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

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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 (PI 35 ‐ b ‐PFMS 5 , PI 200 ‐ b ‐PFMS 10 , and PI 247 ‐ b ‐PFMS 23 ) 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. PI 200 ‐ b ‐PFMS 10 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 PI 247 ‐ b ‐PFMS 23 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

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