Catalysts for producing broad molecular weight distribution polyolefins in the absence of added hydrogen

• US 8,598,061 B2
• Filed: 09/04/2012
• Issued: 12/03/2013
• Est. Priority Date: 07/06/2010
• Status: Active Grant

• Current Assignee: Chevron Phillips Chemical Company LP (Chevron Corp.)
• Original Assignee: Chevron Phillips Chemical Company LP (Chevron Corp.)
• Inventors: Yang, Qing, McDaniel, Max P., Crain, Tony R., Yu, Youlu
• Primary Examiner(s): LU, C CAIXIA
• Application Number:
  US13/602,567
• Publication Number:
  US 20120329641A1
• Time in Patent Office: 455 Days
• Field of Search: 502/113, 502/120, 502/152
• 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 2/14 Organic medium
• 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 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: C08L 23/0815 Copolymers of ethene with aliphatic 1-olefins

Abstract

The present invention provides a polymerization process utilizing a dual metallocene catalyst system for the production of broad or bimodal molecular weight distribution polymers, generally, in the absence of added hydrogen. Polymers produced from the polymerization process are also provided, and these polymers can have a Mn in a range from about 9,000 to about 30,000 g/mol, and a short chain branch content that decreases as molecular weight increases.

Claims

1. A catalyst composition capable of producing an olefin polymer having more short chain branches at Mn than at Mw, the catalyst composition comprising catalyst component I, catalyst component II, and at least one activator, wherein:

catalyst component I comprises;

a compound having formula (A);

a compound having formula (B);

a dinuclear compound formed from an alkenyl-substituted compound having formula (A), formula (B), or a combination thereof;

or

any combination thereof, wherein;

formula (A) is

2. The composition of claim 1, wherein the catalyst composition comprises at least one activator, only one ansa-metallocene compound having formula (A) or formula (B), and only one metallocene compound having formula (C), formula (D), formula (E), or formula (F).

3. The composition of claim 1, wherein the at least one activator comprises at least one activator-support comprising a solid oxide treated with an electron-withdrawing anion, wherein:

the solid oxide comprises silica, alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminophosphate, heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, a mixed oxide thereof, or any mixture thereof; and

the electron-withdrawing anion comprises sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, phospho-tungstate, or any combination thereof.

4. The composition of claim 1, wherein the catalyst composition further comprises at least one organoaluminum compound having the formula:

Al(X^A)_m(X^B)_3-m,

wherein;

X^A is a hydrocarbyl;

X^B is an alkoxide or an aryloxide, a halide, or a hydride; and

m is from 1 to 3, inclusive.

5. The composition of claim 4, wherein:

the at least one organoaluminum compound comprises trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum chloride, or any combination thereof; and

the at least one activator comprises at least one activator-support, and wherein the at least one activator-support comprises fluorided alumina, chlorided alumina, bromided alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, bromided silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, bromided silica-zirconia, sulfated silica-zirconia, fluorided silica-titania, fluorided silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, or any combination thereof.

6. The composition of claim 1, wherein the at least one activator comprises at least one aluminoxane compound, at least one organoboron or organoborate compound, at least one ionizing ionic compound, or any combination thereof.

7. The composition of claim 1, wherein catalyst component I comprises a compound having formula (A), and wherein:

X¹ and X² are independently F, Cl, Br, I, methyl, benzyl, or phenyl; and

R¹, R², and R³ are independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl, or benzyl.

8. The composition of claim 1, wherein catalyst component I comprises a compound having formula (B), and wherein:

X³ is F, Cl, Br, I, methyl, benzyl, or phenyl;

R⁴ is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl, or benzyl; and

R⁵ is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl, or benzyl.

9. The composition of claim 1, wherein catalyst component II comprises a compound having formula (C), and wherein:

X⁴ and X⁵ are independently F, Cl, Br, I, benzyl, phenyl, or methyl;

E³ is a bridging group selected from;

a cyclopentyl or cyclohexyl group,

a bridging group having the formula >

E^3AR^7AR^8A, wherein E^3A is C or Si, and R^7A and R^8A are independently H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl, or benzyl,

a bridging group having the formula —

CR^7BR^8B—

CR^7CR^8C—

, wherein R^7B, R^8B, R^7C, and R^8c are independently H or methyl, or

a bridging group having the formula —

SiR^7DR^8D—

SiR^7ER^8E—

, wherein R^7D, R^8D, R^7E, and R^8E are independently H or methyl; and

R⁹ and R¹⁰ are independently H or t-butyl.

10. The composition of claim 1, wherein catalyst component II comprises a compound having formula (D), and wherein:

X⁶ and X⁷ are independently F, Cl, Br, I, benzyl, phenyl, or methyl;

E⁴ is a bridging group selected from;

a cyclopentyl or cyclohexyl group,

a bridging group having the formula >

E^4AR^12AR^13A, wherein E^4A is C or Si, and R^12A and R^13A are independently H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl,

a bridging group having the formula —

CR^12BR^13B—

CR^12CR^13C—

, wherein R^12B, R^13B, R^12C, and R^13C are independently H or methyl, or

a bridging group having the formula —

SiR^12DR^13DSiR^12ER^13E—

, wherein R^12D, R^13D, R^12E, and R^13E are independently H or methyl; and

R¹⁴, R¹⁵, R¹⁶, and R¹⁷ are independently H or t-butyl.

11. The composition of claim 1, wherein catalyst component II comprises a compound having formula (E), and wherein:

X⁸ and X⁹ are independently F, Cl, Br, I, benzyl, phenyl, or methyl; and

E⁵ is a bridging group selected from;

a cyclopentyl or cyclohexyl group,

bridging group having the formula >

E^5AR^20AR^21A, wherein E^5A is C or Si, and R^20A and R^21A are independently H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl, or benzyl,

a bridging group having the formula —

(CH₂)_n—

, wherein n is equal to 2, 3, or 4, or

a bridging group having the formula —

SiR^20BR^21BSiR^20CR^21C, wherein R^20B, R^21B, R^20C, and R^21C are independently H or methyl.

12. The composition of claim 1, wherein catalyst component II comprises a compound having formula (F), and wherein:

X¹⁰ and X¹¹ are independently F, Cl, Br, I, benzyl, phenyl, or methyl; and

Cp² and Cp³ are independently a cyclopentadienyl or indenyl group, any substituent on Cp² and Cp³ is independently H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, phenyl, tolyl, or benzyl.

13. The composition of claim 1, wherein a weight ratio of catalyst component I to catalyst component II in the catalyst composition is in a range from about 100:

1 to about 1;

100.

14. The composition of claim 1, wherein catalyst component I comprises:

15. The composition of claim 14, wherein a weight ratio of catalyst component I to catalyst component II in the catalyst composition is in a range from about 10:

1 to about 1;

10.

16. The composition of claim 15, wherein the at least one activator comprises at least one aluminoxane compound, at least one organoboron or organoborate compound, at least one ionizing ionic compound, or any combination thereof.

17. The composition of claim 15, wherein the at least one activator comprises a solid oxide treated with an electron-withdrawing anion.

18. The composition of claim 17, wherein the catalyst composition further comprises at least one organoaluminum compound.

19. The composition of claim 15, wherein catalyst component II comprises a compound having formula (C), and wherein:

X⁴ and X⁵ are independently F, Cl, Br, I, benzyl, phenyl, or methyl;

E³ is a bridging group selected from;

a cyclopentyl or cyclohexyl group,

a bridging group having the formula >

E^3AR^7AR^8A, wherein E^3A is C or Si, and R^7A and R^8A are independently H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl, or benzyl,

a bridging group having the formula —

CR^7BR^8B—

CR^7CR^8C—

, wherein R^7B, R^7C, and R^8C are independently H or methyl, or

a bridging group having the formula —

SiR^7DR^8D —

SiR^7ER^8E—

, wherein R^7D, R^8D, R^7E, and R^8E are independently H or methyl; and

R⁹ and R¹⁰ are independently H or t-butyl.

20. The composition of claim 1, wherein catalyst component I comprises a meso isomer of:

21. The composition of claim 20, wherein a weight ratio of catalyst component I to catalyst component II in the catalyst composition is in a range from about 10:

1 to about 1;

10.

22. The composition of claim 21, wherein the at least one activator comprises at least one aluminoxane compound, at least one organoboron or organoborate compound, at least one ionizing ionic compound, or any combination thereof.

23. The composition of claim 21, wherein the at least one activator comprises a solid oxide treated with an electron-withdrawing anion.

24. The composition of claim 23, wherein the catalyst composition further comprises at least one organoaluminum compound.

25. The composition of claim 21, wherein catalyst component II comprises a compound having formula (C), and wherein:

X⁴ and X⁵ are independently F, Cl, Br, I, benzyl, phenyl, or methyl;

E³ is a bridging group selected from;

a cyclopentyl or cyclohexyl group,

a bridging group having the formula >

E^3AR^7AR^8A, wherein E^3A is C or Si, and R^7A and R^8A are independently H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl, or benzyl,

a bridging group having the formula —

CR^7BR^8B—

CR^7CR^8C—

, wherein R^7B, R^8B, R^7C, and R^8C are independently H or methyl, or

a bridging group having the formula —

SiR^7DR^8D—

SiR^7ER^8E—

, wherein R^7D, R^8D, R^7E, and R^8E are independently H or methyl; and

R⁹ and R¹⁰ are independently H or t-butyl.