Diimine metal complex, preparation method therefor, and application thereof

Patent metadata

Field	Value
Publication number	US-12454586-B2
Application number	US-202017755554-A
Country	US
Kind code	B2
Filing date	Oct 30, 2020
Priority date	Oct 31, 2019
Publication date	Oct 28, 2025
Grant date	Oct 28, 2025

Abstract

A diimine metal complex represented by Formula I, a preparation method therefor, and application thereof are provided. The complex is used as a main catalyst in catalysts for olefin polymerization, and can achieve catalytic ethylene polymerization at a high temperature to prepare high molecular weight branched polyethylene.

First claim

What is claimed is:

1. A diimine-metal complex represented by Formula I:

wherein,
R 1 and R 2 are each independently a C1-C30 hydrocarbyl with or without a substituent Q;
R 3 and R 4 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C20 hydrocarbyl with or without the substituent Q, C1-C20 alkoxy with or without the substituent Q, C2-C20 alkenoxy with or without the substituent Q, C2-C20 alkynoxy with or without the substituent Q, C6-C20 aryloxy with or without the substituent Q, C7-C20 aralkoxy with or without the substituent Q, and C7-C20 alkaryloxy with or without the substituent Q, and adjacent R 3 and R 4 groups are optionally joined to form a ring or ring system;
each R 11 is independently a C1-C20 hydrocarbyl with or without the substituent Q;
each Y is independently a Group VIA non-metal atom;
each M is independently a Group VIII metal; and
each X is independently selected from the group consisting of halogen, C1-C10 hydrocarbyl with or without the substituent Q, and C1-C10 hydrocarbyloxy with or without the substituent Q, wherein each substituent Q is independently selected from the group consisting of halogen, hydroxy, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, and halogenated C1-C10 alkoxy;
R 3 and R 4 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C10 alkyl with or without the substituent Q, C2-C10 alkenyl with or without the substituent Q, C2-C10 alkynyl with or without the substituent Q, C3-C10 cycloalkyl with or without the substituent Q, C1-C10 alkoxy with or without the substituent Q, C2-C10 alkenoxy with or without the substituent Q, C2-C10 alkynoxy with or without the substituent Q, C3-C10 cycloalkoxy with or without the substituent Q, C6-C15 aryl with or without the substituent Q, C6-C15 aryloxy with or without the substituent Q, C7-C15 aralkyl with or without the substituent Q, C7-C15 aralkoxy with or without the substituent Q, C7-C15 alkaryl with or without the substituent Q, and C7-C15 alkaryloxy with or without the substituent Q.

2. The diimine-metal complex as claimed in claim 1 , wherein each substituent Q is independently selected from the group consisting of halogen, hydroxy, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, and halogenated C1-C6 alkoxy, and wherein R 1 and R 2 are independently selected from the group consisting of C1-C20 alkyl with or without the substituent Q and C6-C20 aryl with or without the substituent Q; and/or
each M is independently selected from the group consisting of nickel and palladium; and/or
each Y is independently selected from the group consisting of O and S; and/or
each X is independently selected from the group consisting of halogen, C1-C10 alkyl with or without the substituent Q and C1-C10 alkoxy with or without the substituent Q; and/or
each R 11 is independently a C1-C20 alkyl with or without the substituent Q; and/or
R 3 and R 4 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C20 alkyl with or without the substituent Q, C2-C20 alkenyl with or without the substituent Q, C2-C20 alkynyl with or without the substituent Q, C1-C20 alkoxy with or without the substituent Q, C2-C20 alkenoxy with or without the substituent Q, C2-C20 alkynoxy with or without the substituent Q, C6-C20 aryl with or without the substituent Q, C6-C20 aryloxy with or without the substituent Q, C7-C20 aralkyl with or without the substituent Q, C7-C20 aralkoxy with or without the substituent Q, C7-C20 alkaryl with or without the substituent Q, and C7-C20 alkaryloxy with or without the substituent Q.

3. The diimine-metal complex as claimed in claim 1 , which is represented by Formula III:

wherein, R 1 -R 5 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C10 alkyl with or without the substituent Q, C3-C10 cycloalkyl with or without the substituent Q, C1-C10 alkoxy with or without the substituent Q, C3-C10 cycloalkoxy with or without the substituent Q, C6-C15 aryl with or without the substituent Q, C7-C15 aralkyl with or without the substituent Q, and C7-C15 alkaryl with or without the substituent Q;
R 3 and R 4 are each independently selected from the group consisting of hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy and halogen;
each M is nickel;
each Y is O;
each X is independently selected from the group consisting of fluorine, chlorine and bromine; and
each Ru is independently a C1-C20 alkyl with or without the substituent Q.

4. The diimine-metal complex as claimed in claim 3 , wherein in the Formula III,
R 1 -R 5 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C10 alkyl with or without the substituent Q, C3-C10 cycloalkyl with or without the substituent Q, C1-C10 alkoxy with or without the substituent Q, C3-C10 cycloalkoxy with or without the substituent Q, C6-C15 aryl with or without the substituent Q, C7-C15 aralkyl with or without the substituent Q, and C7-C15 alkaryl with or without the substituent Q;
R 3 and R 4 are each independently selected the group consisting of hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, and halogen;
each M is nickel;
each Y is O;
each X is independently selected from the group consisting of fluorine, chlorine, and bromine;
each R 11 is independently C1-C10 alkyl with or without the substituent Q; and
each substituent Q is independently selected from the group consisting of halogen, hydroxy, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, and halogenated C1-C6 alkoxy.

5. The diimine-metal complex as claimed in claim 1 , which is represented by Formula Ia:

wherein, R 5 -R 7 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C20 hydrocarbyl with or without the substituent Q, C1-C10 alkoxy with or without the substituent Q, C2-C10 alkenoxy with or without the substituent Q, C2-C10 alkynoxy with or without the substituent Q, C3-C10 cycloalkoxy with or without the substituent Q, C6-C15 aryloxy with or without the substituent Q, C7-C15 aralkoxy with or without the substituent Q, and C7-C15 alkaryloxy with or without the substituent Q, and R 5 -R 7 are optionally joined to form a ring or ring system; and
R 1 , R 2 , R 11 , Y, M and X are as defined for the Formula I.

6. The diimine-metal complex as claimed in claim 5 , having at least one of the following features:
R 1 and R 2 are independently selected from the group consisting of C1-C20 alkyl with or without the substituent Q and C6-C20 aryl with or without the substituent Q;
each M is independently selected from the group consisting of nickel and palladium;
each Y is independently selected from the group consisting of O and S;
each X is independently selected from the group consisting of halogen, C1-C10 alkyl with or without the substituent Q and C1-C10 alkoxy with or without the substituent Q;
each R 11 is independently a C1-C20 alkyl with or without the substituent Q; and
each substituent Q is independently selected from the group consisting of halogen, hydroxy, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, and halogenated C1-C10 alkoxy.

7. The diimine-metal complex as claimed in claim 5 , which is repre

Assignees

• China Petroleum & Chem Corp
• Beijing Res Inst Chemical Ind China Petroleum & Chemical Corp

Inventors

• Gao Rong
• Lai Jingjing
• Guo Zifang
• Gou Qingqiang
• Zhou Junling
• Liu Dongbing
• Zhang Xiaofan
• Lin Jie
• Li Xinyang
• Zhang Junhui
• Gu Yuanning
• Li Yan
• An Jingyan
• Fu Jie
• Wan Yanhong

Classifications

• C08F4/7006

  NN · CPC title

• C07F15/0066

  without a metal-carbon linkage · CPC title

• C07F15/045 Primary

  without a metal-carbon linkage · CPC title

• C08F110/02

  Ethene · CPC title

• C08F4/65912

  in combination with an organoaluminium compound · CPC title