Copolymer of olefin and unsaturated carboxylic acid or unsaturated carboxylic acid derivative

Patent metadata

Field	Value
Publication number	US-12473387-B2
Application number	US-202318304743-A
Country	US
Kind code	B2
Filing date	Apr 21, 2023
Priority date	Oct 24, 2017
Publication date	Nov 18, 2025
Grant date	Nov 18, 2025

Abstract

A preparation method for a copolymer includes the step(s) of contacting an olefin and an unsaturated carboxylic acid shown in Formula II or a derivative of the unsaturated carboxylic acid shown in Formula II with a catalyst and optionally a chain transfer agent for reaction in the presence of an alkane solvent to obtain the copolymer. The copolymer is a spherical and/or spherical-like copolymer.

First claim

The invention claimed is:

1 . A preparation method for a copolymer, comprising:
in a reaction system, contacting a C 2 -C 16 α-olefin and an unsaturated carboxylic acid of Formula II or a derivative of the unsaturated carboxylic acid of Formula II with a catalyst and optionally a chain transfer agent for reaction in the presence of an alkane solvent to obtain the copolymer,

wherein in the Formula II, each of L 1 , L 2 , and L 3 is independently selected from the group consisting of H and C 1 -C 30 alkyl, and L 4 is a C 1 -C 30 alkylene having a side group selected from the group consisting of C 6 -C 20 aryl, C 1 -C 20 alkyl, and C 1 -C 20 alkoxy, and wherein the catalyst comprises a main catalyst and a co-catalyst, and the main catalyst is selected from at least one metal complex of Formula V:

wherein in the Formula V, R 7 -R 10 are H, and R 1 -R 6 are identical to or different from each other and each independently selected from the group consisting of H and C 1 -C 6 alkyl,
M is nickel,
X is a halogen,
n is 2,
wherein the reaction is carried out at a reaction temperature in a range from 0° C. to 50° C.,
wherein the co-catalyst is selected from the group consisting of an organic aluminum compound and an organic boron compound, and wherein the produced copolymer is in the form of spherical and/or spherical-like particles, at least part of the spherical and/or spherical-like particles of the copolymer have a cavity therein.

2 . The preparation method according to claim 1 , wherein in Formula V, R 7 -R 10 are H, and R 1 -R 6 are identical to or different from each other and each is independently selected from the group consisting of H and C 1 -C 3 alkyl.

3 . The preparation method according to claim 1 , wherein the organic aluminum compound is one or more selected from the group consisting of alkyl aluminoxane, alkylaluminum, and alkylaluminum halides; and
the organic boron compound is selected from the group consisting of aryl boron and borate.

4 . The preparation method according to claim 1 , wherein a concentration of the main catalyst in a reaction system is 0.00001-100 mmol/L; when the co-catalyst is the organic aluminum compound, a molar ratio of aluminum in the co-catalyst and M in the main catalyst is (10-10000000):1; and when the co-catalyst is the organic boron compound, a molar ratio of boron in the co-catalyst and M in the main catalyst is (0.1-1000):1.

5 . The preparation method according to claim 1 , wherein the chain transfer agent is present in the reaction system and is one or more selected from the group consisting of aluminum alkyl, magnesium alkyl, and zinc alkyl, and a molar ratio of the chain transfer agent and M in the main catalyst is (0.1-2000):1.

6 . The preparation method according to claim 1 , wherein a concentration of the unsaturated carboxylic acid of Formula II or the unsaturated carboxylic acid derivative of Formula II in the reaction system is 0.01-6000 mmol/L.

7 . The preparation method according to claim 1 , wherein the reaction is carried out for 10-200 min.

8 . The preparation method according to claim 1 , wherein the copolymer has a number-average molecular weight of 5000-200000.

9 . The preparation method according to claim 1 , wherein a volume of the cavity in the number of the spherical and/or spherical-like particles of the copolymer having a cavity therein is 5-99% of a volume of the spherical and/or spherical-like particles of the copolymer.

10 . The preparation method according to claim 9 , wherein the spherical and/or spherical-like particles of the copolymer have a density of 0.3000-0.8500 g/cm 3 , measured according to GB/T6343-2009.

11 . The preparation method according to claim 9 , wherein an average particle size of the spherical and/or spherical-like particles of the copolymer is 0.1-50.0 mm.

12 . The preparation method according to claim 9 , wherein the produced copolymer comprises a structural unit derived from the C 2 -C 16 α-olefin and a structural unit of Formula I or a structural unit of a derivative of the Formula I,

wherein, in the Formula I, each of L 1 , L 2 , and L 3 is independently selected from the group consisting of H and C 1 -C 30 alkyl, and L 4 is a C 1 -C 30 alkylene having a side group selected from the group consisting of C 6 -C 20 aryl, C 1 -C 20 alkyl, and C 1 -C 20 alkoxy, and the derivative of the Formula I is a IIA, IIIA or IIB Group metal salt of the Formula I.

13 . The preparation method according to claim 12 , wherein, in the copolymer, a content of the structural unit of Formula I or the structural unit of the derivative of Formula I is 0.2-15.0 mol %.

14 . The preparation method according to claim 12 , wherein, in Formula I, L 1 and L 2 are H, L 3 is selected from the group consisting of H and C 1 -C 10 alkyl and L 4 is a C 1 -C 10 alkylene having a side group selected from the group consisting of C 6 -C 10 aryl and C 1 -C 10 alkyl.

Assignees

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

Inventors

• Gao Rong
• Guo Zifang
• Zhou Junling
• Liu Dongbing
• Fu Jie
• Lai Jingjing
• Huang Tingjie
• Xu Shiyuan
• Li Xinyang

Classifications

• C08J2333/02

  Homopolymers or copolymers of acids; Metal or ammonium salts thereof · CPC title

• C08J2323/08

  Copolymers of ethene (C08J2323/16 takes precedence) · CPC title

• C08J2205/04

  characterised by the foam pores · CPC title

• C08J9/16

  Making expandable particles · CPC title

• C08F210/02 Primary

  Ethene · CPC title