Metallocenes and catalyst compositions derived therefrom

Patent metadata

Field	Value
Publication number	US-9249239-B2
Application number	US-201414324314-A
Country	US
Kind code	B2
Filing date	Jul 7, 2014
Priority date	Jul 17, 2013
Publication date	Feb 2, 2016
Grant date	Feb 2, 2016

Abstract

This invention relates to a novel group 2, 3 or 4 transition metal metallocene catalyst compound that is asymmetric having two non-identical indenyl ligands with substitution at R 2 having a branched or unbranched C 1 -C 20 alkyl group substituted with a cyclic group or a cyclic group, R 8 is an alkyl group and R 4 and R 10 are substituted phenyl groups.

First claim

The invention claimed is:

1. A metallocene catalyst compound represented by the formula:

wherein,
R 2 and R 8 are not the same;
R 4 and R 10 are substituted phenyl groups and are not the same, R 4 is a phenyl group substituted at the 2′ position with an aryl group or is a phenyl group substituted at the 3′ and 5′ positions with a C 1 to C 10 alkyl group or aryl group or combinations thereof
R 10 is a phenyl group substituted at the 2′ position with an aryl group; or a phenyl group substituted at the 3′ and 5′ positions with a C 1 to C 10 alkyl group or aryl group or combinations thereof;
M is a group transition 2, 3, or 4 metal;
T is a bridging group;
each X is an anionic leaving group;
each R 1 , R 3 , R 5 , R 6 , R 7 , R 9 , R 11 R 12 R 13 and R 14 is, independently, hydrogen, or a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, or substituted germylcarbyl substituents;
R 2 is a substituted or unsubstituted C 3 -C 12 cycloaliphatic group or is a methylene substituted with a substituted or unsubstituted C 3 -C 12 cycloaliphatic group or an ethylene substituted with a substituted or unsubstituted C 3 -C 12 cycloaliphatic group, wherein the C 3 -C 12 cycloaliphatic group can be substituted at one or more positions with a C 1 -C 10 alkyl group; and
R 8 is a halogen atom, a C 1 -C 10 alkyl group which is optionally halogenated, a C 6 -C 10 aryl group which is optionally halogenated, a C 2 -C 10 alkenyl group, a C 7 -C 40 arylalkyl group, a C 7 -C 40 alkylaryl group, a C 8 -C 40 arylalkenyl group, a —NR′ 2 , —SR′, —OR′, —OSiR′ 3 or —PR′ 2 radical, wherein R′ is a halogen atom, a C 1 -C 10 alkyl group, or a C 6 -C 10 aryl group.

2. The metallocene catalyst compound of claim 1 , wherein R 2 is a cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecanyl, cyclododecyl, a methylcycloalkyl group, an ethylcycloalkyl group, a methylcycloalkyl alkyl substituted group or an ethylcycloalkyl substituted alkyl group.

3. The metallocene catalyst compound of claim 1 , wherein the aryl group of R 4 is a phenyl group.

4. The metallocene catalyst compound of claim 1 , wherein the C 1 to C 10 alkyl groups of R 4 are t-butyl, sec-butyl, n-butyl, isopropyl, n-propyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, phenyl, mesityl, or adamantyl groups.

5. The metallocene catalyst compound of claim 1 , wherein the aryl group of R 10 at the 2′ position is a phenyl group and/or the aryl groups at the 3′ and 5′ positions are phenyl groups.

6. The metallocene catalyst compound of claim 1 , wherein the C 1 to C 10 alkyl groups of le are t-butyl, sec-butyl, n-butyl, isopropyl, n-propyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, phenyl, mesityl, or adamantyl groups.

7. The metallocene catalyst compound of claim 1 , wherein M is Hf or Zr.

8. The metallocene catalyst compound of claim 1 , wherein each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and a combination thereof, or two X's optionally form a part of a fused ring or a ring system.

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

10. The metallocene catalyst 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 , Si(Me 3 SiPh) 2 , or Si(CH 2 ) 5 .

11. The metallocene catalyst compound of claim 1 , wherein the catalyst formula is:

12. The metallocene catalyst compound of claim 1 , wherein the metallocene catalyst compound is a mixture of rac/meso isomers and the rac/meso ratio is 10:1 or greater.

13. The metallocene catalyst compound of claim 1 , wherein the metallocene catalyst compound is a mixture of rac/meso isomers and the rac/meso ratio is 7:1 or greater.

14. The metallocene catalyst compound of claim 1 , wherein the metallocene catalyst compound is a mixture of rac/meso isomers and the rac/meso ratio is 5:1 or greater.

Assignees

• Exxonmobil Chem Patents Inc

Inventors

• Jian Yang
• Holtcamp Matthew W
• Giesbrecht Garth R
• Day Gregory S

Classifications

• C08F4/76 Primary

  selected from titanium, zirconium, hafnium, vanadium, niobium or tantalum · CPC title

• C08F4/65912

  in combination with an organoaluminium compound · CPC title

• C08F4/65927

  two cyclopentadienyl rings being mutually bridged · CPC title

• C08F10/06 Primary

  Propene · CPC title

• C07F17/00

  Metallocenes · CPC title