Catalyst systems containing boron-bridged cyclopentadienyl-fluorenyl metallocene compounds with an alkenyl substituent

Patent metadata

Field	Value
Publication number	US-9303109-B2
Application number	US-201414533161-A
Country	US
Kind code	B2
Filing date	Nov 5, 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, cyclopentadienyl-fluorenyl 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 combination of a flat or a conventional comonomer distribution and low levels of long chain branching.

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;
Cp A is a cyclopentadienyl group with an alkenyl substituent;
Cp B is a fluorenyl 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.

3. The process of claim 1 , wherein the activator comprises a fluorided solid oxide and/or a sulfated solid oxide.

4. 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.

5. 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.

6. 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;
each R independently is H or a C 1 to C 18 hydrocarbyl group;
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.

7. The process of claim 1 , wherein the process is capable of decreasing a density of an olefin copolymer by at least about 0.003 g/cm 3 , based on an increase in comonomer:monomer molar ratio from 0.034:1 to 0.068:1.

8. The process of claim 1 , wherein the olefin polymer is an ethylene polymer characterized by less than about 0.005 long chain branches (LCB) per 1000 total carbon atoms.

9. The process of claim 1 , wherein the olefin polymer is an ethylene/α-olefin copolymer characterized by a conventional comonomer distribution or a substantially flat comonomer distribution.

10. The process of claim 1 , wherein the ratio of Mw/Mn of the olefin polymer increases as the amount of hydrogen added to the polymerization reactor system increases.

11. 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;
Cp B is a substituted fluorenyl group; and
each R independently is H or a C 1 to C 18 hydrocarbyl group.

12. The process of claim 1 , wherein:
M is Zr or Hf;
each X independently is Cl, methyl, phenyl, or benzyl;
Cp A is a cyclopentadienyl group with only one alkenyl substituent;
Cp B is a substituted fluorenyl group; and
each R independently is a C 1 to C 6 alkyl group.

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

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

15. The process of claim 1 , wherein the catalyst composition comprises an organoaluminum co-catalyst, and wherein the activator comprises an activator-support, the activator-support comprising fluorided alumina, sulfated alumina, fluorided silica-alumina, sulfated silica-alumina, fluorided silica-coated alumina, sulfated silica-coated alumina, or any combination thereof.

16. The process of claim 1 , wherein a catalyst activity of the catalyst composition is greater than about 100,000 grams of ethylene polymer per gram of the metallocene compound per hour, under slurry polymerization conditions, with a triisobutylaluminum co-catalyst, using isobutane as a diluent, and with a polymerization temperature of 80° C. and a reactor pressure of 390 psig.

17. The process of claim 1 , wherein:
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 catalyst composition is contacted with ethylene and an olefin comonomer comprising 1-butene, 1-hexene, 1-octene, or a mixture thereof.

18. The process of claim 17 , 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.

19. The process of claim 17 , wherein:
M is Zr or Hf;
each X independently is Cl, methyl, phenyl, or benzyl;
each R independently is a C 1 to C 6 alkyl group; and
the polymerization reactor system comprises a loop slurry reactor.

Assignees

• Chevron Phillips Chemical Co

Inventors

• Greco Jeffrey F

Classifications

• C08F4/65916

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

• C08L23/0815

  with aliphatic 1-olefins containing one carbon-to-carbon double bond · CPC title

• C08F210/16 Primary

  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

• C08F4/65904

  in combination with another component of C08F4/64 · CPC title