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

Patent metadata

Field	Value
Publication number	US-9481750-B2
Application number	US-201615044140-A
Country	US
Kind code	B2
Filing date	Feb 16, 2016
Priority date	Nov 19, 2013
Publication date	Nov 1, 2016
Grant date	Nov 1, 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. A catalyst composition comprising 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 composition of claim 1 , wherein the activator comprises an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof.

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

4. A metallocene compound having 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.

5. The compound of claim 4 , 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.

6. The compound of claim 4 , wherein In A is an indenyl group with only an alkenyl substituent, and In B is an indenyl group that does contain a substituent.

7. The compound of claim 4 , wherein In A is an indenyl group with only an alkenyl substituent, and In B is an indenyl group that does not contain a substituent.

8. The compound of claim 4 , wherein each R independently is a C 1 to C 6 linear or branched alkyl group.

9. The compound of claim 4 , wherein In B is an indenyl group with a C 1 to C 6 linear or branched alkyl substituent.

10. The compound of claim 4 , wherein the alkenyl substituent is a C 3 to C 8 terminal alkenyl group.

11. The compound of claim 4 , wherein:
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.

12. The compound of claim 11 , wherein each R independently is a C 1 to C 6 linear or branched alkyl group.

13. The compound of claim 4 , wherein:
In A is an indenyl group with only an alkenyl substituent; and
each R independently is H or a C 1 to C 18 hydrocarbyl group.

14. The composition 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.

15. The composition 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.

16. The composition of claim 1 , wherein the activator comprises an aluminoxane compound.

17. The composition of claim 16 , 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.

18. The composition of claim 17 , wherein:
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 C 1 to C 6 linear or branched alkyl group.

19. The composition of claim 1 , wherein the activator comprises fluorided alumina, sulfated alumina, fluorided silica-alumina, sulfated silica-alumina, fluorided silica-coated alumina, sulfated silica-coated alumina, or any combination thereof.

20. The composition of claim 1 , wherein:
In A is an indenyl group with only an alkenyl substituent; and
each R independently is H or a C 1 to C 18 hydrocarbyl group.

21. The composition of claim 20 , wherein:
M is Zr or Hf;
In B is an indenyl group with one substituent;
each X independently is a halide or a C 1 to C 18 hydrocarbyl group; and
each R independently is C 1 to C 6 linear or branched alkyl group.

22. The composition of claim 20 , wherein:
each X is Cl; and
the alkenyl substituent is a C 3 to C 8 terminal alkenyl group.

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Greco Jeffrey F

Classifications

• C08F210/16 Primary

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

• C08F2500/03

  Narrow molecular weight distribution, i.e. Mw/Mn < 3 · CPC title

• C08F4/65927

  two cyclopentadienyl rings being mutually bridged · CPC title

• C08F4/65916

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

• C08F2500/08

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