formula:

[(2,4,6-(CH₃)₃C₆H₂)NCH₂CH₂]₂NH}MBz₂(where M is Hf, Zr, Ti, and Bz is a halide or a benzyl group).

21. The method of claim 1 wherein at least one of the two or more different catalyst compounds comprises a Group 15 containing catalyst compound represented by the formulae:

wherein

M is a Group 4, 5, or 6 metal;

each X is independently an anionic leaving group;

y is 0 or 1; and

when y is 0 group L′

is absent;

n is the oxidation state of M;

m is the formal charge of the ligand represented by YZL or the YZL′

;

L is a Group 15 or 16 element;

L′

is a Group 15 or 16 element or Group 14 containing group;

Y is a Group 15 element;

Z is a Group 15 element;

divalent groups R¹ and R² are independently a C₁ to C₂₀ hydrocarbon group or a heteroatom containing group having up to twenty carbon atoms, the heteroatom selected from silicon, germanium, tin, lead, halogen and phosphorus;

R¹ and R² may also be interconnected to each other;

R³ is absent or a hydrocarbon group, hydrogen, a halogen, or a heteroatom containing group;

R⁴ and R⁵ are independently an alkyl group, an aryl group, substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl group, a cyclic arylalkyl group, a substituted cyclic arylalkyl group or multiple ring system;

R⁴ and R⁵ may be interconnected to each other;

R⁶ and R⁷ are independently absent, or hydrogen, an alkyl group, halogen, heteroatom or a hydrocarbyl group; and

R* is absent, or is hydrogen, a Group 14 atom containing group, a halogen, or a heteroatom containing group.

23. The method of claim 8 wherein the bulky ligand metallocene compound is selected from compounds represented by the following formulae:

12. A composition of matter comprising a particle comprising a first supported catalyst system comprising a support, an activator and a metal catalyst compound and second supported catalyst system comprising a support, an activator and a metal catalyst compound;

wherein the particle size of the first supported catalyst system is different from the particle size of the second supported catalyst system.

13. The composition of claim 12 wherein the first catalyst compound is different from the second catalyst compound.

14. The composition of claim 12 wherein the activator of the first supported catalyst system is different from the activator of the second supported catalyst system.

15. The composition of claim 12 wherein at least one of the activators is selected from the group consisting of alumoxanes, modified alumoxanes, non-coordinating ionic activators and ionizing activators.

16. The composition of claim 12 wherein at least one of the activators is selected from the group consisting of:

trimethylammonium tetraphenylborate,

triethylammonium tetraphenylborate,

tripropylammonium tetraphenylborate,

tri(n-butyl)ammonium tetraphenylborate,

tri(t-butyl)ammonium tetraphenylborate,

N,N-dimethylanilinium tetraphenylborate,

N,N-diethylanilinium tetraphenylborate,

N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate,

trimethylammonium tetrakis(pentafluorophenyl)borate,

triethylammonium tetrakis(pentafluorophenyl)borate,

tripropylammonium tetrakis(pentafluorophenyl)borate,

tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,

tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate,

N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,

N,N-diethylanilinium tetrakis(pentafluorophenyl)borate,

N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate,

trimethylammonium tetrakis-(2,3,4,6-tetrafluorophenylborate,

triethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,

tripropylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,

tri(n-butyl)ammonium tetrakis-(2,3,4,6-tetrafluoro-phenyl)borate,

dimethyl(t-butyl)ammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,

N,N-dimethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,

N,N-diethylanilinium tetrakis-(2,3,4,6-tetrafluoro-phenyl)borate, and

N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate;

di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate,

dicyclohexylammonium tetrakis(pentafluorophenyl)borate;

triphenylphosphonium tetrakis(pentafluorophenyl)borate,

tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate,

tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate,

methyl alumoxane,

and modified methyl alumoxane.

17. The composition of claim 12 wherein at least one of the two or more different catalyst compounds comprises a bulky ligand metallocene compound.

18. The composition of claim 12 wherein one or more of the catalyst compounds is selected from the group consisting of:

bis(cyclopentadienyl)titanium dimethyl,

bis(cyclopentadienyl)titanium diphenyl,

bis(cyclopentadienyl)zirconium dimethyl,

bis(cyclopentadienyl)zirconium diphenyl,

bis(cyclopentadienyl)hafnium methyl and diphenyl,

bis(cyclopentadienyl)titanium di-neopentyl,

bis(cyclopentadienyl)zirconium di-neopentyl,

bis(cyclopentadienyl)titanium dibenzyl,

bis(cyclopentadienyl)zirconium dibenzyl,

bis(cyclopentadienyl)vanadium dimethyl,

bis(cyclopentadienyl)titanium methyl chloride,

bis(cyclopentadienyl)titanium ethyl chloride,

bis(cyclopentadienyl)titanium phenyl chloride,

bis(cyclopentadienyl)zirconium methyl chloride,

bis(cyclopentadienyl)zirconium ethyl chloride,

bis(cyclopentadienyl)zirconium phenyl chloride,

bis(cyclopentadienyl)titanium methyl bromide,

cyclopentadienyl titanium trimethyl,

cyclopentadienyl zirconium triphenyl,

cyclopentadienyl zirconium trineopentyl,

cyclopentadienyl zirconium trimethyl,

cyclopentadienyl hafnium triphenyl,

cyclopentadienyl hafnium trineopentyl,

cyclopentadienyl hafnium trimethyl,

pentamethylcyclopentadienyl titanium trichloride,

pentaethylcyclopentadienyl titanium trichloride;

bis(indenyl)titanium diphenyl or dichloride,

bis(methylcyclopentadienyl)titanium diphenyl or dihalide,

bis(1,2-dimethylcyclopentadienyl)titanium diphenyl or dichloride,

bis(1,2-diethylcyclopentadienyl)titanium diphenyl or dichloride,

bis(pentamethylcyclopentadienyl)titanium diphenyl or dichloride;

dimethyl silyldicyclopentadienyl titanium diphenyl or dichloride,

methyl phosphine dicyclopentadienyl titanium diphenyl or dichloride,

methylenedicyclopentadienyl titanium diphenyl or dichloride,

isopropyl(cyclopentadienyl)(fluorenyl)zirconium dichloride,

isopropyl(cyclopentadienyl)(octahydrofluorenyl)zirconium dichloride,

diisopropylmethylene(cyclopentadienyl)(fluorenyl)zircomum dichloride,

diisobutylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,

ditertbutylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,

cyclohexylidene(cyclopentadienyl)(fluorenyl)zirconium dichloride,

diisopropylmethylene(2,5-dimethylcyclopentadienyl)(fluorenyl)zirconium dichloride,

isopropyl(cyclopentadienyl)(fluorenyl)hafnium dichloride,

diphenylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride,

diisopropylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride,

diisobutylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride,

ditertbutylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride,

cyclohexylidene(cyclopentadienyl)(fluorenyl)hafnium dichloride,

diisopropylmethylene(2,5-dimethylcyclopentadienyl)(fluorenyl)-hafnium dichloride,

isopropyl(cyclopentadienyl)(fluorenyl)titanium dichloride,

diphenylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride,

diisopropylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride,

diisobutylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride,

ditertbutylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride,

cyclohexylidene(cyclopentadienyl)(fluorenyl)titanium dichloride,

diisopropylmethylene(2,5 dimethylcyclopentadienyl fluorenyl)titanium dichloride,

racemic-ethylene bis(1-indenyl)zirconium(W)dichloride,

racemic-ethylene bis(4,5,6,7-tetrahydro-1-indenyl)zirconium(IV)dichloride,

racemic-dimethylsilyl bis(1-indenyl)zirconium(IV)dichloride,

racemic-dimethylsilyl bis(4,5,6,7-tetrahydro-1-indenyl)zirconium(IV)dichloride,

racemic-1,1,2,2-tetramethylsilanylene bis(1-indenyl)zirconium(IV)dichloride.

racemic-1,1,2,2-tetramethylsilanylene bis(4,5,6,7-tetrahydro-1-indenyl)zirconium(IV)dichloride,

ethylidene(1-indenyl tetramethylcyclopentadienyl)zirconium(IV)dichloride,

racemic-dimethylsilyl bis(2-methyl-4-t-butyl-1-cyclopentadienyl)zirconium(IV)dichloride,

racemic-ethylene bis(1-indenyl)hafnium(IV)dichloride, racemic-ethylene bis(4,5,6,7-tetrahydro-1-indenyl)hafnium(IV)dichloride,

racemic-dimethylsilyl bis(1-indenyl)hafnium(IV)dichloride,

racemic-dimethylsilyl bis(4,5,6,7-tetrahydro-1-indenyl)hafnium(IV)dichloride,

racemic-1,1,2,2-tetramethylsilanylene bis(1-indenyl)hafnium(IV)dichloride,

racemic-1,1,2,2-tetramethylsilanylene bis(4,5,6,7-tetrahydro-1-indenyl)hafnium(IV)dichloride,

ethylidene(1-indenyl-2,3,4,5-tetramethyl-1-cyclopentadienyl)hafnium(IV)dichloride,

racemic-ethylene bis(1-indenyl)titanium(IV)dichloride, racemic-ethylene bis(4,5,6,7-tetrahydro-1-indenyl)titanium(IV)dichloride,

racemic-dimethylsilyl bis(1-indenyl)titanium(IV)dichloride,

racemic-dimethylsilyl bis(4,5,6,7-tetrahydro-1-indenyl)titanium(IV)dichloride,

racemic-1,1,2,2-tetramethylsilanylene bis(1-indenyl)titanium(IV)dichloride

racemic-1,1,2,2-tetramethylsilanylene bis(4,5,6,7-tetrahydro-1-indenyl)titanium(IV)dichloride,

ethylidene(1-indenyl-2,3,4,5-tetramethyl-1-cyclopentadienyl)titanium(IV)dichloride,

indenyl zirconium tris(diethylcarbamate),

indenyl zirconium tris(pivalate),

indenyl zirconium tris(p-toluate),

indenyl zirconium tris(benzoate),(1-methylindenyl)zirconium tris(pivalate),

(2-methylindenyl)zirconium tris(diethylcarbamate),

(methylcyclopentadienyl)zirconium tris(pivalate),

cyclopentadienyl tris(pivalate),

(pentamethylcyclopentadienyl)zirconium tris(benzoate),

bis(pentamethylcyclopentadienyl)zirconium dichloride,

bis(pentamethylcyclopentadienyl)zirconium dimethyl,

(indenyl)(pentamethylcyclopentadienyl)zirconium dichloride, and

(indenyl)(pentamethylcyclopentadienyl)zirconium dimethyl.

19. The composition of claim 12 wherein at least one of the two or more different catalyst compounds comprises a catalyst compound selected from the group consisting of:

bis(N-methyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-ethyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-iso-propyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-t-butyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-benzyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-hexyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-phenyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-methyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-benzyl-3,5-di-t-butylsalicylimino)zirconium(IV)dichloride;

bis(N-benzyl-3,5-di-t-butylsalicylimino)zirconium(IV)dipivalate;

bis(N-benzyl-3,5-di-t-butylsalicylimino)titanium(IV)dipivalate;

bis(N-benzyl-3,5-di-t-butylsalicylimino)zirconium(IV)di(bis(dimethylamide));

bis(N-iso-propyl-3,5-di-t-amylsalicylimino)zirconium(IV)dibenzyl;

bis(N-iso-propyl-3,5-di-t-octylsalicylimino)zirconium(IV)dibenzyl;

bis(N-iso-propyl-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-iso-propyl-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)titanium(IV)dibenzyl;

bis(N-iso-propyl-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)hafnium(IV)dibenzyl;

bis(N-iso-butyl-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-iso-butyl-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)zirconium(IV)dichloride;

bis(N-hexyl-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-phenyl-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-iso-propyl-3,5-di-(1′

-methylcyclohexyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-benzyl-3-t-butylsalicylimino)zirconium(IV)dibenzyl;

bis(N-benzyl-3-triphenylmethylsalicylimino)zirconium(IV)dibenzyl;

bis(N-iso-propyl-3,5-di-trimethylsilylsalicylimino)zirconium(IV)dibenzyl;

bis(N-iso-propyl-3-(phenyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-benzyl-3-(2′

,6′

-di-iso-propylphenyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-benzyl-3-(2′

,6′

-di-phenylphenyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-benzyl3-t-butyl-5-methoxysalicylimino)zirconium(IV)dibenzyl;

bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)zirconium(IV)dibenzyl;

bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)zirconium(IV)dichloride;

bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)zirconium(IV)di(bis(dimethylamide));

bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1′

,1′

-dimethylbenzyl)phenoxide)zirconium(IV)dibenzyl;

bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)titanium(IV)dibenzyl;

bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1′

,1′

-dimethylbenzyl)phenoxide)titanium(IV)dibenzyl;

bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1′

,1′

-dimethylbenzyl)phenoxide)titanium(IV)dichloride;

bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1′

,1′

-dimethylbenzyl)phenoxide)hafnium(IV)dibenzyl;

(N-phenyl-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)zirconium(IV)tribenzyl;

(N-(2′

,6′

-di-iso-propylphenyl)-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)zirconium(IV)tribenzyl;

(N-(2′

,6′

-di-iso-propylphenyl)-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)titanium(IV)tribenzyl; and

(N-(2′

,6′

-di-iso-propylphenyl)-3,5-di-(1′

,1′

-dimethylbenzyl)salicylimino)zirconium(IV)trichloride.

20. The composition of claim 12 wherein at least one of the two or more different catalyst compounds comprises a catalyst compound represented by the formula:

[(2,4,6-(CH₃)₃C₆H₂)NCH₂CH₂]₂NH}MBz₂(where M is Hf, Zr, Ti, and Bz is a halide or a benzyl group).

22. The composition of claim 12 wherein at least one of the two or more different catalyst compounds comprises a Group 15 containing catalyst compound represented by the formulae:

wherein

M is a Group 4, 5, or 6 metal;

each X is independently an anionic leaving group;

y is 0 or 1; and

when y is 0 group L′

is absent;

n is the oxidation state of M;

m is the formal charge of the ligand represented by YZL or the YZL′

;

L is a Group 15 or 16 element;

L′

is a Group 15 or 16 element or Group 14 containing group;

Y is a Group 15 element;

Z is a Group 15 element;

divalent groups R¹ and R² are independently a C₁ to C₂₀ hydrocarbon group or a heteroatom containing group having up to twenty carbon atoms, the heteroatom selected from silicon, germanium, tin, lead, halogen and phosphorus;

R¹ and R² may also be interconnected to each other;

R³ is absent or a hydrocarbon group, hydrogen, a halogen, or a heteroatom containing group;

R⁴ and R⁵ are independently an alkyl group, an aryl group, substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl group, a cyclic arylalkyl group, a substituted cyclic arylalkyl group or multiple ring system;

R⁴ and R⁵ may be interconnected to each other;

R⁶ and R⁷ are independently absent, or hydrogen, an alkyl group, halogen, heteroatom or a hydrocarbyl group; and

R* is absent, or is hydrogen, a Group 14 atom containing group, a halogen, or a heteroatom containing group.

24. The composition of claim 17 wherein the bulky ligand metallocene compound is selected from compounds represented by the following formulae: