Nonaqueous Interfacial Polymerization-Derived Polyphosphazene Films for Sieving or Blocking Hydrogen Gas

A series of cyclomatrix polyphosphazene films have been prepared by nonaqueous interfacial polymerization (IP) of small aromatic hydroxyl compounds in a potassium hydroxide dimethylsulfoxide solution and hexachlorocyclotriphosphazene in cyclohexane on top of ceramic supports. Via the amount of dissolved potassium hydroxide, the extent of deprotonation of the aromatic hydroxyl compounds can be changed, in turn affecting the molecular structure and permselective properties of the thin polymer networks ranging from hydrogen/oxygen barriers to membranes with persisting hydrogen permselectivities at high temperatures. Barrier films are obtained with a high potassium hydroxide concentration, revealing permeabilities as low as 9.4 × 10^-17 cm³ cm cm^-2 s^-1 Pa^-1 for hydrogen and 1.1 × 10^-16 cm³ cm cm^-2 s^-1 Pa^-1 for oxygen. For films obtained with a lower concentration of potassium hydroxide, single gas permeation experiments reveal a molecular sieving behavior, with a hydrogen permeance of around 10^-8 mol m^-2 s^-1 Pa^-1 and permselectivities of H₂/N₂ (52.8), H₂/CH₄ (100), and H₂/CO₂ (10.1) at 200 °C.