Substituted metallocene catalysts

Patent metadata

Field	Value
Publication number	US-9458254-B2
Application number	US-201414325449-A
Country	US
Kind code	B2
Filing date	Jul 8, 2014
Priority date	Jul 17, 2013
Publication date	Oct 4, 2016
Grant date	Oct 4, 2016

Abstract

This invention relates to novel bridged a hafnium transition metal metallocene catalyst compounds having two indenyl ligands substituted at the 4 positions with a C 1 to C 10 alkyl, where the 3 positions are hydrogen (assuming the bridge position is counted as the one position) and the bridging atom is carbon or silicon which is incorporated into a cyclic group comprising 3, 4, 5, or 6 silicon and/or carbon atoms that make up the cyclic ring.

First claim

The invention claimed is:

1. A metallocene catalyst compound represented by the formula:

where each R 3 is hydrogen; each R 4 is independently a C 1 -C 10 alkyl; each R 2 and R 7 is independently hydrogen or C 1 -C 10 alkyl; each R 5 and R 6 is independently hydrogen, C 1 -C 50 substituted or unsubstituted hydrocarbyl, or C 1 -C 50 substituted or unsubstituted halocarbyl; and R 4 and R 5 , R 5 and R 6 and/or R 6 and R 7 are optionally bonded together to form a ring structure; J is a bridging group represented by the formula R a 2 J, where J is C or Si, and each R a is, independently, C 1 to C 20 substituted or unsubstituted hydrocarbyl, and the two R a form a cyclic structure incorporating J and the cyclic structure is optionally a saturated or partially saturated cyclic or fused ring system; 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 catalyst compound of claim 1 wherein R 2 , R 4 and R 7 are, independently, a C 1 to C 10 alkyl, and R 3 , R 5 and R 6 are hydrogen.

3. The metallocene catalyst compound of claim 1 wherein R 2 , R 4 and R 7 are, independently, selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, heptyl, hexyl, octyl, nonyl, decyl and an isomers thereof.

4. The metallocene catalyst compound of claim 1 wherein R 4 and R 7 are, independently, a C 1 to C 10 alkyl.

5. 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, and two X's optionally form part of a fused ring or a ring system.

6. The metallocene catalyst compound of claim 1 wherein J is represented by the formula:

wherein J′ is a carbon or silicon atom, x is 1, 2, 3, or 4, and each R′ is, independently, hydrogen or C 1 -C 10 hydrocarbyl.

7. The metallocene catalyst compound of claim 1 wherein J is cyclopentamethylenesilylene, cyclotetramethylenesilylene, cyclotrimethylenesilylene.

8. A metallocene catalyst compound selected from the group consisting of:
cyclotetramethylenesilylene-bis(2,4,7-trimethylinden-1-yl)hafnium dimethyl,
cyclopentamethylenesilylene-bis(2,4,7-trimethylinden-1-yl)hafnium dimethyl,
cyclotrimethylenesilylene-bis(2,4,7-trimethylinden-1-yl)hafnium dimethyl,
cyclotetramethylenesilylene-bis(2,4,7-trimethylinden-1-yl)hafnium dichloride,
cyclopentamethylenesilylene-bis(2,4,7-trimethylinden-1-yl)hafnium dichloride,
cyclotrimethylenesilylene-bis(2,4,7-trimethylinden-1-yl)hafnium dichloride,
cyclopentamethylenesilylene-bis(2,4-dimethylinden-1-yl)hafnium dimethyl,
cyclotrimethylenesilylene-bis(2,4-dimethylinden-1-yl)hafnium dimethyl,
cyclopentamethylenesilylene-bis(2,4-dimethylinden-1-yl)hafnium dichloride,
cyclotrimethylenesilylene-bis(2,4-dimethylinden-1-yl)hafnium dichloride,
cyclotetramethylenesilylene-bis(4,7-dimethylinden-1-yl)hafnium dimethyl,
cyclopentamethylenesilylene-bis(4,7-dimethylinden-1-yl)hafnium dimethyl,
cyclotrimethylenesilylene-bis(4,7-dimethylinden-1-yl)hafnium dimethyl,
cyclotetramethylenesilylene-bis(4,7-dimethylinden-1-yl)hafnium dichloride,
cyclopentamethylenesilylene-bis(4,7-dimethylinden-1-yl)hafnium dichloride,
cyclotrimethylenesilylene-bis(4,7-dimethylinden-1-yl)hafnium dichloride,
cyclotetramethylenesilylene-bis(2-methyl-4-cyclopropylinden-1-yl)hafnium dimethyl,
cyclopentamethylenesilylene-bis(2-methyl-4-cyclopropylinden-1-yl)hafnium dimethyl,
cyclotrimethylenesilylene-bis(2-methyl-4-cyclopropylinden-1-yl)hafnium dimethyl,
cyclotetramethylenesilylene-bis(2-methyl-4-cyclopropylinden-1-yl)hafnium dichloride,
cyclopentamethylenesilylene-bis(2-methyl-4-cyclopropylindenyl)hafnium dichloride,
cyclotrimethylenesilylene-bis(2-methyl-4-cyclopropylinden-1-yl)hafnium dichloride,
cyclotetramethylenesilylene-bis(2-ethyl-4-cyclopropylinden-1-yl)hafnium dimethyl,
cyclopentamethylenesilylene-bis(2-ethyl-4-cyclopropylinden-1-yl)hafnium dimethyl,
cyclotrimethylenesilylene-bis(2-ethyl-4-cyclopropylinden-1-yl)hafnium dimethyl,
cyclotetramethylenesilylene-bis(2-ethyl-4-cyclopropylinden-1-yl)hafnium dichloride,
cyclopentamethylenesilylene-bis(2-ethyl-4-cyclopropylinden-1-yl)hafnium dichloride,
cyclotrimethylenesilylene-bis(2-ethyl-4-cyclopropylinden-1-yl)hafnium dichloride,
cyclotetramethylenesilylene-bis(2-methyl-4-t-butylinden-1-yl)hafnium dimethyl,
cyclopentamethylenesilylene-bis(2-methyl-4-t-butylinden-1-yl)hafnium dimethyl,
cyclotrimethylenesilylene-bis(2-methyl-4-t-butylinden-1-yl)hafnium dimethyl,
cyclotetramethylenesilylene-bis(2-methyl-4-t-butylinden-1-yl)hafnium dichloride,
cyclopentamethylenesilylene-bis(2-methyl-4-t-butylinden-1-yl)hafnium dichloride,
cyclotrimethylenesilylene-bis(2-methyl-4-t-butylinden-1-yl)hafnium dichloride,
cyclotetramethylenesilylene-bis(4,7-diethylinden-1-yl)hafnium dimethyl,
cyclopentamethylenesilylene-bis(4,7-diethylinden-1-yl)hafnium dimethyl,
cyclotrimethylenesilylene-bis(4,7-diethylinden-1-yl)hafnium dimethyl,
cyclotetramethylenesilylene-bis(4,7-diethylinden-1-yl)hafnium dichloride,
cyclopentamethylenesilylene-bis(4,7-diethylinden-1-yl)hafnium dichloride,
cyclotrimethylenesilylene-bis(4,7-diethylinden-1-yl)hafnium dichloride,
cyclotetramethylenesilylene-bis(2,4-diethylinden-1-yl)hafnium dimethyl,
cyclopentamethylenesilylene-bis(2,4-diethylinden-1-yl)hafnium dimethyl,
cyclotrimethylenesilylene-bis(2,4-diethylinden-1-yl)hafnium dimethyl,
cyclotetramethylenesilylene-bis(2,4-diethylinden-1-yl)hafnium dichloride,
cyclopentamethylenesilylene-bis(2,4-diethylinden-1-yl)hafnium dichloride,
cyclotrimethylenesilylene-bis(2,4-diethylinden-1-yl)hafnium dichloride,
cyclotetramethylenesilylene-bis(2-methyl-4,7-diethylinden-1-yl)hafnium dimethyl,
cyclopentamethylenesilylene-bis(2-methyl-4,7-diethylinden-1-yl)hafnium dimethyl,
cyclotrimethylenesilylene-bis(2-methyl-4,7-diethylinden-1-yl)hafnium dimethyl,
cyclotetramethylenesilylene-bis(2-methyl-4,7-diethylinden-1-yl)hafnium dichloride,
cyclopentamethylenesilylene-bis(2-methyl-4,7-diethylinden-1-yl)hafnium dichloride,
cyclotrimethylenesilylene-bis(2-methyl-4,7-diethylinden-1-yl)hafnium dichloride,
cyclotetramethylenesilylene-bis(2-ethyl-4-methylinden-1-yl)hafnium dimethyl,
cyclopentamethylenesilylene-bis(2-ethyl-4-methylinden-1-yl)hafnium dimethyl,
cyclotrimethylenesilylene-bis(2-ethyl-4-methylinden-1-yl)hafnium dimethyl,
cyclotetramethylenesilylene-bis(2-ethyl-4-methylinden-1-yl)hafnium dichloride,
cyclopentamethylenesilylene-bis(2-ethyl-4-methylinden-1-yl)hafnium dichloride,
cyclotrimethylenesilylene-bis(2-ethyl-4-methylinden-1-yl)hafnium dichloride,
cyclopentamethylenesilylene-bis(2-methyl-4-isopropylinden-1-yl)hafnium dimethyl,
cyclotrimethylenesilylene-bis(2-methyl-4-isopropylinden-1-yl)hafnium dimethyl,
cyclopentamethylenesilylene-bis(2-methyl-4-isopropylinden-1-yl)hafnium dichloride,
cyclotrimethylenesilylene-bis(2-methyl-4-isopropylinden-1-yl)hafnium dichloride,
cyclotetramethylenesilylene-bis(4,6,8-trimethyl-1,2,3-trihydro-s-indacen-5-yl)hafnium dimethyl,
cyclopentamethylenesilylene-bis(4,6,8-trimethyl-1,2,3-trihydro-s-indacen-5-yl)hafnium dimethyl,
cyclotrimethylenesilylene-bis(4,6,8-trimethyl-1,2,3-trihydro-s-indacen-5-yl)hafnium dimethyl,
cyclotetramethylenesilylene-bis(4,6,8-trimethyl-1,2

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Canich Jo Ann M
• Borisov Ilya S
• Golenishchev Arkady K
• Goryunov Georgy P
• Uborsky Dmitry V
• Kulyabin Pavel S
• Kononovich Dmitry S
• Izmer Vyatcheslav V
• Voskoboynikov Alexander Z

Classifications

• C08F4/65912 Primary

  in combination with an organoaluminium compound · CPC title

• C08F210/06

  Propene · CPC title

• C08F4/65927

  two cyclopentadienyl rings being mutually bridged · CPC title

• C07F17/00

  Metallocenes · CPC title

• C08F110/06

  Propene · CPC title