Bicyclic bridged metallocene compounds and polymers produced therefrom

Patent metadata

Field	Value
Publication number	US-9758600-B1
Application number	US-201715465643-A
Country	US
Kind code	B1
Filing date	Mar 22, 2017
Priority date	May 25, 2016
Publication date	Sep 12, 2017
Grant date	Sep 12, 2017

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. 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 saturated hydrocarbon bicyclic bridging group with a single carbon atom connected to Cp 1 and Cp 2 ; and
Cp 1 and Cp 2 independently are a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group.

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

4. The process of claim 1 , wherein at least one of Cp 1 and Cp 2 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.

5. The process of claim 1 , wherein at least one of Cp 1 and Cp 2 has a substituent selected from a C 1 to C 8 alkyl group or a C 3 to C 8 terminal alkenyl group.

6. The process of claim 1 , wherein:
E is a decalin group; and
at least one of Cp 1 and Cp 2 has a C 1 to C 18 hydrocarbyl substituent.

7. The process of claim 6 , wherein each X is Cl.

8. 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.

9. 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.

10. 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.

11. 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.

12. The process of claim 1 , 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.

13. The process of claim 1 , wherein the olefin polymer is an ethylene polymer characterized by:
a melt index in a range from about 10 to about 200 g/10 min;
a Mn in a range from about 12,000 to about 35,000 g/mol; and
a Mw in a range from about 27,000 to about 65,000 g/mol.

14. The process of claim 13 , wherein the process is conducted in the absence of added hydrogen, and the ethylene polymer is an ethylene homopolymer or an ethylene/α-olefin copolymer.

15. 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 an aromatic hydrocarbon bicyclic bridging group with a single carbon atom connected to Cp 1 and Cp 2 ; and
Cp 1 and Cp 2 independently are a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group.

16. The process of claim 15 , wherein:
M is Zr;
each X is Cl;
Cp 1 is a substituted or unsubstituted indenyl or fluorenyl group; and
Cp 2 is a substituted or unsubstituted cyclopentadienyl group.

17. The process of claim 16 , wherein E is a tetralin group.

18. The process of claim 15 , wherein:
the olefin polymer comprises an ethylene homopolymer or an ethylene/α-olefin copolymer; and
the activator comprises an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof.

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

20. The process of claim 15 , wherein the olefin polymer is an ethylene polymer characterized by:
a melt index greater than 500 g/10 min;
a Mn in a range from about 3,000 to about 13,000 g/mol; and
a Mw in a range from about 10,000 to about 25,000 g/mol.

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 Primary

  two cyclopentadienyl rings being mutually bridged · CPC title

• C08F210/16

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

• C08F4/65908

  in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+ · CPC title

• C08F2420/11

  Non-aromatic cycle-substituted bridge, i.e. Cp or analog where the bridge linking the two Cps or analogs is substituted by a non-aromatic cycle · CPC title