Synthesis, glass transition behavior, and solution characterization of poly[(aryloxy)thionylphosphazenes] with halogen substituents at sulfur

Abstract

The cyclic thionylphosphazenes [(NSOX)(NPCl 2 ) 2 ] (1a, X=Cl; 1b, X=F) undergo thermal ring-opening polymerization to yield the hydrolytically sensitive, elastomeric poly(thionylphosphazenes) [(NSOX)(NPCl 2 ) 2 ] n (2a, X=Cl, 2b, X=F). The reaction of these polymers with several different sodium aryloxides Na[OAr] yielded the moisture-stable poly[(aryloxy)thionylphosphazenes] [(NSOX)(NP(OAr) 2 ) 2 ] n (3a-6a, X=Cl; 1b and 4b, X=F) in which the sulfur-halogen bonds are retained. Tg's range of these polymers was in the range -56 to +55°C. Their hydrodynamic properties in THF solution was investigated