CN-116217967-B - Preparation method of perfluorosulfonic acid resin alcohol aqueous dispersion

Abstract

The invention discloses a preparation method of a perfluorosulfonic acid resin alcohol aqueous dispersion, which is characterized in that perfluorosulfonic acid resin solid is placed in a high-pressure reaction kettle, water is used as a solvent, under the protection of inert gas, the perfluorosulfonic acid resin aqueous dispersion is obtained by stirring and dissolving the perfluorosulfonic acid resin solid at high temperature and high pressure for 4-20 hours, the perfluorosulfonic acid resin aqueous dispersion is placed in a glass reaction kettle, and is mixed with an organic solvent to react for 2-8 hours under a certain temperature condition, so that the perfluorosulfonic acid resin alcohol aqueous dispersion with uniformly dispersed molecular chains is obtained through secondary dispersion. The preparation method has the advantages of simple process, short time consumption and suitability for industrialization, and the prepared perfluorosulfonic acid resin alcohol aqueous dispersion has moderate particle size and uniformly dispersed molecular chains, and is suitable for proton membrane coating process, thereby preparing the composite proton exchange membrane with excellent mechanical property and electrochemical property.

Inventors

• HE TONG
• WANG MING
• YANG DONGDONG
• Lei Xueying
• JIANG SHAOQIANG
• YANG CHAO
• FAN YING

Assignees

• 四川东材新材料有限责任公司

Dates

Publication Date

20260505

Application Date

20230118

Claims (3)

1. 1. The preparation method of the perfluorosulfonic acid resin alcohol aqueous dispersion liquid is characterized by comprising the following steps: a. placing perfluorosulfonic acid resin solid into a high-pressure reaction kettle, taking water as a solvent, and stirring and dissolving for 4-20 hours under the protection of inert gas at the reaction temperature of 180-240 ℃ and the pressure of 1-10 MPa to obtain perfluorosulfonic acid resin aqueous dispersion; The perfluorinated sulfonic acid resin solid is composed of a polytetrafluoroethylene structure (-CF 2 -CF 2 -) serving as a main chain and- [ OCF 2 C(CF 3 )F] m -O[CF 2 CF 2 ]n-SO 3 H serving as a side chain, wherein m=0 or 1 and n=1 or 2; The weight percentage content of the perfluorinated sulfonic acid resin solid is 5% -30%; b. C, placing the perfluorosulfonic acid resin aqueous dispersion liquid obtained in the step a into a glass reaction kettle, mixing with an organic solvent, and reacting for 2-8 hours at the reaction temperature of 40-70 ℃ to obtain perfluorosulfonic acid resin alcohol aqueous dispersion liquid; the organic solvent is one or a mixture of more than two of ethanol, n-propanol, isopropanol, propylene glycol, glycerol and n-butanol, and the weight percentage of the organic solvent is 20% -60%.
2. 2. The process for preparing an aqueous dispersion of perfluorosulfonic acid resin alcohol according to claim 1, wherein said perfluorosulfonic acid resin solid in step a is any one of or a mixture of two or more of Nafion ® NR50, aquivion ® PW-79S, asahi Kabushiki Kaisha, japan, and Flemion ® F-9010 of Dupont.
3. 3. A process for preparing an aqueous dispersion of perfluorosulfonic acid resin alcohol as claimed in claim 1 or 2, wherein the inert gas in step a is one or a mixture of two or more of nitrogen, helium and argon.

Description

Preparation method of perfluorosulfonic acid resin alcohol aqueous dispersion Technical Field The invention belongs to the field of proton exchange membrane preparation, and relates to a preparation method of perfluorosulfonic acid resin alcohol aqueous dispersion liquid. The prepared perfluorosulfonic acid resin alcohol aqueous dispersion has uniform dispersion of molecular chains and excellent performance, and is suitable for proton membrane coating process and further used for preparing proton exchange membrane hydrogen fuel cells. Background In the 21 st century, along with the continuous progress of technology, people have increasingly demanded energy and the problem of shortage of fossil energy has become serious, and various countries in the world have turned technological emphasis to the development of new energy. The hydrogen energy is widely focused due to the characteristics of high cleanness, high efficiency, good storage and transportation performances and the like, and is praised as the final energy source in the 21 st century. The proton exchange membrane hydrogen fuel cell is a clean and efficient electrochemical power generation device, has low operating temperature and high specific power, and has good application prospect in the industries of mobile power sources, automobiles and the like. The perfluorinated sulfonic acid resin dispersion liquid is a key material for preparing proton exchange membrane hydrogen fuel cells, and the wettability of solvents in the solution to porous polytetrafluoroethylene and the particle size and dispersion state of resin molecules have great influence on the performance of the prepared proton exchange membrane. The current commercial perfluorosulfonic acid resin dispersion cannot meet the preparation requirements of the composite proton exchange membrane with porous polytetrafluoroethylene as a matrix. Accordingly, in order to develop a perfluorosulfonic acid resin dispersion suitable for the preparation of a composite proton exchange membrane, researchers have conducted a great deal of research on the preparation method of perfluorosulfonic acid resin solutions. In the prior art, the preparation method of the perfluorosulfonic acid resin dispersion liquid is to directly dissolve the perfluorosulfonic acid resin solid under certain temperature and pressure conditions by adopting an organic solvent (refer to a preparation method of the perfluorosulfonic acid resin dispersion liquid with uniformly dispersed molecular chains disclosed in CN103146001A and a preparation method of the perfluorosulfonic acid resin dispersion liquid disclosed in CN 104140542A). However, impurities such as ethers generated by dehydroxylation of the organic solvent are generated in the process, and the subsequent liquid separation is needed to be processed to obtain a clear perfluorosulfonic acid resin dispersion liquid, which is long in time consumption, complex in operation process and not guaranteed in performance. Therefore, there is a need to develop a method for preparing a perfluorosulfonic acid resin dispersion liquid having a low cost, a short time consumption, and a simple operation, in which molecular chains are uniformly dispersed. Disclosure of Invention The invention aims to overcome the defects that impurities such as ethers and the like are easy to generate in the preparation method of the perfluorosulfonic acid resin dispersion liquid in the prior art, the post-dissolution treatment process is complex and the like, and provides a preparation method of perfluorosulfonic acid resin alcohol aqueous dispersion liquid. The method is characterized by simple process, short time consumption and suitability for industrialization, and the prepared perfluorinated sulfonic acid resin alcohol aqueous dispersion has moderate particle size and uniformly dispersed molecular chains, and has good infiltration effect on PTFE (polytetrafluoroethylene) when the composite proton exchange membrane taking the e-PTFE (expanded polytetrafluoroethylene for short) as a matrix is prepared, and can promote better combination of resin molecules and the matrix, thereby preparing the composite proton exchange membrane with excellent mechanical property and electrochemical property. The invention relates to a preparation method of perfluorosulfonic acid resin alcohol aqueous dispersion liquid, which is characterized by comprising the following steps: a. Placing the perfluorosulfonic acid resin solid into a high-pressure reaction kettle, taking water as a solvent, and stirring and dissolving at high temperature and high pressure for 4-20 hours under the protection of inert gas to obtain perfluorosulfonic acid resin aqueous dispersion; b. And d, placing the perfluorosulfonic acid resin aqueous dispersion liquid obtained in the step a into a glass reaction kettle, mixing with an organic solvent, and reacting for 2-8 hours under a certain temperature condition to obtain the perfluorosulfonic acid resin