Ionic polymers containing spiro structure and preparation method and application thereof

Patent metadata

Field	Value
Publication number	US-12460045-B2
Application number	US-202418652820-A
Country	US
Kind code	B2
Filing date	May 2, 2024
Priority date	May 19, 2023
Publication date	Nov 4, 2025
Grant date	Nov 4, 2025

Abstract

The present invention introduces ionic polymers featuring with a spiro structure, which enhances the solubility and gas permeability of the ionic polymer while maintaining excellent conductivity, mechanical properties, and dimensional stability. This is achieved by incorporating a spiro fragment with a large free volume into the polymer backbone. As a result, the gas permeability of the catalyst layer prepared from this ionic polymer is improved, making it suitable as a catalyst binder for proton exchange membrane fuel cells (PEMFCs) or anion exchange membrane fuel cells (AEMFCs). Furthermore, the electrochemical performance of the fuel cell is enhanced. Additionally, the proton exchange membrane and anion exchange membrane derived from this ionic polymer containing a spiro structure effectively improve the conductivity of both types of membranes by increasing the space volume due to the presence of the large free volume spiro fragment.

First claim

What is claimed is:

1 . An ionic polymer containing a spiro structure, having a structure as shown in Formula I:

wherein m in Formula I determines the size of the spiro, and m is independently an integer between 2 and 4;
x in Formula I is any number between 0.01 and 1.00, y and z are each independently any number between 0 and 0.99, x+y+z=1, and when z is 0, R 2 contains at least a cationic group;
n in Formula I represents a degree of polymerization, and n is an integer between 10 and 1,000,000;
each R 1 in Formula I is:

p being an integer between 1 and 15;
each R 2 in Formula I is independently selected from a hydrogen atom or a cationic group, in which case the ionic polymer of the structure shown in Formula I is a cationic polymer containing a spiro structure, and a counter ion is an anion; wherein R 2 is selected from one or more of the following structures:

and when z=0, R 2 in x and y units cannot simultaneously be a hydrogen atom; R 01 , R 02 , R 03 , R 04 , and R 05 are each independently selected from a hydrocarbyl with the carbon atom number of 1 to 10; a counter anion A − is selected from a halide ion, a hydroxide ion, or a bicarbonate ion; when the polymer of the structure shown in Formula I is the cationic polymer containing the spiro structure, R 4 in —Ar 2 — fragment is a quaternary ammonium cationic group if z is not 0;
each R 3 in Formula I is independently selected from one or more of the following structures:

each —Ar 1 — fragment in Formula I is independently selected from one or more of the following structures:

the —Ar 2 — fragment in Formula I is the following structure with ionic groups:

each R′ being independently selected from the alkylene or arylene groups with the carbon atom number of 1 to 15; R 4 being a cationic group from one or more of the following structures:

R 01 , R 02 , R 03 , R 04 , and R 05 being each independently selected from a hydrocarbyl with the carbon atom number of 1 to 10; a counter ion A − being selected from a halide ion, a hydroxide ion, or a bicarbonate ion.

2 . The ionic polymer containing a spiro structure according to claim 1 , wherein
each R 1 in Formula I is independently selected from one or more of the following structures:

R 2 in Formula I is independently selected from the hydrogen atom or the cationic group, in which case the ionic polymer of the structure shown in Formula I is the cationic polymer containing the spiro structure, and the counter ion is the anion; R 2 is independently selected from

each —Ar 1 — fragment in Formula I is independently selected from one or more of the following structures:

each the —Ar 2 — fragment in Formula I is independently selected from one or more of the following structures:

each R′ being independently selected from an alkylene or an arylene group with the carbon atom number of 1 to 15; R 4 being a cationic group.

3 . A preparation method of the ionic polymer containing a spiro structure according to claim 1 , wherein when each R 2 in Formula I is independently selected from one or more of

R 4 in Formula I is the quaternary ammonium cation, having one or more of the following structures:

R 01 , R 02 , R 03 , R 04 , and R 05 being each independently selected from a hydrocarbyl with the carbon atom number of 1 to 10; a counter ion A − being selected from a halide ion, a hydroxide ion, or a bicarbonate ion;
the ionic polymer of the structure shown in Formula I is a cationic polymer containing a spiro structure, and a preparation method of the cationic polymer containing the spiro structure comprises the following steps:
mixing a halogen-terminated polymer precursor with the structure shown in Formula II, a first organic solvent, and a tertiary amine compound, and then carrying out a first substitution reaction to obtain the cationic polymer containing the spiro structure,

in Formula II, X 1 , X 2 , and X 3 being each independently selected from a halogen atom or a hydrogen atom, and when z=0, X 1 and X 2 being not hydrogen atoms at the same time;
in Formula II, Ar 2 ′ is an arylene unit tethering with halogen atoms, having the following structure:

each R′ being independently selected from an alkylene or an arylene group with the carbon atom number of 1 to 15, and X 4 being a halogen atom selected from one or more of Cl, Br, and I; and
the tertiary amine compound being selected from one or more of

R 01 , R 02 , R 03 , R 04 , and R 05 being each independently selected from a hydrocarbyl with the carbon atom number of 1 to 10.

4 . The preparation method of the ionic polymer containing a spiro structure according to claim 3 , wherein a preparation method of the halogen-terminated polymer precursor with the structure shown in Formula II comprises the following steps:
performing a polycondensation reaction after mixing a spiro-containing aromatic compound, Ar 1 ′, Ar 2 ″, a ketone monomer, and a second organic solvent and an organic strong acid, to obtain the halogen-terminated polymer precursor with the structure shown in Formula II, wherein the polycondensation reaction is shown in Formula III,

wherein in Formula III, when the amount of Ar 1 ′ as a raw material is zero, y=0; in Formula III, when the amount of Ar 2 ″ as a raw material is zero, z=0;
in Formula III, X is independently selected from a halogen atom or a hydrogen atom, X 1 , X 2 , and X 3 are each independently selected from a halogen atom or a hydrogen atom, and when z=0, X 1 and X 2 are not hydrogen atoms at the same time;
the spiro-containing aromatic compound has one or more of the following structures:

a structure of the ketone monomer is

Ar 1 ′ is an aromatic

Assignees

• Univ Hefei Technology

Inventors

• Wei Haibing
• Jiang Tao
• Wang Tao
• Zhao Yu
• Li Xueliang
• Yang Shanzhong
• Ding Yunsheng

Classifications

• H01M2300/0014

  Alkaline electrolytes · CPC title

• H01M8/1081 Primary

  starting from solutions, dispersions or slurries exclusively of polymers · CPC title

• H01M8/1058

  characterised by a porous support having no ion-conducting properties · CPC title

• H01M8/103

  having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh] · CPC title

• C08J5/2218

  Synthetic macromolecular compounds · CPC title