Asymmetric ANSA-metallocene catalyst compounds for producing polyolefins having a broad molecular weight distribution

Patent metadata

Field	Value
Publication number	US-10889663-B2
Application number	US-201816192493-A
Country	US
Kind code	B2
Filing date	Nov 15, 2018
Priority date	Nov 29, 2017
Publication date	Jan 12, 2021
Grant date	Jan 12, 2021

Abstract

The present disclosure relates to asymmetric ansa-metallocene catalyst compounds that include at least one indenyl ligand substituted at the 3-position with a C3-C40 α-branched alkyl, such as 1-methylethyl, 1-methylpropyl, 1-methylbutyl, 1-ethylbutyl, 1,3-dimethylbutyl, 1-methyl-1-ethylbutyl, 1,1-diethylbutyl, 1-propylpentyl, and the like. Catalyst systems prepared with the catalyst compounds, polymerization methods using such catalyst systems, and polyolefins made using the polymerization methods are also described.

First claim

We claim:

1. A catalyst compound represented by Formula (I):

where M is a group 4 metal,
R 3 is a C 3 -C 40 branched alkyl, wherein the branched alkyl group is branched at the α-position,
R 3′ is hydrogen, methyl, ethyl, or a group containing three or more carbon atoms having the formula CH 2 R′, where R′ is an alkyl, aryl, or silyl group;
each of R 2 , R 4 , R 5 , R 6 , R 7 , R 2′ , R 4′ , R 5′ , R 6′ , and R 7′ is independently hydrogen, a C 1 -C 40 substituted or unsubstituted hydrocarbyl, halocarbyl, silylcarbyl, alkoxyl, halogen, or siloxyl, or one or more of R 4 and R 5 , R 5 and R 6 , R 6 and R 7 , R 4′ and R 5′ , R 5′ and R 6′ , and R 6′ and R 7′ are joined to form a completely saturated, partially saturated, or aromatic ring,
T is a bridging group, and
each X is independently a halide or C 1 -C 50 substituted or unsubstituted hydrocarbyl, hydride, amide, alkoxide, sulfide, phosphide, halide, or a combination thereof, or two of X are joined together to form a metallocycle ring, or two of X are joined to form a chelating ligand, a diene ligand, or an alkylidene.

2. The catalyst compound of claim 1 , wherein R 3 is a C 3 -C 40 branched alkyl represented by Formula (II):

where each R z and R x is, independently, a C 1 to C 20 alkyl group and R y is hydrogen or a C 1 to C 4 alkyl group, preferably a C 1 to C 2 alkyl group.

3. The catalyst compound of claim 1 , wherein T is represented by the formula R 8 2 J or (R 8 )J 2 , where each J is independently selected from C, Si, or Ge, and each R 8 is independently hydrogen, halogen, a C 1 to C 40 hydrocarbyl or a C 1 to C 40 substituted hydrocarbyl group, and two R 8 optionally form a cyclic structure including completely saturated, partially saturated, aromatic, or fused ring systems.

4. The catalyst compound of claim 2 , wherein R y is hydrogen.

5. The catalyst compound of claim 2 , wherein each R x , R y , and R z is different from any other R x , R y , and R z such that the catalyst compound has a chiral center on the α-carbon of R 3 .

6. The catalyst compound of claim 4 , wherein R z is n-propyl and R x is methyl.

7. The catalyst compound of claim 1 , wherein one or more of R 4 and R 5 , R 5 and R 6 , R 6 and R 7 , R 4′ and R 5′ , R 5′ and R 6′ , and R 6′ and R 7′ are joined to form a completely saturated, partially saturated, or aromatic ring.

8. The catalyst compound of claim 7 , wherein R 5 and R 6 are joined to form a partially saturated 5-membered ring.

9. The catalyst compound of claim 1 , wherein R 3′ is methyl.

10. The catalyst compound of claim 1 , wherein each of R 2 , R 4 , R 5 , R 6 , R 7 , R 2′ , R 4′ , R 5′ , R 6′ , and R 7′ is hydrogen.

11. The catalyst compound of claim 10 , wherein R 3′ is methyl.

12. The catalyst compound of claim 1 , wherein J is Si and R 8 is a C 1 to C 40 hydrocarbyl or a C 1 to C 40 substituted hydrocarbyl group.

13. The catalyst compound of claim 1 , wherein each R 8 is a methyl group.

14. The catalyst compound of claim 1 , wherein M is Zr.

15. The catalyst compound of claim 1 , wherein each X is a halide.

16. The catalyst compound of claim 1 , wherein each X is chloride.

17. The catalyst compound of claim 1 , wherein the catalyst compound represented by Formula (I) corresponds to any one of the following structures:

18. A catalyst system comprising an activator and the catalyst compound of claim 1 .

19. A catalyst system according to claim 18 , wherein the catalyst system utilizes a single catalyst compound.

20. The catalyst system of claim 18 , wherein the catalyst system comprises a support material.

21. The catalyst system of claim 20 , wherein said support material is silica.

22. The catalyst system of claim 18 , wherein the activator comprises one or more of alumoxanes, aluminum alkyls, and ionizing activators.

23. 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 18 ; and
obtaining a polyolefin.

24. A method of polymerizing olefins to produce at least one polyolefin composition, the method comprising:
contacting two or more different olefins with the catalyst system of claim 18 ; and
obtaining a polyolefin.

25. The method of claim 23 , wherein said at least one olefin is ethylene.

26. The method of claim 24 , wherein said two or more olefins are ethylene and 1-hexene.

27. The method of claim 23 , wherein said polyolefin has an Mw/Mn of about 3.0 to about 13.0.

28. The method according to claim 27 , wherein said polyolefin has an Mw/Mn of about 4.0 to about 13.0.

29. The method according to claim 28 , wherein said polyolefin has an Mw/Mn of about 6.0 to about 13.0.

30. The method of claim 23 , wherein said polyolefin is linear low density polyethylene.

31. The method of claim 23 , wherein said polyolefin has total unsaturation/1000 C greater than 0.25.

32. The method of claim 23 , wherein said polyolefin has g′ vis of about 0.9 to about 1.10.

33. The method of claim 23 , wherein said polyolefin has g′vis of from about 0.98 to 1.0.

34. The method of claim 23 , wherein said method is carried out in a gas phase or slurry process.

35. A catalyst system comprising an activator and the catalyst compound of claim 2 .

36. A catalyst system comprising an activator and the catalyst compound of claim 17 .

37. 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 35 ; and
obtaining a polyolefin.

38. 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 36 ; and
obtaining a polyolefin.

39. The catalyst system of claim 35 , wherein the catalyst system comprises a support material.

40. The catalyst system of claim 36 , claim 17 , wherein the catalyst system comprises a support material.

41. The method of claim 30 , wherein the is linear low density polyethylene is formed into a biaxi

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Yang Jian
• Hagadorn John R
• Karahalis Gregory J
• Boller Timothy M
• Morris Evan J
• Jiang Yan
• Brant Patrick

Classifications

• C08F2420/12

  Long bridge, i.e. Cp or analog where the bridging unit linking the two Cps or analogs is composed of at least two atoms which are not part of a cycle and which are not an ethylene bridge · 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

• C08J2323/08

  Copolymers of ethene (C08J2323/16 takes precedence) · CPC title

• C08J5/18

  Manufacture of films or sheets · CPC title

• C08F210/02

  Ethene · CPC title