Cyclopropyl substituted metallocene catalysts

Patent metadata

Field	Value
Publication number	US-9834628-B2
Application number	US-201414324427-A
Country	US
Kind code	B2
Filing date	Jul 7, 2014
Priority date	Jul 17, 2013
Publication date	Dec 5, 2017
Grant date	Dec 5, 2017

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 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 (1):
A e MX n-e
wherein:
e is 1 or 2; each A is a substituted monocyclic or polycyclic ligand that is pi-bonded to M and optionally includes one or more ring heteroatoms selected from boron, a group 14 atom that is not carbon, a group 15 atom, or a group 16 atom, and when e is 2 each A is the same;
provided that at least one A 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:

where each R′ is, independently, hydrogen, a substituted or unsubstituted hydrocarbyl group, or a halogen;
e is 1 or 2;
M is a transition metal atom having a coordination number of n and selected from group 3, 4, or 5 of the Periodic Table of Elements, or a lanthanide metal atom, or actinide metal atom;
n is 3, 4, or 5;
each X is, independently, selected from the group consisting of linear branched or cyclic non-aromatic hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, alkoxides, halides, dienes, amines, phosphines, ethers, and a combination thereof, optionally two X's optionally form a part of a fused ring or a ring system;
wherein when at least one A is a substituted indenyl substituted with at least one cyclopropyl substituent, the 7 position of the substituted indenyl is hydrogen, a halide or is substituted with a hydrocarbyl radical containing hydrogen atoms and up to 100 carbon atoms and which is linear, branched, or cyclic, and when cyclic, is non-aromatic;
wherein when A is a substituted indenyl, the 2 position of the substituted indenyl is hydrogen, an unsubstituted hydrocarbyl group, or a halide; and
wherein when A is a substituted indenyl, the indenyl ligand is substituted with one or more cyclopropyl substituents in the 2 and/or 4 and/or 6 positions.

2. The metallocene compound of claim 1 , wherein e is 2, the two As are optionally bonded together by a bridging group T, and the two As are the same.

3. The metallocene compound of claim 1 , wherein at least one A is a monocyclic ligand selected from the group consisting of substituted or unsubstituted cyclopentadienyl, heterocyclopentadienyl, and heterophenyl ligands provided that when e is one, the monocyclic ligand is substituted with at least one cyclopropyl substituent.

4. The metallocene compound of claim 1 , wherein at least one A is a polycyclic ligand selected from the group consisting of substituted or unsubstituted indenyl, fluorenyl, cyclopenta[a]naphthyl, cyclopenta[b]naphthyl, heteropentalenyl, heterocyclopentapentalenyl, heteroindenyl, heterofluorenyl, heterocyclopentanaphthyl, heterocyclopentaindenyl, and heterobenzocyclopentaindenyl ligands, provided that when e is one, the polycyclic ligand is substituted with at least one cyclopropyl substituent.

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

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

7. The metallocene compound of claim 1 , wherein at least one A is a substituted or unsubstituted indenyl ligand, provided that when e is one, the indenyl ligand is substituted with at least one cyclopropyl substituent.

8. The metallocene compound of claim 7 , wherein the indenyl ligand is substituted with one or more cyclopropyl substituents.

9. The metallocene compound of claim 8 , wherein the indenyl ligand is substituted with one or more cyclopropyl substituents in the 2 and/or 4 and/or 6 positions.

10. The metallocene compound of claim 2 , wherein at least one A is an indenyl ligand substituted with one or more cyclopropyl substituents in any bondable ring position.

11. The metallocene compound of claim 10 , wherein the indenyl ligand is substituted with one or more cyclopropyl substituents in the 2 and/or 4 and/or 6 positions.

12. The metallocene compound of claim 2 , 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′″ optionally form a cyclic structure including aromatic, partially saturated, or saturated cyclic or fused ring system.

13. The metallocene compound of claim 2 , 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 .

14. The metallocene compound of claim 1 , wherein the metallocene compound is 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;
each X is, independently, selected from the group consisting of linear branched or cyclic non-aromatic hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, alkoxides, halides, dienes, amines, phosphines, ethers, and a combination thereof, optionally two X's optionally form a part of a fused ring or a ring system;
R 7 is hydrogen, a halide or is a hydrocarbyl radical containing hydrogen atoms and up to 100 carbon atoms and which is linear, branched, or cyclic, and when cyclic, is non-aromatic;
each R 2 and R 8 is, independently, hydrogen, an unsubstituted hydrocarbyl group, or a halide;
each R 1 , R 3 , R 4 , R 5 , R 6 , R 9 , R 10 , R 11 , R 12 , R 13 , or R 14 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 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , or R 14 is a cyclopropyl substituent;
provided that any adjacent R 1 to R 14 groups that are not a cyclopropyl substituent optionally form a fused ring or multicenter fused ring system where the rings are aromatic, partially saturated, or saturated, and
wherein R 2 and R 8 are cyclopropyl substituents and/or R 4 and R 10 are cyclopropyl substituents, wherein the two indenyl groups are the same.

15. The metallocene compound of claim 14 , 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.

16. The metallocene compound of claim 14 , wherein when one of 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 substituents is not hydrogen, and when one of R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , and R 14 is a cyclopropyl substituent, at least one of the other R 8 to R 14 groups is not hydrogen.

17. The metallocene of claim 14 , wherein R 2 and R 8 are cyclopropyl and R 4 and R 10 are hydrocarbyl or halogen.

18. The metallocene of claim 14 , wherein R 4 and R 10 are cyclopropyl and/or R 2 and R 8 are hydrocarbyl.

19. A metallocene catalyst compound selected from the group consisting of: dimethylsilylene-bis(2-cyclopropyl-4-carbazol-9-ylindenyl)zirconium dichloride;
dimethylsilylene-bis(2-cyclopropyl-4-naphth

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

• C08F10/02

  Ethene · CPC title

• C08F4/65912

  in combination with an organoaluminium compound · CPC title

• C07F17/00

  Metallocenes · CPC title

• C08F2420/02

  Cp or analog bridged to a non-Cp X anionic donor · CPC title

• C08F110/06 Primary

  Propene · CPC title