Microporous-film-reinforced fluorine-containing cross-linking doping ion-exchange membrane and preparation method thereof
An ion-exchange membrane and ion-doped technology, which is applied in the field of microporous membrane-enhanced fluorine-containing cross-linked doped ion-exchange membrane and its preparation, can solve the problems of alkali instability and strength reduction
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Embodiment 1
[0071] Example 1: The repeating unit is
[0072]
[0073] Polymer with EW=1000 and Zr(HPO 4 ) 2 (Zr(HPO 4 ) 2 The mass ratio with the resin is 3: 100) to make 5wt% propanol aqueous solution, then configure in the perfluoromalonyl peroxide DMF solution with a concentration of 5%, the expanded polytetrafluoroethylene film (pore) with a thickness of 30 μm rate of 70%) was placed in the above solution and soaked for about 1 hour, then the soaked film was dried on a heating plate, and the film was rolled with a rubber roller. Then cast the above solution into a polytetrafluoroethylene mold placed horizontally, and after vacuum drying at 80°C for 12 hours, the film was peeled off. 2 SO 4 The solution was boiled for 1 hour and washed with deionized water. After heat treatment, the membrane was treated with NaOH solution and sulfuric acid solution in sequence to obtain a single-layer perfluorosulfonic acid cross-linked doped ion membrane (1#) of type (I).
Embodiment 2
[0074] Example 2: The repeating unit is
[0075]
[0076] Polymers with EW=800 and the repeating unit as
[0077]
[0078] The polymer with EW=1200 is mixed at a mass ratio of 2:3, and then mixed with SiO with a particle size of 0.03 μm 2 (SiO 2 The mass ratio of perfluorosulfonic acid resin is 5: 100) and tetraphenyltin mixed extrusion to obtain a film thickness of 30 μm and then with 30 μm silicon dioxide modified porous hexafluoropropylene membrane (porosity 94%) passed through at 260 ℃ hot pressing together under vacuum state, then soak in NH in 150℃ vacuum oven for 1 hour 4 Cl in DMF for 5 hours. The soaked membrane was then placed in triethylamine at 200°C for 2 hours to obtain a crosslinked membrane. The membrane was sequentially treated with KOH solution and hydrochloric acid solution to obtain ion-exchange membranes (2#) with cross-linked structures (II) and (V).
Embodiment 3
[0079] Embodiment 3: the repeating unit is
[0080]
[0081] Polymer with EW=1100 and H 3 PW 12 o 40 A 3% polymer solution was prepared at a ratio of 100:1, and the porous Al 2 o 3 Thin film (50% porosity) is immersed in the above-mentioned solution, after 30 minutes, film is taken out and dried, then this film obtains 20 μm cross-linked structure is the ionic membrane of (I) through 50KGy radiation cross-linking. (3#)
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