Synthesis and Solution Self‐Assembly of Polyisoprene‐block‐poly(ferrocenylmethylsilane): A Diblock Copolymer with an Atactic but Semicrystalline Core‐Forming Metalloblock

Abstract

Polyisoprene‐block‐poly(ferrocenylmethylsilane) (PI‐b‐PFMS) copolymers, containing the atactic but semicrystalline PFMS block, have been prepared by sequential anionic polymerization of isoprene and methyl[1]silaferrocenophane. The reaction to form the metalloblock is not living in nature, but still enabled three block copolymers to be prepared (PI35‐b‐PFMS5, PI200‐b‐PFMS10, and PI247‐b‐PFMS23) with relative narrow molar mass distributions (polydispersity < 1.3). The self‐assembly of all three materials was studied in PI selective n‐alkanes and found to afford lenticular platelets, tapered cylindrical micelles, and regular cylinders, as the length of the PFMS block increased. PI200‐b‐PFMS10 micelles could be increased in length by self‐seeding a sample of short micelles at temperatures of 90 °C and above; however, this process also resulted in an increase in width. Addition of a solution of PI247‐b‐PFMS23 copolymer to preformed seed micelles also resulted in an increase in length, although growth is not linearly related to the amount of copolymer added beyond ≈600 nm. image