Methods for controlling die swell in dual catalyst olefin polymerization systems

Patent metadata

Field	Value
Publication number	US-9650459-B2
Application number	US-201514848405-A
Country	US
Kind code	B2
Filing date	Sep 9, 2015
Priority date	Sep 9, 2015
Publication date	May 16, 2017
Grant date	May 16, 2017

Abstract

Methods for controlling the die swell of an olefin polymer produced using a dual catalyst system are disclosed. The die swell of the olefin polymer can be increased or decreased as a function of the catalyst weight ratio and the reactant molar ratio used during the olefin polymerization process.

First claim

We claim:

1. A polymerization process, the process comprising:
(1) contacting a dual catalyst system with an olefin monomer and an olefin comonomer in a polymerization reactor system under polymerization conditions to produce an olefin polymer,
wherein the olefin monomer comprises ethylene and the olefin comonomer comprises a C 3 -C 10 alpha-olefin,
wherein the olefin polymer comprises a higher molecular weight component and a lower molecular weight component,
wherein the dual catalyst system comprises a first metallocene catalyst component that produces the lower molecular weight component and a second metallocene catalyst component that produces the higher molecular weight component, and
wherein the polymerization conditions comprise:
a catalyst weight ratio of the first:second catalyst component, and
a reactant molar ratio of the comonomer:monomer; and

(2) controlling a die swell of the olefin polymer by adjusting the catalyst weight ratio, by adjusting the reactant molar ratio, or by adjusting both the catalyst weight ratio and the reactant molar ratio,
wherein the die swell decreases as the catalyst weight ratio increases, and
wherein the die swell decreases as the reactant molar ratio increases.

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

3. The process of claim 1 , wherein the polymerization reactor system comprises a single reactor.

4. The process of claim 1 , wherein the olefin comonomer comprises 1-hexene.

5. The process of claim 1 , further comprising the steps of:
determining the die swell; and
adjusting the catalyst weight ratio and/or the reactant molar ratio based on the difference between the determined die swell and a target die swell.

6. The process of claim 1 , wherein the first metallocene catalyst component and the second metallocene catalyst component independently comprise titanium, zirconium, hafnium, or a combination thereof.

7. The process of claim 6 , wherein:
the first metallocene catalyst component comprises zirconium; and
the second metallocene catalyst component comprises zirconium and/or hafnium.

8. The process of claim 1 , wherein:
the density of the olefin polymer is substantially unchanged as the catalyst weight ratio and/or the reactant molar ratio increases; and
the amount of the higher molecular weight component of the olefin polymer increases as the catalyst weight ratio and/or the reactant molar ratio increases.

9. A method of controlling a die swell of an olefin polymer, the method comprising:
(i) contacting a dual catalyst system with an olefin monomer and an olefin comonomer in a polymerization reactor system under polymerization conditions to produce the olefin polymer,
wherein the olefin monomer comprises ethylene and the olefin comonomer comprises a C 3 -C 10 alpha-olefin,
wherein the dual catalyst system comprises a first metallocene catalyst component that produces a lower molecular weight component of the olefin polymer and a second metallocene catalyst component that produces a higher molecular weight component of the olefin polymer, and
wherein the polymerization conditions comprise:
a catalyst weight ratio of the first:second catalyst component, and
a reactant molar ratio of the comonomer:monomer; and

(ii) adjusting the catalyst weight ratio, adjusting the reactant molar ratio, or adjusting both the catalyst weight ratio and the reactant molar ratio, to control the die swell of the olefin polymer,
wherein the die swell decreases as the catalyst weight ratio increases, and
wherein the die swell decreases as the reactant molar ratio increases.

10. The method of claim 9 , wherein the dual catalyst system further comprises an activator and a co-catalyst.

11. The method of claim 9 , wherein the die swell is in a range from about 20 to about 65%.

12. The method of claim 9 , wherein:
a Mw of the olefin polymer increases as the catalyst weight ratio and/or the reactant molar ratio increases;
a Mw/Mn of the olefin polymer increases as the catalyst weight ratio and/or the reactant molar ratio increases; and
a ratio of HLMI/MI of the olefin polymer increases as the catalyst weight ratio and/or the reactant molar ratio increases.

13. A process for producing an olefin polymer with a target die swell, the process comprising:
(a) contacting a dual catalyst system with an olefin monomer and an olefin comonomer in a polymerization reactor system under polymerization conditions,
wherein the olefin monomer comprises ethylene and the olefin comonomer comprises 1-butene, 1-hexene, 1-octene, or a mixture thereof,
wherein the dual catalyst system comprises a first metallocene catalyst component that produces a lower molecular weight component of the olefin polymer and a second metallocene catalyst component that produces a higher molecular weight component of the olefin polymer, and
wherein the polymerization conditions comprise:
a catalyst weight ratio of the first:second catalyst component, and
a reactant molar ratio of the comonomer:monomer; and

(b) controlling the catalyst weight ratio, controlling the reactant molar ratio, or controlling both the catalyst weight ratio and the reactant molar ratio, to produce the olefin polymer with the target die swell,
wherein die swell decreases as the catalyst weight ratio increases and the reactant molar ratio increases.

14. The process of claim 13 , wherein:
the first metallocene catalyst component comprises zirconium; and
the second metallocene catalyst component comprises zirconium and/or hafnium.

15. The process of claim 13 , wherein:
the catalyst weight ratio is in a range from about 1:2 to about 2:1;
the reactant molar ratio of the comonomer:monomer is in a range from about 0.02:1 to about 0.15:1; and
the target die swell is in a range from about 25 to about 60%.

16. The process of claim 13 , wherein:
the polymerization reactor system comprises a loop slurry reactor; and
the olefin comonomer comprises 1-hexene.

17. The process of claim 13 , wherein the dual catalyst system comprises:
a first metallocene catalyst component comprising an unbridged metallocene compound containing zirconium;
a second metallocene catalyst component comprising a bridged metallocene compound containing zirconium or hafnium and a fluorenyl group;
an activator comprising an activator-support, an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof; and
a co-catalyst comprising an organoaluminum compound.

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Greco Jeff F
• Yang Qing
• Rohatgi Vivek
• Hlavinka Mark L
• Askew Jim B

Classifications

• C08F210/16 Primary

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

• C08F4/65916

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

• C08F4/65904

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

• C08F210/02

  Ethene · CPC title

• C08F210/14 Primary

  Monomers containing five or more carbon atoms · CPC title