Catalyst composition comprising fluorided support and processes for use thereof

1. A catalyst system comprising the reaction product of fluorided silica support, alkylalumoxane activator and at least two metallocene catalyst compounds, where the first metallocene is a bridged monocyclopentadienyl group 4 transition metal compound and the second metallocene is a biscyclopentadienyl group 4 transition metal compound where the fluorided silica support has not been calcined at a temperature of 100° C. to less than 400° C., wherein said fluorided silica support is (a) fluorided by combining the silica support with a fluoride compound in a polar solvent and (b) free of residual fluoride compound.

2. The catalyst system of claim 1 , wherein the metallocenes are represented by the formula:

T y Cp m MG n X q

wherein each Cp is, independently, a cyclopentadienyl group which is optionally substituted or unsubstituted, M is a group 4 transition metal, G is a heteroatom group represented by the formula JR* z where J is N, P, O or S, and R* is a linear branched or cyclic hydrocarbyl group having from one to twenty carbon atoms and z is 1 or 2, T is a bridging group, and y is 0 or 1, X is a leaving group, and m=1 or 2, n=0, 1, 2 or 3, q=0, 1, 2 or 3, and the sum of m+n+q is equal to the oxidation state of the transition metal; wherein m=1, n=1 and y=1 in the first metallocene catalyst compound; and n=0 and m=2 in the second metallocene catalyst compound.

3. The catalyst system of claim 2 , wherein y is one in the second metallocene compound and at least one Cp in the second metallocene compound is not a substituted or unsubstituted indenyl group.

4. The catalyst system of claim 2 , wherein each Cp is a cyclopentadienyl, an indenyl or a fluorenyl, which is optionally substituted or unsubstituted, each M is titanium, zirconium, or hafnium, and each X is independently, a halide, a hydride, an alkyl group, an alkenyl group or an arylalkyl group.

5. The catalyst system of claim 1 , wherein the activator further comprises a non-coordinating anion activator.

6. The catalyst system of claim 1 , wherein the activator comprises methylalumoxane.

7. The catalyst system of claim 2 , wherein for the bridged monocyclopentadienyl transition metal compound m is one, n is one, J is N, z is 1 and R* is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, cyclooctyl, cyclododecyl, decyl, undecyl, dodecyl, adamantyl or an isomer thereof.

8. The catalyst system of claim 1 , wherein the bridged monocyclopentadienyl transition metal compound comprises one or more of:

dimethylsilyl (tetramethylcyclopentadienyl)(cyclododecylamido)titanium dimethyl,

dimethylsilyl (tetramethylcyclopentadienyl)(cyclododecylamido)titanium dichloride,

dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamido)titanium dimethyl,

dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamido)titanium dichloride,

μ-(CH 3 ) 2 Si(cyclopentadienyl)(1-adamantylamido)M(R) 2 ;

μ-(CH 3 ) 2 Si(3-tertbutylcyclopentadienyl)(1-adamantylamido)M(R) 2 ;

μ-(CH 3 ) 2 (tetramethylcyclopentadienyl)(1-adamantylamido)M(R) 2 ;

μ-(CH 3 ) 2 Si(tetramethylcyclopentadienyl)(1-adamantylamido)M(R) 2 ;

μ-(CH 3 ) 2 C(tetramethylcyclopentadienyl)(1-adamantylamido)M(R) 2 ;

μ-(CH 3 ) 2 Si(tetramethylcyclopentadienyl)(1-tertbutylamido)M(R) 2 ;

μ-(CH 3 ) 2 Si(fluorenyl)(1-tertbutylamido)M(R) 2 ;

μ-(CH 3 ) 2 Si(tetramethylcyclopentadienyl)(1-cyclododecylamido)M(R) 2 ;

μ-(C 6 H 5 ) 2 C(tetramethylcyclopentadienyl 1-cyclododecylamido)M(R) 2 ;

μ-(CH 3 ) 2 Si(η 5 -2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(tertbutylamido)M(R) 2 ;

where M is selected from a group consisting of Ti, Zr, and Hf and R is selected from halogen or C1 to C5 alkyl.

9. The catalyst system of claim 1 , wherein the second metallocene compound comprises one or more of: bis(tetrahydroindenyl)Hf Me 2 ; bis(1-butyl,3-methylcyclopentadienyl)ZrCl 2 ; bis-(n-butylcyclopentadienyl)ZrCl 2 ; (dimethylsilyl) 2 O bis(indenyl)ZrCl 2 ; dimethylsilyl(3-(3-methylbutyl)cyclopentadienyl)(2,3,4,5-tetramethylcyclopentadienyl)ZrCl 2 ; dimethylsilylbis(tetrahydroindenyl)ZrCl 2 ; dimethylsilyl-(3-phenyl-indenyl)(tetramethylcyclopentadienyl)ZrCl 2 ; dimethylsilyl(3-neopentylcyclopentadienyl)(tetramethylcyclopentadienyl)HfCl 2 ; tetramethyldisilylene bis(4-(3,5-di-tert-butylphenyl)-indenyl)ZrCl 2 , cyclopentadienyl(1,3-diphenylcyclopentadienyl)ZrCl 2 ; bis(cyclopentadienyl)zirconium dichloride; bis(pentamethylcyclopentadienyl)zirconium dichloride; bis(pentamethylcyclopentadienyl)zirconium dimethyl; is(pentamethylcyclopentadienyl)hafnium dichloride; bis(pentamethylcyclopentadienyl)zirconium dimethyl; bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dichloride; bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dimethyl; bis(1-methyl-3-n-butylcyclopentadienyl)hafnium dichloride; bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dimethyl; bis(indenyl)zirconium dichloride: bis(indenyl)zirconium dimethyl; bis(tetrahydro-1-indenyl)zirconium dichloride; bis(tetrahydro-1-indenyl)zirconium dimethyl; dimethylsilylbis(tetrahydroindenyl)zirconium dichloride; dimethylsilylbis(tetrahydroindenyl)zirconium dimethyl; dimethylsilylbis(indenyl)zirconium dichloride; dimethylsilyl(bisindenyl)zirconium dimethyl; dimethylsilylbis(cyclopentadienyl)zirconium dichloride; and dimethylsilylbis(cyclopentadienyl)zirconium dimethyl.

10. The catalyst system of claim 1 , wherein the first and second metallocene compounds comprise one or more of:

SiMe 2 (Me 4 Cp)(cC 12 H 23 N)TiMe 2 and bis(1-Bu-3-MeCp) ZrCl 2 :

SiMe 2 (Me 4 Cp)(cC 12 H 23 N)TiMe 2 and (SiMe 2 ) bis(indenyl)ZrCl 2 ;

SiMe 2 (Me 4 Cp)(cC 12 H 23 N)TiMe 2 and (SiMe 2 ) 2 O bis(indenyl)ZrCl 2 ;

SiMe 2 (Me 4 Cp)(cC 12 H 23 N)TiMe 2 and (SiMe 2 ) 2 O bis(indenyl)ZrMe 2 ;

SiMe 2 (Me 4 Cp)(cC 12 H 23 N)TiMe 2 and SiMe 2 (3-neopentylCp)((Me 4 Cp)HfCl 2 ;

SiMe 2 (Me 4 Cp)(cC 12 H 23 N)TiMe 2 and SiMe 2 (3-neopentylcyclopentadienyl)(Me 4 Cp)HfMe 2 ;

SiMe 2 (Me 4 Cp)(1-adamantylamido)TiMe 2 and bis(1-Bu-3-MeCp)ZrCl 2 ; and

SiMe 2 (Me 4 Cp)(1-t-butylamido)TiMe 2 and bis(1-Bu-3-MeCp)ZrCl 2 .

11. A process to produce ethylene polymer comprising: i) contacting, in the gas phase or slurry phase, ethylene and, optionally C 3 to C 20 comonomer, with a catalyst system comprising a fluorided silica support, an alkylalumoxane activator, and at least two metallocene catalyst compounds, where the first metallocene is a bridged monocyclopentadienyl group 4 transition metal compound and the second metallocene is a biscyclopentadientyl group 4 transition metal compound, where the fluorided support has not been calcined at a temperature of 100° C. to less than 400° C., wherein said fluorided silica support is (a) fluorided by combining the silica support with a fluoride compound in a polar solvent and (b) free of residual fluoride compound, and ii) obtaining an ethylene polymer comprising at least 50 mol % ethylene.

12. The process of claim 11 , wherein the ethylene polymer comprises ethylene and at least one C 3 to C 20 comonomer and has a bi-modal composition distribution.

13. The process of claim 12 , wherein the ethylene polymer has a multimodal molecular weight distribution as determined by Gel Permeation Chromatography.

14. A method of preparing fluorided silica supported catalyst systems comprising combining a fluoride compound with a polar solvent to produce a fluorided silica support free of residual fluoride compound, then combining with a slurry of non-polar solvent and the fluorided silica support, removing the non-polar solvent, thereafter combining the calcined support with a second solvent, which is optionally the same as or different from the non-polar solvent, and two catalyst compounds and activator, wherein the fluorided support is calcined at a temperature from 100 to less than 400° C., before or after combination with the activator and/or catalyst compounds.

15. The method of claim 14 , wherein the ratio (by weight) of polar solvent to non-polar solvent is between 1:10 to 1:1000.

16. The method of claim 15 , wherein the polar solvent is water and non-polar solvent is toluene, pentane, hexane, benzene, or chloroform.

17. The method of claim 15 where in the fluoride compound is one or more of NH 4 BF 4 , (NH 4 ) 2 SiF 6 , NH 4 PF 6 , NH 4 F, (NH 4 ) 2 TaF 7 , NH 4 NbF 4 , (NH 4 ) 2 GeF 6 , (NH 4 ) 2 SmF 6 , (NH 4 ) 2 TiF 6 , (NH 4 ) 2 ZrF 6 , MoF 6 , ReF 6 , GaF 3 , SO 2 ClF, F 2 , SiF 4 , SF 6 , ClF 3 , ClF 5 , BrF 5 , IF 7 , NF 3 , HF, BF 3 , NHF 2 and NH 4 HF 2 .

18. The method of claim 15 , wherein the fluoride compound comprises ammonium hexafluorosilicate, ammonium tetrafluoroborate or a mixture thereof.

19. The method of claim 11 , wherein the activator comprises methylalumoxane.

20. The method of claim 19 , wherein the activator further comprises a non-coordinating anion activator.

21. The method of claim 11 , wherein the process occurs at a temperature of from about 0° C. to about 300° C., at a pressure in the range of from about 0.35 MPa to about 10 MPa, and at a time up to 300 minutes.

22. The method of claim 11 , wherein the comonomer is present and is selected from propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene or a mixtures thereof.

23. The process of claim 11 , wherein the fluorided supported catalyst system is prepared by the method comprising combining a fluoride compound with water, then combining with a slurry of non-polar solvent and support, removing the non-polar solvent, thereafter combining the calcined support with a second solvent, which may be the same as or different from the non-polar solvent, two catalyst compounds and activator, wherein the fluorided support is calcined at a temperature from 100 to less than 400° C., before or after combination with the activator and/or catalyst compounds.

24. The method of claim 23 wherein the ratio (by weight) of water to non-polar solvent is between 1:10 to 1:1000; the non-polar solvent is toluene, pentane, hexane, benzene, or chloroform; and the fluoride compound is one or more of NH 4 BF 4 , (NH 4 ) 2 SiF 6 , NH 4 PF 6 , NH 4 F, (NH 4 ) 2 TaF 7 , NH 4 NbF 4 , (NH 4 ) 2 GeF 6 , (NH 4 ) 2 SmF 6 , (NH 4 ) 2 TiF 6 , (NH 4 ) 2 ZrF 6 , MoF 6 , ReF 6 , GaF 3 , SO 2 ClF, F 2 , SiF 4 , SF 6 , ClF 3 , ClF 5 , BrF 5 , IF 7 , NF 3 , HF, BF 3 , NHF 2 and NH 4 HF 2 .