Metallocene catalyst compositions and polymerization process therewith

Patent metadata

Field	Value
Publication number	US-10280240-B2
Application number	US-201715450963-A
Country	US
Kind code	B2
Filing date	Mar 6, 2017
Priority date	May 27, 2016
Publication date	May 7, 2019
Grant date	May 7, 2019

Abstract

This invention relates homogeneous (solution) polymerization of propylene at higher temperatures (80° C. or more) using bisindenyl metallocene catalyst compounds having long (at least 4 carbon atoms) linear alkyl groups substituted at the 2-position and substituted or unsubstituted aryl groups at the 4-position.

First claim

The invention claimed is:

1. A process to polymerize propylene comprising contacting, at a temperature of 80° C. or more, propylene and optional comonomer with a homogeneous catalyst system comprising non-coordinating anion activator and one or more asymmetric metallocene catalyst compounds represented by the formula:

R 2 and R 8 are, independently, a C 1 to C 20 linear alkyl group where R 8 has at least 4 carbon atoms;
R 4 and R 10 are substituted or unsubstituted aryl groups, provided that at least one of the aryl groups is: 1) substituted at an ortho-position with at least one group selected from C 1 to C 40 hydrocarbyls, heteroatoms, and heteroatom containing groups and/or 2) substituted at the 3′, 4′ or 5′-position with at least one group selected from C 1 to C 40 hydrocarbyls, heteroatoms, and heteroatom containing groups;
M is a group 3 or 4 transition 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; and
where if the commoner comprises ethylene, then the ethylene is present at a partial pressure of up to 6900 kPa.

2. The process of claim 1 , wherein R 2 is methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl or n-decyl.

3. The process of claim 1 , wherein R 8 is n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl or n-decyl.

4. The process of claim 1 , wherein at least one of R 4 and R 10 is 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.

5. The process 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 and, optionally, the 4′-position is substituted with a group selected from (XR′ n ) − , wherein X is a Group 14-17 heteroatom having an atomic weight of 13 to 79 and R′ is one of a hydrogen atom, halogen atom, a C 1 -C 10 alkyl group, or a C 6 -C 10 aryl group and n is 0, 1, 2, or 3.

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

7. The process of claim 1 , wherein at least one of R 4 and R 10 is a phenyl group substituted at the 2′-position with an alkyl or aryl group.

8. The process of claim 1 , wherein one of R 5 and R 6 or R 11 and R 12 join together to form a ring structure.

9. The process of claim 1 , wherein T is represented by the formula R 2 a 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 process 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 process of claim 1 , wherein the metallocene catalyst compound is represented by one or more of the following formulas:

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

13. The process of claim 1 , wherein the activator comprises one or more anionic activators represented by the formula:

where:
each R 1 is, independently, a halide;
each R 2 is, independently, a halide, a C 6 to C 20 substituted aromatic hydrocarbyl group or a siloxy group of the formula —O—Si—R a , where R a is a C 1 to C 20 hydrocarbyl or hydrocarbylsilyl group;
each R 3 is a halide, C 6 to C 20 substituted aromatic hydrocarbyl group or a siloxy group of the formula —O—Si—R a , where R a is a C 1 to C 20 hydrocarbyl or hydrocarbylsilyl group;
wherein R 2 and R 3 can form one or more saturated or unsaturated, substituted or unsubstituted rings;
L is an neutral Lewis base; (L-H) + is a Bronsted acid; d is 1, 2, or 3;
wherein the anion has a molecular weight of greater than 1020 g/mol; and
wherein at least three of the substituents on the B atom each have a molecular volume of greater than 250 cubic Å.

14. The process of claim 1 , wherein the activator comprises one or more of N,N-dimethylanilinium tetrakis(perfluoronaphthalen-2-yl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis (3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, and triphenylcarbenium tetrakis(perfluorophenyl)borate.

15. The process of claim 1 , wherein the activator comprises N,N-dimethylanilinium tetrakis(perfluoronaphthalen-2-yl)borate.

16. The process of claim 1 , wherein the process occurs at a temperature of 90° C. or more.

17. The process of claim 1 , wherein the process occurs at a temperature of from about 90° C. to about 200° C., at a pressure in the range of from about 0.35 MPa to about 10 MPa, and at a time up to 300 minutes.

18. The process of claim 1 , wherein the polymerization occurs in the solution phase.

19. The process of claim 1 , wherein R 2 and R 8 have no branches at the alpha or beta-positions.

20. The process of claim 1 , wherein at least one of R 2 and R 8 has at least 6 carbon atoms.

21. The process of claim 1 , wherein when the metallocene catalyst compound comprises rac and meso isomers, the rac/meso ratio is 30:1 or greater.

22. The process of claim 1 wherein when the metallocene catalyst compound comprises rac and meso isomers, the metallocene catalyst comprises greater than 55 mol % of the racemic isomer.

23. The process of claim 1 wherein when the metallocene catalyst compound comprises rac and meso isomers, the metallocene catalyst comprises greater than 85 mol % of the racemic isomer.

24. The process of claim 1 , wherein R 2 is methyl and R 8 is n-butyl, n-pentyl, n-hexyl, n-heptyl, or n-octyl.

25. The process of claim 1 , wherein the catalyst system is not supported on a support and is dissolved in the solvent/monomer mixture.

26. The process of claim 1 wherein R 2 is methyl and R 8 has at least 4 carbon atoms.

27. The process of claim 1 wherein R 8 has at least 6 carbon atoms.

28. The process of claim 1 wherein R 4 and R 10 are different.

29. The process of claim 1 wherein R 2 and R 8 are different.

30. The process of claim 1 wherein R 4 and R 10 are different and R 2 and R 8 are different.

31. The process of claim 1 wherein T is dialkylsilyl, R 2 is methyl, R 8 is butyl, and R 5 and R 6 are joined to form a non-aromatic ring containing 5 or 6 or 7 atoms.

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Hagadorn John R
• Yang Jian

Classifications

• C08F2420/01

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

• C08F2800/20

  as weight or mass percentages · CPC title

• C08F210/16

  Copolymers of ethene with alpha-alkenes, e.g. EP rubbers · CPC title

• C07F17/00 Primary

  Metallocenes · CPC title

• C08F4/65912

  in combination with an organoaluminium compound · CPC title