Cyclopentadienyl/adamantyl phosphinimine zirconium and hafnium complexes

Patent metadata

Field	Value
Publication number	US-12486342-B2
Application number	US-202117919036-A
Country	US
Kind code	B2
Filing date	Apr 16, 2021
Priority date	Apr 21, 2020
Publication date	Dec 2, 2025
Grant date	Dec 2, 2025

Abstract

Provided in this disclosure are zirconium and hafnium complexes that contain 1) a cyclopentadienyl ligand; 2) an adamantyl-phosphinimine ligand; and 3) at least one other ligand. The use of such a complex, in combination with an activator, as an olefin polymerization catalyst is demonstrated. The catalysts are effective for the copolymerization of ethylene with an alpha olefin (such as 1-butene, 1-hexene, or 1-octene).

First claim

The invention claimed is:

1 . A complex having the formula (PI)(Cp)ML 2 , wherein:
I) PI is a phosphinimine ligand defined by the formula:

where N is a nitrogen atom; P is a phosphorus atom; each R 1 is unsubstituted adamantyl, or substituted adamantyl; and R 1′ is selected from the group consisting of unsubstituted adamantyl, substituted adamantyl and C 1 to C 6 hydrocarbyl;
II) Cp is a cyclopentadienyl-type ligand comprising a 5-membered carbon ring having delocalized bonding within the ring and bound to M, which ring is unsubstituted or may be further substituted;
III) each L is an activatable ligand; and
IV) M is zirconium or hafnium.

2 . The complex of claim 1 , wherein R 1′ is unsubstituted adamantyl, or substituted adamantyl.

3 . The complex of claim 1 , wherein R 1′ is unsubstituted adamantyl.

4 . The complex of claim 3 , wherein each R 1 is unsubstituted adamantyl.

5 . The complex of claim 4 , wherein R 1′ and each R 1 is 1-adamantyl.

6 . The complex of claim 1 , wherein Cp is (pentamethyl)cyclopentadienyl.

7 . The complex of claim 1 , wherein Cp is cyclopentadienyl.

8 . The complex of claim 1 , wherein M is zirconium.

9 . The complex of claim 1 , wherein M is hafnium.

10 . An olefin polymerization catalyst system comprising:
A) a complex having the formula (PI)(Cp)ML 2 , wherein:
I) PI is a phosphinimine ligand defined by the formula:

where N is a nitrogen atom; P is a phosphorus atom; each R 1 is unsubstituted adamantyl, or substituted adamantyl; and R 1′ is selected from the group consisting of unsubstituted adamantyl, substituted adamantyl and C 1 to C 6 hydrocarbyl;
II) Cp is a cyclopentadienyl-type ligand comprising a 5-membered carbon ring having delocalized bonding within the ring and bound to M, which ring is unsubstituted or may be further substituted;
III) each L is an activatable ligand; and
IV) M is zirconium or hafnium; and

B) an activator.

11 . The olefin polymerization catalyst of claim 10 , wherein
the activator is selected from the group consisting of an aluminoxane; an organoaluminum compound; an ionic activator; and mixtures thereof.

12 . The olefin polymerization catalyst of claim 10 , wherein R 1′ is unsubstituted adamantyl, or substituted adamantyl.

13 . The olefin polymerization catalyst of claim 10 , wherein R 1′ is unsubstituted adamantyl.

14 . The olefin polymerization catalyst of claim 13 , wherein each R 1 is unsubstituted adamantyl.

15 . The olefin polymerization catalyst of claim 14 , wherein R 1′ and each R 1 is 1-adamantyl.

16 . The olefin polymerization catalyst system of claim 10 , wherein Cp is (pentamethyl)cyclopentadienyl.

17 . The olefin polymerization catalyst system of claim 10 , wherein Cp is cyclopentadienyl.

18 . The olefin polymerization catalyst system of claim 10 , wherein M is zirconium.

19 . The olefin polymerization catalyst system of claim 10 , wherein M is hafnium.

20 . A process for the polymerization of olefins, the process comprising contacting one or more of ethylene and C 3 to C 10 alpha olefins with the olefin polymerization catalyst system of claim 10 under polymerization conditions.

21 . The process according to claim 20 wherein the one or more of ethylene and C 3 to C 10 alpha olefins consists of a) ethylene; and b) one or more olefins selected from the group consisting of 1-butene; 1-hexene; and 1-octene.

22 . A process for the (co) polymerization of ethylene, the process comprising:
A) preparing a first polymer solution by polymerizing ethylene, optionally with one or more C 3 to C 10 alpha olefins, in a solvent in a first polymerization reactor at a temperature of from 80 to 200° C. and a pressure of from 1,000 to 8,000 psi in the presence of (i) the complex according to claim 1 ; and (ii) an activator consisting essentially of an aluminoxane and an ionic activator; and B) passing said first polymer solution into a second polymerization reactor and (co) polymerizing ethylene, optionally with one or more C 3 -C 10 alpha olefins, in the presence of a Ziegler Natta catalyst.

23 . A process for the (co) polymerization of ethylene, the process comprising:
A) preparing a first polymer solution by polymerizing ethylene, optionally with one or more C 3 to C 10 alpha olefins, in a solvent in a first polymerization reactor at a temperature of from 80 to 200° C. and a pressure of from 1,000 to 8,000 psi in the presence of (i) the complex according to claim 1 ; and (ii) an activator consisting essentially of an organoaluminum compound and an ionic activator; and B) passing said first polymer solution into a second polymerization reactor and (co) polymerizing ethylene, optionally with one or more C 3 -C 10 alpha olefins, in the presence of a Ziegler Natta catalyst.

Assignees

• Nova Chemicals International Sa

Inventors

• Gao Xiaoliang
• Carter Charles
• Chisholm P Scott
• Smiley-Wiens Janelle
• Morrison Darryl
• Woo Alva
• Fan Cheng
• Chang Chia Yun
• Chiu Frederick

Classifications

• C08F210/16

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

• C07F17/00 Primary

  Metallocenes · CPC title

• Y02P20/52

  using catalysts, e.g. selective catalysts · CPC title

• C08F2420/07

  Heteroatom-substituted Cp, i.e. Cp or analog where at least one of the substituent of the Cp or analog ring is or contains a heteroatom · CPC title

• C08F2420/06

  Cp analog where at least one of the carbon atoms of the non-coordinating part of the condensed ring is replaced by a heteroatom · CPC title