Synthesis of isocyanate-based brush block copolymers and their rapid self-assembly to infrared-reflecting photonic crystals.

Garret M Miyake, Raymond A Weitekamp, Victoria A Piunova, Robert H Grubbs

Index: J. Am. Chem. Soc. 134(34) , 14249-54, (2012)

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Abstract

The synthesis of rigid-rod, helical isocyanate-based macromonomers was achieved through the polymerization of hexyl isocyanate and 4-phenylbutyl isocyanate, initiated by an exo-norbornene functionalized half-titanocene complex. Sequential ruthenium-mediated ring-opening metathesis polymerization of these macromonomers readily afforded well-defined brush block copolymers, with precisely tunable molecular weights ranging from high (1512 kDa) to ultrahigh (7119 kDa), while maintaining narrow molecular weight distributions (PDI = 1.08-1.39). The self-assembly of these brush block copolymers to solid thin-films and their photonic properties were investigated. Due to the rigid architecture of these novel polymeric materials, they rapidly self-assemble through simple controlled evaporation to photonic crystal materials that reflect light from the ultra-violet, through the visible, to the near-infrared. The wavelength of reflectance is linearly related to the brush block copolymer molecular weight, allowing for predictable tuning of the band gap through synthetic control of the polymer molecular weight. A combination of scanning electron microscopy and optical modeling was employed to explain the origin of reflectivity.