Bicyclic bridged metallocene compounds and polymers produced therefrom

Patent metadata

Field	Value
Publication number	US-10112965-B2
Application number	US-201715666663-A
Country	US
Kind code	B2
Filing date	Aug 2, 2017
Priority date	May 25, 2016
Publication date	Oct 30, 2018
Grant date	Oct 30, 2018

Abstract

Disclosed herein are catalyst compositions containing bicyclic bridged metallocene compounds. These catalyst compositions can be used for the polymerization of olefins. For example, ethylene polymers produced using these catalyst compositions can be characterized by low molecular weights and high melt flow rates, and can be produced without the addition of hydrogen.

First claim

We claim:

1. A metallocene compound having the formula:

wherein:
M is Ti, Zr, or Hf;
each X independently is a monoanionic ligand;
E is a norbornane group, a norbornene group, a norbornadiene group, an indane group, an indene group, or a dicyclopentadiene group; and
Cp 1 and Cp 2 independently are a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group.

2. The compound of claim 1 , wherein:
M is Zr;
each X independently is a halide, a C 1 to C 18 hydrocarbyl group, or a C 1 to C 18 hydrocarbylaminyl group;
Cp 1 is a substituted or unsubstituted indenyl or fluorenyl group; and
Cp 2 is a substituted or unsubstituted cyclopentadienyl group.

3. The compound of claim 1 , wherein E is a norbornane group.

4. The compound of claim 1 , wherein E is a norbornene group.

5. The compound of claim 1 , wherein E is a norbornadiene group.

6. The compound of claim 1 , wherein E is an indane group.

7. The compound of claim 1 , wherein E is an indene group.

8. The compound of claim 1 , wherein E is a dicyclopentadiene group.

9. The compound of claim 1 , wherein at least one of Cp 1 and Cp 2 is unsubstituted.

10. The compound of claim 9 , wherein each X is Cl.

11. The compound of claim 1 , wherein:
M is Zr;
each X is Cl;
Cp 1 is a substituted or unsubstituted indenyl or fluorenyl group;
Cp 2 is a substituted or unsubstituted cyclopentadienyl group; and
at least one of Cp 1 and Cp 2 has a C 1 to C 18 hydrocarbyl substituent.

12. 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;
E is a norbornane group, a norbornene group, a norbornadiene group, an indane group, an indene group, or a dicyclopentadiene group; and
Cp 1 and Cp 1 independently are a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group.

13. The composition of claim 12 , wherein the activator comprises an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof.

14. The composition of claim 12 , wherein the activator comprises an activator-support, the activator-support comprising a solid oxide treated with an electron-withdrawing anion.

15. The composition of claim 12 , wherein:
the catalyst composition comprises an organoaluminum co-catalyst; and
the activator comprises a fluorided solid oxide and/or a sulfated solid oxide.

16. 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;
E is a norbornane group, a norbornene group, a norbornadiene group, an indane group, an indene group, or a dicyclopentadiene group; and
Cp 1 and Cp 1 independently are a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group.

17. The process of claim 16 , 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.

18. The process of claim 16 , wherein:
the olefin polymer comprises an ethylene homopolymer or an ethylene/α-olefin copolymer; and
the activator comprises an activator-support, an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof.

19. The process of claim 16 , wherein E is a norbornane group, a norbornene group, or a norbornadiene group.

20. The process of claim 16 , wherein E is an indane group or an indene group.

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Praetorius Jeremy M
• Yang Qing
• Boxell Connor D
• Crain Tony R

Classifications

• C07F17/00 Primary

  Metallocenes · CPC title

• C08F4/65927

  two cyclopentadienyl rings being mutually bridged · CPC title

• C08F4/65912

  in combination with an organoaluminium compound · CPC title

• C08F2500/03

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

• C08F210/16

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