6533b86efe1ef96bd12ccb26

RESEARCH PRODUCT

Electroactive linear-hyperbranched block copolymers based on linear poly(ferrocenylsilane)s and hyperbranched poly(carbosilane)s.

subject

description

A convenient two-step protocol is presented for synthesis of linear-hyperbranched diblock copolymers consisting of a linear, organometallic poly(ferrocenylsilane) (PFS) block and hyperbranched poly(carbosilane) (hbPCS) segments. Linear PFS diblock copolymers were synthesized through photolytic ring-opening polymerization of dimethyl[1]silaferrocenophane as the first block and methylvinyl[1]sila-ferrocenophane as the second. These block copolymers served as polyfunctional cores in a subsequent hydrosilylation polyaddition of different silane-based AB 2 monomers. Three AB 2 monomers (methyldiallylsilane; methyldiundecenylsilane, and ferrocenyldiallylsilane) were investigated; they introduced structural diversity to the hyperbranched block and showed variable reactivity for the hydrosilylation reaction. In the case with the additional ferrocene moiety in the ferrocenyldiallyl-silane monomer, an electroactive hyperbranched block was generated. No slow monomer addition was necessary for molecular-weight control of the hyperbranching polyaddition, as the core had much higher functionality and reactivity than the carbosilane monomers. Different block ratios were targeted and hybrid block copolymers with narrow polydispersity (< 1.2) were obtained. All the resulting polymers were investigated and characterized by size exclusion chromatography, NMR spectroscopy, cyclic voltammetry, and TEM, and exhibited strongly anisotropic aggregation.