Block sulfonated polyphenylene, and preparation method and application thereof

A technology of sulfonated poly and sulfonated chains, applied in electrical components, circuits, battery pack parts, etc., can solve the problems of poor mechanical properties, poor film-forming properties, and low water resistance of sulfonated polyimides. Achieve the effects of high mechanical strength, high proton conductivity, and excellent chemical stability

Active Publication Date: 2012-11-21
陈康成
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, because these materials have their own shortcomings, such as sulfonated polysulfone, sulfonated polyphenylene ether, sulfonated polyetheretherketone proton ...

Method used

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  • Block sulfonated polyphenylene, and preparation method and application thereof
  • Block sulfonated polyphenylene, and preparation method and application thereof
  • Block sulfonated polyphenylene, and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0043] In this example, the synthesis of sulfonated polyphenylene block polyether ether ketone copolymer is taken as an example. The structural formula is as follows. The specific preparation method includes the following steps:

[0044]

[0045] (1) Preparation of non-sulfonated segment (B) polyether ether ketone with -Cl group as the end group: in N 2 Under protection, first set as Ar 2 monomeric 4,4-dichlorobenzophenone (10 mmol) and as Ar 3 The monomeric 2,2-(4-hydroxybenzene)hexafluoropropane (11 mmol) was dissolved in N,N-dimethylacetamide (DMAC) solvent, and K 2 CO 3 (20mmol), react at 100°C for 2 hours, then react at 160-180°C for 20 hours, and cool to room temperature. At this time, the monomer Ar 2 and Ar 3 After the reaction is completed, an oligomer chain segment terminated by the -OH group is formed, and the length of the oligomer chain segment n=M Ar2 / (M Ar3 -M Ar2 ), wherein M is the number of moles of the monomer, and the length of the oligomer chai...

Embodiment 2

[0049] In this example, the sulfonated polyphenylene block polyetheretherketone copolymer in Example 1 is taken as an example, the structural formula is the same as that in Example 1, and the specific preparation method includes the following steps:

[0050] (1) Preparation of non-sulfonated segment (B) polyether ether ketone with -Cl group as the end group: in N 2 Under protection, first set as Ar 2 monomeric 4,4-difluorobenzophenone (15 mmol) and as Ar 3 Add K 2 CO 3 (20mmol), react at 100°C for 2 hours, then react at 120-140°C for 20 hours, and cool to room temperature. At this time, the monomer Ar 2 and Ar 3 After the reaction is completed, an oligomer chain segment terminated by an -OH group is formed, and the length of the oligomer chain segment is n=15. Adding Ar as a capping group 4 The monomer (4-fluorobenzoyl) p-chlorobenzene was 3.6 mmol, and the temperature of the reaction system was raised to 150°C to continue the reaction for 24 hours.

[0051] The reacti...

Embodiment 3

[0054] This embodiment takes the synthesis of sulfonated polyphenylene block polyoctafluorobiphenyl sulfide copolymer as an example, the structural formula is as follows, and the specific preparation method includes the following steps:

[0055]

[0056] (1) Preparation of non-sulfonated segment (B) polyoctafluorobiphenyl sulfide with -Cl group as the terminal group: in N 2 Under protection, first set as Ar 2 Monomer perfluorobiphenyl (20mmol) and as Ar 3 Monomer 2,2-(4-mercaptophenyl)propane (21mmol) was dissolved in N,N-dimethylformamide solvent, adding K 2 CO 3 (20 mmol), react at 80°C for 2 hours, then react at 120-140°C for 12 hours, and cool to room temperature. At this time, the monomer Ar 2 and Ar 3 After the reaction is completed, an oligomer chain segment terminated by a -SH group is formed, and the length of the chain segment in this embodiment is n=20. Add 2.4 mmol of Ar4 monomer (4-fluorobenzoyl) p-chlorobenzene as a capping group, and raise the temperatu...

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Abstract

The invention provides block sulfonated polyphenylene, and a preparation method and application thereof. According to the invention, the method employs a catalyst system consisting of transition metal Ni[0] used as a catalyst, triphenylphosphine used as a coordination agent and zinc powder used as a reducing agent, and an aprotic solvent is used as a reaction medium for copolymerization of sulfonated monomers having proton conduction performance and non-sulfonated monomers so as to obtain the target block sulfonated polyphenylene copolymer. The copolymer is dissolved in an organic solvent so as to obtain a uniform solution, and a membrane is prepared by using a casting or tape casting process. The sulfonated polyphenylene proton exchange membrane provided by the invention has excellent proton conduction performance under the condition of low humidity, high chemical stability and high mechanical properties, can be used in the fields of proton exchange membrane fuel cells and redox flow batteries, and has a wide application range and a good commercial application prospect.

Description

technical field [0001] The invention belongs to the field of polymer materials, in particular to a block sulfonated polyphenylene and its preparation method and application. Background technique [0002] Proton exchange membranes can not only separate the battery to form two poles but also conduct protons effectively, and are widely used in fuel cells and flow batteries and other fields. At present, the marketed perfluorosulfonic acid polymer proton exchange membrane is not only expensive, but also has the problems of low operating temperature and high fuel and electrolyte permeability, which greatly limits the marketization of fuel cells and flow batteries. . [0003] Sulfonated aromatic polymers, such as sulfonated polysulfone, sulfonated polyphenylene ether, sulfonated polyether ether ketone, and sulfonated polyimide, have been extensively studied as proton exchange membrane materials. However, because these materials have their own shortcomings, such as sulfonated poly...

Claims

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Application Information

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IPC IPC(8): C08G61/12C08L65/00C08J5/18H01M2/16
CPCY02E60/12Y02E60/10
Inventor 陈康成陆一川施立群
Owner 陈康成
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