Titanium phosphinimide and titanium iminoimidazolidide catalyst systems with activator-supports

Patent metadata

Field	Value
Publication number	US-9951156-B2
Application number	US-201615225902-A
Country	US
Kind code	B2
Filing date	Aug 2, 2016
Priority date	Oct 9, 2014
Publication date	Apr 24, 2018
Grant date	Apr 24, 2018

Abstract

Catalyst compositions containing activator-supports and half-metallocene titanium phosphinimide complexes or half-metallocene titanium iminoimidazolidide complexes are disclosed. These catalyst compositions can be used to produce olefin polymers having relatively broad molecular weight distributions and low levels of long chain branching.

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:
(i) a half-metallocene titanium compound;
(ii) an activator-support comprising a solid oxide treated with an electron-withdrawing anion; and
(iii) an optional co-catalyst;
wherein the half-metallocene titanium compound has the formula:

wherein:
Cp is a cyclopentadienyl, indenyl, or fluorenyl group;
each X independently is a monoanionic ligand; and
L is a iminoimidazolidide ligand; and
wherein the olefin polymer has less than or equal to about 0.008 long chain branches (LCB) per 1000 total carbon atoms.

2. The process of claim 1 , wherein:
the catalyst composition comprises an organoaluminum co-catalyst; and
the activator-support comprises a fluorided solid oxide and/or a sulfated solid oxide.

3. The process of claim 1 , wherein the polymerization reactor system comprises a slurry reactor, gas-phase reactor, solution reactor, or a combination thereof.

4. The process of claim 1 , wherein the olefin monomer comprises ethylene or propylene.

5. The process of claim 1 , wherein:
the catalyst composition comprises an organoaluminum co-catalyst comprising 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; and
the activator-support comprises fluorided alumina, chlorided alumina, bromided alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, bromided silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, bromided silica-zirconia, sulfated silica-zirconia, fluorided silica-titania, fluorided silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, or any combination thereof.

6. The process of claim 1 , wherein:
the catalyst composition is contacted with ethylene and an olefin comonomer comprising 1-butene, 1-hexene, 1-octene, or a mixture thereof;
the polymerization reactor system comprises a loop slurry reactor; and
the polymerization conditions comprise a polymerization temperature in a range from about 65° C. to about 110° C.

7. The process of claim 1 , wherein the olefin polymer is an ethylene polymer characterized by:
a ratio of Mw/Mn in a range from about 4 to about 10;
a ratio of HLMI/MI in a range from about 15 to about 75; and
a density in a range from about 0.90 to about 0.96 g/cm 3 .

8. The process of claim 1 , wherein the half-metallocene titanium compound having formula (I) has the structure of formula (III):

wherein:
Cp is a cyclopentadienyl, indenyl, or fluorenyl group;
each X independently is a monoanionic ligand; and
R A and R B independently are H or a halide, C 1 to C 36 hydrocarbyl group, C 1 to C 36 halogenated hydrocarbyl group, C 1 to C 36 hydrocarboxy group, or C 1 to C 36 hydrocarbylsilyl group.

9. The process of claim 8 , wherein, in formula (III):
Cp is a substituted or unsubstituted cyclopentadienyl or indenyl group;
each X independently is a halide or C 1 to C 18 hydrocarbyl group; and
R A and R B independently are H or a C 1 to C 18 hydrocarbyl group.

10. The process of claim 9 , wherein:
R A and R B independently are a C 1 to C 12 alkyl group; and
the heterocyclic carbene group is unsaturated.

11. The process of claim 1 , wherein the olefin polymer is an ethylene/α-olefin copolymer characterized by:
a ratio of Mw/Mn in a range from about 5 to about 9;
a ratio of HLMI/MI in a range from about 25 to about 55;
a density in a range from about 0.92 to about 0.95 g/cm 3 ; and
less than or equal to about 0.003 long chain branches (LCB) per 1000 total carbon atoms.

12. The process of claim 1 , wherein:
the olefin polymer has an increase in melt index of at least about 1 g/10 min, based on an increase in hydrogen:monomer weight ratio from 0 to 150 ppmw; and
the olefin polymer has a decrease in density of at least about 0.01 g/cm 3 , based on an increase in comonomer:monomer molar ratio from 0 to 0.0176:1.

13. The process of claim 1 , wherein an organozinc compound is added to the polymerization reactor system, and the addition of the organozinc compound reduces the Mw/Mn of the olefin polymer and/or reduces the z-average molecular weight (Mz) of the olefin polymer.

14. The process of claim 1 , wherein the half-metallocene titanium compound has any one of the following formulas:

wherein each X independently is a monoanionic ligand.

15. The process of claim 14 , wherein each X independently is a halide or C 1 to C 18 hydrocarbyl group.

16. The process of claim 14 , wherein each X is Cl.

17. The process of claim 1 , wherein the half-metallocene titanium compound comprises:

18. The process of claim 1 , wherein the catalyst composition further comprises:
an unbridged zirconium based metallocene compound with a cyclopentadienyl group and an indenyl group; or
a bridged zirconium or hafnium based metallocene compound with a cyclopentadienyl group and a fluorenyl group.

19. 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:
(i) a half-metallocene titanium compound;
(ii) an activator-support comprising a solid oxide treated with an electron-withdrawing anion; and
(iii) an optional co-catalyst;
wherein the half-metallocene titanium compound has the formula:

wherein:
Cp is a cyclopentadienyl, indenyl, or fluorenyl group;
each X independently is a monoanionic ligand; and
L is a iminoimidazolidide ligand; and
wherein the olefin polymer has an increase in melt index of at least about 1 g/10 min, based on an increase in hydrogen:monomer weight ratio from 0 to 150 ppmw.

20. The process of claim 19 , wherein the half-metallocene titanium compound has any one of the following formulas:

wherein each X independently is a halide or C 1 to C 18 hydrocarbyl group.

21. The process of claim 19 , wherein the activator-support comprises fluorided alumina, chlorided alumina, bromided alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, bromided silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, bromided silica-zirconia, sulfated silica-zirconia, fluorided silica-titania, fluorided silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, or any co

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Cruz Carlos A
• Barr Jared L
• Praetorius Jeremy M

Classifications

• C08F10/02 Primary

  Ethene · CPC title

• C08F4/6592

  containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring · CPC title

• C08F210/16 Primary

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

• C08F4/65925

  two cyclopentadienyl rings being mutually non-bridged · CPC title

• C08F110/02 Primary

  Ethene · CPC title