Catalyst comprising a metallocene complex and a co-catalyst

Patent metadata

Field	Value
Publication number	US-9938360-B2
Application number	US-201515121092-A
Country	US
Kind code	B2
Filing date	Mar 5, 2015
Priority date	Mar 6, 2014
Publication date	Apr 10, 2018
Grant date	Apr 10, 2018

Abstract

A process for the preparation of ethylene α-olefin copolymers by copolymerizing ethylene with α-olefins in the presence of a catalyst formed by contacting a metallocene complex with a cocatalyst, wherein the metallocene complex is a metallocene complex according to formula I or a metallocene complex according to formula II,

wherein M is chosen from the group of Ti, Zr and Hf; Q is halogen (F, Cl, Br, I) or an alkyl group comprising 1 to 20 carbon atoms; k is the number of Q groups, is an integer and equals the valence of M minus 2; and wherein R 1 , R 2 , R 3 and R 4 are identical or different and can be chosen from alkyl groups with 1-20 carbon atoms.

First claim

The invention claimed is:

1. A process for the preparation of ethylene α-olefin copolymers, the process comprising copolymerizing ethylene with α-olefins in the presence of a catalyst formed by contacting a metallocene complex with a cocatalyst,
wherein the metallocene complex is chosen from the group consisting of a metallocene complex according to formula I or a metallocene complex according to formula II,

wherein
M is chosen from the group of Ti, Zr and Hf; Q is halogen or an alkyl group comprising 1 to 20 carbon atoms;
k is the number of Q groups, is an integer and equals the valence of M minus 2; and
R 1 R 2 , R 3 and R 4 are identical or different and are chosen from alkyl groups comprising 1-20 carbon atoms.

2. The process according to claim 1 , wherein the metallocene complex is chosen from the group consisting of a metallocene complex according to formula I or a metallocene complex according to formula II,

wherein
M is chosen from the group of Zr and Hf;
Q is Cl or a methyl group;
k is 2; and
R 1 R 2 , R 3 and R 4 are methyl groups.

3. The process according claim 1 , wherein the co-catalyst is selected from an aluminum- or boron-containing co-catalyst.

4. The process according to claim 1 , wherein the catalyst comprises an inorganic support material.

5. The process according to claim 1 , wherein the cocatalyst contains Al, M is Zr and wherein the Al/Zr molar ratio is between 10 and 1000.

6. The process according to claim 1 , wherein the α-olefin is chosen from 1-butene, 1-hexene or 1-octene.

7. The process according to claim 1 , wherein the ethylene α-olefin copolymer comprises at least 0.6 wt % α-olefin.

8. The process according to claim 1 , wherein the ethylene α-olefin has a weight average molecular weight (Mw) in the range from 80000 to 900000 Da.

9. The process according to claim 1 , wherein the molecular weight distribution (Mw/Mn) of the ethylene α-olefin copolymer ranges from 2 to 5.

10. The process according to claim 1 , wherein the ethylene α-olefin copolymer has a narrow chemical composition distribution wherein only one peak is present in a CEF diagram within a temperature range between 35 and 120 ° C., and this single peak has a broadness index (BI) between 1 and 5 , wherein BI is defined as the as the ratio (PW 20% /PW 80 % ), wherein PW 20 % is defined as the peak width at 20% of the peak height P H at the peak maximum P MAX , and wherein PW 80 % is defined as the peak width at 80% of the peak height P H at the peak maximum P MAX .

11. An article comprising an ethylene α-olefin copolymer obtained by the process according to claim 1 .

12. The process according to claim 1 , wherein Q is F, Cl, Br, or I or an alkyl group comprising 1 to 20 carbon atoms, and R 1 ,R 2 , R 3 and R 4 are identical or different and are chosen from methyl or ethyl groups.

13. The process according to claim 5 , wherein the Al/Zr molar ratio is between 50 and 500.

14. The process according to claim 5 , wherein the Al/Zr molar ratio is between 75 and 300.

15. The process according to claim 7 , wherein the ethylene α-olefin copolymer comprises at least 1.5 wt % α-olefin.

16. The process according to claim 7 , wherein the ethylene α-olefin copolymer comprises at least 2.5 wt % α-olefin.

17. The process according to claim 9 , wherein the molecular weight distribution (Mw/Mn) of the ethylene α-olefin copolymer ranges from 2.1 to 4.

18. The process according to claim 9 , wherein the molecular weight distribution (Mw/Mn) of the ethylene α-olefin copolymer ranges from 2.5 to 3.5.

19. The process according to claim 2 , wherein
the cocatalyst contains Al, M is Zr, and wherein the Al/Zr molar ratio is between 50 and 500;
the ethylene α-olefin copolymer comprises at least 1.5 wt % α-olefin;
the ethylene α-olefin has a weight average molecular weight (Mw) in the range from 80000 to 900000 Da;
the molecular weight distribution (Mw/Mn) of the ethylene α-olefin copolymer ranges from 2.1 to 4;
the ethylene α-olefin has a weight average molecular weight (Mw) in the range from 80000 to 9 00000 Da; and
the ethylene α-olefin copolymer has a narrow chemical composition distribution wherein only one peak is present in a CEF diagram within a temperature range between 35and 120 ° C., and this single peak has a broadness index (BI) between 1 and 5, wherein BI is defined as the as the ratio (PW 20% /PW 80% ), wherein PW 20% is defined as the peak width at 20% of the peak height P H at the peak maximum P MAX , and wherein PW 80% is defined as the peak width at 80% of the peak height P H at the peak maximum P MAX .

20. The process according to claim 19 , wherein
the Al/Zr molar ratio is between 50 and 500;
the ethylene α-olefin copolymer comprises at least 2.5 wt % α-olefin; and
the molecular weight distribution (Mw/Mn) of the ethylene α-olefin copolymer ranges from 2.5 to 3.5.

Assignees

• Saudi Basic Ind Corp
• Sabic Global Technologies Bv

Inventors

• Vadake Kulangara Shaneesh
• Friederichs Nicolaas Hendrika

Classifications

• C08F210/16

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

• C08F10/02 Primary

  Ethene · CPC title

• C08F4/65912

  in combination with an organoaluminium compound · CPC title

• C07F17/00

  Metallocenes · CPC title

• C08F4/65908

  in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+ · CPC title