Pd-initiated polymerization of cyclophosphazene-containing diazoacetates proceeded in a controlled manner.

The cyclotriphosphazene-substituted diazoacetate homopolymer (polyPNDA′) (PNDA′ = hexaphenoxysubstituted phosphazene-containing methylene) and a novel poly(substituted methylene) block copolymer, polyPNDA′block-poly(hexyloxycarbonylmethylene) (polyPNDA'-b-poly-HDA′), 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′-b-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.

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