Method for preparing olefin-polar monomer copolymer

Patent metadata

Field	Value
Publication number	US-12428505-B2
Application number	US-202017755542-A
Country	US
Kind code	B2
Filing date	Oct 30, 2020
Priority date	Oct 31, 2019
Publication date	Sep 30, 2025
Grant date	Sep 30, 2025

Abstract

A method for preparing an olefin-olefinic alcohol copolymer and an olefin-olefinic alcohol copolymer prepared by the method are provided. The catalyst used in the method for preparing the olefin-olefinic alcohol copolymer has a diimine metal complex as shown in Formula I.

First claim

We claim:

1. A method for preparing an olefin-polar monomer copolymer, comprising copolymerizing an olefin and a polar monomer in the presence of a catalyst and optionally a chain transfer agent to produce the olefin-polar monomer copolymer,
wherein, the catalyst comprises a main catalyst and optionally a cocatalyst, the main catalyst comprises 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 a 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 a substituent Q; each Y is independently a Group VIA non-metal atom; each M is independently a Group VIII metal; each X is independently selected from the group consisting of halogen, C1-C10 hydrocarbyl with or without a substituent Q and C1-C10 hydrocarbyloxy with or without a substituent Q, or
the main catalyst comprises an amino-imine 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; each R 3 is independently selected from the group consisting of hydrogen and C1-C20 hydrocarbyl with or without a substituent Q; R 5 to R 8 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, and C1-C20 hydrocarbyl with or without a substituent Q, and R 5 to R 8 groups are optionally joined to form a ring or ring system; each R 12 is independently a C1-C20 hydrocarbyl with or without a substituent Q; each Y is independently a Group VIA non-metal atom; each M is independently a Group VIII metal; each X is independently selected from the group consisting of halogen, C1-C10 hydrocarbyl with or without a substituent Q and C1-C10 hydrocarbyloxy with or without a substituent Q,
wherein each substituent Q in the diimine-metal complex or in the amino-imine metal complex 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,
wherein the olefin is an olefin having 2 to 16 carbon atoms, and
wherein the polar monomer is one or more of olefinic alcohols represented by Formula G:

wherein, L 1 -L 3 are each independently selected from the group consisting of H and C1-C30 alkyl with or without a substituent, L 4 is a C1-C30 alkylene optionally having a pendant group, or
alternatively, the polar monomer is an unsaturated carboxylic acid represented by Formula G′:

wherein, L 1 -L 3 are each independently selected from the group consisting of H and C1-C30 alkyl with or without a substituent, L 4 is a C1-C30 alkylene having a pendant group.

2. The method as claimed in claim 1 , wherein:
the main catalyst comprises a diimine metal complex represented by Formula Ib:

wherein, R 1 and R 2 are each independently a C1-C30 hydrocarbyl with or without the substituent Q; R 5 -R 8 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C20 hydrocarbyl with or without the substituent Q, and R 5 -R 8 are optionally joined to form a ring or ring system; each R 12 is independently a C1-C20 hydrocarbyl with or without the substituent Q; each Y is independently a Group VIA nonmetal 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.

3. The method as claimed in claim 2 , having at least one feature selected from:
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 12 is independently a C1-C20 alkyl with or without the substituent Q; and

the substituent Q is selected from the group consisting of halogen, hydroxy, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy and halogenated C1-C6 alkoxy.

4. The method as claimed in claim 2 , wherein the diimine metal complex is represented by Formula IIIb:

wherein, R 1 -R 11 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, and
M, X, Y and R 12 are as defined in claim 2 .

5. The method as claimed in claim 2 , wherein in the diimine metal complex, R 1 -R 11 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, 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, 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.

6. The method as claimed in claim 5 , wherein the diimine metal complex is selected from the group consisting of:
1) The diimine metal complex represented by Formula IIIb, wherein R 1 =R 3 =methyl, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =methyl, R 12 =ethyl, M=Ni, Y=O, X=Br;
2) The diimine metal complex represented by Formula IIIb, wherein R 1 =R 3 =ethyl, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =methyl, R 12 =ethyl, M=Ni, Y=O, X=Br;
3) The diimine metal complex represented by Formula IIIb, wherein R 1 =R 3 =isopropyl, R 2 =R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =methyl, R 12 =ethyl, M=Ni, Y=O, X=Br;
4) The diimine metal complex represented by Formula IIIb, wherein R 1 -R 3 =methyl, R 4 -R 7 =R 10 =H, R 8 =R 9 =R 11 =methyl, R 12 =ethyl, M=Ni, Y=O, X=Br;
5) The diimine metal complex represented by Formula IIIb, wherein R 1 =R 3 =methyl, R 2 =Br, R 4 R 7 =R 10 =H, R 8 =R 9 =R 11 =methyl, R 12 =ethyl, M=Ni, Y=O, X=Br;
6)

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
• Song Wenbo
• Li Xinyang
• Zhang Xiaofan
• Lin Jie
• Liu Dongbing
• Zhang Junhui
• Wang Hongtao
• Zhang Shijun
• Gu Yuanning
• An Jingyan
• Zhao Hui
• Huang Tingjie
• Ma Dong
• Wang Ruen
• Xu Shiyuan
• Fu Jie

Classifications

• B01J23/40

  of the platinum group metals · CPC title

• B01J31/1805

  the ligands containing nitrogen · CPC title

• C08F4/80

  selected from iron group metals or platinum group metals · CPC title

• C08F220/64

  Acids; Metal salts or ammonium salts thereof · CPC title

• C08L23/08

  Copolymers of ethene (C08L23/16 takes precedence) · CPC title