Metallocenes and catalyst compositions derived therefrom

Patent metadata

Field	Value
Publication number	US-9464145-B2
Application number	US-201414324333-A
Country	US
Kind code	B2
Filing date	Jul 7, 2014
Priority date	Jul 17, 2013
Publication date	Oct 11, 2016
Grant date	Oct 11, 2016

Abstract

This invention relates to a novel group 4 transition metal metallocene catalyst compound that is asymmetric having two non-identical indenyl ligands with substitution at R 2 having a branched C 1 -C 20 alkyl group, R 8 having a linear alkyl group and R 4 and R 10 having substituted phenyl groups, where at least one of R 4 and R 10 is a phenyl group substituted at the 3 and 5 position.

First claim

The invention claimed is:

1. A metallocene catalyst compound represented by the formula:

R 2 and R 8 are not the same;
R 4 and R 10 are substituted phenyl groups, where: both of R 4 and R 10 are a phenyl group substituted at the 3 and 5 positions, or one of R 4 and R 10 is a phenyl group substituted at the 3 and 5 positions and the other is a phenyl group substituted at the 2 position with an aryl group;
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 5 , R 6 , R 7 , 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 20 hydrocarbyl group, where the group is substituted at the alpha position;
R 3 and R 9 are hydrogen; and
R 8 is a linear C 1 -C 10 alkyl group which is optionally halogenated, wherein the metallocene catalyst compound is a mixture of rac/meso isomers and the rac/meso ratio is 10:1 or greater.

2. The metallocene catalyst compound of claim 1 , wherein R 2 is an alkyl group which is branched in α-position.

3. The metallocene catalyst compound of claim 1 , wherein R 8 is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl.

4. The metallocene catalyst compound of claim 1 , wherein the 3 and 5 positions are substituted with C 1 to C 10 alkyl groups or aryl groups or combinations thereof.

5. The metallocene catalyst compound of claim 1 , wherein R 4 and R 10 are independently a phenyl group substituted at the 3 and 5 positions with C 1 to a C 10 alkyl groups or aryl groups or combinations thereof.

6. The metallocene catalyst compound of claim 1 , wherein M is Hf, Ti and/or Zr.

7. 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.

8. 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 R a is, independently, hydrogen, halogen, C 1 to C 20 hydrocarbyl or a C 1 to C 20 substituted hydrocarbyl, and two R a optionally form a cyclic structure including aromatic, partially saturated, or saturated cyclic or fused ring system.

9. 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 .

10. 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 40:1 or greater.

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

12. The catalyst system of claim 11 , wherein the activator comprises alumoxane.

13. The catalyst system of claim 11 , wherein alumoxane is present at a molar ratio of aluminum to catalyst compound transition metal of 100:1 or more.

14. The catalyst system of claim 11 , wherein the activator comprises a non-coordinating anion activator.

15. The catalyst system of claim 11 , wherein activator is represented by the formula:
(Z) d + (A d− )

wherein Z is (L-H) or a reducible Lewis Acid, L is an neutral Lewis base; H is hydrogen; (L-H) + is a Bronsted acid; A d− is a non-coordinating anion having the charge d-; and d is an integer from 1 to 3.

16. The catalyst system of claim 11 , wherein activator is represented by the formula:
(Z) d + (A d− )

wherein Ad− is a non-coordinating anion having the charge d-; d is an integer from 1 to 3, and Z is a reducible Lewis acid represented by the formula: (Ar3C+), where Ar is aryl or aryl substituted with a heteroatom, a C 1 to C 40 hydrocarbyl, or a substituted C 1 to C 40 hydrocarbyl.

17. The catalyst system of claim 11 , wherein the activator is one or more of:
N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,
triphenylcarbenium tetrakis(pentafluorophenyl)borate,
trimethylammonium tetrakis(perfluoronaphthyl)borate,
triethylammonium tetrakis(perfluoronaphthyl)borate,
tripropylammonium tetrakis(perfluoronaphthyl)borate,
tri(n-butyl)ammonium tetrakis(perfluoronaphthyl)borate,
tri(t-butyl)ammonium tetrakis(perfluoronaphthyl)borate,
N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate,
N,N-diethylanilinium tetrakis(perfluoronaphthyl)borate,
N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate,
tropillium tetrakis(perfluoronaphthyl)borate,
triphenylcarbenium tetrakis(perfluoronaphthyl)borate,
triphenylphosphonium tetrakis(perfluoronaphthyl)borate,
triethylsilylium tetrakis(perfluoronaphthyl)borate,
benzene(diazonium)tetrakis(perfluoronaphthyl)borate,
trimethylammonium tetrakis(perfluorobiphenyl)borate,
triethylammonium tetrakis(perfluorobiphenyl)borate,
tripropylammonium tetrakis(perfluorobiphenyl)borate,
tri(n-butyl)ammonium tetrakis(perfluorobiphenyl)borate,
tri(t-butyl)ammonium tetrakis(perfluorobiphenyl)borate,
N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate,
N,N-diethylanilinium tetrakis(perfluorobiphenyl)borate,
N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate,
tropillium tetrakis(perfluorobiphenyl)borate,
triphenylcarbenium tetrakis(perfluorobiphenyl)borate,
triphenylphosphonium tetrakis(perfluorobiphenyl)borate,
triethylsilylium tetrakis(perfluorobiphenyl)borate,
benzene(diazonium)tetrakis(perfluorobiphenyl)borate,
[4-t-butyl-PhNMe 2 H][(C 6 F 3 (C 6 F 5 ) 2 ) 4 B],
trimethylammonium tetraphenylborate,
triethylammonium tetraphenylborate,
tripropylammonium tetraphenylborate,
tri(n-butyl)ammonium tetraphenylborate,
tri(t-butyl)ammonium tetraphenylborate,
N,N-dimethylanilinium tetraphenylborate,
N,N-diethylanilinium tetraphenylborate,
N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate,
tropillium tetraphenylborate,
triphenylcarbenium tetraphenylborate,
triphenylphosphonium tetraphenylborate,
triethylsilylium tetraphenylborate,
benzene(diazonium)tetraphenylborate,
trimethylammonium tetrakis(pentafluorophenyl)borate,
triethylammonium tetrakis(pentafluorophenyl)borate,
tripropylammonium tetrakis(pentafluorophenyl)borate,
tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,
tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate,
N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,
N,N-diethylanilinium tetrakis(pentafluorophenyl)borate,
N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate,
tropillium tetrakis(pentafluorophenyl)borate,
triphenylcarbenium tetrakis(pentafluorophenyl)borate,
triphenylphosphonium tetrakis(pentafluorophenyl)borate,
triethylsilylium tetrakis(pentafluorophenyl)borate,
benzene(diazonium)tetrakis(pentafluorophenyl)borate,
trimethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,
triethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,
tripropylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,
tri(n-butyl)ammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,
dimethyl(t-butyl)ammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Yang Jian
• Lian Xiongdong

Classifications

• C07F17/00

  Metallocenes · CPC title

• C08F10/06 Primary

  Propene · CPC title

• C08F4/65912

  in combination with an organoaluminium compound · CPC title

• C08F4/65925

  two cyclopentadienyl rings being mutually non-bridged · CPC title

• C08F4/76

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