Catalyst Composition Comprising Fluorided Support and Processes for Use Thereof

• US 20180171040A1
• Filed: 03/10/2016
• Published: 06/21/2018
• Est. Priority Date: 04/20/2015
• Status: Active Grant

• Current Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Original Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Inventors: YE, Xuan, HOLTCAMP, Matthew W., LUO, Lubin, McCULLOUGH, Laughlin G., DAY, Gregory S., RIX, Francis C., CANICH, Jo Ann M., SANDERS, David F., BEDOYA, Matthew S.
• Granted Patent: US 10,640,583 B2
• Time in Patent Office: Days
• CPC Class Codes: C08F 10/02 Ethene
• 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 2410/07 Catalyst support treated by an anion, e.g. Cl-, F-, SO42-
• CPC Class Codes: C08F 2420/02 Cp or analog bridged to a non-Cp X anionic donor
• CPC Class Codes: C08F 2420/10 Heteroatom-substituted bridge, i.e. Cp or analog where the bridge linking the two Cps or analogs is substituted by at least one group that contains a heteroatom
• CPC Class Codes: C08F 2420/12 Long bridge, i.e. Cp or analog where the bridging unit linking the two Cps or analogs is composed of at least two atoms which are not part of a cycle and which are not an ethylene bridge
• CPC Class Codes: C08F 2500/05 Bimodal or multimodal molecular weight distribution
• CPC Class Codes: C08F 2500/08 Low density, i.e. < 0.91 g/cm3
• CPC Class Codes: C08F 2500/12 Melt flow index or melt flow ratio
• CPC Class Codes: C08F 2500/18 Bulk density
• CPC Class Codes: C08F 4/02 Carriers therefor
• 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 4/6592 containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
• CPC Class Codes: C08F 4/65927 two cyclopentadienyl rings being mutually bridged

Abstract

This invention relates to a catalyst system comprising fluorided silica, 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 400° C. or more, and is preferably produced using a west mixing method, such as an aqueous method.

Claims

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 biscyclopentadientyl group 4 transition metal compound where the fluorided silica support has not been calcined at a temperature of 400°

C. or more.

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

T_yCp_mMG_nX_q

wherein each Cp is, independently, a cyclopentadienyl group which may be 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 indene group.

4. The catalyst system of claim 2, wherein each Cp is a cyclopentadiene, indene or fluorene, which may be 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 1, wherein for the bridged monocyclopentadienyl transition metal compound m is one, n is one, J is N, 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

-(CH₃)₂Si(cyclopentadienyl)(1-adamantylamido)M(R)₂;

μ

-(CH₃)₂Si(3-tertbutylcyclopentadienyl)(1-adamantylamido)M(R)₂;

μ

-(CH₃)₂(tetramethylcyclopentadienyl)(1-adamantylamido)M(R)₂;

μ

-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-adamantylamido)M(R)₂;

μ

-(CH₃)₂C(tetramethylcyclopentadienyl)(1-adamantylamido)M(R)₂;

μ

-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-tertbutylamido)M(R)₂;

μ

-(CH₃)₂Si(fluorenyl)(1-tertbutylamido)M(R)₂;

μ

-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-cyclododecylamido)M(R)₂;

μ

-(C₆H₅)₂C(tetramethylcyclopentadienyl)(1-cyclododecylamido)M(R)₂;

μ

-(CH₃)₂Si(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 Me₂;

Bis(1-butyl,3-methylcyclopentadienyl)ZrCl₂;

Bis-(n-butylcyclopentadienyl)ZrCl₂;

(Dimethylsilyl)₂O bis(indenyl)ZrCl₂;

Dimethylsilyl(3-(3-methylbutyl)cyclopentadienyl)(2,3,4,5-tetramethylcyclopentadienyl)ZrCl₂;

Dimethylsilylbis(tetrahydroindenyl)ZrCl₂;

Dimethylsilyl-(3-phenyl-indenyl)(tetramethylcyclopentadienyl)ZrCl₂;

Dimethylsilyl(3-neopentylcyclopentadienyl)(tetramethylcyclopentadienyl)HfCl₂;

Tetramethyldisilylene bis(4-(3,5-di-tert-butylphenyl)-indenyl)ZrCl₂;

Cyclopentadienyl(1,3-diphenylcyclopentadienyl)ZrCl₂;

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)zixconium 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:

SiMe₂(Me₄Cp)(cC₁₂N)TiMe₂ and bis(1-Bu,3-Me-Cp) ZrCl₂;

SiMe₂(Me₄Cp)(cC₁₂N)TiMe₂ and (SiMe₂) bis(indenyl)ZrCl₂;

SiMe₂(Me₄Cp)(cC₁₂N)TiMe₂ and (SiMe₂)₂O bis(indenyl)ZrCl₂;

SiMe₂(Me₄Cp)(cC₁₂N)TiMe₂ and (SiMe₂)₂O bis(indenyl)ZrMe₂;

SiMe₂(Me₄Cp)(cC₁₂N)TiMe₂and SiMe₂(3-neopentylCp)((Me₄Cp)HfCl₂;

SiMe₂(Me₄Cp)(cC₁₂N)TiMe₂ and SiMe₂(3-neopentylcyclopentadienyl)(Me₄Cp)HfMe₂;

SiMe₂(Me₄Cp)(1-adamantylamido)TiMe₂ and bis(1-Bu,3-MeCp)ZrCl₂; and

SiMe₂(Me₄Cp)(1-t-butylamido)TiMe₂ and bis(1-Bu,3-MeCp)ZrCl₂.

11. The catalyst system of claim 1, wherein the flourided support has been calcined at a temperature of 100 to less than 400°

C.

12. A process to produce ethylene polymer comprising:

i) contacting, in the gas phase or slurry phase, ethylene and, optionally C₃ to C₂₀ 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 400°

C. or more, and ii) obtaining an ethylene polymer comprising at least 50 mol % ethylene.

13. The process of claim 12, wherein the ethylene polymer comprises ethylene and at least one C₃ to C₂₀ comonomer and has a bi-modal composition distribution.

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

20. The method of claim 12, wherein the activator comprises methylalumoxane.

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

22. The method of claim 12, 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.

23. The method of claim 12, wherein the comonomer is present and is selected from propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene or a mixtures thereof.

24. The process of claim 12, 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.

25. The method of claim 24 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 NH₄BF₄, (NH₄)₂SiF₆, NH₄PF₆, NH₄F, (NH₄)₂TaF₇, NH₄NbF₄, (NH₄)₂GeF₆, (NH₄)₂SmF₆, (NH₄)₂TiF₆, (NH₄)₂ZrF₆, MoF₆, ReF₆, GaF₃, SO₂ClF, F₂, SiF₄, SF₆, ClF₃, ClF₅, BrF₅, IF, NF₃, HF, BF₃, NHF₂ and NH₄HF₂.

15. A method of preparing fluorided silica supported catalyst systems comprising combining a fluoride compound with a polar solvent, then combining with a slurry of non-polar solvent and silica 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, 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.

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

10 to 1;

1000.

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

18. The method of claim 16 where in the fluoride compound is one or more of NH₄BF₄, (NH₄)₂SiF₆, NH₄PF₆, NH₄F, (NH₄)₂TaF₇, NH₄NbF₄, (NH₄)₂GeF₆, (NH₄)₂SmF₆, (NH₄)₂TiF₆, (NH₄)₂ZrF₆, MoF₆, ReF₆, GaF₃, SO₂ClF, F₂, SiF₄, SF₆, ClF₃, ClF₅, BrF₅, IF₇, NF₃, HF, BF₃, NHF₂ and NH₄HF₂.

19. The method of claim 16, wherein the fluoride compound comprises ammonium hexafluorosilicate, ammonium tetrafluoroborate or a mixture thereof.