Ziegler-Natta catalysts doped with non-group IV metal chlorides

Patent metadata

Field	Value
Publication number	US-9944724-B2
Application number	US-201615171105-A
Country	US
Kind code	B2
Filing date	Jun 2, 2016
Priority date	Feb 16, 2011
Publication date	Apr 17, 2018
Grant date	Apr 17, 2018

Abstract

A process may include contacting ethylene monomer with Ziegler-Natta catalyst to form polyethylene. The Ziegler-Natta catalyst may be formed by contacting an alkyl magnesium compound with an alcohol and a metal reagent to form a blend, and contacting the blend with a first agent to form a solution of reaction product “A”. The solution of reaction product “A” may be contacted with a second agent to form a solid reaction product “B”, and the solid reaction product “B” may be contacted with a third agent to form a solid reaction product “C”. The solid reaction product “C” may be contacted with a fourth agent to form a solid reaction product “D”, and the solid reaction product “D” may be contacted with a fifth agent to form a catalyst component.

First claim

What is claimed is:

1. A polymerization process comprising:
providing ethylene monomer;
contacting the ethylene monomer with a Ziegler-Natta catalyst within a polymerization reactor under conditions sufficient to form polyethylene; and
recovering polyethylene from the polymerization reactor, wherein the Ziegler-Natta catalyst is formed by a process comprising:
contacting an alkyl magnesium compound with an alcohol and a metal reagent to form a blend of a magnesium dialkoxide compound and a metal;
contacting the blend of the magnesium dialkoxide compound and the metal with a first agent to form a solution of reaction product “A”, the first agent comprising a halogenating/titanating agent;
contacting the solution of reaction product “A” with a second agent to form a solid reaction product “B”, the second agent comprising a blend of a first metal halide and a metal alkoxide;
contacting the solid reaction product “B” with a third agent to form a solid reaction product “C”, the third agent comprising a second metal halide;
contacting the solid reaction product “C” with a fourth agent to form a solid reaction product “D”, the fourth agent comprising a third metal halide; and
contacting the solid reaction product “D” with a fifth agent to form a catalyst component, the fifth agent comprising an organoaluminum compound;
wherein the metal reagent is selected from Ba(2-EHO) 2 (barium(II) 2-ethyl hexyl alkoxide), Mn(2-ethylhexanoate) 2 (manganese(II) 2-ethylhexanoate), Cr(2-ethylhexanoate) 3 (chromium(III) 2-ethylhexanoate) and 2-butylferrocene.

2. The process of claim 1 , wherein a shear response and activity for the polyethylene is greater than a shear response and activity for an identically formed polyethylene absent the metal reagent in the Ziegler-Natta catalyst.

3. The process of claim 1 , wherein the polyethylene exhibits an SR2 of from about 30 to about 50.

4. The process of claim 1 , wherein the polyethylene exhibits a Mz/Mw of from about 4.0 to about 9.0.

5. The process of claim 1 , wherein the polymerization process exhibits an activity of from about 23,000 g/g/h to about 70,000 g/g/h.

6. Polyethylene formed by the process of claim 1 .

7. A polymerization process comprising:
providing ethylene monomer;
contacting the ethylene monomer with a Ziegler-Natta catalyst within a polymerization reactor under conditions sufficient to form polyethylene; and
recovering polyethylene from the polymerization reactor, wherein the Ziegler-Natta catalyst is formed by a process comprising:
contacting an alkyl magnesium compound with an alcohol and a metal reagent to form a blend of a magnesium dialkoxide compound and a metal;
contacting the blend of the magnesium dialkoxide compound and the metal with a first agent to form a solution of reaction product “A”, the first agent comprising a halogenating/titanating agent;
contacting the solution of reaction product “A” with a second agent to form a solid reaction product “B”, the second agent comprising a blend of a first metal halide and a metal alkoxide;
contacting the solid reaction product “B” with a third agent to form a solid reaction product “C”, the third agent comprising a second metal halide;
contacting the solid reaction product “C” with a fourth agent to form a solid reaction product “D”, the fourth agent comprising a third metal halide; and
contacting the solid reaction product “D” with a fifth agent to form a catalyst component, the fifth agent comprising an organoaluminum compound;
wherein the metal in the metal reagent is selected from Cr 3+ , Fe 2+ , Mn 2+ , and Ba 2+ .

8. A polymerization process comprising:
providing ethylene monomer;
contacting the ethylene monomer with a Ziegler-Natta catalyst within a polymerization reactor under conditions sufficient to form polyethylene; and
recovering polyethylene from the polymerization reactor, wherein the Ziegler-Natta catalyst is formed by a process comprising:
contacting a metal component with a magnesium dihalide support material to form a Ziegler-Natta catalyst precursor, wherein the metal component is represented by the formula:
MR A x

wherein M is a transition metal; wherein R A is a halogen, an alkoxy, or a hydrocarboxyl group; and wherein x is the valence of M;

contacting the magnesium dihalide support material in the Ziegler-Natta catalyst precursor with a dopant comprising a non-Group IV metal to form a doped catalyst precursor; and
activating the doped catalyst precursor by contact with an organoaluminum compound to form the Ziegler-Natta catalyst;
wherein the dopant is selected from Ba(2-EHO) 2 (barium(II) 2-ethyl hexyl alkoxide), Mn(2-ethylhexanoate) 2 (manganese(II) 2-ethylhexanoate), Cr(2-ethylhexanoate) 3 (chromium(III) 2-ethylhexanoate), 2-butylferrocene and combinations thereof.

9. The process of claim 8 , wherein a shear response and activity for the polyethylene is greater than a shear response and activity for an identically formed polyethylene absent the dopant in the Ziegler-Natta catalyst.

10. The process of claim 8 , wherein the polyethylene exhibits an SR2 of from about 30 to about 50.

11. The process of claim 8 , wherein the polyethylene exhibits a Mz/Mw of from about 4.0 to about 9.0.

12. The process of claim 8 , wherein the polymerization process exhibits an activity of from about 23,000 g/g/h to about 70,000 g/g/h.

13. Polyethylene formed by the process of claim 8 .

Assignees

• Fina Technology

Inventors

• Zhang Lei
• Knoeppel David

Classifications

• C08F2500/18

  Bulk density · CPC title

• C08F2500/11

  Melt tension or melt strength · CPC title

• C08F110/02 Primary

  Ethene · CPC title

• C08F2500/20

  Activation energy or enthalpy · CPC title

• C08F4/6574

  and magnesium or compounds thereof · CPC title