Boron-bridged bis-indenyl metallocene catalyst systems and polymers produced therefrom

Patent metadata

Field	Value
Publication number	US-9303110-B2
Application number	US-201414538830-A
Country	US
Kind code	B2
Filing date	Nov 12, 2014
Priority date	Nov 19, 2013
Publication date	Apr 5, 2016
Grant date	Apr 5, 2016

Abstract

Disclosed herein are catalyst compositions containing boron bridged, bis-indenyl metallocene compounds with an alkenyl substituent. These catalyst compositions can be used for the polymerization of olefins. For example, ethylene copolymers produced using these catalyst compositions can be characterized by a density less than 0.92 g/cm 3 and a melt index greater than 25 g/10 min.

First claim

I claim:

1. An olefin polymerization process, the process comprising:
contacting a catalyst composition with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to produce an olefin polymer, wherein the catalyst composition comprises a metallocene compound, an activator, and an optional co-catalyst,
wherein the metallocene compound has the formula:

wherein:
M is Ti, Zr, or Hf;
each X independently is a monoanionic ligand;
In A is an indenyl group with an alkenyl substituent;
In B is an indenyl group; and
each R independently is H, a C 1 to C 36 hydrocarbyl group, or a C 1 to C 36 hydrocarbylsilyl group.

2. The process of claim 1 , wherein:
the catalyst composition comprises an organoaluminum co-catalyst; and
the activator comprises a fluorided solid oxide and/or a sulfated solid oxide.

3. The process of claim 1 , wherein the activator comprises an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof.

4. The process of claim 1 , wherein:
the polymerization reactor system comprises a slurry reactor, gas-phase reactor, solution reactor, or a combination thereof; and
the olefin monomer comprises ethylene, and the olefin comonomer comprises 1-butene, 1-hexene, 1-octene, or a mixture thereof.

5. The process of claim 1 , wherein the olefin polymer is an ethylene/α-olefin copolymer characterized by a number of short chain branches (SCB) per 1000 total carbon atoms at Mn that is greater than at Mz.

6. The process of claim 1 , wherein In B has a substituent selected from H, a halide, a C 1 to C 36 hydrocarbyl group, a C 1 to C 36 halogenated hydrocarbyl group, a C 1 to C 36 hydrocarboxy group, or a C 1 to C 36 hydrocarbylsilyl group.

7. The process of claim 1 , wherein the activator comprises an activator-support, the activator-support comprising a solid oxide treated with an electron-withdrawing anion.

8. The process of claim 1 , wherein:
M is Zr or Hf;
each X independently is a halide or a C 1 to C 18 hydrocarbyl group; and
each R independently is H or a C 1 to C 18 hydrocarbyl group.

9. The process of claim 8 , wherein each R independently is a C 1 to C 6 linear or branched alkyl group.

10. The process of claim 8 , wherein In B is an indenyl group with a C 1 to C 6 linear or branched alkyl substituent.

11. The process of claim 1 , wherein In A is an indenyl group with only an alkenyl substituent, and In B is an indenyl group that does contain a substituent.

12. The process of claim 1 , wherein the alkenyl substituent is a C 3 to C 8 terminal alkenyl group.

13. The process of claim 1 , wherein the polymerization reactor system comprises a loop slurry reactor.

14. The process of claim 1 , wherein the olefin polymer is an ethylene/α-olefin copolymer characterized by:
a melt index greater than or equal to about 25 g/10 min;
a density of less than or equal to about 0.92 g/cm 3 ; and
a ratio of Mw/Mn of less than or equal to about 6.

15. The process of claim 1 , wherein the olefin polymer is an ethylene/α-olefin copolymer characterized by:
a melt index in a range from about 50 to about 2000 g/10 min; and
a density in a range from about 0.88 to about 0.92 g/cm 3 .

16. The process of claim 1 , wherein the olefin polymer is an ethylene/α-olefin copolymer characterized by:
a Mn in a range from about 3,000 to about 18,000 g/mol; and
a ratio of Mw/Mn in a range from about 2.5 to about 5.5.

17. The process of claim 1 , wherein the olefin polymer is an ethylene/α-olefin copolymer characterized by:
a Mw in a range from about 20,000 to about 55,000 g/mol; and
a ratio of Mw/Mn in a range from about 3 to about 5.

18. The process of claim 1 , wherein:
the catalyst composition comprises an organoaluminum co-catalyst;
the olefin monomer comprises ethylene or propylene;
M is Zr or Hf;
each X is Cl;
In A is an indenyl group with a C 3 to C 8 terminal alkenyl substituent; and
each R independently is H or a C 1 to C 8 hydrocarbyl group.

19. The process of claim 18 , wherein:
the activator comprises a fluorided solid oxide and/or a sulfated solid oxide; and
the polymerization reactor system comprises a slurry reactor, gas-phase reactor, solution reactor, or a combination thereof.

Assignees

• Chevron Phillips Chemical Co

Inventors

• Greco Jeffrey F

Classifications

• C08F210/16 Primary

  Copolymers of ethene with alpha-alkenes, e.g. EP rubbers · CPC title

• C08F2500/09

  Long chain branches · CPC title

• C08F2500/08

  Low density, i.e. < 0.91 g/cm3 · CPC title

• C08F4/025

  Metal oxides · CPC title

• C08F4/65916

  supported on a carrier, e.g. silica, MgCl2, polymer · CPC title