One-Step Anionic Copolymerization Enables Formation of Linear Ultrahigh-Molecular-Weight Block Copolymer Films Featuring Vivid Structural Colors in the Bulk State.

Ultrahigh-molecular-weight (UHMW) tapered block copolymers (BCPs) consisting of polyisoprene- block-poly(4-methylstyrene) featuring overall molar masses in the range of 1101-2033 kg mol-1 ( Mw) are synthesized via a convenient one-step anionic copolymerization protocol. The obtained UHMW BCPs are investigated by differential scanning calorimetry, size exclusion chromatography, and 1H NMR spectroscopy. Microphase separation for the UHMW BCPs in the bulk state is investigated by transmission electron microscopy (TEM) measurements and scanning electron microscopy (SEM), revealing well-ordered lamellar and spherical domains with large domain sizes in the range of 100-200 nm. Excellent order and periodicity are observed for lamellar morphologies over large film areas of 90 × 120 μm. Because of this high order of the underlying domains and the different refractive indices of the block segments, vivid structural colors can be observed in the bulk state. Structural colors of BCP films are investigated by angle-dependent UV/vis measurements, revealing intensive reflection colors according to Bragg's law of diffraction. The optical characteristics are directly correlated to TEM and SEM results. Moreover, colored BCP films featuring spherical domains for one block segment with domain sizes of 97-122 nm revealed blue structural colors stemming from disordered particle scattering.