Self-Assembly of Hierarchical Structures Using Cyclotriphosphazene-Containing Poly(substituted methylene) Block Copolymers.

The cyclotriphosphazene-substituted diazoacetate homopolymer (polyPNDA') (PNDA' = hexaphenoxy-substituted phosphazene-containing methylene) and a novel poly(substituted methylene) block copolymer, polyPNDA'--poly(hexyloxycarbonylmethylene) (polyPNDA'--polyHDA'), were synthesized, and the self-assembly behavior of these polymers was studied in detail. A hexagonally packed aggregated structure was observed in the self-assembled structure of polyPNDA', whereas a lamellar structure was observed in the microphase-separated nanoassembly of polyPNDA'--polyHDA'. These results indicate that a hierarchical structure composed of highly regular polyPNDA' nanoaggregates and the long-range microphase-separated polyPNDA' and polyHDA' domains had formed.