Higher Density Polyolefins With Improved Stress Crack Resistance

Patent metadata

Field	Value
Publication number	US-2016304644-A1
Application number	US-201615193195-A
Country	US
Kind code	A1
Filing date	Jun 27, 2016
Priority date	Sep 5, 2013
Publication date	Oct 20, 2016
Grant date	—

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

1 - 14 . (canceled)

15 . 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 titanium or chromium half-metallocene compound; an activator; and optionally, a co-catalyst.

16 . The composition of claim 15 , wherein the activator comprises an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof.

17 . An olefin polymerization process, the process comprising contacting the catalyst composition of claim 15 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) or formula (IIIB):

wherein:
Ind is an indenyl group; Cp C is a cyclopentadienyl, indenyl, or fluorenyl group; each X independently is a monoanionic ligand; and each L is a neutral ligand, and integer n is 0, 1 or 2;
an activator-support comprising a solid oxide treated with an electron-withdrawing anion; and
an organoaluminum compound.

18 . The process of claim 17 , 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.

19 . The process of claim 17 , wherein the polymerization reactor system comprises a slurry reactor, gas-phase reactor, solution reactor, or a combination thereof.

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

21 . The composition of claim 15 , 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.

22 . The composition of claim 21 , wherein:
a weight ratio of catalyst component Ito 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.

23 . The composition of claim 22 , wherein catalyst component III has formula (IIIA):

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

24 . The composition of claim 23 , wherein:
Ind is an unsubstituted indenyl group or a mono-substituted indenyl group; and each X is Cl.

25 . The composition of claim 22 , wherein catalyst component III has formula (IIIB):
Cr(Cp C )(X)(X)(L) n   (IIIB); wherein:
Cp C is a cyclopentadienyl, indenyl, or fluorenyl group; each X independently is a monoanionic ligand; and each L is a neutral ligand, and integer n is 0, 1 or 2.

26 . The composition of claim 25 , wherein:
Cp C is a cyclopentadienyl group; each X independently is a halide or a C 1 to C 18 hydrocarbyl group; and n is equal to 0 or 1.

27 . The composition of claim 21 , wherein:
a weight ratio of catalyst component Ito 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.

28 . The composition of claim 21 , wherein the activator comprises an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof.

29 . The composition of claim 21 , wherein:
the activator comprises a fluorided solid oxide and/or a sulfated solid oxide; and the co-catalyst comprises an organoaluminum compound.

30 . The composition of claim 29 , 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;

31 . The process of claim 20 , wherein catalyst component I comprises an unbridged zirconium based metallocene compound containing two indenyl groups.

32 . The process of claim 20 , wherein catalyst component I comprises an unbridged zirconium based metallocene compound containing a cyclopentadienyl and an indenyl group.

33 . The process of claim 20 , wherein the half-metallocene compound has formula (IIIA).

wherein each X is Cl.

34 . The process of claim 20 , wherein the half-metallocene compound has formula (IIIB):
Cr(Cp C )(X)(X)(L) n   (IIIB); wherein:
Cp C is a cyclopentadienyl group; each X independently is a monoanionic ligand; and L is a neutral ligand, and integer n is 0 or 1.

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

• C08F4/65927

  two cyclopentadienyl rings being mutually bridged · CPC title

• C08L23/0815

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

• C08F4/65912

  in combination with an organoaluminium compound · CPC title

• C08J2323/08

  Copolymers of ethene (C08J2323/16 takes precedence) · CPC title

• C08F4/65925

  two cyclopentadienyl rings being mutually non-bridged · CPC title