Organometallic complex, olefin polymerization catalyst system and polymerization process

Patent metadata

Field	Value
Publication number	US-12275751-B2
Application number	US-202418640307-A
Country	US
Kind code	B2
Filing date	Apr 19, 2024
Priority date	Mar 22, 2022
Publication date	Apr 15, 2025
Grant date	Apr 15, 2025

Abstract

Organometallic complexes are described which are useful as pre-polymerization catalysts which may form part of olefin polymerization catalyst systems. The catalyst systems find use in the polymerization of ethylene, optionally with one or more C 3-12 alpha-olefin comonomers. The organometallic complexes are broadly represented by formula I:

wherein L is a bridging group containing a contiguous chain of atoms connecting P with Cy, wherein the contiguous chain contains 2 or 3 atoms and wherein Cy is a cyclopentadienyl-type ligand. The olefin polymerization catalyst system is effective at polymerizing ethylene with alpha-olefins in a solution phase polymerization process at high temperatures and produces ethylene copolymers with high molecular weight and high degrees of alpha-olefin incorporation. Pre-metallation compounds, metallation processes and synthetic methods to make the organometallic complexes as well as polymerization processes are also described.

First claim

The invention claimed is:

1. An olefin polymerization catalyst system comprising:
i) an organometallic complex represented by formula I:

wherein
M is Ti, Zr or Hf;
R 1 and R 2 are each independently selected from the group consisting of hydrogen and R X ;
or R 1 and R 2 together with the P atom to which they are attached form a 3-10 membered heterocyclic group which is unsubstituted or further substituted by one or more substituent selected from the group consisting of a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, a C 7-20 alkylaryl group, a C 7-20 arylalkyl group, a C 6-20 aryl group, a C 6-20 aryloxy group, a C 7-20 alkylaryloxy group, and a C 7-20 arylalkyloxy group;
each R X is independently selected from the group consisting of a halogen atom; a C 1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one halogen atom, C 1-20 alkyl group, C 1-20 alkoxy group, C 7-20 alkylaryl group, C 7-20 arylalkyl group, C 6-20 aryl group, C 6-20 aryloxy group, C 7-20 alkylaryloxy group, and/or C 7-20 arylalkyloxy group; an amido group of the formula —NR′ 2 ; a silyl group of the formula —Si(R a ) 3 ; a germanyl group of the formula —Ge(R a ) 3 ; and a phosphinimine group of the formula —N═P(R b )(R c )(R d ); wherein each R′ is independently selected from the group consisting of hydrogen, C 1-20 alkyl group, and
C 6-20 aryl group; wherein each R a is independently selected from the group consisting of hydrogen, C 1-8 alkyl group, C 1-8 alkoxy group, C 6-20 aryloxy group and C 6-20 aryl group; and R b , R c , R d , are each independently a C 1-20 alkyl group;
each X 1 is an activatable ligand;
Cy is a cyclopentadienyl-type ligand covalently bound to L and coordinated to M via n-bonding; and
L is a bridging group containing a contiguous chain of atoms connecting P with Cy, wherein the contiguous chain of atoms consists of 2 or 3 atoms; and
ii) a catalyst activator.

2. The olefin polymerization catalyst system according to claim 1 , wherein the organometallic complex is represented by formula II:

wherein R 3 , R 4 , R 5 and R 6 are each independently selected from the group consisting of
halogen;
hydrogen;
a C 1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, a C 7-20 alkylaryl group, a C 7-20 arylalkyl group, a C 6-20 aryl group, a C 6-20 aryloxy group, a C 7-20 alkylaryloxy group, and a C 7-20 arylalkyloxy group;
a heteroatom containing C 1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, a C 7-20 alkylaryl group, a C 7-20 arylalkyl group, a C 6-20 aryl group, a C 6-20 aryloxy group, a C 7-20 alkylaryloxy group, and a C 7-20 arylalkyloxy group;
an oxy group, —OR′;
an amido group, —NR′ 2 ;
a phosphido group, —PR′ 2 ;
a thiolate group, —SR′;
a silyl group of the formula —Si(R a ) 3 ; and
a germanyl group of the formula —Ge(R a ) 3 ;
wherein two adjacent groups of R 3 , R 4 , R 5 and R 6 may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, a C 7-20 alkylaryl group, a C 7-20 arylalkyl group, a C 6-20 aryl group, a C 6-20 aryloxy group, a C 7-20 alkylaryloxy group, a C 7-20 arylalkyloxy group, an amido group of the formula —NR′ 2 , a phosphido group of the formula —PR′ 2 , a thiolate group of the formula —SR′, a silyl group of the formula —Si(R a ) 3 , and a germanyl group of the formula —Ge(R a ) 3 ;
wherein each R′ is independently selected from the group consisting of hydrogen, C 1-20 alkyl group, and C 6-20 aryl group; and
wherein each R a is independently selected from the group consisting of hydrogen, C 1-8 alkyl group, C 1-8 alkoxy group, C 6-20 aryloxy group, and C 6-20 aryl group.

3. The olefin polymerization catalyst system according to claim 2 , wherein the organometallic complex is represented by formula III:

wherein R 7 , R 8 , R 9 and R 10 are each independently selected from the group consisting of
halogen;
hydrogen;
a C 1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, a C 7-20 alkylaryl group, a C 7-20 arylalkyl group, a C 6-20 aryl group, a C 6-20 aryloxy group, a C 7-20 alkylaryloxy group, and a C 7-20 arylalkyloxy group;
a heteroatom containing C 1-30 hydrocarbyl group, which heteroatom containing hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, a C 7-20 alkylaryl group, a C 7-20 arylalkyl group, a C 6-20 aryl group, a C 6-20 aryloxy group, a C 7-20 alkylaryloxy group, and a C 7-20 arylalkyloxy group;
an oxy group, —OR′;
an amido group, —NR′ 2 ;
a phosphido group, —PR′ 2 ;
a thiolate group, —SR′;
a silyl group of the formula —Si(R a ) 3 ; and
a germanyl group of the formula —Ge(R a ) 3 ;
wherein two adjacent groups of R 7 , R 8 , R 9 and R 10 may optionally be bonded to form a cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group, the cyclic hydrocarbyl group or cyclic heteroatom containing hydrocarbyl group being unsubstituted or further substituted by one or more than one substituent selected from the group consisting of a halogen atom, a C 1-20 alkyl group, a C 1-20 alkoxy group, a C 7-20 alkylaryl group, a C 7-20 arylalkyl group, a C 6-20 aryl group, a C 6-20 aryloxy group, a C 7-20 alkylaryloxy group, a C 7-20 arylalkyloxy group, an amido group of the formula —NR′ 2 , a phosphido group of the formula —PR′ 2 , a thiolate group of the formula —SR′, a silyl group of the formula —Si(R a ) 3 , and a germanyl group of the formula —Ge(R a ) 3 ;
wherein each R′ is independently selected from the group consisting of hydrogen, C 1-20 alkyl group, and C 6-20 aryl group; and
wherein each R a is independently selected from the group consisting of hydrogen, C 1-8 alkyl group, C 1-8 alkoxy group, C 6-20 aryloxy group, and C 6-20 aryl group.

4. The olefin polymerization catalyst system according to claim 2 , wherein the organometallic complex is represented by formula IV:

wherein G is C or Si;
wherein R Q and R Q* are each independently selected from the group consisting of
halogen;
hydrogen;
a C 1-30 hydrocarbyl group, which hydrocarbyl group is unsubstituted or further substituted by one or more than one substituent selected from the group consisting

Assignees

• Nova Chemicals International Sa

Inventors

• Fan Cheng
• Carter Charles
• Morrison Darryl
• Gao Xiaoliang
• Goettel James T
• Cruz-Milette Daisy
• Chiu Frederick

Classifications

• C07F9/5728

  condensed with carbocyclic rings or carbocyclic ring systems · CPC title

• B01J2531/49

  Hafnium · CPC title

• B01J2531/46

  Titanium · CPC title

• B01J2523/49

  Hafnium · CPC title

• B01J2523/47

  Titanium · CPC title