AbstractThe permeability of four structurally related poly(alkoxyphosphazenes), three isomers of poly(dibutoxyphosphazenes) (PBuP), and poly(di‐neopentyloxyphosphazene) (Pneo‐PeP), to 13 gases has been determined by the time‐lag method. Systematic variations in chemical structure have shown a large effect of side chains on permeabilities and permselectivities. The permeability of poly(di‐n‐butoxyphosphazene) (Pn‐BuP) is of the order of 10−8cm3(STP) cm/(cm2s cmHg) for many gases, and the value for a large gas is higher than that for a smaller one. For small gases such as He and H2, poly(di‐sec‐butoxyphosphazene) (Ps‐BuP) is as permeable as Pn‐BuP, but its diffusivities for larger gases such as Xe and C3H8are about one order lower than those of Pn‐BuP. While the permselectivity of Pn‐BuP is determined by the solubility, that of Ps‐BuP depends on both the diffusivity and solubility factors. The property of poly(diisobutoxyphosphazene) (Pi‐BuP) is intermediate between them. These polymers are constitutionally identical, and the only difference is the arrangements of carbons in the side groups. As the side chains become bulky, the permeability decreases, whereas the permselectivity increases. Further decreases of diffusivity and then permeability are observed for Pneo‐PeP, whose side groups have one more methyl group than does Pi‐BuP. But the solubility data are not much different from other three polymers and the diffusivity factor becomes more significant in permselectivity. The diffusivity depends on the polymer structure much more than does the solubility. The relationships between chemical structure and gas diffusi
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