Precise Synthesis of Clickable Poly(n-hexyl isocyanate)

Well-defined clickable poly(n-hexyl isocyanate) (PHIC) with an azido or alkyne end group as rod-like building block has been prepared by the living coordination polymerization using organotitanium catalysts. The obtained clickable PHIC was subjected to the Cu-catalyzed azide/alkyne cycloaddition for the synthesis of well-defined macromolecular architectures based on PHIC as a rod polymer, e.g., PHIC-b-poly(N-isopropyl acrylamide) as rod–coil block copolymer and 4-arm star PHIC as a rod star polymer. Additionally, PHIC-b-poly(l-lactide) and PHIC-b-poly(e-caprolactone) as novel rod–coil block copolymers were respectively synthesized by the ring-opening polymerizations of l-lactide and e-caprolactone initiated from hydroxyl end-functionalized PHIC. All products were characterized by 1H NMR spectroscopy, MALDI–TOF mass spectrometry, and size exclusion chromatography equipped with multiangle laser light scattering and viscosity detectors.