Search

CN-122011429-A - Method for preparing perfluorosulfonic acid resin dispersion based on liquid phase laser ablation technology

CN122011429ACN 122011429 ACN122011429 ACN 122011429ACN-122011429-A

Abstract

The invention belongs to the technical field of polymer material processing, and particularly relates to a method for preparing perfluorosulfonic acid resin dispersion liquid based on a liquid phase laser ablation technology. The invention takes solid particles of perfluorosulfonic acid resin as raw materials, infiltrates the solid particles into an organic alcohol-water mixed solution after being crushed, regulates and controls laser beams through a galvanometer control system to enable the solid particles to carry out laser ablation on the perfluorosulfonic acid resin infiltrated in a solvent, and promotes the solid perfluorosulfonic acid resin to be dissolved and dispersed in the solvent to form dispersion liquid by utilizing the transient high-temperature high-pressure effect generated by laser in a liquid phase environment. Meanwhile, a water cooling device is adopted to carry out system thermal management, and homogenization treatment is assisted, so that uniformity of the perfluorinated sulfonic acid resin dispersion liquid prepared by laser ablation reaction is ensured to be maintained in the preparation process, and denaturation is avoided. The finally prepared dispersion liquid has the application performance consistent with that of the mature products in the industry, has excellent storage stability, and can be applied to the fields of proton exchange membrane preparation, catalyst coating preparation and the like.

Inventors

  • XU RUIQI
  • LIU PU
  • FU GUOSHUAI

Assignees

  • 激光纳创(佛山)科技有限公司
  • 中山大学

Dates

Publication Date
20260512
Application Date
20260225

Claims (10)

  1. 1. A method for preparing perfluorosulfonic acid resin dispersion based on liquid phase laser ablation technology is characterized in that perfluorosulfonic acid resin solid particles are used as raw materials, dispersed in an organic alcohol-water mixed solvent, a laser path is accurately regulated and controlled through a galvanometer control system, meanwhile, system thermal management is carried out by matching with a water cooling device, the temperature of the system is ensured to be stably maintained within a range of 20-25 ℃, on the basis, perfluorosulfonic acid resin in a step laser ablation technology treatment system is adopted, firstly, resin particles are subjected to irradiation pretreatment by utilizing unfocused low-medium-energy medium-high-frequency laser, then the pretreated resin is subjected to homogenization regulation and control, the laser is switched into a medium-high energy medium-high frequency laser focusing ablation mode, the resin is subjected to deep ablation, and the perfluorosulfonic acid resin solid particles are efficiently dissolved and dispersed in the mixed solvent by means of a high-temperature high-pressure local environment formed when laser acts on a liquid phase, so that the perfluorosulfonic acid resin dispersion with stable performance is finally prepared.
  2. 2. The method for preparing a perfluorosulfonic acid resin dispersion based on liquid phase laser ablation technique according to claim 1, comprising the steps of: S1, crushing solid perfluorosulfonic acid resin particles to millimeter-sized particle size, and dispersing the solid perfluorosulfonic acid resin particles in an organic alcohol-water mixed solvent; S2, applying a temperature external field to the mixed system in the S1 through a water cooling device to realize thermal management, so that the temperature of the system in the subsequent laser liquid phase ablation treatment process is stabilized at 20-25 ℃; S3, carrying out laser liquid phase ablation treatment on the resin in the mixed solvent under the condition of carrying out laser scanning control by a galvanometer control system, wherein the resin in the mixed solvent is pretreated by adopting low-medium-energy medium-high frequency laser unfocused irradiation, the pretreated resin is subjected to homogenization treatment, and the pretreated resin is switched to a medium-high energy medium-high frequency laser focusing mode to ablate, so that the perfluorinated sulfonic acid resin is dissolved under the action of high-energy focusing laser ablation to form perfluorinated sulfonic acid resin dispersion liquid.
  3. 3. The method for preparing a perfluorosulfonic acid resin dispersion based on liquid phase laser ablation technology according to claim 2, wherein the perfluorosulfonic acid resin solid particles have an EW of 800-1100.
  4. 4. The method for preparing the perfluorosulfonic acid resin dispersion liquid based on the liquid phase laser ablation technology according to claim 2, wherein the organic alcohol used in the organic alcohol-water mixed solvent is n-propanol or isopropanol or ethanol, and the volume content of the organic alcohol is 40-80%.
  5. 5. The method for preparing the perfluorosulfonic acid resin dispersion liquid based on the liquid phase laser ablation technology according to claim 2, wherein the laser liquid phase ablation treatment of S3 is performed by adopting a YAG high-energy laser, and the laser is matched with a 355 nm-1064 nm nanosecond laser and a 355 nm-1064 nm laser light guiding system, or a 355 nm-1064 nm picosecond laser and a 355 nm-1064 nm laser light guiding system, or a 355 nm-1064 nm millisecond laser and a 355 nm-1064 nm laser light guiding system.
  6. 6. The method for preparing the perfluorosulfonic acid resin dispersion liquid based on the liquid phase laser ablation technology according to claim 2, wherein in the step S3, the laser energy used for pretreatment is 200-600 mj, the frequency is 10-50 hz, the time is 5 min-30 min, the laser energy used for laser focusing ablation is 600 mj-1000 mj, the frequency is 10-50 hz, and the time is 15 min-6 h.
  7. 7. The method for preparing the perfluorosulfonic acid resin dispersion liquid based on the liquid phase laser ablation technology according to claim 2, wherein in S3, the scanning mode of the galvanometer control system is full coverage or only outer diameter, the scanning track is rectangular or circular, and the scanning speed is 10 mm/S-100 mm/S.
  8. 8. The method for producing a perfluorosulfonic acid resin dispersion based on liquid phase laser ablation according to claim 2, wherein S1 is pulverizing solid perfluorosulfonic acid resin particles to a particle-to-millimeter size by shearing or grinding.
  9. 9. The method for preparing the perfluorosulfonic acid resin dispersion liquid based on the liquid phase laser ablation technology according to claim 2, wherein the mass concentration of the perfluorosulfonic acid resin dispersion liquid is 5% -20%.
  10. 10. A perfluorosulfonic acid resin dispersion prepared by the method according to any one of claims 1 to 9.

Description

Method for preparing perfluorosulfonic acid resin dispersion based on liquid phase laser ablation technology Technical Field The invention belongs to the technical field of polymer material processing, and particularly relates to a method for preparing perfluorosulfonic acid resin dispersion liquid based on a liquid phase laser ablation technology. Background Perfluorosulfonic acid resin (PFSA), nafion-H, is an ionomer composed of a hydrophobic perfluorocarbon backbone and hydrophilic sulfonic acid group (-SO 3 H) side chains, and is also the strongest solid superacid known at present. The internal hydrophilic ion clusters are dispersed in the resin matrix, and the ion clusters are mutually communicated through channels, so that water molecules and ions can complete migration through the channels. This unique structure imparts excellent heat resistance, excellent chemical and electrochemical stability, high mechanical strength, and excellent high proton conductivity and selective ion transport properties to the perfluorosulfonic acid resin. The perfluorinated sulfonic acid resin dispersion liquid is a derivative product of perfluorinated sulfonic acid resin, and the material takes submicron or nanometer colloid particles as a form of existence, can be stably dispersed in alcohol-water mixed solvent, and belongs to a typical colloid system. The perfluorinated sulfonic acid resin dispersion liquid is often used as a binder, is suitable for preparing materials such as electrolyte films, proton exchange films, catalyst coating films and the like, and can be used as an ion conductor to effectively promote mass transfer process and promote electrochemical reaction efficiency. The mass concentration of the commercially available perfluorosulfonic acid resin dispersion liquid covers 5%, 10%, 15% and 20% of four specifications, wherein the 5% concentration product is widely applied to experimental researches such as electrode modification and catalyst slurry preparation of universities and scientific research institutions due to good fluidity and easy preparation, and the 15% concentration product and the 20% concentration product are more suitable for industrial mass production application. The main flow preparation technology of the commercial perfluorosulfonic acid resin dispersion liquid is an alcohol-water solvent high-temperature high-pressure method. The perfluorinated sulfonic acid resin has special physicochemical properties and extremely low solubility in water, so that a stable dispersion system can be formed by adding a corresponding organic solvent and assisting in a high-temperature and high-pressure environment. The process generally takes a mixed solution of high-boiling-point alcohols and water as a solvent, reacts for a plurality of hours in a reaction furnace under the high-temperature and high-pressure condition of more than 200 ℃, and then is replaced by a target alcohol solvent through a complex process, so that the perfluorosulfonic acid resin dispersion is finally prepared. However, the main flow process has the obvious defects that the high-temperature and high-pressure reaction conditions have strict requirements on the material and safety performance of a reaction kettle, the perfluorosulfonic acid resin is easy to denature after long-time high-temperature and high-pressure treatment, the product performance is further influenced, the whole process flow is complicated, the time is long, the production efficiency is low, and meanwhile, the process energy consumption and the production cost are both at high levels. Disclosure of Invention In order to overcome the defects of the prior art, the invention provides a method for preparing the perfluorosulfonic acid resin dispersion liquid based on a laser liquid phase melting technology, which adopts the laser liquid phase melting technology, a galvanometer control system is used for regulating and controlling laser parameters in the processing process, a water cooling device is matched for realizing system heat management, and homogenization treatment of the perfluorosulfonic acid resin is finished by means of homogenization treatment, so that high-efficiency and rapid batch preparation of the perfluorosulfonic acid resin dispersion liquid is realized under the condition of normal temperature and normal pressure, the application performance of the obtained product is equal to that of an industry mature product, and the method has excellent storage stability, and meanwhile, the method can obviously reduce the production energy consumption and cost, and provides a better technical route for preparing the perfluorosulfonic acid resin dispersion liquid. In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: the invention provides a method for preparing a perfluorosulfonic acid resin dispersion based on a liquid phase laser ablation technology, which comprises the steps of taking perfluorosulfonic acid res