Bimodal ethylene, alpha-olefin, and diene polymers using dual organometallic catalysts

Patent metadata

Field	Value
Publication number	US-11008449-B2
Application number	US-201816152979-A
Country	US
Kind code	B2
Filing date	Oct 5, 2018
Priority date	Nov 14, 2017
Publication date	May 18, 2021
Grant date	May 18, 2021

Abstract

The present disclosure provides catalyst systems having a bridged metallocene compound and a transition metal pyridyldiamide compound for use in alkene polymerization to produce multimodal polyolefins, such as multimodal ethylene, propylene, diene monomer copolymers. In some embodiments, the present disclosure provides for polyolefins and processes for producing a polyolefin composition including contacting at least one olefin with a catalyst system of the present disclosure.

First claim

What is claimed is:

1. A catalyst system comprising:
A) a bridged biscyclopentadienyl transition metal compound comprising:
i) at least one unsubstituted cyclopentadienyl ligand or aromatic fused-ring substituted cyclopentadienyl ligand,
ii) one aromatic fused-ring substituted cyclopentadienyl ligand,
iii) a bridge group connecting the two cyclopentadienyl ligands, said bridge comprising one or more carbon or silicon atoms, and
iv) a group 4 transition metal bound to both ligands; and

B) a transition metal pyridyldiamide compound is represented by Formula (III):

wherein:
each of R 12 , R 13 , R 14 , R 15 , and R 16 is independently hydrogen, methyl, ethyl, propyl, isopropyl, isobutyl, or tertbutyl; and
each of X 1 and X 2 is independently halogen or alkyl.

2. The catalyst system of claim 1 , wherein the transition metal pyridyldiamide compound is:

3. A catalyst system comprising:
(a) the catalyst system of claim 1 ; and
(b) a bridged or unbridged metallocene catalyst compound different than the bridged biscyclopentadienyl compound of of (A) and a transition metal pyridyldiamide compound different than the transition metal pyridyldiamide compound of (B).

4. The catalyst system of claim 1 , further comprising an activator.

5. The catalyst system of claim 1 , further comprising a support.

6. The catalyst system of claim 4 , wherein the activator comprises one or more of:
N,N-dimethylanilinium tetrakis(perfluorophenyl)borate,
N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate,
N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate,
N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,
triphenylcarbenium tetrakis(perfluoronaphthyl)borate,
triphenylcarbenium tetrakis(perfluorobiphenyl)borate,
triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,
triphenylcarbenium tetrakis(perfluorophenyl)borate,
trimethylammonium tetrakis(perfluoronaphthyl)borate,
triethylammonium tetrakis(perfluoronaphthyl)borate,
tripropylammonium tetrakis(perfluoronaphthyl)borate,
tri(n-butyl)ammonium tetrakis(perfluoronaphthyl)borate,
tri(t-butyl)ammonium tetrakis(perfluoronaphthyl)borate,
N,N-diethylanilinium tetrakis(perfluoronaphthyl)borate,
N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis(perfluoronaphthyl)borate, and
tropillium tetrakis(perfluoronaphthyl)borate.

7. The catalyst system of claim 4 , wherein the activator comprises alumoxane.

8. The catalyst system of claim 4 , further comprising an activator represented by the formula:
Z d + (A d− )

wherein A d− is a non-coordinating anion having the charge d−; d is an integer from 1 to 3; and Z is a reducible Lewis acid represented by the formula: (Ar 3 C + ), where Ar is aryl or heteroaryl, a C 1 to C 40 hydrocarbyl, or a substituted C 1 -C 40 hydrocarbyl.

9. The catalyst system of claim 1 , further comprising an activator represented by the formula:
Z d + (A d− )

wherein Z is (L-H) or a reducible Lewis acid, L is a neutral base; H is hydrogen; (L-H) + is a Bronsted acid; A d− is a non-coordinating anion having the charge d−; and d is an integer from 1 to 3.

10. The catalyst system of claim 1 , wherein the molar ratio of the bridged biscyclopentadienyl compound to the transition metal pyridyldiamide compound is from about 0.25 to about 2.

11. A method of polymerizing olefins to produce at least one polyolefin composition, the method comprising contacting at least one olefin with the catalyst system of claim 1 and activator, and obtaining a polyolefin.

12. The method of claim 11 , wherein the method occurs at a temperature of about 0° C. to about 300° C., at a pressure in the range of from about 0.35 MPa to about 50 MPa, and at a time up to about 300 min.

13. The method of claim 11 , wherein the olefins comprise ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, 5-ethylidene-2-norbornene, dicyclopentadiene, vinyl norbornene, or mixtures thereof.

14. The method of claim 11 , wherein the olefins comprise ethylene, one or more of propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, and dodecene, and one or more of 5-ethylidene-2-norbornene, dicyclopentadiene, and vinyl norbornene.

15. The method of claim 11 , wherein the olefins comprise ethylene, propylene, one or more of 5-ethylidene-2-norbornene, dicyclopentadiene, and vinyl norbornene.

16. The method of claim 11 , wherein the olefins comprise ethylene, propylene, and 5-ethylidene-2-norbornene.

17. The method of claim 11 , further comprising introducing the catalyst system and activator into a reactor as a slurry.

18. The method of claim 11 , where the polymerization occurs in the solution phase.

19. The method of claim 11 , where the polymerization occurs in the slurry phase.

20. The method of claim 11 , where scavenger represented by the formula ((R z —Al—) y O—) x , wherein z is 1-2, y is 1-2, x is 1-100, and R is a C 1 -C 12 hydrocarbyl group, is present in the polymerization.

21. The method of claim 11 , where scavenger is present in the polymerization and has an oxygen to aluminum (O/Al) molar ratio of from about 0.25 to about 1.5.

22. The method of claim 11 , where the polymerization occurs in a single reactor.

23. The method of claim 11 , wherein the method occurs at a temperature of about 100° C. to about 300° C.

24. The method of claim 11 , further comprising obtaining a copolymer having 50 to 99.9 wt% of a low molecular weight component and 0.1 to 50 wt% of a high molecular weight component (based upon the weight of the copolymer); wherein:
a) the high molecular weight component has:
i) a peak molecular weight of 2,500,000 g/mol to 10,000,000 g/mol;
ii) optionally, a spread (half-peak width) from 2 to 20;
iii) an ethylene content of more than 40 to 80 wt%;
iv) a C 3 to C 40 alpha olefin (preferably propylene) content of 20 to 60 wt%;
v) a diene content of 0.1 to 12 wt%;

b) the low molecular weight component has:
i) a peak molecular weight of 100,000 to less than 2,000,000 g/mol;
ii) optionally, a spread (half peak width) of 2 to 20;
iii) an ethylene content of about 10 to about 50 wt%;
iv) a C 3 to C 40 alpha olefin (preferably propylene) content of 50 to 90 wt%;
v) a diene content of 0.1 to 12 wt%;

wherein the copolymer has:
1) a g′ vis value of about 0.95 or greater;
2) an Mw of 500,000 g/mol or more;
3) an Mn of 75,000 g/mol or more;
4) an Mw/Mn of from 3 to 15; and
5) an ethylene content of 55 wt% or less.

25. The catalyst system of claim 1 , wherein the transition metal pyridyldiamide compound is one or more of:

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Tsou Andy H
• Hagadorn John R

Classifications

• C08F210/06 Primary

  Propene · CPC title

• C08F2420/10

  Heteroatom-substituted bridge, i.e. Cp or analog where the bridge linking the two Cps or analogs is substituted by at least one group that contains a heteroatom · CPC title

• C08F4/65908

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

• C08F210/18

  with non-conjugated dienes, e.g. EPT rubbers · CPC title

• C08L23/12

  Polypropene · CPC title