Cyclopropyl substituted metallocene catalysts

Patent metadata

Field	Value
Publication number	US-10487161-B2
Application number	US-201715798945-A
Country	US
Kind code	B2
Filing date	Oct 31, 2017
Priority date	Jul 17, 2013
Publication date	Nov 26, 2019
Grant date	Nov 26, 2019

Abstract

This invention relates to a novel group 2, 3 or 4 transition metal metallocene catalyst compound having at least one arenyl ligand substituted with: 1) a cyclopropyl group and, optionally, 2) at at least one other group, such as a hydrocarbyl, a heteroatom or a heteroatom containing group.

First claim

We claim:

1. A metallocene compound represented by the formula (2):

wherein:
M is a group 3, 4, 5 or 6 transition metal atom, or a lanthanide metal atom, or actinide metal atom;
A is a substituted monocyclic or polycyclic ligand that is pi-bonded to M and is substituted with at least one cyclopropyl substituent directly bonded to any sp 2 carbon atom at a bondable ring position of the ligand;
wherein the cyclopropyl substituent is represented by the formula:

wherein each R′ is, independently, hydrogen, a substituted hydrocarbyl group, an unsubstituted hydrocarbyl group, or a halogen;
T is an optional bridging group that is bonded to A and J, and is present when y is one and absent when y is zero;
y is zero or one;
J is a heteroatom with a coordination number of three from group 15 or with a coordination number of two from group 16 of the Periodic Table of Elements;
R″ is selected from a C 1 -C 100 substituted or unsubstituted hydrocarbyl radical;
x is the coordination number of the heteroatom J where “x-1-y” indicates the number of R″ substituents bonded to J; and
each X is a univalent anionic ligand, or two Xs are joined and bound to the metal atom to form a metallocycle ring, or two Xs are joined to form a chelating ligand, a diene ligand, or an alkylidene ligand.

2. The metallocene compound of claim 1 , wherein A is a monocyclic ligand and is selected from the group consisting of substituted cyclopentadienyl, heterocyclopentadienyl, and heterophenyl ligands.

3. The metallocene compound of claim 1 , wherein A is a polycyclic ligand and is selected from the group consisting of substituted indenyl, fluorenyl, cyclopenta[a]naphthyl, cyclopenta[b]naphthyl, heteropentalenyl, heterocylopentapentalenyl, heteroindenyl, heterofluorenyl, heterocyclopentanaphthyl, heterocyclopentaindenyl, and heterobenzocyclopentaindenyl ligands.

4. The metallocene compound of claim 1 , wherein M is a group 4 metal and T is represented by the formula, (R′″ 2 G) g , where each G is C, Si, or Ge, g is 1 or 2, and each R′″ is, independently, hydrogen, halogen, C 1 to C 20 hydrocarbyl or a C 1 to C 20 substituted hydrocarbyl, and two or more R′″ can form a cyclic structure including aromatic, partially saturated, or saturated cyclic or fused ring system.

5. The metallocene compound of claim 1 , wherein A is a substituted indenyl ligand, optionally substituted with one or more cyclopropyl substituents in the 2 and/or 4 positions.

6. The metallocene compound of claim 1 , wherein J is nitrogen, phosphorus, oxygen or sulfur.

7. A metallocene compound represented by one of the following formulae:

wherein:
M is a transition metal atom selected from group 3, 4, or 5 of the Periodic Table of Elements;
T is a bridging group;
J is a heteroatom with a coordination number of three from group 15 or a heteroatom with a coordination number of two from group 16 of the Periodic Table of Elements;
n represents the number of R″ substituents, and n is one when J is a group 15 heteroatom and T is present, or a group 16 heteroatom and T is absent; n is two when J is a group 15 heteroatom and T is absent; n is zero when J is a group 16 heteroatom and T is present;
R″ is selected from a C 1 -C 100 substituted or unsubstituted hydrocarbyl radical;
each X is a univalent anionic ligand, or two X groups are joined and bound to the metal atom to form a metallocycle ring, or two X groups are joined to form a chelating ligand, a diene ligand, or an alkylidene ligand;
each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 is, independently, hydrogen, a substituted hydrocarbyl group, an unsubstituted hydrocarbyl group, or a halide, provided that at least one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 is a cyclopropyl substituent;
provided that any adjacent R 1 to R 7 groups that are not a cyclopropyl substituent may form a fused ring or multicenter fused ring system where the rings may be aromatic, partially saturated or saturated.

8. The metallocene compound of claim 7 , wherein M is hafnium, zirconium or titanium and T is represented by the formula, (R′″ 2 G) g , where each G is C, Si, or Ge, g is 1 or 2, and each R′″ is, independently, hydrogen, halogen, C 1 to C 20 hydrocarbyl or a C 1 to C 20 substituted hydrocarbyl, and two or more R′″ can form a cyclic structure including aromatic, partially saturated, or saturated cyclic or fused ring system.

9. The metallocene compound of claim 7 , wherein R 2 and/or R 4 are cyclopropyl substituents.

10. The metallocene compound of claim 7 , wherein J is nitrogen, phosphorus, oxygen or sulfur.

11. The metallocene compound of claim 8 , wherein when one R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 is a cyclopropyl substituent, at least one of the other R 1 to R 7 substitutents is not hydrogen.

12. A metallocene catalyst compound selected from the group consisting of:
dimethylsilylene-(2-cyclopropylindenyl)(tert-butylamido)zirconium dichloride;
dimethylsilylene-(2-cyclopropylindenyl)(tert-butylamido)titanium dichloride;
where, in alternate embodiments, the dichloride in any of the compounds listed above may be replaced with dialkyl, dialkaryl, diflouride, diiodide, or dibromide, or a combination thereof.

13. The metallocene compound of claim 1 , wherein each X is independently selected from halides and C 1 to C 5 alkyl groups.

14. The metallocene compound of claim 1 , wherein each X is a methyl group.

15. The metallocene compound of claim 1 , wherein A is a monocyclic ligand selected from the group consisting of substituted or unsubstituted cyclopentadienyl, heterocyclopentadienyl, and heterophenyl ligands.

16. The metallocene compound of claim 1 , wherein M is a group 4 metal.

17. The metallocene compound of claim 1 , wherein each R′ is hydrogen.

18. The metallocene compound of claim 1 , wherein A is a substituted or unsubstituted indenyl ligand.

19. The metallocene compound of claim 1 , wherein A is a substituted indenyl ligand and the indenyl ligand is substituted with one or more cyclopropyl substituents in the 2 and/or 4 and/or 6 positions.

20. The metallocene compound of claim 1 , wherein T is represented by the formula, (R′″ 2 G) g , where each G is C, Si, or Ge, g is 1 or 2, and each R′″ is, independently, hydrogen, halogen, C 1 to C 20 hydrocarbyl or a C 1 to C 20 substituted hydrocarbyl, and two or more R′″ can form a cyclic structure including aromatic, partially saturated, or saturated cyclic or fused ring system.

21. The metallocene compound of claim 1 , wherein T is CH 2 , CH 2 CH 2 , C(CH 3 ) 2 , SiMe 2 , SiPh 2 , SiMePh, Si(CH 2 ) 3 , Si(CH 2 ) 4 , or Si(CH 2 ) 5 .

22. A catalyst system comprising activator and the metallocene catalyst compound of claim 1 .

23. The catalyst system of claim 22 , wherein the activator comprises alumoxane.

24. The catalyst system of claim 22 , wherein the activator comprises a non-coordinating anion activator.

25. The catalyst system of claim 22 , wherein activator is represented by the

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Canich Jo Ann M
• Voskoboynikov Alexander Z
• Uborsky Dmitry V
• Borisov Ilya S
• Tsarev Alexey A
• Kulyabin Pavel S
• Sharikov Mikhail I
• Samsonov Oleg V
• Goryunov Georgy P

Classifications

• C08F2/00

  Processes of polymerisation · CPC title

• C08F4/65908

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

• C08F4/65927

  two cyclopentadienyl rings being mutually bridged · CPC title

• C08F110/06 Primary

  Propene · CPC title

• C08F10/02

  Ethene · CPC title