Metallocenes and catalyst compositions derived therefrom

Patent metadata

Field	Value
Publication number	US-9745390-B2
Application number	US-201615000731-A
Country	US
Kind code	B2
Filing date	Jan 19, 2016
Priority date	Jul 17, 2013
Publication date	Aug 29, 2017
Grant date	Aug 29, 2017

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 catalyst system comprising activator and 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;
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 is optionally 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; and
R 4 is a phenyl group substituted at the 2′ position with an aryl group or is a phenyl group substituted at the 3′ position with a C 1 to C 10 alkyl group or aryl group and the 5′ position with a C 1 to C 10 alkyl group or aryl group, wherein, when a substitutent on the phenyl group of R 4 is an aryl group which is further substituted with an aryl group, the two groups bound together are optionally joined together directly or by linker groups.

2. The catalyst system of claim 1 , wherein R 2 is a cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecanyl, cyclododecyl, a methylcycloalkyl group, an ethylcycloalkyl group, wherein the alkyl in the cycloalkyl group of the methylcycloalkyl or the ethylcycloalkyl is a C 3 -C 12 alkyl.

3. The catalyst system of claim 1 , wherein the linker group is an alkyl, vinyl, phenyl, alkynyl, silyl, germyl, amine, ammonium, phosphine, phosphonium, ether, thioether, borane, borate, alane or aluminate groups.

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

5. The catalyst system 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.

6. The catalyst system of claim 1 , wherein R 10 is 1) a phenyl group substituted at the 2′ position with an aryl group; or 2) a phenyl group substituted at the 3′ position with a C 1 to C 10 alkyl group or aryl group and the 5′ position with a C 1 to a C 10 alkyl group or aryl group.

7. The catalyst system of claim 6 , wherein the aryl groups at the 3′ and 5′ positions are phenyl groups.

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

9. The catalyst system of claim 1 , wherein M is Hf or Zr; 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 combinations thereof, or two X's optionally form a part of a fused ring or a ring system; and 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 can form a cyclic structure including aromatic, partially saturated, or saturated cyclic or fused ring system.

10. The catalyst system of claim 1 , wherein the catalyst formula is:

or mixtures thereof.

11. The catalyst system 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.

12. The catalyst system 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.

13. The catalyst system of claim 1 , 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 1 , wherein the activator comprises a non-coordinating anion activator and or alumoxane.

15. The catalyst system of claim 1 , wherein the activator is one or more of: N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, or N,N-dimethylanilinium tetrakis(pentafluoronaphthyl)borate.

16. The catalyst system of claim 1 , wherein the catalyst system is supported.

17. A process to polymerize olefins comprising contacting one or more olefins with the catalyst system of claim 1 .

18. The process of claim 17 , wherein the catalyst system is in solution phase producing a polymer having an Mw/Mn of from about 1.7 to about 2.5.

19. The process of claim 17 , wherein the catalyst system is on a support to produce a polymer having a Mw/Mn from about 2.5 to about 15.

20. The process of claim 17 , wherein: 1) polymer is obtained from the process; and 2) said polymer has an MFR of 10 dg/min or more and a 1% Secant flexural modulus of than 1500 MPa or more.

21. The process of claim 17 , wherein no hydrogen is added to the polymerization.

22. The process of claim 17 , wherein the polymer obtained has Tm of 155° C. or more and an Mw of 330,000 g/mol or more.

23. The catalyst system 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, wherein the alkyl in the cycloalkyl group of the methylcycloalkyl or the ethylcycloalkyl is a C 3 -C 12 alkyl;
R 10 is 1) a phenyl group substituted at the 2′ position with an aryl group; or 2) a phenyl group substituted at the 3′ position with a C 1 to C 10 alkyl group or aryl group and the 5′ position with a C 1 to C 10 alkyl group or aryl group;
M is Hf, Ti and/or Zr;
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;
T is represented by 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 can form a cyclic structure including aromatic, partially saturated, or saturated cyclic or f

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

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

Classifications

• C08F10/06 Primary

  Propene · CPC title

• C08F4/65925

  two cyclopentadienyl rings being mutually non-bridged · CPC title

• C08F4/65916

  supported on a carrier, e.g. silica, MgCl2, polymer · CPC title

• C07F17/00

  Metallocenes · CPC title

• C08F4/65912

  in combination with an organoaluminium compound · CPC title