Dihydrocarbyl-silyl-bridged-1,3 disubstituted-2-indenyl metallocene complexes for olefin polymerization

Patent metadata

Field	Value
Publication number	US-11427608-B2
Application number	US-201816500658-A
Country	US
Kind code	B2
Filing date	Apr 4, 2018
Priority date	Apr 4, 2017
Publication date	Aug 30, 2022
Grant date	Aug 30, 2022

Abstract

The invention relates to a metallocene complex according to formula (A): wherein R1 is selected from C1-C10 alkyl, C6-C20 aryl, C7-C20 aralkyl groups, and C1-C10 alkoxy groups, wherein R2 is selected from H, C1-C10 alkyl; wherein R3-R6, R10 are independently selected from H, C1-C10 alkyl, C6-C10 aryl, and wherein R3 and R4, R4 and R5, or R5 and R6 can be connected to form a ringstructure; wherein M is selected from Ti, Zr and Hf, X is an anionic ligand to M, z is the number of X groups and equals the valence of M minus 2, and wherein each R7 independently is selected from C1-C6 alkyl or aryl groups. The invention also relates to a catalyst comprising the reaction product of the metallocene complex and a cocatalyst. Further the invention relates to a (co)polymerization process of olefinic monomers.

First claim

The invention claimed is:

1. A metallocene complex according to formula (A):

wherein R1 is selected from C1-C10 alkyl, C6-C20 aryl, or C7-C20 aralkyl groups;
wherein R2 is selected from H, C1-C10 alkyl, or C6-C10 aryl;
wherein R3 is H or C1-C10 alkyl;
wherein R4-R6 and R10 are independently selected from H, C1-C10 alkyl, or C6-C10 aryl, and wherein R3 and R4, R4 and R5, or R5 and R6 are optionally connected to form a ring structure;
wherein M is selected from Ti, Zr, or Hf, and X is an anionic ligand to M; and
wherein each R7 is independently selected from C1-C6 alkyl groups.

2. A metallocene complex according to claim 1 wherein the complex is according to formula I,

wherein R1 is selected from C1-C10 alkyl, C6-C20 aryl, or C7-C20 aralkyl groups;
wherein R2 is selected from H or C1-C10 alkyl;
wherein R3 is H or C1-C10 alkyl;
wherein R4-R6 and R10 are independently selected from H, C1-C10 alkyl, or C6-C10 aryl, and R3 and R4, R4 and R5, or R5 and R6 are optionally connected to form a ring structure; and
wherein M is selected from Ti, Zr, or Hf, and X is an anionic ligand to M.

3. The metallocene complex according to claim 1 , wherein M is chosen from Zr or Hf.

4. The metallocene complex according to claim 1 , wherein X is a methyl group, Cl, Br or I.

5. The metallocene complex according to claim 1 , wherein R10 is a methyl group.

6. The metallocene complex according to claim 1 , wherein R1 is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, phenyl, or 3,5-dialkyl-1-phenyl; and wherein R2 is H.

7. The metallocene complex according to claim 1 , wherein R3 is chosen from H, methyl, ethyl, propyl, or isopropyl, or R3 and R4 are connected to form a ring structure.

8. The metallocene complex according to claim 1 , wherein R3 is H or a methyl group, or R3 and R4 are connected to form a 6-membered aromatic ring structure.

9. The metallocene complex according to claim 1 , wherein R4 is H, or forms a ring structure together with R3 and the carbon atoms of the 1-indenyl group to which R3 and R4 are attached, and wherein R5 and R6 are each independently H, or a C1-C4 alkyl group.

10. A metallocene complex having a structure (II):

wherein R2 is H, R7 and R8 are chosen from H, methyl, isopropyl or tertiary butyl,
wherein
(i) R3-R6 are chosen from H, a methyl group, or a phenyl group, or
(ii) R3 and R4 are connected to form a six membered ring structure, and R5 and R6 are independently H or a methyl group, and
wherein M is selected from Ti, Zr, or Hf, X is an anionic ligand to M, and
z is the number of X groups and equals the valence of M minus 2.

11. The metallocene complex according to claim 1 , wherein the metallocene complex has structure according to formula (III),

wherein R1 is chosen from methyl, ethyl, propyl, or isopropyl, and
(i) R3 is H or a methyl group, R4-R6 are chosen from H, a methyl group, or a phenyl group or
(ii) R3 and R4 are connected to form a six membered ring structure, and R5 and R6 are each independently H, a methyl group, or a phenyl group.

12. A catalyst comprising the metallocene complex according to claim 1 and a cocatalyst.

13. The catalyst of claim 1 , wherein the cocatalyst includes aluminium- or boron-containing cocatalysts.

14. A process for the preparation of olefin polymers, the process comprising polymerizing one or more olefins in the presence of a cocatalyst and the metallocene complex according to claim 1 , wherein the metallocene complex optionally is immobilized on a support.

15. An article comprising the polyolefins obtainable by the process according to claim 14 .

16. The metallocene complex of claim 1 , wherein R2 is selected from H or C1-C10 alkyl.

17. The metallocene complex of claim 1 , wherein Xis a methyl group or Cl.

18. The metallocene complex of claim 1 ,
wherein R1 is chosen from methyl, ethyl, propyl, or isopropyl,
wherein
(i) R3 is chosen from H or a methyl group, R4-R6 are H, or
(ii) R3 and R4 are connected to form a six membered ring structure, and R5 and R6 are independently H or a methyl group, and
wherein M is Zr or Hf, X is a methyl group, Cl, Br or I, and R10 is a methyl group.

19. A catalyst comprising the metallocene complex according to claim 10 and a cocatalyst.

20. The catalyst of claim 19 , wherein the cocatalyst includes aluminium- or boron-containing cocatalysts.

Assignees

• Sabic Global Technologies Bv

Inventors

• Friederichs Nicolaas Hendrika
• Vittoria Antonio
• Cipullo Roberta
• Busico Vincenzo
• Borisov Ilya
• Guzeev Bogdan A
• Mladentsev Dmitry Y
• Sharikov Mikhail I
• Uborsky Dmitry
• Voskoboynikov Alexander
• Coen Hendriksen

Classifications

• C07F17/00 Primary

  Metallocenes · CPC title

• C08F4/65927

  two cyclopentadienyl rings being mutually bridged · CPC title

• C08F4/65912

  in combination with an organoaluminium compound · CPC title

• C08F210/16

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

• C08F10/00

  Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond · CPC title