Process for producing polymers

• US 20020007023A1
• Filed: 07/19/2001
• Published: 01/17/2002
• Est. Priority Date: 05/18/1998
• Status: Active Grant

• Current Assignee: Chevron Phillips Chemical Company LP (Chevron Corp.)
• Original Assignee: Christopher E. Wittner, Elizabeth A. Benham, Gil R. Hawley, James L. Smith, Kathy S. Collins, Max P. McDaniel, Michael D. Jensen, Shirley J. Martin
• Inventors: Hawley, Gil R., Jensen, Michael D., Benham, Elizabeth A., Smith, James L., McDaniel, Max P., Collins, Kathy S., Martin, Shirley J., Wittner, Christopher E.
• Granted Patent: US 6,831,141 B2
• Time in Patent Office: Days
• US Class Current: 526/64
• CPC Class Codes: B01J 21/04 Alumina
• CPC Class Codes: B01J 21/08 Silica
• CPC Class Codes: B01J 21/12 Silica and alumina
• 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 27/053 Sulfates
• CPC Class Codes: B01J 27/125 with scandium, yttrium, aluminium, gallium, indium or thallium
• CPC Class Codes: B01J 31/143 of aluminium
• CPC Class Codes: B01J 31/1608 the ligands containing silicon
• CPC Class Codes: B01J 31/2295 Cyclic compounds, e.g. cyclopentadienyls
• CPC Class Codes: B01J 31/38 of titanium, zirconium or hafnium
• CPC Class Codes: B01J 35/60 characterised by their surface properties or porosity
• CPC Class Codes: B01J 37/0207 Pretreatment of the support
• 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 110/02 Ethene
• CPC Class Codes: C08F 2410/07 Catalyst support treated by an anion, e.g. Cl-, F-, SO42-
• CPC Class Codes: C08F 2500/03 Narrow molecular weight distribution, i.e. Mw/Mn < 3
• CPC Class Codes: C08F 2500/12 Melt flow index or melt flow ratio
• 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

Abstract

This invention provides a compositions that are useful for polymerizing at least one monomer into at least one polymer.

Claims

1. A process to produce a composition of matter, said process comprising contacting an organometal compound, a treated solid oxide compound, and an organoaluminum compound to produce said composition,

wherein said composition consists essentially of a post-contacted organometal compound, a post-contacted treated solid oxide compound, and optionally, a post-contacted organoaluminum compound, and

wherein said composition can polymerize ethylene into a polymer with an activity greater than a composition that uses the same organometal compound, and the same organoaluminum compound, but uses untreated Ketjen grade B alumina instead of said treated solid oxide compound, and

wherein said organometal compound has the following general formula

(X¹)(X²)(X³)(X⁴)M¹

wherein M is selected from the group consisting of titanium, zirconium, and hafnium, and wherein (X¹) is independently selected from the group consisting of cyclopentadienyls, indenyls, fluorenyls, substituted cyclopentadienyls, substituted indenyls, and substituted fluorenyls, and wherein said substituents on said substituted cyclopentadienyls, substituted indenyls, and substituted fluorenyls, are selected from the group consisting of aliphatic groups, cyclic groups, combinations of aliphatic and cyclic groups, and organometallic groups, and hydrogen;

and wherein (X³) and (X⁴) are independently selected from the group consisting of halides, aliphatic groups, cyclic groups, combinations of aliphatic and cyclic groups, and organometallic groups, and wherein (X²) is selected from the group consisting of Group OMC-I or Group OMC-II, and

wherein said organoaluminun compound has the following general formula.

Al(X⁵)_n(X⁶)<sub>3−

n</sub>

wherein (X⁵) is a hydrocarbyl having from 1-20 carbon atoms, and

wherein (X⁶) is a halide, hydride, or alkoxide, and

wherein “

n”

is a number from 1 to 3 inclusive.

2. A process to produce a composition of matter, said process comprising contacting an organometal compound, a treated solid oxide compound, and an organoaluminum compound to produce said composition,

wherein said composition consists essentially of a post-contacted organometal compound, a post-contacted treated solid oxide compound, and optionally, a post-contacted organoaluminum compound, and

wherein said composition can polymerize ethylene into a polymer with an activity greater than 100 (gP/(gS·

hr)), and

wherein said organometal compound has the following general formula

(X¹)(X²)(X³)(X⁴)M¹

wherein M¹ is selected from the group consisting of titanium, zirconium, and hafnium, and

wherein (X¹) is independently selected from the group consisting of cyclopentadienyls, indenyls, fluorenyls, substituted cyclopentadienyls, substituted indenyls, and substituted fluorenyls. and wherein said substituents on said substituted cyclopentadienyls, substituted indenyls, and substituted fluorenyls, are selected from the group consisting of aliphatic groups, cyclic groups, combinations of aliphatic and cyclic groups, and organometallic groups, and hydrogen; and

wherein (X³) and (X⁴) are independently selected from the group consisting of halides, aliphatic groups, cyclic groups, combinations of aliphatic and cyclic groups, and organometallic groups, and wherein (X²) is selected from the group consisting of Group OMC-I or Group OMC-II, and

wherein said organoaluminun compound has the following general formula.

Al(X⁵)_n(X⁶)<sub>3−

n</sub>

wherein (X⁵) is a hydrocarbyl having from 1-20 carbon atoms, and

wherein (X⁶) is a halide, hydride, or alkoxide, and

wherein “

n”

is a number from 1 to 3 inclusive, and

wherein said treated solid oxide compounds comprise oxygen and at least one element selected from the group consisting of groups 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, and 15 of the periodic table, including lanthanides and actinides.

3. A process according to claim 2 wherein said activity is greater than 250.

4. A process according to claim 3 wherein said activity is greater than 500.

5. A process according to claim 4 wherein said activity is greater than 1000.

6. A process according to claim 5 wherein said activity is greater than 2000.

7. A composition produced by the process of claim 2.

8. A process of using the composition of claim 7 to polymerize monomers into polymers.

9. A manufacture that comprises polymers produced according to claim 8.

10. A machine that comprises manufactures according to claim 9.

11. A process according to claim 8 wherein said polymers are produced under slurry polymerization conditions.

12. A process according to claim 11 wherein said polymerization is conducted in a loop reactor.

13. A process according to claim 12 wherein said polymerization is conducted in the presence of a diluent that comprises, in major part, isobutane.

14. A manufacture that comprises polymers produced according to claim 13.

15. A machine that comprises manufactures according to claim 14.

16. A composition produced by the process of claim 6.

17. A process of using the composition of claim 16 to polymerize monomers into polymers.

18. A manufacture that comprises polymers produced according to claim 17.

19. A machine that comprises manufactures according to claim 18.

20. A process according to claim 17 wherein said polymers are produced under slurry polymerization conditions.

21. A process according to claim 20 wherein said polymerization is conducted in a loop reactor.

22. A process according to claim 21 wherein said polymerization is conducted in the presence of a diluent that comprises, in major part, isobutane.

23. A manufacture that comprises polymers produced according to claim 22.

24. A machine that comprises manufactures according to claim 23.

25. A process to produce a composition of matter, said process comprising contacting an organometal compound, a treated solid oxide compound, and an organoaluminum compound to produce said composition,

wherein said composition consists essentially of a post-contacted organometal compound, a post-contacted treated solid oxide compound, and optionally, a post-contacted organoaluminum compound, and

wherein said composition can polymerize ethylene into a polymer with an activity greater than 2000 (gpl(gS·

hr)), and

wherein said organometal compound is selected from the group consisting of

bis(cyclopentadienyl) hafnium dichloride;

bis(cyclopentadienyl) zirconium dichloride;

[ethyl(indenyl)₂] hafnium dichloride;

[ethyl(indenyl)₂] zirconium dichloride;

[ethyl(tetrahydroindenyl)₂] hafnium dichloride;

[ethyl(tetrahydroindenyl)₂] zirconium dichloride;

bis(n-butylcyclopentadienyl ) hafnium dichloride;

bis(n-butylcyclopentadienyl) zirconium dichloride;

((dimethyl)(diindenyl) silane) zirconium dichloride;

((dimethyl)(diindenyl) silane) hafnium dichloride;

((dimethyl)(ditetrahydroindenyl) silane) zirconium dichloride;

((dimethyl)(di(2-methyl indenyl)) silane) zirconium dichloride;

bis(fluorenyl) zirconium dichloride, and

wherein said organoaluminum compound is selected from the group consisting of

trimethylaluminum;

triethylaluminum;

tripropylaluminum;

diethylaluminum ethoxide;

tributylaluminum;

triisobutylaluminum hydride;

triisobutylaluminum;

diethylaluminum chloride, and

wherein said solid oxide compounds are selected from the group consisting of Al₂O₃, B₂O₃, BeO, Bi₂O₃, CdO, Co₃O₄, Cr₂,O₃, CuO, Fe₂O₃, Ga₂O₃, La₂O₃, Mn₂O₃, MoO₃, NiO, P₂O₅, Sb₂O₅, SiO₂, SnO₂, SrO, ThO₂, TiO₂, V₂O₅,WO₃, Y₂O₃, ZnO, ZrO₂; and

mixtures thereof, and wherein said treated solid oxides have been treated with fluoride or chloride or both.