Dual catalyst composition

Patent metadata

Field	Value
Publication number	US-11274171-B2
Application number	US-201816633675-A
Country	US
Kind code	B2
Filing date	Aug 2, 2018
Priority date	Aug 2, 2017
Publication date	Mar 15, 2022
Grant date	Mar 15, 2022

Abstract

The present invention relates to a catalyst composition comprising:
catalyst component A comprising a bridged metallocene compound with two indenyl groups, each indenyl being substituted with one or more substituents, wherein at least one of the substituent is an aryl or heteroaryl; catalyst component B comprising a bridged metallocene compound with a substituted or unsubstituted cyclopentadienyl group and a substituted or unsubstituted fluorenyl group; an optional activator; an optional support; and an optional co-catalyst.

The present invention also relates to a polymerization process using said composition. The invention further relates to olefin polymers at least partially catalyzed by said catalyst composition and articles comprising said olefin polymers.

First claim

The invention claimed is:

1. A catalyst composition comprising:
catalyst component A comprising a bridged metallocene compound with two indenyl groups each indenyl being independently substituted with one or more substituents, wherein at least one of the substituent is an aryl or heteroaryl;
catalyst component B comprising a bridged metallocene compound with a substituted or unsubstituted cyclopentadienyl group and a substituted or unsubstituted fluorenyl group;
an optional activator; an optional support; and an optional co-catalyst, wherein the bridged metallocene compound of catalyst component B comprises at least one alkenyl, cycloalkenyl, or cycloalkenylalkyl substituent.

2. The catalyst composition according to claim 1 , wherein the bridged metallocene compound of catalyst component B comprises at least one alkenyl, cycloalkenyl, or cycloalkenylalkyl substituent on the bridge.

3. The catalyst composition according to claim 1 , wherein catalyst component B contains a C, Si, Ge, or B bridging atom.

4. The catalyst composition according to claim 1 , wherein the activator comprises an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof.

5. The catalyst composition according to claim 1 , wherein the catalyst composition comprises a co-catalyst.

6. The catalyst composition according to claim 1 , wherein the catalyst composition comprises an organoaluminum co-catalyst selected from the group comprising trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum chloride, and any combination thereof.

7. The catalyst composition according to claim 1 , wherein the support comprises a solid oxide, wherein the solid oxide comprises titanated silica, silica, alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminophosphate, heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, a mixed oxide thereof, or any mixture thereof.

8. The catalyst composition according to claim 1 , comprising an alumoxane activator; and a titanated silica or silica solid support; and an optional co-catalyst.

9. The catalyst composition according to claim 1 , wherein catalyst component A comprises a bridged metallocene compound of formula (I), wherein

each of R 1 and R 3 is independently selected from the group consisting of alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R 10 ) 3 , heteroalkyl; wherein at least one of R 1 or R 3 is aryl, wherein each R 10 is independently hydrogen, alkyl, or alkenyl; and m, n, p, q is each independently an integer selected from 0, 1, 2, 3, or 4;
each of R 2 and R 4 is are independently selected from the group consisting of alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, phenyl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R 10 ) 3 , heteroalkyl; wherein at least one of R 2 or R 4 is aryl, wherein each R 10 is independently hydrogen, alkyl, or alkenyl; and m, n, p, q are each independently an integer selected from 0, 1, 2, 3, or 4;
L 1 is —[CR 8 R 9 ] h —, SiR 8 R 9 , GeR 8 R 9 , or BR 8 ; wherein h is an integer selected from 1, 2, or 3;
each of R 8 , and R 9 are independently selected from the group comprising hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, aminoalkyl, and arylalkyl; or R 8 and R 9 together with the atom to which they are attached form a cycloalkyl, cycloalkenyl or heterocyclyl;
M 1 is a transition metal selected from the group consisting of zirconium, titanium, hafnium, and vanadium; and
Q 1 and Q 2 are each independently selected from the group consisting of halogen, alkyl, —N(R 11 ) 2 , alkoxy, cycloalkoxy, aralkoxy, cycloalkyl, aryl, alkylaryl, aralkyl, and heteroalkyl;
wherein R 11 is hydrogen or alkyl.

10. The catalyst composition according to claim 1 , wherein the catalyst component A contains a SiR 8 R 9 , or —[CR 8 R 9 ] h — bridging group; wherein h is an integer selected from 1, 2, or 3; each of R 8 , and R 9 are independently selected from the group comprising hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, aminoalkyl, and arylalkyl; or R 8 and R 9 together with the atom to which they are attached form a cycloalkyl, cycloalkenyl or heterocyclyl.

11. The catalyst composition according to claim 1 , wherein catalyst component B comprises a bridged metallocene compound of formula (II), wherein

each of R 5 , R 6 , and R 7 is independently selected from the group consisting of alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, alkoxy, alkylaryl, arylalkyl, halogen, Si(R 10 ) 3 , heteroalkyl; wherein each R 10 is independently hydrogen, alkyl, or alkenyl; and r, s, t are each independently an integer selected from 0, 1, 2, 3, or 4;
L 2 is —[CR 8 R 9 ] h —, SiR 8 R 9 , GeR 8 R 9 , or BR 8 ; wherein h is an integer selected from 1, 2, or 3;
each of R 8 and R 9 is independently selected from the group comprising hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkenylalkyl, aryl, aminoalkyl, and arylalkyl; or R 8 and R 9 together with the atom to which they are attached form a cycloalkyl, cycloalkenyl or heterocyclyl;
M 2 is a transition metal selected from the group consisting of zirconium, titanium, hafnium, and vanadium; and
Q 3 and Q 4 are each independently selected from the group consisting of halogen, alkyl, —N(R 11 ) 2 , alkoxy, cycloalkoxy, aralkoxy, cycloalkyl, aryl, alkylaryl, aralkyl, and heteroalkyl;
wherein R 11 is hydrogen or alkyl.

12. An olefin polymerization process, the process comprising: contacting a catalyst composition according to claim 1 , with an olefin monomer, optionally hydrogen, and optionally one or more olefin co-monomers; and polymerizing the monomer, and the optionally one or more olefin co-monomers, in the presence of the at least one catalyst composition, and optional hydrogen, thereby obtaining a polyolefin.

13. An olefin polymer at least partially catalyzed by at least one catalyst composition according to claim 1 .

14. An article comprising the olefin polymer according to claim 13 .

Assignees

• Total Res & Technology Feluy

Inventors

• Cirriez Virginie
• Welle Alexandre
• Vantomme Aurélien

Classifications

• C08F4/65904

  in combination with another component of C08F4/64 · CPC title

• C08F210/16 Primary

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

• C08F4/65927

  two cyclopentadienyl rings being mutually bridged · CPC title

• C08F4/6465

  containing silicium · CPC title

• C08F4/65912

  in combination with an organoaluminium compound · CPC title