Dual metallocene catalysts for polymerization of bimodal polymers

• US 8,138,113 B2
• Filed: 04/26/2011
• Issued: 03/20/2012
• Est. Priority Date: 02/22/2006
• Status: Active Grant

• Current Assignee: Chevron Phillips Chemical Company LP (Chevron Corp.)
• Original Assignee: Chevron Phillips Chemical Company LP (Chevron Corp.)
• Inventors: Yang, Qing, Jayaratne, Kumudini C., Jensen, Michael D., McDaniel, Max P., Martin, Joel L., Thorn, Matthew G., Lanier, Jerry T., Crain, Tony R.
• Primary Examiner(s): LU, C CAIXIA
• Application Number:
  US13/094,174
• Publication Number:
  US 20110201770A1
• Time in Patent Office: 329 Days
• Field of Search: 502/103, 502/113, 502/120, 502/152, 526/113, 526/114, 526/129, 526/160, 526/165, 526/943
• US Class Current: 502/113
• 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 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 2410/07 Catalyst support treated by an anion, e.g. Cl-, F-, SO42-
• CPC Class Codes: C08F 2500/04 Broad molecular weight distribution, i.e. Mw/Mn > 6
• CPC Class Codes: C08F 2500/12 Melt flow index or melt flow ratio
• 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
• CPC Class Codes: Y10S 526/943 Polymerization with metallocene catalysts

Abstract

This invention relates to catalyst compositions, methods, and polymers encompassing at least one first Group 4 metallocene compound comprising bridging η⁵-cyclopentadienyl-type ligands, in combination with at least one second Group 4 metallocene with non-bridging η⁵-cyclopentadienyl-type ligands, typically in combination with at least one cocatalyst, and at least one activator. The compositions and methods disclosed herein provide ethylene polymers with a bimodal molecular weight distribution.

Claims

1. A catalyst composition comprising a contact product of:

1) at least one first metallocene;

     2) at least one second metallocene;

     3) optionally, at least one organoaluminum compound; and

     4) at least one activator, wherein;

a) the at least one first metallocene comprises an ansa-metallocene having the formula;

(X¹)(X²)(X³)(X⁴)M¹ 

 

(M1-A), wherein

M¹ is titanium, zirconium, or hafnium;

(X¹) and (X²) are independently a substituted cyclopentadienyl, a substituted indenyl, or a substituted fluorenyl;

one substituent on (X¹) and (X²) is a bridging group having the formula ER¹R², wherein E is a carbon atom, a silicon atom, a germanium atom, or a tin atom, and E is bonded to both (X¹) and (X²), and wherein R¹ and R² are independently an alkyl group or an aryl group, either of which having up to 12 carbon atoms, or hydrogen, wherein at least one of R¹ and R² is an aryl group;

at least one substituent on (X¹) is a substituted or an unsubstituted alkenyl group having up to 12 carbon atoms;

at least one substituent on (X²) is an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms;

or a halide;

(X³) and (X⁴) are independently;

     1) F, Cl, Br, or I;

     2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH₄;

     3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms;

or

     4) OBR^A₂ or SO₃R^A, wherein R^A is an alkyl group or an aryl group, any of which having up to 12 carbon atoms; and

any additional substituent on the substituted cyclopentadienyl, substituted indenyl, substituted fluorenyl, or substituted alkenyl group is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms;

a halide;

or hydrogen;

b) the at least one second metallocene comprises an unbridged metallocene having the formula;

i) (X⁵)(X⁶)(X⁷)(X⁸)M² 

 

(M2-A), wherein

M² is titanium, zirconium, or hafnium;

(X⁵) and (X⁶) are independently a cyclopentadienyl, an indenyl, a substituted cyclopentadienyl, or a substituted indenyl;

(X⁷) and (X⁸) are independently;

     1) F, Cl, Br, or I;

     2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH₄;

     3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms;

or

     4) OBR^B₂ or SO₃R^B, wherein R^B is an alkyl group or an aryl group, any of which having up to 12 carbon atoms; and

any substituent on the substituted cyclopentadienyl or substituted indenyl is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms;

a halide;

or hydrogen;

ii) (X⁹)(X¹⁰)(X¹¹)(X¹²)M³ 

 

(M3-A), wherein

M³ is titanium, zirconium, or hafnium;

(X⁹) is a substituted cyclopentadienyl group, wherein one substituent is an aliphatic group, an aromatic group, or a combination of aliphatic and cyclic groups, any of which having up to 20 carbon atoms;

(X¹⁰) is a substituted indenyl group, wherein one substituent is an aliphatic group, an aromatic group, or a combination of aliphatic and cyclic groups, any of which having up to 20 carbon atoms;

(X¹¹) and (X¹²) are independently;

     1) F, Cl, Br, or I;

     2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH₄;

     3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms;

or

     4) OBR^C₂ or SO₃R^C, wherein R^C is an alkyl group or an aryl group, any of which having up to 12 carbon atoms; and

any additional substituent on the substituted cyclopentadienyl or substituted indenyl is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms;

a halide;

or hydrogen;

or

iii) any combination thereof;

c) the at least one organoaluminum compound comprises a compound having the formula;

Al(X¹³)_n(X¹⁴)<sub>3−

n</sub>,

wherein (X¹³) is a hydrocarbyl having from 1 to 20 carbon atoms;

(X¹⁴) is an alkoxide or an aryloxide, any of which having from 1 to 20 carbon atoms, halide, or hydride; and

n is a number from 1 to 3, inclusive; and

d) the at least one activator comprises an organoaluminoxane compound, an organoboron or organoborate compound, or any combination thereof;

wherein the at least one organoaluminum compound is optional when at least one of the following conditions exist;

1) a) at least one of (X³) and (X⁴) is a hydrocarbyl group having up to 20 carbon atoms, H, or BH₄;

b) at least one of (X⁷) and (X⁸) is a hydrocarbyl group having up to 20 carbon atoms, H, or BH₄; and

c) at least one of (X¹¹) and (X¹²) is a hydrocarbyl group having up to 20 carbon atoms, H, or BH₄;

2) the catalyst composition comprises at least one organoaluminoxane compound;

or

3) both conditions 1 and 2 exist.

2. The catalyst composition of claim 1, wherein the at least one first metallocene comprises a compound having the formula:

3. The catalyst composition of claim 1, wherein the at least one first metallocene is:

4. The catalyst composition of claim 1, wherein the at least one second metallocene comprises an unbridged metallocene having the formula:

i) (X⁵)(X⁶)(X⁷)(X⁸)M² 

 

(M2-B), wherein

M² is zirconium or hafnium;

(X⁵) and (X⁶) are independently a cyclopentadienyl, an indenyl, a substituted cyclopentadienyl, or a substituted indenyl;

(X⁷) and (X⁸) are independently a hydrocarbyl group having up to 12 carbon atoms, H, BH₄, F, Cl, Br, or I; and

any substituent on the substituted cyclopentadienyl or substituted indenyl is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, any of which having from 1 to 20 carbon atoms;

ii) (X⁹)(X¹⁰)(X¹¹)(X¹²)M³ 

 

(M3-B), wherein

M³ is zirconium or hafnium;

(X⁹) is a substituted cyclopentadienyl group, wherein any substituent is independently a linear or branched alkyl group having from 1 to 12 carbon atoms;

(X¹⁰) is a substituted indenyl group, wherein any substituent is independently an aliphatic group, an aromatic group, or a combination of aliphatic and cyclic groups, any of which having from 1 to 20 carbon atoms; and

(X¹¹) and (X¹²) are independently a hydrocarbyl group having up to 12 carbon atoms, H, BH₄, F, Cl, Br, or I;

or

iii) any combination thereof.

5. The catalyst composition of claim 1, wherein the at least one second metallocene comprises a compound having the formula:

6. The catalyst composition of claim 1, wherein the at least one second metallocene comprises a compound having the formula:

7. The catalyst composition of claim 1, wherein the at least one second metallocene is:

8. The catalyst composition of claim 1, wherein the at least one organoaluminum compound comprises trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum ethoxide, diisobutylaluminum hydride, diethylaluminum chloride, or any combination thereof.

9. The catalyst composition of claim 1, wherein the at least one activator comprises an organoaluminoxane compound.

10. The catalyst composition of claim 1, wherein the at least one activator comprises an organoboron compound, an organoborate compound, or a combination thereof.

11. The catalyst composition of claim 1, wherein:

a) the at least one first metallocene comprises a compound having the formula;

12. The catalyst composition of claim 1, wherein:

a) the at least one first metallocene comprises a compound having the formula;

13. The catalyst composition of claim 1, wherein:

a) the at least one first metallocene comprises;

14. The catalyst composition of claim 1, wherein:

a) the at least one first metallocene is;

15. The catalyst composition of claim 1, wherein:

a) the at least one first metallocene comprises a compound having the formula;

16. The catalyst composition of claim 1, wherein:

a) the at least one first metallocene comprises a compound having the formula;

17. The catalyst composition of claim 1, wherein the at least one first metallocene comprises a compound having the formula:

18. A method of polymerizing olefins, comprising:

contacting an olefin monomer and an optional α

-olefin comonomer with the catalyst composition of claim 1 under polymerization conditions to form a polymer or copolymer.

19. A catalyst composition comprising a contact product of:

1) at least one first metallocene;

     2) at least one second metallocene; and

     3) at least one activator, wherein;

a) the at least one first metallocene comprises an ansa-metallocene having the formula;

(X¹)(X²)(X³)(X⁴)M¹ 

 

(M1-B), wherein

M¹ is titanium, zirconium, or hafnium;

(X¹) and (X²) are independently a substituted cyclopentadienyl, a substituted indenyl, or a substituted fluorenyl;

one substituent on (X¹) and (X²) is a bridging group having the formula ER¹R², wherein E is a carbon atom, a silicon atom, a germanium atom, or a tin atom, and E is bonded to both (X¹) and (X²), and wherein R¹ and R² are independently an alkyl group or an aryl group, either of which having up to 12 carbon atoms, or hydrogen, wherein at least one of R¹ and R² is an aryl group;

at least one substituent on (X¹) is a substituted or an unsubstituted alkenyl group having up to 12 carbon atoms;

at least one substituent on (X²) is an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms;

or a halide;

(X³) and (X⁴) are independently;

     1) F, Cl, Br, or I;

     2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH₄;

     3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms;

or

     4) OBR^A₂ or SO₃R^A, wherein R^A is an alkyl group or an aryl group, any of which having up to 12 carbon atoms;

wherein at least one of (X³) and (X⁴) is a hydrocarbyl group having up to 20 carbon atoms, H, or BH₄; and

any additional substituent on the substituted cyclopentadienyl, substituted indenyl, substituted fluorenyl, or substituted alkenyl group is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms;

a halide;

or hydrogen;

b) the at least one second metallocene comprises an unbridged metallocene having the formula;

i) (X⁵)(X⁶)(X⁷)(X⁸)M² 

 

(M2-C), wherein

M² is titanium, zirconium, or hafnium;

(X⁵) and (X⁶) are independently a cyclopentadienyl, an indenyl, a substituted cyclopentadienyl, or a substituted indenyl;

(X⁷) and (X⁸) are independently;

     1) F, Cl, Br, or I;

     2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH₄;

     3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms;

or

     4) OBR^B₂ or SO₃R^B, wherein R^B is an alkyl group or an aryl group, any of which having up to 12 carbon atoms;

wherein at least one of (X⁷) and (X⁸) is a hydrocarbyl group having up to 20 carbon atoms, H, or BH₄; and

any substituent on the substituted cyclopentadienyl or substituted indenyl is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms;

a halide;

or hydrogen;

ii) (X⁹)(X¹⁰)(X¹¹)(X¹²)M³ 

 

(M3-C), wherein

M³ is titanium, zirconium, or hafnium;

(X⁹) is a substituted cyclopentadienyl group, wherein one substituent is an aliphatic group, an aromatic group, or a combination of aliphatic and cyclic groups, any of which having up to 20 carbon atoms;

(X¹⁰) is a substituted indenyl group, wherein one substituent is an aliphatic group, an aromatic group, or a combination of aliphatic and cyclic groups, any of which having up to 20 carbon atoms;

(X¹¹) and (X¹²) are independently;

     1) F, Cl, Br, or I;

     2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH₄;

     3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms;

or

     4) OBR^C₂ or SO₃R^C, wherein R^C is an alkyl group or an aryl group, any of which having up to 12 carbon atoms;

wherein at least one of (X¹¹) and (X¹²) is a hydrocarbyl group having up to 20 carbon atoms, H, or BH₄; and

any additional substituent on the substituted cyclopentadienyl or substituted indenyl is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms;

a halide;

or hydrogen;

or

iii) any combination thereof; and

c) the at least one activator comprises an organoaluminoxane compound, an organoboron or organoborate compound, or any combination thereof.

20. A catalyst composition comprising a contact product of:

1) at least one first metallocene;

     2) at least one second metallocene;

     3) at least one organoaluminum compound; and

     4) at least one activator, wherein;

a) the at least one first metallocene comprises an ansa-metallocene having the formula;

(X¹)(X²)(X³)(X⁴)M¹ 

 

(M1-A), wherein

M¹ is titanium, zirconium, or hafnium;

(X¹) and (X²) are independently a substituted cyclopentadienyl, a substituted indenyl, or a substituted fluorenyl;

one substituent on (X¹) and (X²) is a bridging group having the formula ER¹R², wherein E is a carbon atom, a silicon atom, a germanium atom, or a tin atom, and E is bonded to both (X¹) and (X²), and wherein R¹ and R² are independently an alkyl group or an aryl group, either of which having up to 12 carbon atoms, or hydrogen, wherein at least one of R¹ and R² is an aryl group;

at least one substituent on (X¹) is a substituted or an unsubstituted alkenyl group having up to 12 carbon atoms;

at least one substituent on (X²) is an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms;

or a halide;

(X³) and (X⁴) are independently;

     1) F, Cl, Br, or I;

     2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH₄;

     3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms;

or

     4) OBR^A₂ or SO₃R^A, wherein R^A is an alkyl group or an aryl group, any of which having up to 12 carbon atoms; and

any additional substituent on the substituted cyclopentadienyl, substituted indenyl, substituted fluorenyl, or substituted alkenyl group is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms;

a halide;

or hydrogen;

b) the at least one second metallocene comprises an unbridged metallocene having the formula;

i) (X⁵)(X⁶)(X⁷)(X⁸)M² 

 

(M2-A), wherein

M² is titanium, zirconium, or hafnium;

(X⁵) and (X⁶) are independently a cyclopentadienyl, an indenyl, a substituted cyclopentadienyl, or a substituted indenyl;

(X⁷) and (X⁸) are independently;

     1) F, Cl, Br, or I;

     2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH₄;

     3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms;

or

     4) OBR^B₂ or SO₃R^B, wherein R^B is an alkyl group or an aryl group, any of which having up to 12 carbon atoms; and

any substituent on the substituted cyclopentadienyl or substituted indenyl is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms;

a halide;

or hydrogen;

ii) (X⁹)(X¹⁰)(X¹¹)(X¹²)M³ 

 

(M3-A), wherein

M³ is titanium, zirconium, or hafnium;

(X⁹) is a substituted cyclopentadienyl group, wherein one substituent is an aliphatic group, an aromatic group, or a combination of aliphatic and cyclic groups, any of which having up to 20 carbon atoms;

(X¹⁰) is a substituted indenyl group, wherein one substituent is an aliphatic group, an aromatic group, or a combination of aliphatic and cyclic groups, any of which having up to 20 carbon atoms;

(X¹¹) and (X¹²) are independently;

     1) F, Cl, Br, or I;

     2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH₄;

     3) a hydrocarbyloxide group, a hydrocarbylamino group, or a trihydrocarbylsilyl group, any of which having up to 20 carbon atoms;

or

     4) OBR^C₂ or SO₃R^C, wherein R^C is an alkyl group or an aryl group, any of which having up to 12 carbon atoms; and

any additional substituent on the substituted cyclopentadienyl or substituted indenyl is independently an aliphatic group, an aromatic group, a cyclic group, a combination of aliphatic and cyclic groups, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group, an arsenic group, a carbon group, a silicon group, or a boron group, any of which having from 1 to 20 carbon atoms;

a halide;

or hydrogen;

or

iii) any combination thereof;

c) the at least one organoaluminum compound comprises a compound having the formula;

Al(X¹³)_n(X¹⁴)<sub>3−

n</sub>,

wherein (X¹³) is a hydrocarbyl having from 1 to 20 carbon atoms;

(X¹⁴) is an alkoxide or an aryloxide, any of which having from 1 to 20 carbon atoms, halide, or hydride; and

n is a number from 1 to 3, inclusive; and

d) the at least one activator comprises an organoaluminoxane compound, an organoboron compound or organoborate compound, or any combination thereof.

21. The catalyst composition of claim 20, wherein:

a) the at least one first metallocene comprises a compound having the formula;