Synthesis and characterization of ferrocene containing block copolymers

Narrowly dispersed diblock copolymers containing poly(methyl methacrylate) [PMMA] or poly(nonafluorohexyl methacrylate) [PF9MA] as the first block and poly(ferrocenylmethyl methacrylate) [PFMMA] as the second block, were prepared by anionic polymerization for the first time. Disordered bulk morphologies in the case of PMMA‐ b ‐PFMMA were observed and explained in terms of low Flory–Huggins interaction parameter ( χ  ≤ 0.04). In the case of PF9MA‐ b ‐PFMMA hexagonally packed cylinder morphology (HEX) was substantiated from TEM and SAXS observations. Furthermore, high incompatibility between PF9MA and PFMMA blocks allowed for the formation of well‐ordered ferrocene containing cylinders on silica substrate upon exposure of the thin films to a saturated solvent vapor. It was shown that the cylinder orientation, parallel or perpendicular to the surface, could easily be controlled by appropriate choice of the solvent and without the need for preliminary surface modification, for example by means of grafted brush layer. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 495–503