Higher density polyolefins with improved stress crack resistance

Patent metadata

Field	Value
Publication number	US-9605100-B2
Application number	US-201615193195-A
Country	US
Kind code	B2
Filing date	Jun 27, 2016
Priority date	Sep 5, 2013
Publication date	Mar 28, 2017
Grant date	Mar 28, 2017

Abstract

Disclosed herein are polymerization processes for the production of olefin polymers. These polymerization processes can employ a catalyst system containing two or three metallocene components, resulting in ethylene-based copolymers that can have a medium density and improved stress crack resistance.

First claim

The invention claimed is:

1. A catalyst composition comprising:
catalyst component I comprising an unbridged Group IV transition metal based metallocene compound;
catalyst component II comprising a bridged Group IV transition metal based metallocene compound with a fluorenyl group;
catalyst component III comprising a half-metallocene compound having formula (IIIA):

 wherein:
Ind is an indenyl group; and
each X independently is a monoanionic ligand;

an activator; and
optionally, a co-catalyst.

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. 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:
an unbridged metallocene compound containing two cyclopentadienyl groups, two indenyl groups, or a cyclopentadienyl and an indenyl group;
a bridged metallocene compound with a cyclopentadienyl group and fluorenyl group, and an alkenyl substituent on the cyclopentadienyl group and/or on the bridging group;
a half-metallocene compound having formula (IIIA):

 wherein:
Ind is an indenyl group; and
each X independently is a monoanionic ligand;

an activator-support comprising a solid oxide treated with an electron-withdrawing anion; and
an organoaluminum compound.

4. The process of claim 3 , wherein:
the activator-support comprises a fluorided solid oxide and/or a sulfated solid oxide;
the organoaluminum compound comprises trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum chloride, or any combination thereof;
catalyst component I comprises an unbridged metallocene compound having formula (I) and catalyst component II comprises a bridged metallocene compound having formula (II):

each M independently is Zr or Hf;
Cp A and Cp B independently are a cyclopentadienyl or indenyl group;
Cp is a cyclopentadienyl group;
each X independently is a monoanionic ligand;
R X and R Y independently are 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; and
E is a bridging group.

5. The process of claim 3 , wherein the polymerization reactor system comprises a slurry reactor, gas-phase reactor, solution reactor, or a combination thereof.

6. The process of claim 3 , wherein the catalyst composition is contacted with ethylene and an olefin comonomer comprising 1-butene, 1-hexene, 1-octene, or a mixture thereof.

7. The composition of claim 1 , wherein:
the catalyst composition comprises a co-catalyst;
catalyst component I comprises an unbridged zirconium based metallocene compound containing two cyclopentadienyl groups, two indenyl groups, or a cyclopentadienyl and an indenyl group; and
catalyst component II comprises a bridged zirconium or hafnium based metallocene compound with a cyclopentadienyl group and a fluorenyl group.

8. The composition of claim 7 , wherein:
a weight ratio of catalyst component I to catalyst component II is from about 10:1 to about 1:10; and
a weight percentage of catalyst component III is in a range from about 5 to about 50 wt. %, based on the total weight of catalyst components I, II, and III.

9. The composition of claim 8 , wherein:
Ind is an unsubstituted indenyl group or a mono-substituted indenyl group; and
each X is Cl.

10. The composition of claim 7 , wherein:
a weight ratio of catalyst component I to catalyst component II is from about 5:1 to about 1:5; and
a weight percentage of catalyst component III is in a range from about 10 to about 45 wt. %, based on the total weight of catalyst components I, II, and III.

11. The composition of claim 7 , wherein the activator comprises an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof.

12. The composition of claim 7 , wherein:
the activator comprises a fluorided solid oxide and/or a sulfated solid oxide; and
the co-catalyst comprises an organoaluminum compound.

13. The composition of claim 12 , wherein the organoaluminum compound comprises trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum chloride, or any combination thereof.

14. The process of claim 6 , wherein catalyst component I comprises an unbridged zirconium based metallocene compound containing two indenyl groups.

15. The process of claim 6 , wherein catalyst component I comprises an unbridged zirconium based metallocene compound containing a cyclopentadienyl and an indenyl group.

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

17. The composition of claim 1 , wherein catalyst component I comprises an unbridged metallocene compound having formula (I) and catalyst component II comprises a bridged metallocene compound having formula (II):

each M independently is Zr or Hf;
Cp A and Cp B independently are a cyclopentadienyl or indenyl group;
Cp is a cyclopentadienyl group;
each X independently is a monoanionic ligand;
R X and R Y independently are 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; and
E is a bridging group.

18. The composition of claim 7 , wherein:
the activator comprises a fluorided solid oxide and/or a sulfated solid oxide; and
the co-catalyst comprises an organoaluminum compound.

19. The composition of claim 18 , wherein a weight ratio of catalyst component I to catalyst component II is from about 2:1 to about 1:2.

20. The composition of claim 18 , wherein Ind is an unsubstituted indenyl group or a mono-substituted indenyl group.

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Hlavinka Mark L
• Ding Errun
• Deslauriers Paul
• Inn Yongwoo
• Cui Lili
• Yang Qing
• Sukhadia Ashish M
• St Jean Guylaine
• Buck Richard M

Classifications

• C08F4/65916

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

• C08F4/65922

  containing at least two cyclopentadienyl rings, fused or not · CPC title

• C08J5/00

  Manufacture of articles or shaped materials containing macromolecular substances (manufacture of semi-permeable membranes B01D67/00 - B01D71/00) · CPC title

• C08F4/69

  Chromium, molybdenum, tungsten or compounds thereof · CPC title

• C08F4/65904

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