Preparation of a New Type of Phosphazene High Polymers Containing 2,2‘-Dioxybiphenyl Groups

Abstract

The direct reaction of [NPCl2]n with the difunctional reagent 2,2‘-dihydroxybiphenyl (HOC6H4C6H4OH) and K2CO3 in tetrahydrofuran gave soluble linear phosphazene high polymers instead of the expected cross-linked products. The reaction of [N3P3Cl6] with 1, 2, or 3 equiv of HOC6H4C6H4OH and K2CO3 in acetone gave the known spiro derivatives [N3P3Cl4(O2C12H8)], [N3P3Cl2(O2C12H8)2], and [N3P3(O2C12H8)3] without formation of bridging products, and the dichloro derivative reacted directly with para-substituted phenols HOC6H4R and K2CO3 in acetone to give the new compounds [N3P3(OC6H4R)2(O2C12H8)2] (R = Br, COC6H5, or OCH3), without signs of replacement of the bis(aryloxy) substituents. In an analogous manner, poly(dichlorophosphazene) [NPCl2]n reacted with HOC6H4C6H4OH and K2CO3 in THF without significant cross-linking to give, depending on the mole ratio, the soluble polymer [NP(O2C12H8)]n (Mw = 450 000, Tg = 160 °C) or the partially substituted polymers {[NP(O2C12H8)]0.35[NPCl2]0.65}n. The latter were subseque...