Amorphous Diblock Copolymers with a High Organometallic Block Volume Fraction: Synthesis, Characterization and Self-Assembly of Polystyrene-block-Poly(ferrocenylethylmethylsilane) in the Bulk State

The preparation of polystyrene-b-poly(ferrocenylethylmethylsilane) diblock copolymers (PS-b-PFEMS) with a high volume fraction of the organometallic block (phi(PFEMS) = 0.69-0.87) has been achieved via the sequential living anionic polymerization of styrene and ethylmethylsila[1]ferrocenophane. High molecular weights (M-n = 50000 to 250000 g/mol) and narrow molecular weight distributions (PDI = 1.05-1.17) were achieved. As both of the blocks are amorphous, the resulting diblock copolymers undergo predictable self-assembly in the bulk and well-ordered microdomains are reported. The data described complement previous results on analogous block copolymers with a low PFEMS volume fraction and a morphology diagram for PS-b-PFEMS is described.